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Abstract

The global utilization of hydrogen peroxide, a green oxidant that decomposes in water and oxygen, has gone from 0.5 million tonnes per year three decades ago to 4.5 million tonnes per year in 2014, and is still climbing. With the aim of expanding the utilization of this eminent green chemical across different industrial and civil sectors, the production and use of hydrogen peroxide as a green industrial oxidant is reviewed herein to provide an overview of the explosive growth of its industrial use over the last three decades and of the state of the art in its industrial manufacture, with important details of what determines the viability of the direct production from oxygen and hydrogen compared with the traditional auto-oxidation process.

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... Presently, H 2 O 2 is principally produced using the anthraquinone process, which has many advantages, but also disadvantages, as it requires complex and large-scale infrastructure and generates a substantial volume of waste chemicals. As such, the energy consumption and sustainability of this production process have been debated [4][5][6]. To decrease distribution costs, H 2 O 2 is produced and sent to chemical companies as a concentrated solution (70 wt%), which nevertheless ends up being diluted (2-5 wt%). ...
... Additionally, the multi-step process entails several energy-consuming reactions, making it a process that consumes high amounts of energy. Recent studies have estimated energy consumption at 17.6 kWh kg H2O2 -1 , corresponding to ~ 8.6 GW/yr in 2015, which represents an estimated operating cost of $700 t -1 H2O2 , including materials, maintenance, and capital costs, with estimated sales ranging from $700 to $1200 t − 1 [6,166]. However, it is worth noting its sustainability is currently under discussion [6]. ...
... Recent studies have estimated energy consumption at 17.6 kWh kg H2O2 -1 , corresponding to ~ 8.6 GW/yr in 2015, which represents an estimated operating cost of $700 t -1 H2O2 , including materials, maintenance, and capital costs, with estimated sales ranging from $700 to $1200 t − 1 [6,166]. However, it is worth noting its sustainability is currently under discussion [6]. ...
Article
Hydrogen peroxide (H2O2) is a clean oxidizing reagent with many industrial, environmental, medical, and domestic applications. It has been frequently produced using the anthraquinone oxidation process. However, more recently, the electrochemical production of H2O2 has become a popular alternative, as this process is chemically green and sustainable since it employs abundant and inexpensive starting molecules (O2 and H2O). This review focuses on the electrochemical synthesis of H2O2 using the two-electron water oxidation reaction (2e− WOR) and two-electron oxygen reduction reaction (2e− ORR), both on boron-doped diamond (BDD) electrodes functioning as an anode or cathode, respectively. This review begins by identifying the important and fundamental characteristics of BDD electrodes, as well as the influence of their chemical and physical properties in the electrochemical production of H2O2. The principles and mechanism of the 2e− WOR and 2e− ORR are also discussed. In addition, various environmental applications of H2O2 electrochemical production (via the 2e− ORR and 2e−WOR) are addressed. Finally, the sustainability and costs of BDD electrodes and future strategies to improve BDD performance are considered.
... It is well established that one of the key molecules in chemical industry is hydrogen peroxide, thanks to oxidizing ability of both organic and inorganic substrate under mild condition, being H2O the only coproduct [1]. For example, in chemical synthesis could be used instead of potassium permanganate or dichromate. ...
... At the moment the commercially available H2O2 mainly comes from the anthraquinone oxidation process, which employs hydrogen, anthraquinone and air (O2) as raw materials and Ni or Pd as catalyst [1,4], and is carried out in organic solvents. The use of expensive catalyst and organic solvent are the two main reason that push the research to find green alternatives, which translate to carbonbased material used in aqueous media. ...
Article
Hydrogen peroxide (H2O2) is a key molecule in chemical industrial processes and alterative processes and catalysts are needed to achieve a green in-situ generation. The electrochemical two-electron oxygen reduction (2e-ORR) reactions is one of the most attractive routes along with the water oxidation or the direct synthesis. Here we focused on the 2e-ORR, summarizing the recent advances in the finalization of catalysts for specifically catalyse the generation of H2O2 and technical measures to improve material screening, especially to obtain reliable activity and selectivity data. Firstly, a brief overview of metal-free catalysts is given and secondly a focus on how different strategies are adopted to improve activity and selectivity is reported. Such strategies include to tune the thermodynamic energy barriers by changing the material composition/functionalization and/or to facilitate mass transfer for reactants and products by acting on morphology. Finally, a brief overview of challenges in ink and electrode preparation for the correct screening of H2O2 electrocatalysts is reported.
... % is mainly used for bacteriostatic disinfection of skin, oral mucosa, and wound surfaces. H 2 O 2 solutions of 25~50% concentration are applied in the field of industrial disinfection, such as GMP standard workshops, medical precision instruments and equipment, pipe tuyere, pulp, fabric bleaching, etc. [5]. Its nontoxic, harmless, and pure characteristics make it an ideal medical disinfectant. ...
... According to Equation (5), for this case of 8~35 wt. % concentration, the effective surface tension gradually increases with the increase in the concentration. ...
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Hydrogen peroxide (H2O2) can be considered as a sterilant or a green propellant. For a common use in industrial application, spray is an effective method to form fine H2O2 droplets. In this paper, electrostatic atomization based on the configuration of needle ring electrodes is proposed to produce H2O2 spray by minimizing its effective surface tension. The breakup performances of H2O2 ligaments can be improved by increasing the electric field intensity, reducing the nozzle size, and adjusting suitable volume flow rate. The smallest average diameter of breakup droplets for 35 wt. % concentration H2O2 solution reached 92.8 μm under optimum operation conditions. The H2O2 concentration significantly influenced the breakup performance owing to the concentration effect on comprehensive physical properties such as density, surface tension, viscosity, and permittivity. The average diameters of breakup droplets decreased with decreasing H2O2 concentration. At 8 wt. % concentration, the average breakup droplet diameter was reduced to 67.4 μm. Finally, electrostatic atomization mechanism of H2O2 solution was analyzed by calculating dimensionless parameters of Re, We, and Oh numbers with the combination of the operation conditions and physical properties for in-depth understanding the breakup behaviors. The calculation showed that the minimum average diameter of breakup droplets was obtained at 8 wt. % concentration at the investigated range of H2O2 concentration, which kept in agreement with the experimental results.
... Oxidation reactions play an important role in the synthesis of platform chemicals for the manufacturing of various everyday products (Goor et al., 2000;Wilson et al., 2017). While chlorinated oxidizers have found a wide application in these processes, their severe impact on the environment and human health has motivated the search for less hazardous reagents (Ciriminna et al., 2016;Flaherty, 2018). With its only oxidation byproduct being water (H 2 O), hydrogen peroxide (H 2 O 2 ) is such a ''green" alternative (Campos-Martin et al., 2006;Ciriminna et al., 2016). ...
... While chlorinated oxidizers have found a wide application in these processes, their severe impact on the environment and human health has motivated the search for less hazardous reagents (Ciriminna et al., 2016;Flaherty, 2018). With its only oxidation byproduct being water (H 2 O), hydrogen peroxide (H 2 O 2 ) is such a ''green" alternative (Campos-Martin et al., 2006;Ciriminna et al., 2016). ...
Article
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Microstructured membrane reactors present a promising approach to master the productivity and safety challenges during the direct synthesis of hydrogen peroxide. However, various mass transport processes occur in this complex system. In order to gain a deeper understanding of these processes, the saturation and desaturation behaviour of the liquid reaction medium with the gaseous reactants is investigated experimentally to examine possible cross-contamination. Moreover, the employed PDMS membrane’s permeances to hydrogen and oxygen are researched at different pressures, by using a variable-pressure/constant-volume setup for the behaviour at ambient pressure and a constant-pressure/variable-volume setup for the behaviour at elevated pressures. A mathematical model in MATLAB is applied to simulate the results. It is shown that a certain desaturation of the gasses through the membrane occurs, and the results are underlined by the modelled ones using a solution-diffusion model in MATLAB. Thus a constant flushing of the gas channels of the reactor is required for safety reasons. Moreover, the measured permeance values indicate that the species transport is mainly limited by the diffusion in the liquid phase and not the membrane resistance.
... The average plant capacity of H 2 O 2 production was 20-40 kT per year with a world capacity of 1.5 million tons up to mid of 1990 (Ranganathan and Sieber, 2018). The plant capacity increases to 300 kT per year with a world capacity of 100% H 2 O 2 which is around 5.5 million tons in 2015 (Ciriminna et al. 2016;Ranganathan and Sieber, 2018). The global producers of H 2 O 2 involves Solvay (30%), Evonik (20%), and Arkema (13%) (Garcia-Serna et al. 2014). ...
Article
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This paper reviews the improvement in the field of catalytic hydrogenation of 2-ethylanthraquinone to 2-ethylanthrahydroquinone for the successful production of hydrogen peroxide. Hydrogen peroxide is being used in almost all industrial areas, particularly in the chemical industry and in environmental protection, as the most promising oxidant for cleaner and environmentally safer processes. A variety of hydrogenation catalysts have been introduced for hydrogenation of 2-ethylanthraquinone in the production of hydrogen peroxide via anthraquinone (AQ) process. The aim of the present study is to describe the catalysts used in the hydrogenation of 2-ethylanthraquinone and the reaction mechanism involved with different catalytic systems. The hydrogenation of 2-ethylanthraquinone using metals, alloy, bimetallic composite, and supported metal catalyst with the structural modifications has been incorporated for the production of hydrogen peroxide. The comprehensive comparison reveals that the supported metal catalysts required lesser catalyst amount, produced lower AQ decay, and provided higher catalyst activity and selectivity. Furthermore, the replacement of conventional catalysts by metal and metal alloy–supported catalyst rises as a hydrogenation trend, enhancing by several times the catalytic performance.
