Engineering Amorphous/Crystalline Ru(OH)3/CoFe-Layered Double Hydroxide for Hydrogen Evolution at 1000 mA cm-2.

For large-scale industrial applications, it is highly desirable to create effective, economical electrocatalysts with long-term stability for the hydrogen evolution reaction (HER) at a large current density. Herein, we report a unique motif with crystalline CoFe-layered hydroxide (CoFe-LDH) nanosheets enclosed by amorphous ruthenium hydroxide (a-Ru(OH)3/CoFe-LDH) to realize the efficient hydrogen production at 1000 mA cm-2, with a low overpotential of 178 mV in alkaline media. During the continuous HER process for 40 h at such a large current density, the potential remains almost constant with only slight fluctuations, indicating good long-term stability. The remarkable HER performance can be attributed to the charge redistribution caused by abundant oxygen vacancies in a-Ru(OH)3/CoFe-LDH. The increased electron density of states lowers the charge-transfer resistance and promotes the formation and release of H2 molecules. The water-splitting electrolyzer with a-Ru(OH)3/CoFe-LDH as both an anode and a cathode in 1.0 M KOH demonstrates stable hydrogen production and a 100% faradic efficiency. The design strategy of interface engineering in this work will inspire the design of practical electrocatalysts for water splitting on an industrial scale.

Continuous Flow Upgrading of Selected C2-C6 Platform Chemicals Derived from Biomass.

The ever increasing industrial production of commodity and specialty chemicals inexorably depletes the finite primary fossil resources available on Earth. The forecast of population growth over the next 3 decades is a very strong incentive for the identification of alternative primary resources other than petro-based ones. In contrast with fossil resources, renewable biomass is a virtually inexhaustible reservoir of chemical building blocks. Shifting the current industrial paradigm from almost exclusively petro-based resources to alternative bio-based raw materials requires more than vibrant political messages; it requires a profound revision of the concepts and technologies on which industrial chemical processes rely. Only a small fraction of molecules extracted from biomass bears significant chemical and commercial potentials to be considered as ubiquitous chemical platforms upon which a new, bio-based industry can thrive. Owing to its inherent assets in terms of unique process experience, scalability, and reduced environmental footprint, flow chemistry arguably has a major role to play in this context. This review covers a selection of C2 to C6 bio-based chemical platforms with existing commercial markets including polyols (ethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerol, 1,4-butanediol, xylitol, and sorbitol), furanoids (furfural and 5-hydroxymethylfurfural) and carboxylic acids (lactic acid, succinic acid, fumaric acid, malic acid, itaconic acid, and levulinic acid). The aim of this review is to illustrate the various aspects of upgrading bio-based platform molecules toward commodity or specialty chemicals using new process concepts that fall under the umbrella of continuous flow technology and that could change the future perspectives of biorefineries.

Aerosol processing: a wind of innovation in the field of advanced heterogeneous catalysts.

Aerosol processing is long known and implemented industrially to obtain various types of divided materials and nanomaterials. The atomisation of a liquid solution or suspension produces a mist of aerosol droplets which can then be transformed via a diversity of processes including spray-drying, spray pyrolysis, flame spray pyrolysis, thermal decomposition, micronisation, gas atomisation, etc. The attractive technical features of these aerosol processes make them highly interesting for the continuous, large scale, and tailored production of heterogeneous catalysts. Indeed, during aerosol processing, each liquid droplet undergoes well-controlled physical and chemical transformations, allowing for example to dry and aggregate pre-existing solid particles or to synthesise new micro- or nanoparticles from mixtures of molecular or colloidal precursors. In the last two decades, more advanced reactive aerosol processes have emerged as innovative means to synthesise tailored-made nanomaterials with tunable surface properties, textures, compositions, etc. In particular, the "aerosol-assisted sol-gel" process (AASG) has demonstrated tremendous potential for the preparation of high-performance heterogeneous catalysts. The method is mainly based on the low-cost, scalable, and environmentally benign sol-gel chemistry process, often coupled with the evaporation-induced self-assembly (EISA) concept. It allows producing micronic or submicronic, inorganic or hybrid organic-inorganic particles bearing tuneable and calibrated porous structures at different scales. In addition, pre-formed nanoparticles can be easily incorporated or formed in a "one-pot" bottom-up approach within the porous inorganic or hybrid spheres produced by such spray drying method. Thus, multifunctional catalysts with tailored catalytic activities can be prepared in a relatively simple way. This account is an overview of aerosol processed heterogeneous catalysts which demonstrated interesting performance in various relevant chemical reactions like isomerisation, hydrogenation, olefin metathesis, pollutant total oxidation, selective oxidation, CO2 methanation, etc. A short survey of patents and industrial applications is also presented. Our objective is to demonstrate the tremendous possibilities offered by the coupling between bottom up synthesis routes and these aerosol processing technologies which will most probably represent a major route of innovation in the mushrooming field of catalyst preparation research.

Innovative Sol-Gel Routes for the Bottom-Up Preparation of Heterogeneous Catalysts.

