Michele Aresta

Michele Aresta
Innovative Catalysis for Carbon Recycling-IC2R · Chemistry

Doctor Industrial Chemistry

About

347
Publications
36,511
Reads
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17,382
Citations
Introduction
Carbon Recycling for Cyclic Carbon Economy. Use of CO2 as building block and source of carbon for fuels. Use of residual and grown biomass for the production of new monomers for bio-polymers. Non-isocyanate oligo-poly-urethanes.
Additional affiliations
March 2013 - present
Innovative Catalysis for Carbon Recycling-IC2R
Position
  • CEO
Description
  • IC2R develops new catalysts and processes for CO2 and residual (or grown) biomass valorization
January 2015 - December 2016
University of Bath
Position
  • David Parkin Professor
Description
  • Development of new reactors
January 2012 - August 2016
National University of Singapore
Position
  • IMM Chair

Publications

Publications (347)
Article
Full-text available
The photochemical and photoelectrochemical reduction of CO2 is a promising approach for converting carbon dioxide into valuable chemicals (materials) and fuels. A key issue is ensuring the accuracy of experimental results in CO2 reduction reactions (CO2RRs) because of potential sources of false positives. This paper reports the results of investiga...
Article
Full-text available
Carbon dioxide capture and utilization is a strategic technology for moving away from fossil‐C. The conversion of CO2 into fuels demands energy and hydrogen that cannot be sourced from fossil‐C. Co‐processing of CO2 and water under solar irradiation will have a key role in the long‐term for carbon‐recycling and energy products production. This arti...
Article
Full-text available
The enzymatic effectiveness in the reaction cascade that reduces CO2 to methanol in water at room‐temperature faces various constraints. One of the major challenges is the short life of costly enzymes: immobilization is used to make them more stable and recyclable. The comparative analysis of the several immobilization techniques reported in the li...
Chapter
Carbon dioxide can be used as building block for chemicals or source of carbon for energy products (fuels). The latter have a market that is over fifteen times that of chemicals and are, thus, of greater interest for the large-scale implementation of the CCU strategy (capture and utilization of CO2). The drawback is that while the chemical use of C...
Article
To keep the engine of humanity running, dependence on fossil resources must be curbed due to potent environmental impacts underlying Anthropocene. The paradigm shift towards an integration of bioeconomy with...
Article
Full-text available
This paper tells the recent history of CO2 chemistry through the contributions from members of CIRCC to its birth and growth. Starting with the first transition metal complex bearing CO2 as a ligand synthesized in 1975 by the Aresta Group in Bari, the mode of bonding and the reactivity of coordinated CO2 are discussed. The early applications in che...
Article
Full-text available
The need to decrease the concentration of CO2 in the atmosphere has led to the search for strategies to reuse such molecule as a building block for chemicals and materials or a source of carbon for fuels. The enzymatic cascade of reactions that produce the reduction of CO2 to methanol seems to be a very attractive way of reusing CO2; however, it is...
Article
The reaction between ethene glycol-EG and CO2 to afford the cyclic ethene carbonate-EC has been studied in solvent-less conditions and in absence of water traps but using pervaporation membranes to eliminate water. The parameter space of the reaction (temperature, pressure, catalyst loading, time of reaction) has been investigated, filling a gap ex...
Article
Full-text available
This paper discusses the epochal change in the reputation of carbon dioxide, which is now considered as a raw material alternative to fossil C for the synthesis of chemicals, materials and fuels, as opposed to a waste material that must be confined underground. In particular, its use as renewable C is compared to biomass. In this paper, a specific...
Article
Full-text available
Semiconductor materials are the basis of electronic devices employed in the communication and media industry. In the present work, we report the synthesis and characterization of mixed metal oxides (MOs) as p,n-junction photocatalysts, and demonstrate the correlation between the preparation technique and the properties of the materials. Solid-state...
Chapter
This article presents the state of the art and perspectives in the conversion of CO2 into energy products, implementing a Carbon Cyclic Economy strategy. Two conditions are essential for the reduction of CO2 using technologies on stream: (1) Energy necessary for CO2 reduction must come from C-free perennial energy sources (Solar, Wind, Hydro, Geoth...