... Furthermore, Table 3 shows that PM and LC produced almost equal MIC values, 2-fold of LF alone. This result is predicted due to the microbial activity contribution of CA, which has been reported to exhibit a weak antimicrobial activity against bacteria such as E. coli and S. aureus [26]. ...
Article
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This research dealt with the composition, structure determination, stability, and antibiotic potency of a novel organic salt composed of levofloxacin (LF) and citric acid (CA), named levofloxacin-citrate (LC). After a stoichiometric proportion screening, the antibiotic-antioxidant reaction was conducted by slow and fast evaporation methods. A series of characterizations using thermal analysis, powder X-ray diffractometry, vibrational spectroscopy, and nuclear magnetic resonance confirmed LC formation. The new organic salt showed a distinct thermogram and diffractogram. Next, Fourier transform infrared indicated the change in N-methylamine and carboxylic stretching, confirmed by 1H nuclear magnetic resonance spectra to elucidate the 2D structure. Finally, single-crystal diffractometry determined LC as a new salt structure three-dimensionally. The attributive improvements were demonstrated on the stability toward the humidity and lighting of LC compared to LF alone. Moreover, the antibiotic potency of LF against Staphylococcus aureus (Gram-positive) and Escherichia coli (Gram-negative) enhanced ~1.5–2-fold by LC. Hereafter, LC is a potential salt antibiotic-antioxidant combination for dosage formulas development.
... H ydrogen peroxide (H 2 O 2 ) is used on a huge scale in applications, such as paper and textile bleaching, chemical synthesis, wastewater treatment, and (on a smaller scale) fuel cells. 1 H 2 O 2 is mainly prepared via the anthraquinone process, which uses large amounts of energy and creates a lot of chemical waste. 2 The clean production of H 2 O 2 via the photocatalytic reaction of H 2 O and O 2 under solar illumination has therefore sparked much recent interest. 3 To achieve efficient H 2 O 2 production, photocatalysts must absorb sunlight, produce separated charges, and drive redox reactions. ...
Article
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Hydrogen peroxide (H2O2) is one of the most important industrial oxidants. In principle, photocatalytic H2O2 synthesis from oxygen and H2O using sunlight could provide a cleaner alternative route to the current anthraquinone process. Recently, conjugated organic materials have been studied as photocatalysts for solar fuels synthesis because they offer synthetic tunability over a large chemical space. Here, we used high-throughput experiments to discover a linear conjugated polymer, poly(3-4-ethynylphenyl)ethynyl)pyridine (DE7), which exhibits efficient photocatalytic H2O2 production from H2O and O2 under visible light illumination for periods of up to 10 h or so. The apparent quantum yield was 8.7% at 420 nm. Mechanistic investigations showed that the H2O2 was produced via the photoinduced stepwise reduction of O2. At longer photolysis times, however, this catalyst decomposed, suggesting a need to focus the photostability of organic photocatalysts, as well as the initial catalytic production rates.
... [6][7][8][9] In this sense, hydrogen peroxide is an easy-handling liquid reactant that is inexpensive, atom-efficient, and non-ammable; it is also a green oxidant that generates only water as a by-product. 10,11 The choice of an adequate solvent avoids the use of a phase transfer agent as well as the addition of pH controllers. [12][13][14] Nonetheless, hydrogen peroxide requires an activation step, which is generally performed by a metal catalyst such as an oxide, salt, or organometallic compound. ...
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The activity of the sodium salts of vanadium-doped phosphomolybdic acid was assessed in the oxidative esterification reaction of benzaldehyde with hydrogen peroxide in alkyl alcohol solutions. The effect of main reaction parameters, such as temperature, catalyst load, vanadium doping level, and reactant stoichiometry, on the conversion and reaction selectivity was investigated. Among the tested heteropoly salts, Na4PMo11VO40 was the most active and selective catalyst, achieving almost complete conversion of benzaldehyde and high ester selectivity regardless of the alcohol investigated. The efficiency of the catalyst was correlated with its vanadium content. The size of the carbon chain of alcohol and the steric hindrance on the hydroxyl group played a key role in the reaction selectivity. While methyl and ethyl alcohols selectively provided the ester as the main product (ca. 90-95%) and benzoic acid as a subproduct, the other alcohols also afforded acetal, a condensation product, and benzaldehyde peroxide, an oxidation reaction intermediate, as secondary products. The use of an inexpensive, environmentally benign, and atom-efficient oxidant, mild conditions, and short reaction times were the positive aspects of this one-pot process.
Article
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Electrochemical synthesis of hydrogen peroxide (H2O2) via the 2‐electron oxygen reduction reaction (ORR) has emerged as a promising alternative to the energy‐intensive anthraquinone process and catalysts combining high selectivity with superior activity are crucial for enhancing the efficiency of H2O2 electrosynthesis. In recent years, single‐atom catalysts (SACs) with the merits of maximum atom utilization efficiency, tunable electronic structure, and high mass activity have attracted extensive attention for the selective reduction of O2 to H2O2. Although considerable improvements are made in the performance of SACs toward the 2‐electron ORR process, the principles for modulating the catalytic properties of SACs by adjusting the electronic structure remain elusive. In this review, the regulation strategies for optimizing the 2‐electron ORR activity and selectivity of SACs by different methods of electronic structure tuning, including the altering of the central metal atoms, the modulation of the coordinated atoms, the substrate effect, and alloy engineering are summarized. Finally, the challenges and future prospects of advanced SACs for H2O2 electrosynthesis via the 2‐electron ORR process are proposed. In this review, the recent advances regarding the strategies for regulating the electronic structure of single‐atom catalysts for 2‐electron oxygen reduction reaction, including the altering of the central metal atoms, the regulation of the coordinated atoms, substrate effect, and alloy engineering, are summarized.
Article
Electrocatalytic oxygen reduction reaction (ORR) via two-electron pathway is a promising approach to decentralized and on-site hydrogen peroxide (H2O2) production beyond the traditional anthraquinone process. In recent years, electrochemical H2O2 production in acidic media has attracted increasing attention owing to its stronger oxidizing capacity, superior stability, and higher compatibility with various applications. Here, recent advances of H2O2 electrosynthesis in acidic media are summarized. Specifically, fundamental aspects of two-electron ORR mechanism are firstly presented with an emphasis on the pH effect on catalytic performance. Major categories of promising electrocatalysts are then reviewed, including noble-metal-based materials, non-noble-metal single-atom catalysts, non-noble-metal compounds, and metal-free carbon-based materials. The innovative development of electrochemical devices and in situ/on-site application of electrogenerated H2O2 are also highlighted to bridge the gap between laboratory-scale fundamental research and practically relevant H2O2 electrosynthesis. Finally, critical perspectives on present challenges and promising opportunities for future research are provided.
Article
The addition of non-precious-metal is a promising approach to develop Pd-based catalysts for the direct synthesis of H2O2. Herein, we prepare W modified Pd/Al2O3 for enhanced synthesis towards H2O2. With fixed Pd loading, the H2O2 productivity show a volcano relationship with increasing W addition, and reach up to peak value for slice W content. It is found that W species in the form of WO3 existing on the surface of Pd particles. The small addition of W optimizes the ratio between surface PdO and Pd, which simultaneously augments the productivity of H2O2 and hinders hydrogenation/decomposition of H2O2. Nevertheless, excess W addition not only leads to overmuch metallic state of Pd species, but also impedes the O2 adsorption on Pd particles surface, resulting in a decrease in H2O2 synthesis. This work demonstrates the promoter mechanism of W and offers a promising strategy developing Pd-based catalysts for the direct synthesis of H2O2.
Article
Hydrogen peroxide (H2O2) is extensively applied in environmental remediation, disinfection, bleaching, and so on. Two-electron oxygen reduction reaction for synthesizing H2O2 is the most promising alternative to the traditional energy-intensive anthraquinone process. Existing strategies for electrocatalytic synthesis of H2O2 generally proceed well in alkaline electrolytes. But environmental application demands the reaction to take place in a broad pH range, especially in acidic medium. Here a zinc-air battery technology is developed for on-site production of H2O2 in alkaline, neutral, and acidic conditions. A key component of the battery is the tubular cathode fabricated by partially oxidized carbon nanotubes self-assembled on the substrate of nickel foam. The battery exhibits an unusual 2e⁻ discharge property and achieves an appreciable H2O2 accumulation (215.1 µmol, 497 ppm, 162.5 mg L⁻¹ h⁻¹) in acidic solution within 3 h, which is among the highest value ever been reported through electrosynthesis. Excitingly, the battery coupled with UV light demonstrates a promising application in water purification, which enables rapid degradation of model pollutants and actual pollutants ranging from municipal sewage to dye and pesticide wastewaters. Furthermore, this water treatment technology can be self-powered, as the battery in the system generates the power that is available to drive UV lights.