Heterogeneous catalysts can be prepared by different methods offering various levels of control on the final properties of the solid. In this account, we exemplify bottom-up preparation routes that are based on the sol-gel chemistry and allow to tailor some decisive properties of solid catalysts. First, an emulsion templating strategy is shown to lead to macrocellular self-standing monoliths with a macroscopic 3D structure. The latter can be used as catalyst or catalyst supports in flow chemistry, without requiring any subsequent shaping step. Second, the aerosol-assisted sol-gel process allows for the one-step and continuous production of porous mixed oxides. Tailored textural properties can be obtained together with an excellent control on composition and homogeneity. Third, the application of non-hydrolytic sol-gel routes, in the absence of water, leads to mixed oxides with outstanding textural properties and with peculiar surface chemistry. In all cases, the resulting catalytic performance can be correlated with the specificities of the preparation routes presented. This is exemplified in catalytic reactions in the fields of biomass conversion, petro chemistry, enantioselective organic synthesis, and air pollution mitigation.

In Situ Solid-Gas Reactivity of Nanoscaled Metal Borides from Molten Salt Synthesis.

Metal borides have mostly been studied as bulk materials. The nanoscale provides new opportunities to investigate the properties of these materials, e.g., nanoscale hardening and surface reactivity. Metal borides are often considered stable solids because of their covalent character, but little is known on their behavior under a reactive atmosphere, especially reductive gases. We use molten salt synthesis at 750 °C to provide cobalt monoboride (CoB) nanocrystals embedded in an amorphous layer of cobalt(II) and partially oxidized boron as a model platform to study morphological, chemical, and structural evolutions of the boride and the superficial layer exposed to argon, dihydrogen (H2), and a mixture of H2 and carbon dioxide (CO2) through a multiscale in situ approach: environmental transmission electron microscopy, synchrotron-based near-ambient-pressure X-ray photoelectron spectroscopy, and near-edge X-ray absorption spectroscopy. Although the material is stable under argon, H2 triggers at 400 °C decomposition of CoB, leading to cobalt(0) nanoparticles. We then show that H2 activates CoB for the catalysis of CO2 methanation. A similar decomposition process is also observed on NiB nanocrystals under oxidizing conditions at 300 °C. Our work highlights the instability under reactive atmospheres of nanocrystalline cobalt and nickel borides obtained from molten salt synthesis. Therefore, we question the general stability of metal borides with distinct compositions under such conditions. These results shed light on the actual species in metal boride catalysis and provide the framework for future applications of metal borides in their stability domains.

Bifunctional Au-Sn-SiO2 catalysts promote the direct upgrading of glycerol to methyl lactate.

Valuable alkyl lactates can be obtained from (waste) glycerol, through a two-step process that entails (i) the oxidation of glycerol to dihydroxyacetone (DHA) catalyzed by support Au nanoparticles and (ii) a rearrangement of DHA with an alcohol effectively catalyzed by Sn-based heterogeneous catalysts. To solve selectivity and processing issues we propose to run the process as a cascade reaction, in one step, and with a single bifunctional catalyst. Tackling the challenge associated with the preparation of such bifunctional catalysts, here, an aerosol-assisted sol-gel route is exploited. The catalysts feature small Au nanoparticles (3-4 nm) embedded at the surface of mesoporous Sn-doped silica microspheres. The preparation successfully leads to insert both active sites in their most active forms, and in close proximity. With the bifunctional catalysts, the yield for the final product of the cascade reaction (methyl lactate) is higher than the DHA yield when only the first reaction is carried out. This highlights a beneficial substrate channeling effect which alleviates side reactions. Interestingly, the bifunctional catalysts also markedly outcompeted mechanical mixtures of the corresponding monofunctional Au- and Sn-based catalysts. Thus, the spatial proximity between the two active sites in bifunctional catalysts is identified as a key to stir the cascade reaction towards high lactate yield.

Calibration of the X-ray photoelectron spectroscopy binding energy scale for the characterization of heterogeneous catalysts: is everything really under control?

Investigations of X-ray photoelectron spectra from solid samples need corrections for the surface charging effect. For powder samples such as heterogeneous catalysts and their supports, the C-(C,H) component of the C 1s peak is often used as an internal standard for the calibration of the binding energy scale. Although this method is widely recognized as suitable for the study of heterogeneous catalysts, we show that a significant calibration bias can be encountered upon comparing samples with different bulk composition. In this paper, a series of SiO2-Al2O3 supports and Pd/SiO2-Al2O3 catalysts with various Si/Al ratios were studied. The spectra issued from these samples were processed with the classical calibration method on the basis of the carbon peak. Important discrepancies in the relative position of the photoelectron peaks were noticed. After systematically discarding instrument-related issues, a true chemical influence of the bulk matrix on the analyzed surface species was evidenced. The extent of this chemical effect was dependent on the composition of the sample and more precisely on its ionicity. Two possible mechanisms for this chemical effect were proposed and discussed. Finally, an alternative calibration method was offered.

Non-hydrolytic sol-gel routes to heterogeneous catalysts.