Article
The oxidative cleavage of nonedible monounsaturated lipids such as restaurant olive oil or oil extracted from high oleic sunflowers (HOSO) is a method to produce useful C9 mono- and dicarboxylic acids, namely, pelargonic and azelaic acids. In this study, we describe the synthesis and application of mixed oxides as cheap, recoverable, and reusable c...
Chapter
Fossil-C, in the form of coal, natural gas, and oil, covers 81+% of the energy necessary to satisfy the needs of our society. The continued use of fossil-C causes the accumulation of carbon dioxide in the atmosphere. The reduction of the emission of CO2 is becoming urgent.
Chapter
The utilization of solar energy for driving reactions in which CO2 is converted into energy-rich products is discussed in this chapter. Three approaches are considered: i. electrolysis of water by photovoltaic energy to generate hydrogen used, in turn, for the hydrogenation of CO2 to gaseous or liquid fuels; ii. use of concentrated solar power for...
Chapter
In this chapter, carbon-free perennial primary energy sources are described and the potential of relevant technologies to produce electric or thermal energy is highlighted. Solar, wind, hydro, and geothermal power are analyzed for their contribution to substitute fossil-C in coming decades.
Chapter
In this chapter, the use of fossil-C as source of energy (compared to other sources) and as raw material for the chemical industry is discussed. Some fundamental processes are illustrated for the production of liquid fuels from either coal or natural gas. Emissions of CO2 are quoted for several sectors. The syngas and Fischer–Tropsch processes are...
Chapter
The efficiency technologies in both the production of energy (electric–thermal–mechanic, others) from fossil-C and the use of the various forms of derived energies can play a strategic role in the reduction of the production and emission of CO2. Additionally, the use of biomass as source of fuels is shortly presented and the putative “zero-emission...
Chapter
The potential of carbon recycling through CO2 utilization is “sized” here by merging all options discussed in previous chapters. It is interesting to note that in the medium-long term some 7–9 GtCO2/y can be avoided, and this is a very interesting news: coupled to the use of biomass and utilization of perennial energies (SWHG) will make possible th...
Chapter
This Chapter provides an overview of possible solutions to convert carbon dioxide into various bioproducts, such as biofuels, bioplastics and bio-sourced chemicals, mimicking Nature, or even enhancing natural systems. Biotechnological techniques or hybrid systems, made by integrating chemical(electro)catalysis and biological systems, are discussed.
Chapter
The Capture and Storage of Carbon Dioxide (CCS) is illustrated in this chapter. CO2 can be captured from point sources (power plants and industries) or directly from the atmosphere (Direct Air Capture (DAC)) or even from mobile sources. Technologies for the capture are illustrated here and some examples of disposal in natural fields are described,...
Chapter
In this chapter, the relevance of Carbon Dioxide Utilization (CCU) to Innovation and Sustainability of the Chemical Industry and to the strategy of the Circular Economy is discussed. A number of examples are presented of processes which may convert CO2 into added-value chemicals, polymeric materials, and fuels which have each a market higher than 1...
Chapter
This Chapter describes the “non-chemical” uses of CO2, which means all those applications in which CO2 is not converted into other chemicals, but remains the same species. Some of the applications are quite familiar to the public (food packaging, low temperature cooling agent, fluid as fire extinguisher, cleaning fluid, smoke effects, and water tre...
Chapter
The basic aspects of the reactivity of carbon dioxide are featured, related to the electronic structure of the molecule. The phase diagram of CO2 is also discussed for understanding how CO2 exists in different conditions of temperature and pressure.
Chapter
In this chapter, the structure of the atmosphere is presented with the natural cycles of several species. The natural green house effect is discussed and the way in which CO2 and other GHGs contribute to its enhancement is analyzed.
Book
This book focuses on carbon dioxide and its global role in our everyday life. Starting with society's dependency on energy, it demonstrates the various sources of carbon dioxide and discusses the putative effects of its accumulation in the atmosphere and its impact on the climate. It then provides an overview of how we can reduce carbon dioxide pro...
Chapter
The substitution of fossil-C is an urgent task for both the scarcity of resources and stopping the emission of green-house gases, (GHGs) that impact the climate of our planet. The transfer to the atmosphere of heat, due to the inefficiency of conversion of chemical energy into other forms of energy, and CO2 is also causing the increase of atmospher...