Article
The properties of the catalyst based on structurally disordered Pd‐P nanoparticles supported on a carbon support (Pd‐P/C) in the preparation of hydrogen peroxide by the anthraquinone method have been studied. It is shown that a high yield of Н 2 О 2 is observed upon sequential hydrogenation of 2000 mol of eAQ (mol Pd) −1 . The Н 2 О 2 yield reaches 96%–97%. Pd‐P nanoparticles are more active in the hydrogenation of 2‐ethyl‐9,10‐anthraquinone than Pd 6 P crystalline phosphide. In terms of H 2 O 2 yield, Pd‐P/C catalysts are superior to known catalysts: Pd/C, Pd/Al 2 O 3 . Based on the data of X‐ray powder diffraction, X‐ray photoelectron spectroscopy, Inductively Coupled Plasma and thermogravimetry, the main reasons for the deactivation of Pd‐P/C catalysts have been established. Crystallization of the structurally disordered Pd‐P nanoparticles, poisoning by eAQ conversion products and leaching of the active component are considered to be possible reasons of the Pd‐P/C catalyst deactivation.
Article
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Hydrogen peroxide (H2O2) is an environment‐friendly and efficient oxidant with a wide range of applications in different industries. Recently, the production of hydrogen peroxide through direct electrosynthesis has attracted widespread research attention, and has emerged as the most promising method to replace the traditional energy‐intensive multi‐step anthraquinone process. In ongoing efforts to achieve highly efficient large‐scale electrosynthesis of H2O2, carbon‐based materials have been developed as 2e− oxygen reduction reaction catalysts, with the benefits of low cost, abundant availability, and optimal performance. This review comprehensively introduces the strategies for optimizing carbon‐based materials toward H2O2 production, and the latest advances in carbon‐based hybrid catalysts. The active sites of the carbon‐based materials and the influence of coordination heteroatom doping on the selectivity of H2O2 are extensively analyzed. In particular, the appropriate design of functional groups and understanding the effect of the electrolyte pH are expected to further improve the selective efficiency of producing H2O2 via the oxygen reduction reaction. Methods for improving catalytic activity by interface engineering and reaction kinetics are summarized. Finally, the challenges carbon‐based catalysts face before they can be employed for commercial‐scale H2O2 production are identified, and prospects for designing novel electrochemical reactors are proposed. This review comprehensively introduces the latest advances in carbon‐based hybrid catalysts toward hydrogen peroxide (H2O2) production. In particular, the design of functional groups and the dependence of electrolyte pH play important roles to further improve the selectivity of H2O2 production via the oxygen reduction reaction.
Article
Hydrogen peroxide (H2O2) is widely used as a green oxidant for varying applications. Electrosynthesis is an economical and environmentally-friendly strategy to directly produce H2O2. Its practical production is hindered, however,...
Article
The electrosynthesis of H2O2 via the 2e⁻ oxygen reduction reaction (ORR) is an attractive method for the clean and continuous on-site production of H2O2, for which the development of active and selective electrocatalysts remains a significant challenge. Although carbon nanomaterials have demonstrated promising performance for H2O2 production, the lack of understanding of the active sites and key structural factors has impeded their development. In this work, we have prepared carbon-based model catalysts to investigate the active oxygen functional groups and structural factor. We have identified that the carboxyl group at the edge sites of graphitic carbons is the major active site for the 2e⁻ ORR, and the carbonyl group is a secondary active site. The nanoporous carbon catalyst with abundant active edge sites and optimized structure exhibited the highest H2O2 electrosynthesis activity among the carbon-based catalysts reported to date and excellent long-term stability (168 h) with 99% H2O2 faradic efficiency.
Article
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Electrocatalytic two-electron reduction of oxygen is a promising method for producing sustainable H2O2 but lacks low-cost and selective electrocatalysts. Here, the Chevrel phase chalcogenide Ni2Mo6S8 is presented as a novel active motif for reducing oxygen to H2O2 in an aqueous electrolyte. Although it has a low surface area, the Ni2Mo6S8 catalyst exhibits exceptional activity for H2O2 synthesis with >90% H2O2 molar selectivity across a wide potential range. Chemical titration verified successful generation of H2O2 and confirmed rates as high as 90 mmol H2O2 gcat⁻¹ h⁻¹. The outstanding activities are attributed to the ligand and ensemble effects of Ni that promote H2O dissociation and proton-coupled reduction of O2 to HOO*, and the spatial effect of the Chevrel phase structure that isolates Ni active sites to inhibit OO cleavage. The synergy of these effects delivers fast and selective production of H2O2 with high turn-over frequencies of ≈30 s⁻¹. In addition, the Ni2Mo6S8 catalyst has a stable crystal structure that is resistive for oxidation and delivers good catalyst stability for continuous H2O2 production. The described Ni-Mo6S8 active motif can unlock new opportunities for designing Earth-abundant electrocatalysts to tune oxygen reduction for practical H2O2 production.
Article
This study investigated the effects of electrode wettability on hydrogen peroxide (H2O2) production from oxygen reduction reaction (ORR) during electrolysis with superaerophilic electrodes. When the electrode was in the underwater Wenzel-Cassie (UWC) state, it could quickly adsorb aerated oxygen microbubbles, which significantly enhanced oxygen transfer. Meanwhile, H2O2 reduction was effectively inhibited. Consequently, high ORR currents and current efficiencies (CEs) of H2O2 production could be obtained in the UWC state. However, oxygen can only be transferred to the electrode by dissolved oxygen (DO) diffusion when the electrode was in the underwater Wenzel (UW) state. Due to the slow DO diffusion and enhanced H2O2 reduction at the wetted electrode, the rate and CEs of H2O2 production decreased dramatically in the UW state. Maintaining a stable UWC state by controlling the rate of O2 bubbling and rate of O2 consumption in ORR is thus critical to maximizing H2O2 electrosynthesis with the superaerophilic electrodes.
Article
The electrochemical reduction of oxygen to H2O2 is a sustainable substitution for the current anthraquinone process. However, the concentration, transportation, and storage of H2O2 increases not only the cost but also the risks in safety. Herein, we report a method of coupling electrochemical production of H2O2 with its in situ application in the selective oxidation of organics in a dual-membrane microflow electrolyzer, where the OOH⁻ generated from 2e⁻ reduction of O2 at cathode subsequently oxidizes organic substrates into value-added products under the catalysis of TS-1. When applied to phenol oxidation, the selectivity to target catechol and hydroquinone is as high as 94.68% with an overall Faradic efficiency (FE) up to 30.25% at a conversion of 10.61% under the optimized condition. Further study revealed that this method is also feasible for the coupling of various other organic oxidation reactions such as alcohol oxidation, styrene epoxidation and ammoximation with high selectivity and FE. Additionally, an overall FE of 132.79% was achieved in the paired oxidation of furfural to furoic acid, where furfural was oxidized both indirectly via H2O2 generated on cathode and directly on the anode.
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One key objective in electrocatalysis is to design selective catalysts, particularly in cases where the desired products require thermodynamically unfavorable pathways. Electrochemical synthesis of hydrogen peroxide (H 2 O 2 ) via the two-electron...
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Photocatalytic H2O2 production is a prospective alternative to the traditional anthraquinone oxidation method for H2O2 production. Compared to well-established inorganic counterparts, organic photocatalysts show greater promise owing to their structural diversity and functional tunability, but unfortunately suffer from limited activity at present. Here, a comonomer doping strategy is reported to tune the electronic structures of covalent triazine framework nanoshells by introducing strong electron-withdrawing benzothiadiazole units into the conjugated networks. The product exhibits much enhanced charge separation as evidenced by multiple spectroscopic analyses. When investigated as the photocatalyst in aqueous solution, the best sample can enable an impressive H2O2 production rate of 1630 µmol g⁻¹ h⁻¹, which is approximately three times higher than that of the undoped sample and superior to most other inorganic and organic competitors.
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Hydrogen peroxide (H 2 O 2 ) in dilute aqueous solution can be efficiently captured by co-crystallisation with enantiomeric and racemic amino acids as evidenced by colourimetric titration and the single crystal X-ray structural...
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H2O2 is an important chemical with multiple uses across domestic and industrial settings. A global need for wider adoption of green synthetic methods, there has been a growing interest in the electrochemical synthesis of H2O2 from oxygen reduction or water oxidation. State of the art catalyst and reactor developments are beginning to advance to a stage where electrochemical synthesis is discussed as a viable alternative to current industrial methods. In this review, we highlight some of the most promising candidates for H2O2 electrosynthesis technologies, and what further advancements are needed before the electrochemical route could challenge the ubiquitous anthraquinone process.
