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107
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Introduction
My current research activity is mainly focused on the development of materials for hydrogen production, such as bimetallic heterogeneous catalysts for reforming reactions.
Additional affiliations
January 2003 - December 2004
November 1998 - November 2001
Position
- PhD Student
Description
- PhD in Chemical Sciences, research on "SHB" catalysts for selective hydrogenations and on Pt-Ba/Al2O3 "Toyota" SNR catalysts.
Publications
Publications (107)
We report on the use of In as an effective H2 production promoter in a Cu/SiO2 catalyst for the steam reforming of methanol. To date, In promotion has been limited to noble metals because of its tendency to “bury” other metals thus compromising the catalytic activity. Here, we prepared a silica-supported Cu-In catalyst via a urea-assisted co-precip...
In this manuscript, we investigated in detail one of the critical parameters that governs the reactivity of the carbonylic group towards hydrogenation and hydrodeoxygenation: the effect of the side chain of aldehydes. We observed that the presence of a π-electron conjugation on the side chain strongly affects the conversion of aldehydes to alcohols...
Flame spray pyrolysis was used to produce nanosized Ni-based catalysts starting from different mixed oxides. LaNiO3 and CeNiO3 were used as base materials and the formulation was varied by mixing them or incorporating variable amounts of ZrO2 or SrO during the synthesis. The catalysts were tested for the steam reforming of glycerol. One of the key...
Zr/Si mixed oxides with different amounts of silica (0–50 wt%) were prepared by a simple sol–gel method.
These catalysts were tested in a cascade reaction of furfural and 5-hydroxymethyl furfural (HMF) with
2-butanol to form the corresponding alcohols or ethers through a combination of transfer hydrogenation
and etherification processes under mild...
Anisotropic gold nanoparticles (AuNPs), with their unique physical and optical properties, are emerging as smart and key nanomaterials, and are being exploited in many crucial fields. To further improve their range of action, anisotropic AuNPs have been coupled with semiconductors, mainly TiO2 (titania), receiving great interest as powerful platfor...
Au nanoparticles, generated by the metal vapor synthesis technique, were supported onto cerium oxycarbonate monohydrate (Ce2O(CO3)2·H2O) giving [email protected]2O(CO3)2·H2O. The obtained heterogeneous catalyst was used in the aerobic allyl alcohol oxidation reaction performed in toluene, showing a notably higher catalytic substrate conversion and...
This Handbook is part of the EU CBRN CoE Project65 “Strengthening chemical and biological waste management in Central Asia countries for improved security and safety risk mitigation” – CABICHEM (http://www.cabichem.eu/index.php/en/)
The book is implemented by the CNR - Institute of Chemical Sciences and Technologies (Milan, Italy) and Fondazione FO...
The role of carbonaceous deposits (coke) formed in dehydrogenation catalysis has been extensively investigated over the last decades mainly with respect to the deactivation of metal-based and metal-free heterogeneous catalysts. Although much less emphasized, coke deposits grown on selected metal-oxides have also been described as active and selecti...
The addition of a specific amount of silica (10 wt.%) to zirconia was found to significantly influence the morphological and electronic properties of supported copper nanoparticles in a Cu/ZrO2-SiO2 catalyst. The so-developed catalyst was tested in the methanol steam reforming reaction and reached at 3500 h⁻¹ of space velocity a hydrogen productivi...
Fuel cell is to date on the brink of large-scale commercialization. Still, long-term stability is of concern, especially in the automotive field, mainly due to the stability of the cathodic catalyst support. Carbonaceous materials, that to date are the state of the art, suffer from severe corrosion phenomena during discontinuous operation. As shown...
Dating from the seminal work of Fujishima et al. [...]
Hematite-based photoanodes were used for the photoelectrocatalysed batch oxidation of As(III) in water at pH 7 and 10. Tests were carried out at different As(III) initial concentrations, ranging from 150 μg/L to 30 mg/L. With no pre-treatments, an initial inactive period of 40–50 min was always observed at the beginning of every test. This initial...
Layered treatments of natural stones based on dispersions of experimental nano-TiO2 and commercial TEOS, showing photocatalytic and self-cleaning properties have been set-up and tested. To enhance nano-TiO2 efficacy, a surface pre-treatment with tetraethyl orthosilicate has been proposed to avoid the penetration of NPs into the crystalline porous s...