Article
Full-text available
In the present paper, we report the synthesis and characterization of both binary (Cu2O, Fe2O3, and In2O3) and ternary (Cu2O-Fe2O3 and Cu2O-In2O3) transition metal mixed-oxides that may find application as photocatalysts for solar driven CO2 conversion into energy rich species. Two different preparation techniques (High Energy Milling (HEM) and Co-...
Article
Full-text available
The conversion of CO2 into added value chemicals, materials and fuels is a case of transition from the linear to the cyclic-C economy, a necessary change for stopping the putative negative effect of CO2 on climate and the environment. Several strategies can be implemented for CO2 conversion and their potential and timeframe is discussed in this per...
Chapter
This chapter makes the analysis of the possible routes for large scale CO2 utilization (CCU). Processes that convert CO2 into chemicals, materials and fuels are discussed, as they are part of the strategy for reducing the CO2 emission into the atmosphere. Technical uses of CO2, which do not imply its chemical conversion, are discussed in Chap. 3, w...
Chapter
CCU is a step towards a Cyclic Carbon Economy, with different effects over diverse time-scale. In this chapter, the potential benefits of CCU are summarized with a perspective look on the amount of used/avoided CO2 in the short, medium, long term and on the conditions that must be fulfilled for an extensive utilization of such abundant source of ca...
Article
Full-text available
5-Hydroxymethylfurfural (5-HMF) can be considered a prominent building block: because of the presence of the alcohol and aldehyde moieties, it can be used to generate useful molecules as chemicals of industrial interest with high added value, monomers for polymers, and even fuels. This article shows how building up mixed oxides of different complex...
Article
Ethanol conversion to butanol was investigated over mixed oxides derived from hydrotalcites modified with copper, palladium or indium. The reaction was carried out in the 403–573 K temperature range using stainless steel reactors. The presence of indium or palladium in the catalyst influences the temperature of reaction so that it was possible obta...
Article
Sustainable chemical industry encompasses the shift from fossil carbon to renewable carbon. The synthesis of chemicals from non-edible biomass (cellulosic or oily) represents one of the key steps for "greening" the chemical industry. In this paper we report the aerobic oxidation-cleavage of C6 polyols (5-HMF, glucose, fructose, sucrose) in water to...
Chapter
Carbon dioxide can be used as building block for chemicals and materials or source of carbon for fuels. The former application, if implemented at the correct scale, may boost the sustainability of the chemical industry. The latter is more relevant to the energy sector and requires cheap hydrogen from water or renewables for the hydrogenation of the...
Article
Popped graphene oxide (PGO), either bare or loaded with CuO (or Cu2O), has been characterized for its photoelectrochemical properties and used for the first time as photocatalyst for CO2 insertion into CH bonds, a challenging reaction of great industrial interest. PGO joins, thus, the restricted number of modified polymeric C-species (fullerenes an...
Article
This review discusses the state of the art of the aerobic selective oxidation of 5-hydroxymetylfurfural (5-HMF) with heterogeneous catalysts in water, for the preparation of added value products. Aspects such as kind of metals used for making the catalysts and external additives will be examined. The paper is divided into four main parts each deali...
Article
In this study the LCA methodology is applied in order to satisfy two goals: i) to evaluate the hot spots in site-specific production chain of biodiesel from terrestrial and micro-algae feedstock; ii) to compare quantitatively, utilizing primary data, the impacts of the first generation in respect to the third generation bio-fuels. Results show that...
Article
Fe(0)(dipyridine)(2-aminoethyl-pyridine) 2, a 16-electron species, was synthesized by reduction of FeCl2(dipyridine)(2-aminoethyl-pyridine) 1 using Na-strips. It is a diamagnetic low-melting solid (m.p. 295 K) stable under N2 and easily decomposed by radiations even at low temperature. It was fully characterized by elemental analyses and multinucle...
Article
Full-text available
In the present work, microalgae strains, such as Scenedesmus obliquus and Phaeodactylum tricornutum grown in indoor/outdoor photobioreactors (PBRs) and in open ponds (this is the first study on such strains cultivated in the local Southern Italy climatic conditions), were fully analyzed for their protein content, carbohydrates, lipids, and fatty ac...