Article
Achieving high selectivity and production efficiency simultaneously in electrocatalytic H2O2 production to replace the anthraquinone process via two-electron (2e⁻) oxygen reduction reaction (ORR) and 2e⁻ water oxidation reaction (WOR) is a long-sought-after goal. However, sluggish kinetics and intrinsically unfavored thermodynamics make the electrochemical method still far from practical implementation. Herein, we experimentally demonstrate a high-efficiency two-side H2O2 generation system (WOR//ORR coupling cell) based on an active and stable bifunctional plasma-induced defective TiO2-x nanocatalyst that exhibits dramatically boosted activity/selectivity for both 2e⁻ ORR and 2e⁻ WOR. Such a WOR-ORR coupling strategy enables the H2O2-producing cell to provide an ultrahigh H2O2 yield rate of ∼20 mmol L⁻¹ h⁻¹ and a remarkable cell Faradaic efficiency of up to 134%. In situ Raman spectroscopy results and density functional theory calculations together uncover that oxygen vacancies located at the inner atomic layer and surface distortion are responsible for enhanced 2e⁻ ORR and 2e⁻ WOR performance, respectively.
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Oxygen-doped carbon materials (OCM) have received a lot of attention for catalyzing the two-electron oxygen reduction reaction (2eORR) towards hydrogen peroxide generation, but the origin of their activity is not well understood. Based on density functional theory calculations, we introduce the Fukui function (f0), a more comprehensive and accurate method for identifying active sites and systematically investigating the activity of carbon materials doped with typical oxygen functional groups (OGs). According to the results, only ether or carbonyl has the potential to become the activity origin. The 2eORR activities of carbon materials co-doped by different OGs were then investigated, and a significant synergistic effect was discovered between different OGs (particularly between epoxy and other OGs), which might be the real active centers in OCM. To further understand the cause of the activity, the Fundamental Gap (Eg) was introduced to investigate the ability of various OCM to gain and lose electrons. The results show that the decrease in overpotential after oxygen co-doping can be attributed to the decrease in Eg. This work introduces descriptors (f0 and Eg) that can aid in the efficient design of catalysts and adds to our understanding of the 2eORR activity origin of OCM.
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For the mono-metal Pd based catalysts, O–O bond of O 2 and H 2 O 2 is easy to be dissociated due to the higher energy sites of Pd, which decreases the selectivity and...
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Electrochemical oxygen reduction to hydrogen peroxide (H 2 O 2 ) in acidic media, especially in proton exchange membrane (PEM) electrode assembly reactors, suffers from low selectivity and the lack of low-cost catalysts. Here we present a cation-regulated interfacial engineering approach to promote the H 2 O 2 selectivity (over 80%) under industrial-relevant generation rates (over 400 mA cm ⁻² ) in strong acidic media using just carbon black catalyst and a small number of alkali metal cations, representing a 25-fold improvement compared to that without cation additives. Our density functional theory simulation suggests a “shielding effect” of alkali metal cations which squeeze away the catalyst/electrolyte interfacial protons and thus prevent further reduction of generated H 2 O 2 to water. A double-PEM solid electrolyte reactor was further developed to realize a continuous, selective (∼90%) and stable (over 500 hours) generation of H 2 O 2 via implementing this cation effect for practical applications.
Article
In 2003, Martı́n et al. reported a green alcohol oxidation with FeBr3(cat.)/H2O2 and proposed a high-valent iron species (HIS) responsible for the alcohol oxidation. Reinvestigating this FeBr3(cat.)/H2O2 method led us to propose a different mechanism that involves a reactive brominating species (RBS) for the oxidation of alcohols. The evidence to support this RBS-based mechanism includes (1) our recent findings of in situ-generated RBS from the related FeBr2/H2O2 or CeBr3/H2O2 systems, (2) our results of a series of controlled experiments, and (3) some related RBS-based precedents (NBS, NBA, or Br2) showing similar high oxidation selectivity of secondary over primary alcohols. These studies enable us to discover that a RBS from CeBr3/H2O2 is much more efficient for the oxidation of secondary and benzylic alcohols, which represents a new green protocol for selective oxidation of alcohols to carbonyls.
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The ammoximation of cyclohexanone using preformed hydrogen peroxide (H 2 O 2 ) is currently applied commercially to produce cyclohexanone oxime, an important feedstock in nylon-6 production. We demonstrate that by using supported gold-palladium (AuPd) alloyed nanoparticles in conjunction with a titanium silicate-1 (TS-1) catalyst, H 2 O 2 can be generated in situ as needed, producing cyclohexanone oxime with >95% selectivity, comparable to the current industrial route. The ammoximation of several additional simple ketones is also demonstrated. Our approach eliminates the need to transport and store highly concentrated, stabilized H 2 O 2 , potentially achieving substantial environmental and economic savings. This approach could form the basis of an alternative route to numerous chemical transformations that are currently dependent on a combination of preformed H 2 O 2 and TS-1, while allowing for considerable process intensification.
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This study reports a seeding-polymer-assisted method using inexpensive tetrapropylammonium bromide (TPABr) to synthesize titanium silicalite-1 (TS-1) ranging from supported embryonic (<8 nm) to crystalline nano-/micrometersized (≈0.1–1.0 μm) particles by kinetic regulation. The in situ grown embryonic TS-1 on the amorphous silica presents defective Ti(OH)(OSi)3, tetrahedral framework Ti (“TiO4”), and extraframework Ti (“TiO6”) species, while crystalline nano-/micro-metersized TS-1 particles exhibit either “TiO4” or both “TiO4” and “TiO6” species and a smaller external surface area, Sext. Turnover frequency (TOF) of TS-1 catalysts in the oxidation of dibenzothiophene (DBT) changes by an order of magnitude with the alteration of active Ti species. For instance, the TOF of supported embryonic TS-1 is 224.3 h⁻¹ while it is 32.6 h⁻¹ for the micro-metersized particles due to differences in the active Ti species. However, the TOF of the different TS-1 samples with similar Ti active sites scales only in proportion to Sext. The supported embryonic TS-1 on amorphous silica presents similar structural and chemical stability in comparison with crystalline nano-/micro-metersized TS-1 catalysts under water-free reaction conditions. Consequently, in situ prepared supported embryonic TS-1 combining improved accessibility (via increased external surface area) of different types of Ti species is a promising alternative for the conversion of bulky substrates.
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A high-value product of microbial electrolysis desalination and chemical-production cell (MEDCC) is a promising method for reducing costs and broadening the cell’s application. This study proposed a modified MEDCC in terms of hydrogen peroxide (H2O2) production, electrochemical performance, desalination, energy consumption by comparing it with conventional MEDCC. At the optimal voltage (1.0 V), the improved system achieved the H2O2 concentration of 1183 ± 32 mg/L, the energy consumption of 8.42 ± 1.39 kWh/kg H2O2, the desalination efficiency of 60.36 ± 9.24% within 12 h. Although the MEDCC-H2O2 system had a lower transfer rate of electrons, the system had analogous performances on current density, desalination, and acid and alkali productions with the conventional system. These results meant that the ideal voltage for achieving bipolar membrane and electrochemically active bacteria (EAB) synergism was 1.0 V in the improved MEDCC. In terms of chemical production in the cathode chamber of the MEDCC, the application of H2O2 production increased the rate of return by four times when compared to conventional alkali production. Only about 55% of total consumption was attributed to bioenergy in the substrate, suggesting the system was energy-saving. Therefore, the revised MEDCC had great potential in the field of energy-efficient and green H2O2 generation and desalination whilst maintaining acid and alkali productions.
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Solar-driven photocatalytic production of hydrogen peroxide (H2O2) requires only sunlight, oxygen, and water, making it a green and sustainable alternative to conventional H2O2 production processes. We present photocatalytic carbon dots (CDs) as a new candidate for high-performance H2O2 production. Owing to the generation of an excellent charge carrier and the presence of various oxygen-containing functional groups, CDs showed an outstanding H2O2 production capability of 609.4 μmol g⁻¹ h⁻¹ even in the absence of an electron donor, demonstrating promising self-electron-donating capabilities. Hydroxyl groups on their surface, in particular, serve a dual role as photocatalytic active sites and as electron and proton donors toward the oxygen reduction reaction (ORR). The photocatalytic activity of CDs was significantly improved to 1187.8 μmol g⁻¹ by functionalizing their surfaces with anthraquinone (AQ) as a co-catalyst; it promoted the charge carrier separation and electrochemically favored the two-electron pathway of ORR. These carbon-based metal-free nanohybrids that are a unique combination of CDs and AQ could offer insights into designing efficient photocatalysts for future solar-to-H2O2 conversion systems.
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Efficient and selective oxygen reduction reaction (ORR) electrocatalysts are critical to realizing decentralized H2O2 production and utilization. Here we demonstrate a facile interfacial engineering strategy using a hydrophobic ionic liquid (IL, i.e., [BMIM][NTF2]) to boost the performance of a nitrogen coordinated single atom cobalt catalyst (i.e., cobalt phthalocyanine (CoPc) supported on carbon nanotubes (CNTs). We find a strong correlation between the ORR performance of CoPc/CNT and the thickness of its IL coatings. Detailed characterization revealed that a higher O2 solubility (2.12 × 10⁻³ mol/L) in the IL compared to aqueous electrolytes provides a local O2 enriched surface layer near active catalytic sites, enhancing the ORR thermodynamics. Further, the hydrophobic IL can efficiently repel the as-synthesized H2O2 molecules from the catalyst surface, preventing their fast decomposition to H2O, resulting in improved H2O2 selectivity. Compared to CoPc/CNT without IL coatings, the catalyst with an optimal ~8 nm IL coating can deliver a nearly 4 times higher mass specific kinetic current density and 12.5% higher H2O2 selectivity up to 92%. In a two-electrode electrolyzer test, the optimal catalyst exhibits an enhanced productivity of 3.71 molH2O2 gcat–1 h–1, and robust stability. This IL-based interfacial engineering strategy may also be extended to many other electrochemical reactions by carefully tailoring the thickness and hydrophobicity of IL coatings.