A class of heterogeneous catalysts based on commercial bentonite from natural origin, containing at least 80 wt% of montmorillonite clay, was designed to transform selectively and under mild conditions toxic organosulfur and organophosphorus chemical warfare agents into non-noxious products with reduced impact on health and environment. The bentoni...
In this work a study of the shelf life of an iron impregnated MgO (Fe/MgO) sample and an explanation of the effect of its aging on morphology and electroactivity of nitrogen-doped carbon nanostructures prepared by using this catalyst at different ages is presented. Characterizations of Fe/MgO by TGA, TPD-MS, HR-XRPD and XPS have been performed at d...
The Lewis-acidity of a series of bis-cationic Pt(II)(aqua) complexes bearing phosphane ligands was exploited to catalyze the conversion of dihydroxyacetone to ethyl lactate. The Pt(II) complex bearing 1,2-bis(diphenylphosphanyl)ethane and triflate as counter anion showed high catalytic activity (TOF = 530 h⁻¹) and chemoselectivity (>96%) at 70 °C....
The catalytic performances in steam reforming (SR) and aqueous phase reforming (APR) of glycerol of a bimetallic Pt-Mn catalyst supported on activated carbon are investigated and correlated with the surface properties of the catalyst. Under SR conditions, Mn showed a significant promoting effect over Pt/C, both in terms of hydrogen production rate...
Pure and titanium- or silicon-doped iron oxide fibres are synthesised by electro-spinning over conductive fluorine doped tin oxide (FTO)/glass substrates, and the effect of the type of dopant on the morphology of the fibres and the crystalline phase of the oxide is investigated by means of several complementary characterisation techniques. Results...
Doubly functionalized, hierarchical porosity silica monoliths were synthesized by post-grafting of sulfonic groups and in-situ growth of Pd nanoparticles in the order. PdNP of 3.1 nm size located in the mesopores of the material showed to be evenly distributed within 4.6% wt Pd monoliths. The system was explored in the continuous flow, catalytic pa...
Photocatalytic reactions could enhance the share of chemicals produced through renewable sources. The efficiency of photocatalysts drastically depends on light absorption, on surface energy of the crystals, and on the properties of nano-building blocks assembled in devices. Here, we show that photoelectrochemical water oxidation on brookite TiO2 na...
A new protocol to synthesize size-controlled Au nanoparticles (NPs) loaded onto vertically aligned anatase TiO2 nanotubes arrays (TNTAs) prepared by electrochemical anodization is reported. Ligand-free Au NPs (< 10 nm) were deposited onto anatase TNTAs supports, finely tuning the Au loading by controlling the immersion time of the support into meta...
The lively acidic properties in water of niobium phosphate (NBP) catalyst and NBP modified samples by acidic treatments in HCl solutions at 0.1, 1.0, and 10 M concentration (NBP01, NBP1, and NBP10, respectively) have been exploited for the direct conversion reaction of cellobiose to hydroxymethylfurfural (HMF) at temperature of 80–130 °C. Acidity o...
Mg(Al)O supported Ru and Rh catalysts with low loading of active metal (0.5wt.%) were tested in the steam reforming (SR) of acetic acid (AA) to hydrogen rich mixtures. Two synthetic procedures were adopted to deposit metal nanoparticles on support material: conventional impregnation from metal chlorides aqueous solutions and size-controlled metal n...
Aiming at understanding how plasmonic reactions depend on important parameters such as metal loading and strong metal–support interaction (SMSI), we report the plasmonic photodegradation of formic acid (FA) under green LED irradiation employing three TiO2 supports (stoichiometric TiO2, N-doped TiO2, black TiO2) modified with Au nanoparticles (NPs)...
We investigated how the outcome of the solvothermal synthesis of manganese(II) sulfide (MnS) nanocrystals (NCs) is affected by the type and amount of long chain surfactant present in the reaction mixture. Prompted by a previous observation that a larger than stoichiometric amount of sulfur is required [Puglisi, A.; Mondini, S.; Cenedese, S.; Ferret...
The development of a scanning reactor for planar catalysts (SCR-PC) is here presented. With respect to other existing models, this reactor is able to scan catalysts even with low turnover frequencies, with a minimum sensed circular area of about 6 mm diameter. The downstream gas analysis is performed with a quaprupole mass spectrometer. The apparat...
