Unité de catalyse et de chimie du solide de Lille

Furfural and 5-hydroxymethylfurfural stand out as bridges connecting biomass raw materials to the biorefinery industry. Their reductive transformations by hydroconversion are key routes toward a wide variety of chemicals and biofuels, and heterogeneous catalysis plays a central role in these reactions. The catalyst efficiency highly depends on the nature of metals, supports, and additives, on the catalyst preparation procedure, and obviously on reaction conditions to which catalyst and reactants are exposed: solvent, pressure, and temperature. The present review focuses on the roles played by the catalyst at the molecular level in the hydroconversion of furfural and 5-hydroxymethylfurfural in the gas or liquid phases, including catalytic hydrogen transfer routes and electro/photoreduction, into oxygenates or hydrocarbons (e.g., furfuryl alcohol, 2,5-bis(hydroxymethyl)furan, cyclopentanone, 1,5-pentanediol, 2-methylfuran, 2,5-dimethylfuran, furan, furfuryl ethers, etc.). The mechanism of adsorption of the reactant and the mechanism of the reaction of hydroconversion are correlated to the specificities of each active metal, both noble (Pt, Pd, Ru, Au, Rh, and Ir) and non-noble (Ni, Cu, Co, Mo, and Fe), with an emphasis on the role of the support and of additives on catalytic performances (conversion, yield, and stability). The reusability of catalytic systems (deactivation mechanism, protection, and regeneration methods) is also discussed.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTCatalytic NOx Abatement Systems for Mobile Sources: From Three-Way to Lean Burn after-Treatment TechnologiesPascal Granger*† and Vasile I. Parvulescu*‡View Author Information† Unité de Catalyse et de Chimie du Solide, UMR CNRS 8181, University of Lille 1, 59655 Villeneuve d'Ascq, France‡ Department of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, Romania, 4 − 12 Regina Elisabeta Boulevard, Bucharest 030016, Romania*P.G.: tel. +32 3 20 43 49 38, fax +32 3 20 43 65 61, e-mail [email protected]. V.I.P.: tel. +4021 4103178, fax +4021 3159249, e-mail [email protected]Cite this: Chem. Rev. 2011, 111, 5, 3155–3207Publication Date (Web):March 18, 2011Publication History Received1 June 2010Published online18 March 2011Published inissue 11 May 2011https://pubs.acs.org/doi/10.1021/cr100168ghttps://doi.org/10.1021/cr100168greview-articleACS PublicationsCopyright © 2011 American Chemical SocietyRequest reuse permissionsArticle Views9350Altmetric-Citations639LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Byproducts,Catalysts,Catalytic reactions,Oxides,Redox reactions Get e-Alerts

Due to its three hydroxyl groups, glycerol is a potential starting material for various high value fine chemicals such as dihydroxyacetone, tartronic acid and mesoxalic acid. The corresponding oxidation reactions are catalysed by various metals such as palladium, platinum, bismuth or gold. Nevertheless, the selectivity not only depends on the type of the active phase, but is also influenced by numerous parameters such as the metal particles size, the pore size of the support and the pH of the reaction medium. This review not only describes the recent developments in the field of research for new catalysts but also spotlights the role of the reaction conditions as well as the possible transport limitations in this tri-phasic system. Furthermore, an economical analysis of some processes is given, which shows that this is realistic to envision sustainable production of, e.g., dihydroxyacetone.

), a calcium phosphate biomaterial, is a very promising candidate for the treatment of air, water and soil pollution. Indeed, hydroxyapatite (Hap) can be extremely useful in the field of environmental management, due in one part to its particular structure and attractive properties, such as its great adsorption capacities, its acid-base adjustability, its ion-exchange capability and its good thermal stability. Moreover, Hap is able to constitute a valuable resource recovery route. The first part of this review will be dedicated towards presenting Hap's structure and defining properties that result in its viability as an environmental remediation material. The second will focus on its use as adsorbent for wastewater and soil treatment, while indicating the mechanisms involved in this remediation process. Finally, the last part will impart all findings on Hap's applications in the field of catalysis, whether it be as catalyst, as photocatalyst, or as active phase support. Hence, all of the above will have served in showcasing the benefits gained by employing hydroxyapatite in air, water and soil clean-up.

Catalytic dehydration of glycerol to acrolein has the potential to valorise the glut of crude glycerol issuing from biodiesel production. This reaction requires catalysts with appropriate acidity, and intensive research activities have been focused on the application of families of catalysts including zeolites, heteropolyacids, mixed metal oxides and (oxo)-pyrophosphates, as their acidic properties are well-known. Nevertheless, their deactivation by coking remains the main obstacle in the way of large-scale industrial applications. Considering this important issue, various technologies have been proposed for regenerating the catalysts. This review shows that a well-balanced combination of an appropriate catalytic system together with an adapted regeneration process could put large-scale industrial applications within reach.