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With an increasing global emphasis on renewable energy, electrosynthetic technologies stand to play a substantial role in generating the fuels and chemicals that power today’s society. While directions such as water electrolysis and CO2 directions have been heavily researched in the last decade, the scope of electrosynthesis can be greatly expanded to cover the full range of chemical targets that serve as building blocks for materials, pharmaceuticals, fertilizers, and more. To this end, the main challenges lie in the discovery of novel reaction routes and innovative catalytic systems that circumvent conventional limitations of electrocatalysis. Against this backdrop, this perspective will focus on the use of emerging methodologies to pioneer new electrosynthetic reaction systems. In this work, strategies of environmental control, phase change materials, reactant-selective membranes, and mediated approaches are discussed, before touching on the innovative spectroscopic approaches used to probe these systems and wrapping up with a forward-thinking outlook.
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We report the production and characterization of effective amperometric sensors for cathodic hydrogen peroxide (H2O2) detection. The proposed electrodes involve a combination of a H2O2-signaling Prussian Blue (PB)/carbon nanotube (CNT) layer with a glaze of the biopolymers gelatin (top) and zein (beneath) for protection against PB leakage. The sandwich-type sensor was constructed through simple "drop and dry" steps with (1) suspensions of the CNTs in a soluble PB solution, (2) zein in ethanol, and (3) gelatin in water, applied sequentially to the carbon working electrode disk of a screen-printed carbon electrode (SPCE) platform. The PB in the signaling layer acted as the electrocatalyst for H2O2 reduction at -150 mV vs Ag/AgCl/3 M KCl, enabling cathodic H2O2 amperometry with good target proportionality. Calibration trials confirmed the linearity of the response up to 700 μM (R2 > 0.998), with a sensitivity of 0.425 μA μM-1 cm-2 and a practical detection limit of 1 μM. Quantification of H2O2 in model and real samples with gelatin-zein-PB/CNT-SPCEs had a recovery of close to 100% of the true value. Since they are easily and cheaply made and yield accurate target assessments, gelatin-zein-PB/CNT-SPCEs are an ideal tool for electrochemical H2O2 analyses in human body fluids, health care products, and samples from industries that use H2O2 as a bleach and germicide. Workers with little experience in sensor fabrication and limited funding will particularly benefit from utilization of the proposed H2O2 probes, which as well as being used in H2O2 testing also have a potential application as the transducer unit of oxidase-based biosensors with amperometric H2O2 readout.
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Metal nanoparticles (NPs) are typically synthesized via crystallization by exploiting the difference in the solution solubilities of the metal ions (precursors) and the metal atoms (monomers) that are formed during reduction reactions. However, in this method, it is difficult to control the size and composition of the NPs, as the rate of the reduction reactions of the precursors into monomers affects the supersaturation, which is the greatest variable in crystallization. In this study, antisolvent crystallization was used to separate the reduction reaction and crystallization processes in the synthesis of metal alloy NPs. Salt NPs of Cu and Au precursors were first synthesized by adding ethanol as an antisolvent to an aqueous solution of Cu and Au precursors and stabilizers. Then, Cu–Au alloy NPs were synthesized via the reduction of the salt NPs. Overall, this new antisolvent-based synthesis is facile and the composition of the synthesized NPs can be well controlled.
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Electrosynthesis of hydrogen peroxide (H2O2) through oxygen reduction reaction (ORR) is an attractive alternative to the traditional anthraquinone process. It offers decentralized and on-site generation of H2O2 with a cost-effective system. Noble metals electrocatalysts through alloying or in a single-atomic structure and a few non-precious metals have been demonstrated with high selectivity but the stability remains challenging. Here, we propose a surface ion isolated platinum-thiocyanate (PtSCNx) catalyst as a promising electrocatalyst for the H2O2 electrosynthesis in acidic media. The SCN– binding remarkably weakens the absorption of crucial *OOH intermediate on the Pt surface, leading to the change of ORR electron transfer pathway. The carbon supported PtSCNx exhibits an onset potential of 0.68 V (versus RHE) and ∼90% selectivity. Significantly, the PtSCNx/C shows a continual and stable electrolysis over 130 h, which outperforms the state-of-the-art 2e– ORR catalysts. Moreover, an on-site electrochemical rapid removal of organic pollutant is achieved through an electro-Fenton process.
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H2O2 is a bulk chemical used as “green” alternative in a variety of applications, but has an energy and waste intensive production method. The electrochemical O2 reduction to H2O2 is viable alternative with examples of the direct production of up to 20% H2O2 solutions. In that respect, we found that the dinuclear complex Cu2(btmpa) (6,6’‐bis[[bis(2‐pyridylmethyl)amino]methyl]‐2,2’‐bipyridine) reduces O2 to H2O2 with a selectivity up to 90 % according to single linear sweep rotating ring disk electrode measurements. Microbalance experiments showed that complex reduction leads to surface adsorption thereby increasing the catalytic current. More importantly, we kept a high Faradaic efficiency for H2O2 between 60 and 70 % over the course of 2 h of amperometry by introducing high potential intervals to strip deposited copper (depCu). This is the first example of extensive studies into the long term electrochemical O2 to H2O2 reduction by a molecular complex which allowed to retain the high intrinsic selectivity of Cu2(btmpa) towards H2O2 production leading to relevant levels of H2O2. Optimised catalytic activity: Electrochemical H2O2 production is a promising sustainable alternative to the anthraquinone method. In that perspective, we have studied the dinuclear copper complex Cu2(btmpa) that has a high intrinsic H2O2 selectivity. By extensive, long term studies, we found that complex accumulation on the electrode increases the catalytic activity and that high potential intervals strip away deposited copper. Through this procedure we were able to reach a 60 to 70 % Faradaic efficiency during long term amperometry experiments.
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A novel strategy was first employed to prepare the Pd-IL complex catalysts for the anthraquinone hydrogenation reaction, taking advantage of the ionic liquid (IL). The IL microphase provides an excellent...
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Although the oxygen reduction process to hydrogen peroxide (H2O2) is a green option for H2O2 generation, the low activity and selectivity hindered the industry's process. In recent years, the electrochemical synthesis of H2O2 through a 2e– transfer method of oxygen reduction reaction (ORR) has piqued the interest of both academics and industry. Metal oxide catalysts have emerged as a novel family of electrochemical catalysts due to their unusual physical, chemical, and electrical characteristics. In this work, we first developed a Ruddlesden–Popper perovskite oxide (Pr2NiO4+δ) as a highly selective and active catalyst for 2e– ORR to produce H2O2. Molybdenum was introduced here to adjust the oxidation states of these transition metals with successful substitution into Ni‐site to prepare Pr2Ni1‐xMoxO4+δ, and the molybdenum substitution improves the H2O2 selectivity during the ORR process, in 0.1 M KOH, from 60% of Pr2NiO4+δ to 79% of Pr2Ni0.8Mo0.2O4+δ at 0.55 V versus RHE. A limiting H2O2 concentration of 0.24 mM for Pr2NiO4+δ and 0.42 mM for Pr2Ni0.8Mo0.2O4+δ was obtained at a constant current of 10 mA/cm2 using a flow‐cell reactor using a gas‐diffusion electrode. The electrochemical synthesis of hydrogen peroxide through a 2e‐ transfer method of oxygen reduction reaction (ORR) has piqued the interest of both academics and industry. This article reported the Ruddlesden–‐Popper perovskite Pr2Ni1‐xMoxO4+δ as the highly selective and active catalysts for 2e‐ ORR to produce H2O2. The synthesized Pr2Ni1‐xMoxO4+δ displays better H2O2 selectivity than the parent perovskite Pr2NiO4+δ. For example, Pr2Ni0.8Mo0.2O4+δ displays 79% selectivity toward H2O2 at 0.55 V versus reversible hydrogen electrode (RHE) during ORR, which is higher than the parent Pr2NiO4+δ (60%). This work advances the perovskite catalysts for 2e– ORR to H2O2.
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Poly(3-alkylthiophene) films play a central role in various organic devices owing to their solvent-processability and their remarkable electrical and optical properties. The (photo)electrocatalytic abilities of unsubstituted and solvent-insoluble polythiophenes in the reduction of O2 to H2O2 in a basic aqueous electrolyte have recently emerged as an advanced function. In this study, the electrocatalytic and photoelectrocatalytic abilities of solvent-processable poly(3-alkylthiophene) films at pH 12 are demonstrated, as well as their characteristics are re-examined from the viewpoints of the polymer structure, electrochemistry, photochemistry, and film nanostructure. Comparison of the above characteristics reveals the requirements for effective (photo)electrocatalytic O2 reduction to H2O2 production. In addition, the addition of an organic salt to the polymer solution changes the formed film characteristics. The thin film of the regioregular poly(3-hexylthiophene-2,5-diyl) containing a small amount of tetramethylammonium bis(trifluoromethanesulfonyl) imide is easily formed by a solvent-based process, and is featuring lower crystallinity, a porous film nanostructure, and high conductivity. This polymer acts as a robust photoelectrocatalyst for the reduction of O2 to H2O2 with a conversion rate of 3.9×10³ mg (H2O2) gphotocat ⁻¹ h⁻¹ or ∽0.040 mg (H2O2) cm⁻² h⁻¹, and a high Coulombic efficiency of >95% at 0.1 V bias from the theoretical potential. This article is protected by copyright. All rights reserved.