The study of the semiconductor/electrocatalyst interface in electrodes for photoelectrochemical water splitting is of paramount importance to obtain enhanced solar-to-fuel efficiency. Here, we take into consideration the multiple effects that a thin layer of photodeposited amorphous Ni-oxyhydroxide (NiOOH) induces on hematite (α-Fe2O3) photoanodes....
The direct in-situ stabilization of an anatase-based nanocrystalline photocatalyst (Degussa P25) was obtained by sintering the catalyst powder in presence of Zr4+ organic salts. This approach allows the doping of an already-formed nanocrystalline photocatalyst instead of introducing the dopant in the crystal lattice during the catalyst synthesis. T...
Pd nanoparticles within a nitrogen-containing covalent triazine framework (CTF) material are investigated to understand if the highly tunable CTF chemistry mediates the catalytic properties of the Pd nanoparticles. Surprisingly, our results demonstrate that the CTF stabilizes the formation of 2.6 nm PdHx particles within the pores. These confined P...
Nanostructured mesoporous ZrO2 was obtained by hydrothermal synthesis using surfactant assisted approach. Copper modifications of thus obtained ZrO2 (4-25 wt.% copper) were prepared by incipient wetness impregnation with the corresponding nitrate or acetyl acetonate precursors and further treatment in oxidative or reduction atmosphere. The obtained...
Exploiting plasmonic Au nanoparticles to sensitize TiO2 to visible light is a widely employed route to produce efficient photocatalysts. However, a description of the atomic and electronic structure of the semiconductor sites in which charges are injected is still not available. Such a description is of great importance in understanding the underly...
Cathodoluminescence spectroscopy is profitably exploited to study energy transfer mechanisms in Au and Pt/black TiO2 heterostructures. While Pt nanoparticles absorb light in the UV region, Au nanoparticles absorb light by surface plasmon resonance and interband transitions, both of them occurring in the visible region. The intra-bandgap states (oxy...
A new nanostructured α-Fe2O3 photoelectrode synthesized through plasma-enhanced chemical vapor deposition (PE-CVD) is presented. The α-Fe2O3 films consist of nanoplatelets with (001) crystallographic planes strongly oriented perpendicular to the conductive glass surface. This hematite morphology was never obtained before and is strictly linked to t...
We propose here a novel voltammetric method for the determination of platinum at trace levels. The method is based on the interference that platinum generates on the anodic stripping signal of tin acidic solutions: in appropriate conditions platinum uses the intermediate formation of tin (II) ions, taking place during the tin cathodic reduction, to...
Continuous flow heterogeneous asymmetric cyclopropanations catalysed by supported hydrogen-bonded (SHB) chiral copper(i) complexes of pyridine containing tetraazamacrocyclic ligands Pc-L* using CO2 as a transport vector are described. The catalytic system showed high stability and good recyclability without loss of activity for at least 24 h in CO2...
The grafting of the preformed Pc-L* (pyridine containing macrocyclic ligands) copper(I) complexes on different ordered and non-ordered silicas, and their use, under heterogeneous batch conditions, as catalysts for the olefin cyclopropanation are reported. High yields (up to 99%) and good recyclability in halogen-free solvent reactions were obtained...
First time a combined wet impregnation (WI)-organometallics chemical vapor deposition (OMCVD) strat-egy was applied for loading of 3–7 wt.% copper in mesoporous silica KIT-6 matrix nanoparticles withtailored particle size. XRD, HRTEM, nitrogen physisorption, UV–vis, XPS and temperature programmedreduction with hydrogen were used for the samples cha...
Ir-Sn bimetallic silica-based materials have been prepared via deposition of the molecular organometallic clusters (NEt4)2[Ir4(CO)10(SnCl3)2] and NEt4[Ir6(CO)15(SnCl3)] or via deposition of Sn organometallic precursor Sn(n-C4H9)4 onto pre-formed Ir metal particles. These solids possess promising properties, in terms of selectivity, as catalysts for...
Metal-loaded TiO2 is, by far, one of the most important class of photocatalysts in hydrogen production through photoreforming of organics and water photosplitting. In this study anatase loaded with Au and Pt nanoparticles (Au/TiO2 and Pt/TiO2) by an impregnation-reduction method was investigated as for morphological, electronic (XPS) and photocatal...