Article
Full-text available
In the recent decade carbon dioxide has increasingly been regarded not only as a greenhouse gas, but even more as a chemical feedstock for carbon based materials. Different strategies evolved to realize carbon dioxide utilization and conversion to fuels and chemicals. Particularly biological approaches have drawn attention as natural CO2 conversion...
Article
The Inside cover picture shows the concept of using p-type semiconductors as photocatalysts for carbon dioxide conversion into chemicals and fuels. Although p- and n-type semiconductors are mainly considered as basic components used in electronics, the distinction between these two types of semiconductors may also be crucial for photocatalysis. The...
Article
A p-type semiconductor, CuI, has been synthesized, characterized, and tested as a photocatalyst for CO2 reduction under UV/Vis irradiation in presence of isopropanol as a hole scavenger. Formation of CO, CH4 , and/or HCOOH was observed. The photocatalytic activity of CuI was attributed to the very low potential of the conduction band edge (i.e., -2...
Article
This paper tells part of the contemporary CO2 story through the chemistry developed in my laboratory at the University of Bari or wherever I have been in the world, since the discovery of the first Ni-CO2 complex up to the various catalytic conversion reactions of CO2 into several added-value products. Most of the reactions are described with relev...
Article
The need to reduce the emission of carbon dioxide into the atmosphere is pushing toward the use of "renewable carbon", so to avoid as much as possible burning "fossil carbon". It would be possible to complement the natural "carbon cycle" by developing man-made industrial processes for "carbon recycling", converting, thus, "spent carbon" as CO2 into...
Article
A simple, cheap, and selective catalyst based on copper/cerium oxides is described for the oxidation of 5-(hydroxymethyl)furfural (5-HMF) in water. An almost quantitative conversion (99 %) with excellent (90 %) selectivity towards the formation of 5-formyl-2-furancarboxylic acid, a platform molecule for other high value chemicals, is observed. The...
Article
This paper aims at highlighting the hurdles and traps on the way back from CO2 to chemicals (or even fuels). The case of the synthesis of dialkyl carbonates is discussed, considering several synthetic conditions and comparing the relevant amount of energy necessary for product separation. The calculations show that the post-reaction separation proc...
Article
The synthesis of di-n-butyl carbonate has been studied starting from n-butanol and either CO2 or urea. A comparison of the two synthetic routes is reported. Several mixed oxides have been synthesized and tested with the aim of finding a catalyst active in mild conditions (T, t), recoverable and reusable. Different strategies to push the reaction to...
Article
The International Conference on CO2 Utilization-ICCDU and the Journal of CO2 Utilization (JCOU) have different stories, lifes and roles, but a common objective: gathering the scientific community interested in the development of CO2 conversion and its technological applications. ICCDU and JCOU are a forum for the dissemination and advancement of kn...
Article
This chapter discusses the CO2 molecule in its ground and excited states, correlating the energy to the molecular geometry. The effect of adding or taking out an electron is illustrated, opening the way to the coordination of CO2 to metal centers. Several modes of bonding of CO2 are presented and the IR and multinuclear NMR spectroscopic data of tr...
Chapter
This chapter deals with the enzymatic conversion of CO2. It covers the two aspects of the fixation of the entire CO2 molecule into substrates (carboxylation) and the reduction of CO2 to other C1 (or C2) energy-richer molecules. The known mechanisms are discussed and barriers to exploitation at the industrial level highlighted.
Chapter
This chapter deals with the utilization of CO2 in the carboxylation of alcohols, diols, polyols, and epoxides to create a variety of compounds such as linear carbonates, cyclic monomeric carbonates, and polycarbonates. Homogeneous, heterogenized, and heterogeneous catalysts are described. The problem of “water elimination” is considered and routes...
Chapter
This chapter deals with the “insertion” reactions of carbon dioxide (CO2) into E–X bonds, where E and X represent several different (sets of) atoms, such as M–H, M–OH, M–C, M–OR, M–O2, M–N, M–P, C–C, C–N, Si–H, and M–M (M = metal). Such reactions are relevant to catalysis for the formation of new bonds in which CO2 may be implied (C–C bonds or C–E...