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In recent years, water pollution has become a major problem for the environment and human health due to the industrial effluents discharged into the water bodies. Day by day, new molecules such as pesticides, dyes, and pharmaceutical drugs are being detected in the water bodies, which are bio-refractory to microorganisms. In the last two decades, scientists have tried different advanced oxidation processes (AOPs) such as Fenton, photocatalytic, hydrodynamic, acoustic cavitation processes, etc. to mineralize such complex molecules. Among these processes, hydrodynamic cavitation (HC) has emerged as a new energy-efficient technology for the treatment of various bio-refractory pollutants present in aqueous effluent. In this review, various geometrical and operating parameters of HC process have been discussed emphasizing the effect and importance of these parameters in the designing of HC reactor. The advantages of combining HC with other oxidants and AOPs such as H
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Hydrogen peroxide (H2O2) as a highly efficient and green oxidant has become one of the 100 most important chemicals in the world. Some current research progress in the direct synthesis of H2O2 from H2 and O2 by noble-metal catalyst, fuel cell and plasma methods has been reviewed systematically in this paper. Perspectives about the development direction and application prospect of the above-mentioned three methods have also been discussed.
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This study offers a unified perspective into the unexpected solar energy photovoltaic revolution, and its far reaching impact onto both energy generation and electricity markets. Practically relevant aspects, such as those related to the value of solar PV electricity, land consumption, energy return on energy invested, reliability of the technology, the structure of the global PV industry, the cost of Li ion batteries and related market trends are clarified. We identify the main barriers to overcome for solar PV to expand beyond a niche market (say, <10% of a country's power generation), and the related societal benefits with electrification of energy end uses.
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17α-ethinylestradiol (EE2), a synthetic oestrogen in oral contraceptives, is one of many pharmaceuticals found in inland waterways worldwide as a result of human consumption and excretion into wastewater treatment systems. At low parts per trillion (ppt), EE2 induces feminisation of male fish, diminishing reproductive success and causing fish population collapse. Intended water quality standards for EE2 set a much needed global precedent. Ozone and activated carbon provide effective wastewater treatments, but their energy intensities and capital/operating costs are formidable barriers to adoption. Here we describe the technical and environmental performance of a fast- developing contender for mitigation of EE2 contamination of wastewater based upon small- molecule, full-functional peroxidase enzyme replicas called “TAML activators”. From neutral to basic pH, TAML activators with H2O2 efficiently degrade EE2 in pure lab water, municipal effluents and EE2-spiked synthetic urine. TAML/H2O2 treatment
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We investigate hydrodynamic cavitation to inactivate commonly employed Sac-charomyces cerevisiae yeast strains in an aqueous solution using different reac-tors and hydraulic circuit selected to demonstrate the process feasibility on the industrial scale. The target to achieve an useful lethality of the yeast at lower temperature when compared with standard thermal and even with other cavita-tion processes was achieved, with 90% yeast strains lethality at lower tempera-ture (6.3–9.5°C), and about 20% lower energy input. A separate model simulating the combined thermal and cavitational effects on yeast lethality allows to accommodate the data into a comprehensive framework providing a tool to design further targeted experiments and to predict results when chang-ing the process parameters.
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Present health and daily life rely on synthetic materials such as pharmaceuticals, fine chemicals, synthetic fibers, and plastics, which are mainly produced by multi-step chemical conversions of petroleum products. However, the current standards of chemical synthesis need to be much improved. Oxidation is a core technology for converting petroleum-based materials to useful chemicals in higher oxidation states. Aqueous hydrogen peroxide is an ideal oxidant, because the atom efficiency is excellent and water is the only theoretical side product. A catalytic system consisting of ternary catalyst (tungsten complex, phase transfer catalyst, and phosphonic acid) allowed epoxidation of various olefins using aqueous 30 % hydrogen peroxide without any organic solvent. Palladium catalysts were also very effective for oxidation of α,β-unsaturated aldehydes to the corresponding acids under mild conditions without organic solvent or halogen-containing chemicals. Additionally, kilogram-scale syntheses of super-fine chemicals using hydrogen peroxide in collaboration with commercial laboratories confirmed the individual targeted result for various products.
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As a Dutch kid growing up in the early 1980s I devoured the 'Euro 5' science fiction series by Bert Benson. They were typical boy's adventures: in each book a secret team of European policemen had some 200 pages to track down a menagerie of rampaging robots, mutant criminals and murderous scientists hell-bent on terrorizing Earth and the solar system. The bad guys were usually seeking world domination, which they inevitably intended to obtain via some overly complicated but fascinating scheme. As required by the genre, the good guys always managed to arrest the interplanetary villains before they could bring their devious schemes to fruition. Just in the nick of time of course. It was ideal literature for a certain somewhat nerdy would-be aerospace engineer. The books were all written in Dutch, and much later I found out that writer Bert Benson's real name was Adrianus Petrus Maria de Beer, which sounds about as futuristic in Dutch as is does in English. In spite of this, the stories breathed a kind of cosmopolitan atmosphere, with a diverse team of agents from various European countries (the leader was Dutch, naturally) flying to exotic countries, forgotten islands and hostile moons and planets. Their means of transportation was the Euro 5, a wedgeshaped rocket spaceplane with a set of large wings at the back and smaller 'canard' wings in front, four rotating ray-guns, and a small boat-shaped plane for short reconnaissance trips (which I now know looks a lot like NASA's M2-F3 'lifting body' experimental rocket plane of the early 1970s). In the final pages of each book, it was usually this marvelous machine that saved the day, if not the entire universe. For me this gigantic blue vehicle was really the centerpiece of the stories, rather than the colorful team of international heroes. I guess kids in other countries at the time were reading similar adventure books with rocket planes in a starring role. © Springer Science+ Business MediaN ew York 2012. All rights are reserved.
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Controlled hydrodynamic cavitation is an energy-and chemicals-saving technology increasingly applied to water sanitation and wastewater remediation via mechanical, oxidative, and thermal degradation of chemical and biological pollutants , including recalcitrant contaminants. Reviewing the advances that have allowed hydrocavitation to emerge as an economically and technically viable environmental technology, we identify the key design parameters that decide its efficacy in degrading biological and chemical contaminants. The ongoing renewable energy boom, lowering the cost of electricity across the world, will only accelerate the adoption of hydrodynamic cavitation as an eminent technology of our common path to sustainability, with energy and clean water access for all.
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Gold catalysis has recently found its first large-scale applications in the chemical industry. This Minireview provides a critical analysis of the success factors and of the main obstacles that had to be overcome on the long way from the discovery to the commercialization of gold catalysts. The insights should be useful to researchers in both academia and industry working on the development of tomorrow's gold catalysts to tackle significant environmental and economic issues.
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The direct synthesis of hydrogen peroxide (H2O2) from H2 and O2 represents a potentially atom-efficient alternative to the current industrial indirect process. We show that the addition of tin to palladium catalysts coupled with an appropriate heat treatment cycle switches off the sequential hydrogenation and decomposition reactions, enabling selectivities of >95% toward H2O2. This effect arises from a tin oxide surface layer that encapsulates small Pd-rich particles while leaving larger Pd-Sn alloy particles exposed. We show that this effect is a general feature for oxide-supported Pd catalysts containing an appropriate second metal oxide component, and we set out the design principles for producing high-selectivity Pd-based catalysts for direct H2O2 production that do not contain gold.
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This study investigated the reduction of antibiotic resistance genes (ARGs), intI1 and 16S rRNA genes, by advanced oxidation processes (AOPs), namely Fenton oxidation (Fe2 +/H2O2) and UV/H2O2 process. The ARGs include sul1, tetX, and tetG from municipal wastewater effluent. The results indicated that the Fenton oxidation and UV/H2O2 process could reduce selected ARGs effectively. Oxidation by the Fenton process was slightly better than that of the UV/H2O2 method. Particularly, for the Fenton oxidation, under the optimal condition wherein Fe2 +/H2O2 had a molar ratio of 0.1 and a H2O2 concentration of 0.01 mol L− 1 with a pH of 3.0 and reaction time of 2 h, 2.58–3.79 logs of target genes were removed. Under the initial effluent pH condition (pH = 7.0), the removal was 2.26–3.35 logs. For the UV/H2O2 process, when the pH was 3.5 with a H2O2 concentration of 0.01 mol L− 1 accompanied by 30 min of UV irradiation, all ARGs could achieve a reduction of 2.8–3.5 logs, and 1.55–2.32 logs at a pH of 7.0. The Fenton oxidation and UV/H2O2 process followed the first-order reaction kinetic model. The removal of target genes was affected by many parameters, including initial Fe2 +/H2O2 molar ratios, H2O2 concentration, solution pH, and reaction time. Among these factors, reagent concentrations and pH values are the most important factors during AOPs.