Ni-based catalysts supported on TiO2, ZrO2 and SiO2 (in the form of mesoporous Santa Barbara Amorphous 15 (SBA-15) and amorphous dense nanoparticles), were employed in the steam reforming of glycerol. Each sample was prepared by liquid phase synthesis of the support followed by impregnation with the active phase and calcination at 800 °C or by dire...
A series of titanium-containing silica catalysts (Ti4/SiO2) with small oligomeric Ti centres is obtained by impregnation of the air-stable and water-soluble tetranuclear Ti complex (NH4)8[Ti4(C6H4O7)4(O2)4]·8H2O onto commercial non-ordered mesoporous silica supports. Catalyst preparation is performed under very mild conditions, with no controlled a...
Polymetallic heterogeneous catalysts, mainly consisting in bimetallic metal nanoparticles supported on inorganic oxides, allow, in principle, to obtain high performances (increased activity, and selectivity to desired products, extended lifetime, high resistance to poisoning/coke deposition/sintering/etc.) thanks to the positive effects arising fro...
Subject collections (10 articles) organometallic chemistry (9 articles) inorganic chemistry Articles on similar topics can be found in the following collections The main methods for the design and preparation of single-site heterogeneous catalysts on inorganic oxide supports are described and reviewed. Catalytically active metal sites can be either...
A novel preparation strategy was performed to obtain uniform and size controlled, in a large scale, copper nanoparticles, hosted into mesoporous silica matrix. The method includes the initial deposition of finely dispersed copper nanoparticles, using a conventional incipient wetness impregnation of silica matrix with small amount of nitrate precurs...
Bimetallic Pt-Au nanoparticles supported on reduced anatase nanocrystals represent a new class of promising photocatalysts with high activity in hydrogen production by photoreforming of aqueous solution of renewable feedstock, such as ethanol and glycerol. The catalysts are easily obtained by metal impregnation of commercial TiO(2) , followed by a...
Mg(Al)O supported Ru catalysts with low loading of active metal (0.6 wt.%), obtained from simple inorganic salts, were tested, for the first time, in the steam reforming (SR) of glycerol to hydrogen rich mixtures. The catalysts, obtained by simple wet impregnation of Ru salts on a Mg(Al)O mixed oxide followed by high temperature oxidation/reduction...
The increasing need for new materials capable of solar fuel generation is central in the development of a green energy economy. In this contribution, we demonstrate that black TiO(2) nanoparticles obtained through a one-step reduction/crystallization process exhibit a bandgap of only 1.85 eV, which matches well with visible light absorption. The el...
Gold nanoparticles were obtained by reduction of a tetrachloroaurate aqueous solution in the presence of a RGD-(GC)(2) peptide as stabilizer. As comparison, the behavior of the (GC)(2) peptide has been studied. The (GC)(2) and RGD-(GC)(2) peptides were prepared ad hoc by Fmoc synthesis. The colloidal systems have been characterized by UV-visible, T...
A new class of bimetallic Au-Pt/TiO 2 photocatalysts were developed and employed in H 2 photoassisted production using ethanol as a sacrificial reagent both under UV-A and simulated sunlight irradiation. Remarkably, preliminary experiments show promising hydrogen evolution under visible light using Au0.5-Pt0.5/TiO 2 with methanol. The presence of b...
Novel modified “chemisorption–hydrolysis” technique and conventional “incipient wetness impregnation” procedure were compared for loading of cobalt species on mesoporous silica supports. Effect of cobalt amount, pH of the precursor solution, duration of the “chemisorption” procedure and pre-treatment medium, as well as topological characteristics o...
In this work the activity of Ni catalysts in hydrogen production by glycerol steam reforming was studied. Moreover the effect of the support (TiO2, SBA-15 and ZrO2) on the catalytic performance of Ni was evaluated. A strong effect of the support on the activity of the samples was detected. The Ni/TiO2 sample showed negligible activity mainly due to...
Copper modifications of ordered mesoporous materials with different pore topology (SBA-15 and KIT-6) were prepared by incipient wetness impregnation and “chemisorption–hydrolysis” methods and further oxidative or consecutive oxidative/reductive treatment. The samples were characterized by nitrogen physisorption, XRD, XPS, FTIR, UV–vis and TPR–TG te...
This paper studies the role of Au as a promoter for vanadyl pyrophosphate, catalyst for n-butane oxidation to maleic anhydride. Samples were prepared with a stoichiometric P/V ratio (P/V=1.0), and then doped with increasing amounts of Au. It was found that the addition of the Au promoter had a profound influence on its catalytic behaviour, as sampl...