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Over the last few years, extraordinary advances in experimental and theoretical tools have allowed us to monitor and control matter at short time and atomic scales with a high degree of precision. An appealing and challenging route toward engineering materials with tailored properties is to find ways to design or selectively manipulate materials, especially at the quantum level. To this end, having a state-of-the-art ab initio computer simulation tool that enables a reliable and accurate simulation of light-induced changes in the physical and chemical properties of complex systems is of utmost importance. The first principles real-space-based Octopus project was born with that idea in mind, i.e., to provide a unique framework that allows us to describe non-equilibrium phenomena in molecular complexes, low dimensional materials, and extended systems by accounting for electronic, ionic, and photon quantum mechanical effects within a generalized time-dependent density functional theory. This article aims to present the new features that have been implemented over the last few years, including technical developments related to performance and massive parallelism. We also describe the major theoretical developments to address ultrafast light-driven processes, such as the new theoretical framework of quantum electrodynamics density-functional formalism for the description of novel light-matter hybrid states. Those advances, and others being released soon as part of the Octopus package, will allow the scientific community to simulate and characterize spatial and time-resolved spectroscopies, ultrafast phenomena in molecules and materials, and new emergent states of matter (quantum electrodynamical-materials).

Abstract Plasma treatment is often used to modify the surface properties of polymer films, since it offers numerous advantages over the conventional surface modification techniques. In this paper, a polypropylene (PP) film is plasma‐treated using a dielectric barrier discharge (DBD) operating in air at medium pressure (5.0 kPa). The modified polymer films are characterized using contact angle measurements, XPS‐analysis and attenuated total reflectance‐Fourier transform infrared (ATR‐FTIR) spectroscopy. Results show that plasma treatment leads to a remarkable decrease in contact angle owing to the implantation of oxygen‐containing functional groups. Using XPS and ATR‐FTIR, these oxygen‐containing groups can be identified as CO, CO and OCO. In this paper, it is also shown that XPS is well‐suited to provide quantitative chemical analysis of the PP films, while ATR‐FTIR can only give qualitative information. To perform quantitative ATR‐FTIR measurements, chemical derivatization will be explored in the near future. Copyright © 2008 John Wiley & Sons, Ltd.

Presently, conventional technologies in water treatment are not efficient enough to completely mineralize refractory water contaminants. In this context, the implementation of catalytic processes could be an alternative. Despite the advantages provided in terms of kinetics of transformation, selectivity, and energy saving, numerous attempts have not yet led to implementation at an industrial scale. This review examines investigations at different scales for which controversies and limitations must be solved to bridge the gap between fundamentals and practical developments. Particular attention has been paid to the development of solar-driven catalytic technologies and some other emerging processes, such as microwave assisted catalysis, plasma-catalytic processes, or biocatalytic remediation, taking into account their specific advantages and the drawbacks. Challenges for which a better understanding related to the complexity of the systems and the coexistence of various solid-liquid-gas interfaces have been identified.

Al together now! A new stable aluminum aminoterephthalate system contains octameric building blocks that are connected by organic linkers to form a 12-connected net (see picture). The structure adopts a cubic centered packing motive in which octameric units replace individual atoms, thus forming distorted octahedral (red sphere) and tetrahedral cages (green spheres) with effective accessible diameters of 1 and 0.45 nm, respectively.

Catalytic dehydration is one of the possible reactions to valorize the large amounts of glycerol yielding from the transesterification process. Thus, since the biodiesel boom in 2004–2005, many publications proposing various catalytic systems can be found. In this review, the current state of the art based on the most recent publications is presented and discussed in detail with respect to the observed catalytic performance as well as long-term stability. Next to the applied development of new catalysts, a main focus is the influence of the most critical parameter: the acidity of the catalyst and its correlation to the catalytic performance (selectivity and conversion). In addition, recent results on the thermodynamic calculation are presented, thus giving an insight into the most probably involved intermediates.

A series of aluminum-based metal-organic frameworks were investigated for sorption of iodine (I2) in cyclohexane. The best sorption uptake was obtained with solids decorated by electro-donor groups attached either to the organic ligand (-NH2) or the inorganic sub-network (-OH).

Abstract Global pollution by plastics derived from petroleum has fostered the development of carbon–neutral, biodegradable bioplastics synthesized from renewable resources such as modern biomass, yet knowledge on the impact of bioplastics on ecosystems is limited. Here we review the polylactic acid plastic with focus on synthesis, biodegradability tuning, environmental conversion to microplastics, and impact on microbes, algae, phytoplankton, zooplankton, annelids, mollusk and fish. Polylactic acid is a low weight semi-crystalline bioplastic used in agriculture, medicine, packaging and textile. Polylactic acid is one of the most widely used biopolymers, accounting for 33% of all bioplastics produced in 2021. Although biodegradable in vivo , polylactic acid is not completely degradable under natural environmental conditions, notably under aquatic conditions. Polylactic acid disintegrates into microplastics faster than petroleum-based plastics and may pose severe threats to the exposed biota.