Chapter
Gas hydrates are clathrate solid crystalline compounds consisting of a lattice formed by water molecules and entrapped gas molecules inside. They are stable under high pressure and low temperature. CO2 hydrates, specifically, are composed of CO2 as the guest molecule and water as the host molecule. CO2 hydrates have a number of applications includi...
Chapter
This chapter deals with the mechanism of reduction of “free” and coordinated CO2 by electron transfer. One-e− and multi-e− transfer pathways are compared energetically and their role in the conversion of CO2 into higher energy C1 or C1+-species is highlighted. The state of the knowledge is presented through the analysis of reference cases.
Chapter
This chapter deals with high temperature reactions in which carbon dioxide (CO2) is used either as dehydrogenation agent (“soft oxidant”) or hydrogen user (“reduction to other C1 molecules”). The first part of the chapter covers reactions such as the oxidative coupling of methane, the dehydrogenation of alkanes to olefins, the dehydrogenation of et...
Chapter
The basic aspects of the reactivity of carbon dioxide (CO2) are featured in this chapter and related to the electronic structure of the molecule. The electronic properties of neutral CO2 are compared with those of the radical ions \( {\mathrm{CO}}_2^{-} \) and \( {\mathrm{CO}}_2^{+} \). The potential of a few spectroscopic techniques (infrared, ult...
Chapter
In the presence of low-valent transition metal centers, CO2 can react with unsaturated organic substrates, such as alkenes, alkynes, and conjugated and cumulated dienes, to give carboxylated products. This chapter focuses on the main mechanistic features of these carboxylation processes. A key step of these transformations is the metal-promoted oxi...
Chapter
The modes of coordination of carbon dioxide (CO2) to metal centres are presented in this chapter. The coordination at both room temperature and low temperature in gas matrices is discussed with the reactivity of the coordinated cumulene. X-ray diffraction structural data are presented and discussed together with spectroscopic properties of the comp...
Chapter
In this chapter the direct, non-metal-mediated interaction of carbon dioxide with electron-rich elemental or molecular species is discussed. Anionic species such as H−, OH−, and R3C− and covalent species such as amines have been taken into consideration, in view of their relevance to systems of potential or real industrial interest.
Article
We describe a process for the selective conversion of C6 -polyols into 5-hydroxymethylfurfural (5-HMF) in biphasic systems of organic carbonate/water (OC/W), with cerium(IV) phosphates as catalysts. Different reaction parameters such as the OC/W ratio, catalyst loading, reaction time, and temperature, were investigated for the dehydration of fructo...
Article
Industrial utilization of CO2 is an important research area not only due to the potential contribution to the reduction of emissions into atmosphere, but also for saving carbon resources through the recycle of carbon. The use of solar energy in the conversion of CO2 appears to be a major challenge and opportunity for the future. A group of nanocrys...
Article
New Zn- and Ca-based mixed oxides have been tested in the ethanolysis of urea. Cerium and magnesium have revealed to be able to stabilize and enhance the activity of Zn and Ca. All the used compounds act as heterogeneous catalysts in a batch reactor and can be easily recovered and re-used in several catalytic runs. However, although ZnO dissolves a...
Article
New iron(II) compounds with N-donor ligands [2,2′-bipyridine (bpy) and 2-(2-pyridyl)ethylamine (pyea)] were synthesized, and their reactivity with carbon dioxide was investigated. The reactions of Fe(bpy)(pyea)Cl2 (1) with CO2 (0.9 MPa) afforded the carbamato derivative Fe(bpy)(pyea-CO2)Cl2 (2), which reacted with CH3Li to afford the monomethyl car...
Article
Full-text available
Multifunctional monomers based on glycerol carbonate are employed in the chemical industry for the production of polyurethanes and polycarbonates. To avoid the use of toxic phosgene as carboxylating reagent, eco-friendly routes have been developed using alternative agents. In this paper, a series of binary and ternary oxides have been tested as cat...