The impregnation of Ketjen Black (C) with iron and cobalt phthalocyanines (MPc) taken one by one or as a 1:1 stoichiometric mixture, followed by heat treatment at 600 °C under inert atmosphere, gave materials containing arrays of single metal ions coordinated by four nitrogen atoms (M-N4 units). Increasing the pyrolysis temperature to 800° resulted...
SiO2 and Al2O3 supported copper catalysts were prepared by “chemisorption–hydrolysis” or incipient wetness impregnation methods and investigated by XRD, TG-TPR, UV–vis diffuse reflectance and FTIR spectroscopy. Formation of finely dispersed copper oxide species was registered for the samples prepared by “chemisorption–hydrolysis” method, while a si...
The organometallics chemical vapor deposition (OM-CVD) technique, using Pd(hfac)2 as a precursor, was employed for the preparation of a series of heterogeneous catalysts based on Pd nanoparticles supported on nanometric oxides (CeO2, ZnO and TiO2). The properties of metal nanoparticles were tuned by proper pretreatment of the oxidic support.Complet...
The interactions among inorganic materials and biological environments occurring at the nanoscale level are crucial to understand the mechanisms behind the bioactivity of biomaterials and for their better design. In the present study, we prepare TiO2 and TiO2/hydroxyapatite (HA) scaffolds for Tissue Engineering (TE) via a sol–gel/polymeric sponge m...
Bimetallic Ru-Sn heterogeneous catalysts for glycerol steam reforming (SR) to hydrogen-rich mixtures are developed using organometallic (OM)CVD of commercial metal precursors as the preparation technique of choice. This methodology produces monometallic Ru nanoparticles (NPs) supported on Mg(Al)O mixed oxide with high activity and selectivity for g...
We report the evidence for the cellular uptake of gold nanoparticles via the phagocytosis mechanism in murine macrophage cells strongly supported by TEM and optical microscopy. Nanoparticles were prepared using several biocompatible molecules of choice (5-aminovaleric acid, l-DOPA, melatonin, and serotonin hydrochloride) as stabilizers for gold col...
Nanostructured single-site heterogeneous catalysts possess the advantages of classical solid catalysts, in terms of easy recovery and recycling, together with a defined tailored chemical and steric environment around the catalytically active metal site. The use of inorganic oxide supports with selected shape and porosity at a nanometric level may h...
The combination of chiral- and nano-technologies is potentially one of the most promising strategies for "green" catalytic conversions aimed at fine-chemical production. This paper reviews the most representative examples and highlights recent achievements in the field of enantioselective processes catalyzed by metal nanoparticles (MNPs), with a vi...
A rotary-bed OMCVD device was developed and successfully applied to the scale-up of the preparation of supported rhodiumnanoparticles. The device revealed suitability for the preparation of up to ten grams of material. A multistep CVD protocol was established and allowed a catalytic material with tailored structural/morphological properties of the...
The development of two different in-flow scanning reactors that could be successfully used for testing the activity of planar catalysts are presented. The first one, which allows stepwise scans, is composed by a reactor probe which is sealed over the planar system using a Teflon or Viton mask that also defines the reaction chamber volume. The prese...
This work extends a previous study on the conditioning of Rh/Al2O3 during CH4-CPO experiments at high space velocity. The effect of the preparation procedure was investigated by comparing well-known preparation techniques such as incipient wetness impregnation and grafting, and a novel CVD technique. Catalysts prepared by impregnation of the suppor...
The catalytic hydrogenation of 1,10-phenanthroline (Phen) or 2,9-dimethyl-1,10-phenanthroline (DMPhen) has been achieved using silica-supported palladium nanoparticles (Pd/SiO2) with metal contents of 1.98 or 9.95wt%. With either catalyst, the hydrogenation regiochemistry has been effectively controlled by the reaction temperature. The catalyst wit...
The organometallics chemical vapour deposition (OM-CVD) technique, using Rh(acac)(CO)2 as a precursor, was employed for the preparation of heterogeneous Rh catalysts supported on low surface area refractory oxides (α-Al2O3, ZrO2, MgO and La2O3). Prepared systems were tested in the methane catalytic partial oxidation (CH4-CPO) reaction in a fixed be...