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Hydrogen peroxide (H2O2) was entrapped in silica hydrogels using the sol–gel approach, and its transition to xerogel was studied by monitoring H2O2 retention as a function of weight loss at ambient temperature. The transition took place in different drying regimes, and the maximum H2O2 concentration was obtained at 80% weight loss of the initial hydrogel. The stability of H2O2 at a higher initial concentration of 33.2 wt % was studied and found to be comparable to the values obtained with hydrogels having lower initial concentrations (10–20 wt %). The release rate of entrapped H2O2 from silica gel was studied as a function of the initial H2O2 concentration, the sodium content of the gel, the pH of the aqueous medium, and the form of the gel (hydrogel/xerogel). The release occurred via a biphasic process, with an initial fast liberation during the first 10 min where 60–70% of the H2O2 was released, followed by a much slower release rate from 10 to 60 min. The release rate was independent of the initial H2O2 concentration but was affected significantly by the other parameters. Thermal stability of the silica gels was studied using thermogravimetric analysis, and was found to depend strongly on the sodium content. The form of the gel (hydrogel/xerogel) did not have an appreciable effect on the thermal stability. Substituting sodium partially with magnesium decreased the gelation time and increased the stability of entrapped H2O2.
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Pulp and Paper Industry: Chemicals features in-depth and thorough coverage of Chemical additives in the Pulp and Paper Industry. It discusses use of Enzymes "Green Chemicals" that can improve operations in pulp and paper, describes Chemicals demanded by the end user and many key and niche players such as Akzo Nobel NV, Eka Chemicals AB, Ashland, Inc., BASF, Buckman Laboratories International, Inc., Clariant, Cytec Industries, Inc., Enzymatic Deinking Technologies, LLC, ERCO Worldwide, FMC Corporation, Georgia-Pacific Corporation, Georgia-Pacific Chemicals LLC, Imerys SA, Momentive Specialty Chemicals, Inc., Novozymes, Kemira Chemicals, Nalco Holding Company, Omya AG, Solvay AG, and Solvay Chemicals, Inc.. Paper and pulp processing and additive chemicals are an integral part of the total papermaking process from pulp slurry, through sheet formation, to effluent disposal. Environmental concerns, increased use of recycled waste paper as a replacement for virgin pulp, changes in bleaching and pulping processes, increased efficiency requirements for the papermaking process, limits on effluent discharge as well as international competitiveness have greatly impacted the paper and pulp chemical additive market. This book features in-depth and thorough coverage of Chemical additives in Pulp and Paper Industry. • Detailed and up-to-date coverage of Chemicals in Pulp and Paper Industry • Authoritative, thorough, and comprehensive content on a wide variety of Enzymes "Green Chemicals" • Comprehensive list of Paper and Pulp Related Chemicals • Comprehensive list of all Pulp and paper Suppliers • Comprehensive Indexing.
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Water is a life-giving source, fundamental to human existence, yet, over a billion people lack access to clean drinking water. Present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH$^*$ can be used as a descriptor to screen for selectivity trends between the 2e$^-$ water oxidation to H$_2$O$_2$ and the 4e$^-$ oxidation to O$_2$. We show that materials that bind oxygen intermediates sufficiently weakly, such as SnO$_2$, can activate hydrogen peroxide evolution. We present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H$_2$O$_2$ evolution selectively.
Chapter
Hydrogen peroxide is a widely used antimicrobial chemical. It is used in both liquid and gas form for preservative, disinfection and sterilization applications. Its advantages include its potent and broad spectrum antimicrobial activity, flexibility in use, and safety profile in comparison to other microbiocides. Hydrogen peroxide has been shown to be effective against all forms of microorganisms, including dormant forms with known high resistance such as bacterial spores and protozoal cysts, and also infectious proteins such as prions depending on the specific use of the chemical. It also has advantages with regard to its toxicity and environmental profile. However, overall, the effective and safe use of hydrogen peroxide depends on the way it is used, in particular the concentration. In aqueous form it is used in solution with water directly as a preservative, in products as a preservative or on the skin, including in wounds, and on inanimate surfaces. Recent technology advances have been made in the formulation of peroxide with other chemicals to enhance the antimicrobial activity at lower target concentrations of the active agent. Hydrogen peroxide gas is also widely used for disinfection and sterilization. The gas form is particularly effective in comparison liquid forms and at lower concentrations. Hydrogen peroxide gas processes have become popular alternatives to other chemical and physical based antimicrobial methods due to its rapid efficacy, low temperature, compatibility with surface materials and limited toxicity concerns. The mechanism of action of hydrogen peroxide is not fully understood and is associated with its oxidation activity. The oxidation of the various molecules that constitute microorganisms will lead to significant disruptions in structure/function and the loss of viability or infectivity. Despite this generalization, liquid preparations, formulations and the gas form of hydrogen peroxide can show remarkable differences in their antimicrobial effects, such as their attack on proteins, nucleic acids, and lipids. The general mechanisms of action of hydrogen peroxide significantly reduce any risk of the development of resistance to the biocide over time, unlike many other types of anti-infective drugs or biocides. Microbial resistance to peroxide is primarily due to the various natural differences observed in the growth and survival of microorganisms but can be overcome by the right process and application with hydrogen peroxide-containing products. The many benefits in the use of liquid and gas hydrogen peroxide for antimicrobial applications make it attractive for future and optimal developments with this microbiocide.Keywords:hydrogen peroxide;biocide;antisepsis;disinfection;sterilization;mode of action;liquid;gas;resistance
Book
This book provides a thorough presentation of polyurethane (PU) science, technology, markets and trends. Although it does not provide ultimate detail (such as explicit information typically in patents), the book has a flow and continuity that allows readers to find all the background necessary to understand any other more detailed PU information found elsewhere. The author presents chapters about PU chemistry, characteristics, analytical methods, theoretical methods, and a host of applications examples: foams, elastomers, coatings, adhesives, and medical. Additionally, there is discussion of medical applications and non-isocyanate/non-phosgene routes to urethane structure. Governmental regulation of polyurethane reagents and building blocks is covered in detail, as well industrial means of mitigating risks.
Article
Hydrogen peroxide (H2O2) entrapment in silica hydrogels has potential to be used in various industrially important applications to increase H2O2 stability. In this study, optimum conditions for hydrogel formation and H2O2 stability were determined by varying the sodium content and initial H2O2 concentration. Higher retention and better stability of H2O2 were achieved with hydrogels at room temperature at low sodium concentration. Retention values of 89% were obtained with initial H2O2 concentrations up to 10 wt %. H2O2 decomposition in hydrogels followed a first-order reaction. Hydrogels were characterized by measuring their surface area, pore size, and pore size distribution by Brunauer-Emmett-Teller analysis and scanning electron microscopy. Mesoporous (3-24 nm) hydrogels with high surface area (1000-1400 m2/g) were obtained. In addition, the melting point of the entrapped H2O2-water mixture in the hydrogels was studied by low temperature differential scanning calorimetry.
Article
Until a decade ago, the industrial technologies for producing propylene oxide from propylene were predominantly based on variations of the venerable chlorohydrin and organic hydroperoxide processes. Within the past decade, highly selective H2O2-based propylene epoxidation technologies have been developed by Dow-BASF (HPPO process) and the University of Kansas Center for Environmentally Beneficial Catalysis (CEBC-PO process). We present comparative economic and environmental impact analyses based on plant scale simulations of the processes for an assumed 200,000 tonnes/yr of PO production capacity and employing relevant process data from the literature. The predicted capital costs for the CEBC-PO process ($228 million) and HPPO process ($275 million) are lower than the conventional PO/TBA process ($372 million). The PO production costs via the conventional PO/TBA and HPPO processes are 150.4¢/lb PO (profit 87.9¢/lb, assuming a market value of 41¢/lb for the TBA co-product and 42¢/lb for the enriched propane co-product) and 107.1¢/lb PO (profit 36.1¢/lb, assuming a market value of 42¢/lb for the enriched propane co-product), respectively. For the CEBC-PO process, the production cost is 90.6¢/lb PO (profit 30.4¢/lb), assuming a life of one year for the methyltrioxorhenium catalyst and a catalyst leaching rate of 9.3 × 10–2 lb/h (or 1.6 ppm Re in the reactor effluent). The comparative economic analysis suggests that the CEBC-PO process has potential for being economically competitive and establishes quantitative catalyst performance metrics for achieving the same. Quantitative cradle-to-gate LCA shows that the environmental impacts of producing PO by the conventional PO/TBA, HPPO, and CEBC-PO processes are of the same order of magnitude. The lower GHG emissions predicted for the HPPO and CEBC-PO technologies, compared to the PO/TBA process, lie within the prediction uncertainty of this analysis. This comparative LCA analysis traces the adverse environmental impacts to sources outside the propylene oxide plant in all three processes: fossil fuel-based energy (natural gas, transportation fuel) utilization during raw material (i-butane, propylene and hydrogen peroxide) production.