Article
Full-text available
The utilization of solar energy may represent a real breakthrough in the conversion of CO2 to afford different products, from functionalised organic substrates to C1 and Cn energy rich molecules. In this paper we describe the photocatalytic incorporation of CO2 into 2,3-dihydrofuran (2,3-DHF). Ru-decorated ZnS was used as photocatalyst, that has be...
Article
Full-text available
In this paper, we present the results of a study on 5-HMF production from fructose by means of heterogeneous catalysts in aqueous media. Mild conditions were used setting the temperature between 393 K and 443 K. Cerium(IV) phosphates, differently from other metal(IV)-phosphates, such as titanium and zirconium, have been characterized only recently....
Article
New Zn-based catalysts are described that act as heterogenized or heterogeneous catalysts, with easy recovery and re-utilization with a limited or even zero Zn-leaching. For stabilizing in the heterogeneous form the catalytically active Zn centre, mixed oxides, ZIF-8 and Zn-tethered systems have been synthesized and found to sensibly reduce the lea...
Article
Dialkylcarbonates, (RO)2CO, can be prepared from alcohols and CO2. Such reaction is clean (water is the co-product) but thermodynamically disfavored. In principle, the reaction mechanism of formation of carbonates requires the acid–base activation of alcohols. Existing data support that the first step is the formation of the alkoxo group RO− that r...
Article
This chapter deals with selected aspects of man-made solar-driven photoreduction of CO2. In particular, direct photosynthetic processes are discussed which include the use of man-made materials for solar energy capture and utilization in enzymatically driven CO2 reduction to energy-rich C1 molecules. The enzymatic reduction of CO2 requires cofactor...
Book
This book provides an analysis of the reaction mechanisms relevant to a number of processes in which CO2 is converted into valuable products. Several different processes are considered that convert CO2 either in specialty chemicals or in bulk products or fuels. For each reaction, the mechanism is discussed and the assessed steps besides the dark si...
Article
CO2 is today at the center of the attention of scientists and technologists for its potential as a source of carbon. The actual utilization of CO2 although significant "per se" (ca. 200 Mt/y) represents a minor fraction of the anthropogenic emission (32,000 Mt/y). This chapter describes old and new uses of carbon dioxide in synthetic chemistry, wit...
Article
Alcoholysis of urea is an attractive methodology for the synthesis of organic acyclic carbonates. It has low environmental impact and represents an indirect way of using CO2. ZnO, known to have interesting performances, is reported in the literature to behave as a homogeneous catalyst in the form of Zn(NCO)2(NH3)2 in the methanolyis of urea. In thi...
Article
Full-text available
The need for a better carbon management and the reduction of CO2 emissions push away from the linear-carbon economy (LCE) towards a better carbon management including carbon recycling (CR). This implies the utilization of gaseous and liquid process streams so far under-utilized, and often either sent to combustion or disposed of. In this paper, fou...
Patent
Full-text available
The present invention relates to a synthesis process of polyol carbonate, such as glycerol carbonate, from polyols such as glycerol, propylene glycol or ethylene glycol and urea conducted in using a solvent selective for polyols (glycerol) carbonates. Said process comprises reacting polyol with urea in the presence of a catalyst, extracting produce...
Article
Full-text available
A hybrid enzymatic/photocatalytic approach for the conversion of CO2 into methanol is described. For the approach discussed here, the production of one mol of CH3OH from CO2 requires three enzymes and the consumption of three mol of NADH. Regeneration of the cofactor NADH from NAD(+) was achieved by using visible-light-active, heterogeneous, TiO2-b...
Article
Samples of styrene-co-(2-vinylfuran) polymers (S-co-2VFs) were obtained in a wide range of composition via ATRP catalyzed by Cu(I)-PMDETA using 1-phenylethyl bromide (1-PEBr) as initiator. Investigation of the copoly-merization kinetics allowed evaluating the reactivity ratios r s and r VF (r s = k S‑S /k S‑VF ; r VF = k VF‑VF /k VF‑S ; M S = styre...
Chapter
This article summarizes a number of applications of CO2 in the synthesis of molecular compounds, materials and fuels. The actual and perspective amount of used CO2 is given for 2016 and 2030. Barriers to a full exploitation are discussed and future areas of major interest are highlighted.Keywords:carbon dioxide;building block for chemicals;source o...