Catalytic carbon dioxide (CO 2 ) hydrogenation is a potential route for producing sustainable fuels and chemicals, but existing catalysts need improvement. In particular, identifying active sites and understanding the interaction between components and the dynamic behavior of the participant species remain unclear. This fundamental knowledge is essential for the design of more efficient and stable catalysts. Because the nature of the active site (metal, oxide, carbide) is the main factor that determines the catalytic activity of the catalysts, this Review focuses on various types of heterogeneous catalysts that have been recently reported in the literature as efficient for CO 2 conversion to C1 [carbon monoxide (CO), methanol (CH 3 OH), methane (CH 4 )], and higher hydrocarbons. We focus on establishing key connections between active-site structures and selectivity, regardless of catalyst composition.

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The origin of the exceptionally high activity of (B, Ag)-codoped TiO(2) catalysts under solar-light irradiation has been investigated by XPS and (11)B solid-state NMR spectroscopy in conjunction with density functional theory (DFT) calculations. XPS experimental results demonstrated that a portion of the dopant Ag (Ag(3+)) ions were implanted into the crystalline lattice of (B, Ag)-codoped TiO(2) and were in close proximity to the interstitial B (B(int.)) sites, forming [B(int.)-O-Ag] structural units. In situ XPS experiments were employed to follow the evolution of the chemical states of the B and Ag dopants during UV-vis irradiation. It was found that the [B(int.)-O-Ag] units could trap the photoinduced electron to form a unique intermediate structure in the (B, Ag)-codoped TiO(2) during the irradiation, which is responsible for the photoinduced shifts of the B 1s and Ag 3d peaks observed in the in situ XPS spectra. Solid-state NMR experiments including (11)B triple-quantum and double-quantum magic angle spinning (MAS) NMR revealed that up to six different boron species were present in the catalysts and only the tricoordinated interstitial boron (T*) species was in close proximity to the substitutional Ag species, leading to formation of [T*-O-Ag] structural units. Furthermore, as demonstrated by DFT calculations, the [T*-O-Ag] structural units were responsible for trapping the photoinduced electrons, which prolongs the life of the photoinduced charge carriers and eventually leads to a remarkable enhancement in the photocatalytic activity. All these unprecedented findings are expected to be crucial for understanding the roles of B and Ag dopants and their synergistic effect in numerous titania-mediated photocatalytic reactions.

Aliphatic PNP pincer-supported earth-abundant manganese(I) dicarbonyl complexes behave as effective catalysts for the acceptorless dehydrogenative coupling of a wide range of alcohols to esters under base-free conditions. The reaction proceeds under neat conditions, with modest catalyst loading and releasing only H2 as byproduct. Mechanistic aspects were addressed by synthesizing key species related to the catalytic cycle (characterized by X-ray structure determination, multinuclear (1H, 13C, 31P, 15N, 55Mn) NMR, infrared spectroscopy, inter alia), by studying elementary steps connected to the postulated mechanism, and by resorting to DFT calculations. As in the case of related ruthenium and iron PNP catalysts, the dehydrogenation results from cycling between the amido and amino-hydride forms of the PNP-Mn(CO)2 scaffold. For the dehydrogenation of alcohols into aldehydes, our results suggest that the highest energy barrier corresponds to the hydrogen release from the amino-hydride form, although its value is close to that of the outer-sphere dehydrogenation of the alcohol into aldehyde. This contrasts with the ruthenium and iron catalytic systems, where dehydrogenation of the substrate into aldehyde is less energy-demanding compared to hydrogen release from the cooperative metal–ligand framework.

Compared to other molecules such as benzene, toluene, xylene, and chlorinated compounds, the catalytic oxidation of formaldehyde has been studied rarely. However, standards for the emission level of this pollutant will become more restrictive because of its extreme toxicity even at very low concentrations in air. As a consequence, the development of a highly efficient process for its selective elimination is needed. Complete catalytic oxidation of formaldehyde into CO2 and H2 O using noble-metal-based catalysts is a promising method to convert this pollutant at room temperature, making this process energetically attractive from an industrial point of view. However, the development of a less expensive active phase is required for a large-scale industrial development. Nanomaterials based on oxides of manganese are described as the most promising catalysts. The objective of this Minireview is to present promising recent studies on the removal of formaldehyde through heterogeneous catalysis to stimulate future research in this topic.

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Abstract The massive increase in biodiesel production by transesterification of vegatable oils goes hand‐in‐hand with the availability of a large volume of glycerol, which must be valorized. Glycerol dehydration to acrolein over acid catalysts is one of the most promising ways of valorization, because this compound is an important chemical intermediate used in, for example, the DL‐methionine synthesis. In this Minireview, we give a detailed critical view of the state‐of‐the‐art of this dehydration reaction. The processes developed in both the liquid and the gas phases are detailed and the best catalytic results obtained so far are reported as a benchmark for future developments. The advances on the understanding of the reaction mechanism are also discussed and we further focus particularly on the main obstacles for an immediate industrial application of this technology, namely catalyst coking and crude glycerol direct‐use issues.