Article
Propene oxide is a very important chemical whose production technology has changed a lot during the last 30 years. Nowadays, the most promising technology is the HPPO process in which the propene oxide is produced by oxidizing propene with hydrogen peroxide, via titanium silicalite-1 (TS-1) catalysis. Even if this technology has been patented in the early 1980s and some chemical plants are already in production, only few papers have been published until now dealing with the catalytic and kinetic aspects of the process. In this paper, the state of the art of the scientific knowledge and technical aspects related to propene oxide synthesis in the presence of TS-1 catalyst have been reviewed.
Article
Methyl parathion (C8H10NO5PS), which is an organophosphorus pesticide that has been widely used as an agricultural insecticide in India, can result in significant water pollution due to its biorefractory nature and longer stability. In the present work, degradation of methyl parathion has been investigated using hydrodynamic cavitation reactors with possible intensification studies using different approaches. Effect of different parameters like operating pressures (1–8 bar), operating temperatures (sets of intense cooling, moderate cooling and uncontrolled operation) and initial pH (2.2–8.2) has been investigated initially. Under the optimized set of operating parameters, the effect of process intensifying parameters like hydrogen peroxide (25–200 mg/l), carbon tetrachloride (1–6 g/l) and Fenton’s reagent (H2O2:FeSO4 ranging from 1:1 to 1:6) on the extent of degradation has been investigated. Effect of radical scavengers like sodium bicarbonate and tert-butanol on the extent of degradation was also investigated with an objective of establishing the controlling mechanism. More than 90% degradation of methyl parathion was achieved using combination of hydrodynamic cavitation with H2O2 and Fenton’s reagent. TOC analysis at optimum conditions was also performed to quantify the extent of mineralization and it has been observed that a maximum of 76% TOC reduction is obtained. The study has also focused on the determination of intermediate products formed during the degradation. It has been established that hydrodynamic cavitation in the presence of additives can be effectively used for complete removal of methyl parathion.
Book
An introduction to the preparation and properties of hydrogen peroxide The activation of hydrogen peroxide using inorganic and organic species The application of hydrogen peroxide for the synthesis of fine chemicals The heterogeneous activation and application of hydrogen peroxide The environmental application of hydrogen peroxide Miscellaneous uses for hydrogen peroxide technology.
Article
Hydrogen peroxide (H2O2) is widely used in almost all industrial areas, particularly in the chemical industry and environmental protection. The only degradation product of its use is water, and thus it has played a large role in environmentally friendly methods in the chemical industry. Hydrogen peroxide is produced on an industrial scale by the anthraquinone oxidation (AO) process. However, this process can hardly be considered a green method. It involves the sequential hydrogenation and oxidation of an alkylanthraquinone precursor dissolved in a mixture of organic solvents followed by liquid–liquid extraction to recover H2O2. The AO process is a multistep method that requires ignificant energy input and generates waste, which has a negative effect on its sustainability and production costs. The transport, storage, and handling of bulk H2O2 involve hazards and escalating expenses. Thus, novel, cleaner methods for the production of H2O2 are being explored. The direct synthesis of H2O2 from O2 and H2 using a variety of catalysts, and the factors influencing the formation and decomposition of H2O2 are examined in detail in this Review.
Article
Hydrogen peroxide was incorporated into silica xerogel matrix over the concentration range from 3.8 to 68.0 wt% via the sol-gel route. The obtained composites were characterized by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The release rates of H(2)O(2) from the composites into the aqueous phase were examined. In most cases, a 90% release was attained after ca. 10 min, and it was only slightly dependent on H(2)O(2) concentration and particle size. The antimicrobial activity of the composite containing 3.59% H(2)O(2) was evaluated against Escherichia coli and Micrococcus luteus. A comparative assay was carried out for aqueous solution of H(2)O(2) of the same concentration. The results demonstrated a potent microbicidal efficacy of the composite. Furthermore, diffusion range of the hydrogen peroxide from the solid composite into an agar medium matched that of the H(2)O(2) in aqueous solution. The stability tests with the xerogels containing 3.8, 26.4, and 68.0% of H(2)O(2) showed that after 63 days respective losses of the H(2)O(2) at 3 degrees C were 8.8, 9.7, and 6.2%. Both the DSC results and the stability tests have shown that the molecular water present in the pores stabilizes the composite, probably through improving the binding of the H(2)O(2) molecules onto the silica surface.
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S. Rajoriya, J. Carpenter, V. K. Saharan, A. B. Pandit, Rev. Chem. Eng. 2016, 32, 379-411.
Evonik's New Hydrogen Peroxide Plant Officially Opened in Jilin
Evonik's New Hydrogen Peroxide Plant Officially Opened in Jilin (China), http://evonik.com, July 9, 2014.
Solvay's Position and Strategy in Hydrogen Peroxide
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Solvay, Solvay's Position and Strategy in Hydrogen Peroxide, London Investors Morning, September 30, 2010.
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F. Sudur, B. Pleskowicz, N. Orbey, Ind. Eng. Chem. Res. 2015, 54, 1930 – 1940.
The Use of Hydrogen Peroxide in the Bleaching of Chemical Pulp, Southeastern TAPPI and TAPPI Bleaching Committee Joint Meeting
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R. Anderson, The Use of Hydrogen Peroxide in the Bleaching of Chemical Pulp, Southeastern TAPPI and TAPPI Bleaching Committee Joint Meeting, St. Augustine (FL), June 13, 2002.
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Solvay to Build High-Purity H 2 O 2 Plant in Italy to Serve Electronics Customer
IHS Chemical Week, Solvay to Build High-Purity H 2 O 2 Plant in Italy to Serve Electronics Customer, http://chemweek.com, July 29, 2015.
[34] US Environmental Protection Agency, Innovative, Environmentally Benign Production of Company Propylene Oxide via Hydrogen Peroxide, The Presidential United States Environmental Protection Agency Green Chemistry Challenge Awards Program: Summary of 2010 Award Entries and Recipients
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M. Taramasso, G. Perego, B. Notari, US 4410501, 1983. [34] US Environmental Protection Agency, Innovative, Environmentally Benign Production of Company Propylene Oxide via Hydrogen Peroxide, The Presidential United States Environmental Protection Agency Green Chemistry Challenge Awards Program: Summary of 2010 Award Entries and Recipients, Washington, 2010, p. 5.
Evonik Completes Netherlands Hydrogen Peroxide Acquisition
IHS Chemical Week, Evonik Completes Netherlands Hydrogen Peroxide Acquisition, http://chemweek.com, November 9, 2015.
Nano-Enabled Catalysts for the Commercially Viable Production of H 2 O 2 , Lawrenceville (NJ); see: http://hydrogen-peroxide.us/chemical-mfg-stor- age/Headwaters-Nano-Enabled-Production
  • B Zhou
B. Zhou (Headwaters Technology Innovation), Nano-Enabled Catalysts for the Commercially Viable Production of H 2 O 2, Lawrenceville (NJ), September 26, 2007; see: http://hydrogen-peroxide.us/chemical-mfg-stor- age/Headwaters-Nano-Enabled-Production-H2O2-2007.pdf (accessed, October 1, 2016).
Solvay Expands Hydrogen Peroxide Grade Production in the Netherlands for the Pharmaceutical Industry to Meet Growing Demand
  • E Palmer
E. Palmer, Solvay Expands Hydrogen Peroxide Grade Production in the Netherlands for the Pharmaceutical Industry to Meet Growing Demand, http://fiercepharma.com, January 26, 2015.
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M. Ghanta, D. R. Fahey, D. H. Busch, B. Subramanian, ACS Sustainable Chem. Eng. 2013, 1, 268-277.
Pulp and Paper Industry Ullmann's Encyclopedia of Industrial Chemistry
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P. Bajpai, Pulp and Paper Industry, Elsevier, Amsterdam, 2015, Chap. 3. [5] G. Goor, J. Glenneberg, S. Jacobi, Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2012, pp. 393-427.
Introduction to the Preparation and Properties of Hydrogen Peroxide
  • C W Jones
  • J H Clark
"Introduction to the Preparation and Properties of Hydrogen Peroxide": C. W. Jones, J. H. Clark, Applications of Hydrogen Peroxide and Derivatives, RSC, Cambridge, 1999, Chap. 1, p. 12.
Could an Israeli-Created Innovation End World Hunger?
  • D Shamah
D. Shamah, Could an Israeli-Created Innovation End World Hunger?, http://timesofisrael.com, October 30, 2014.
Oxidation in Ullmann's Encyclopedia of Industrial Chemistry
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J. H. Teles, I. Hermans, G. Franz, R. A. Sheldon, Oxidation in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2015, pp. 1-103.
Evonik Gets GMP Certification for Pharmaceutical-Grade Hydrogen Peroxide
IHS Chemical Week, Evonik Gets GMP Certification for Pharmaceutical-Grade Hydrogen Peroxide, http://chemweek.com, October 8, 2015.
Sanctions Convince Russia to Produce Its Own Rocket Fuel
  • S Arkhangelskaya
S. Arkhangelskaya, Sanctions Convince Russia to Produce Its Own Rocket Fuel, http://rbth.com, May 3, 2016.