Oxides and mixed oxides have a tremendous importance in the field of heterogeneous catalysis, serving either as catalysts or as supports for active species. The performance of a catalyst depends directly on its composition, texture, structure and surface properties, which have to be precisely controlled and adapted to each application. In this context, the sol-gel process is a unique tool for the preparation and understanding of catalytic materials, owing to its exceptional versatility. In the last 10 years, the non-hydrolytic sol-gel (NHSG) or non-aqueous sol-gel process based on nonhydrolytic condensations in nonaqueous media has established itself as a simple and powerful method for the design of a wide range of oxide, mixed oxide and hybrid materials with controlled composition, morphology, texture and structure. NHSG proved particularly interesting for the preparation of catalytic materials, notably mesoporous xerogels, single site catalysts and highly crystalline nanoparticles. This critical review addresses the application of NHSG to the preparation of heterogeneous catalysts, emphasizing the specificities of this process, and giving a comprehensive overview of the literature (251 references).

Key Parameters Impacting the Crystal Formation in Antisolvent Membrane-Assisted Crystallization.

Antisolvent crystallization is commonly used in the formation of heat-sensitive compounds as it is the case for most active pharmaceutical ingredients. Membranes have the ability to control the antisolvent mass transfer to the reaction medium, providing excellent mixing that inhibits the formation of local supersaturations responsible for the undesired properties of the resulting crystals. Still, optimization of the operating conditions is required. This work investigates the impact of solution velocity, the effect of antisolvent composition, the temperature and gravity, using glycine-water-ethanol as a model crystallization system, and polypropylene flat sheet membranes. Results proved that in any condition, membranes were consistent in providing a narrow crystal size distribution (CSD) with coefficient of variation (CV) in the range of 0.5-0.6 as opposed to 0.7 obtained by batch and drop-by-drop crystallization. The prism-like shape of glycine crystals was maintained as well, but slightly altered when operating at a temperature of 35 °C with the appearance of smoother crystal edges. Finally, the mean crystal size was within 23 to 40 µm and did not necessarily follow a clear correlation with the solution velocities or antisolvent composition, but increased with the application of higher temperature or gravity resistance. Besides, the monoclinic form of α-glycine was perfectly maintained in all conditions. The results at each condition correlated directly with the antisolvent transmembrane flux that ranged between 0.0002 and 0.001 kg/m2. s. In conclusion, membrane antisolvent crystallization is a robust solution offering consistent crystal properties under optimal operating conditions.

Leveraging Metal Nodes in Metal-Organic Frameworks for Advanced Anodic Hydrazine Oxidation Assisted Seawater Splitting.

Metal-organic frameworks (MOFs) show great promise for electrocatalysis owing to their tunable ligand structures. However, the poor stability of MOFs impedes their practical applications. Unlike the general pathway for engineering ligands, we report herein an innovative strategy for leveraging metal nodes to improve both the catalytic activity and the stability. Our electrolysis cell with a NiRh-MOF||NiRh-MOF configuration exhibited 10 mA cm-2 at an ultralow cell voltage of 0.06 V in alkaline seawater (with 0.3 M N2H4), outperforming its counterpart benchmark Pt/C||Pt/C cell (0.12 V). Impressively, the incorporation of Rh into a MOF secured a robust stability of over 60 h even when working in the seawater electrolyte. Experimental results and theoretical calculations revealed that Rh atoms serve as the active sites for hydrogen evolution while Ni nodes are responsible for the hydrazine oxidation during the hydrazine oxidation assisted seawater splitting. This work provides a paradigm for green hydrogen generation from seawater.

Toward a Hydrogen-Free Reductive Catalytic Fractionation of Wheat Straw Biomass.

The reductive catalytic fractionation (RCF) of lignocellulosic biomass is an attractive method for the conversion of lignin toward valuable low-molecular weight aromatics. A limitation to the upscaling of such technology is represented by the use ofpressurized hydrogen gas. Here, the role of hydrogen gas within the RCF of wheat straw biomass is investigated. The use of H2 is shown to enhance lignin depolymerization, by virtue of an improved hydrogenolysis and hydrogenation of lignin fragments, with a yield of phenolic monomers that increased from ca. 12 wt % of acid-insoluble lignin in the initial biomass under inert atmosphere to up to ca. 25 wt % under H2 (in methanol, at 250 °C, with Ru/C). The adoption of methanol, ethanol or isopropanol as hydrogen-donor solvents was also investigated in the absence of H2 . Ethanol was found to give the highest yield of monophenolic compounds (up to ≈20 wt %) owing to a better balance between solvolysis, hydrogenolysis, and hydrogenation of lignin. Nevertheless, a substantial loss of the carbohydrate fraction was observed. The use of a lower temperature (200 °C) in combination with H3 PO4 resulted in an improved recovery of cellulose in the pulp and in the solubilization of hemicellulose and lignin, with the formation of monosaccharides (≈14 wt % of polysaccharides in the initial biomass) and phenolic monomers (up to 18 wt %, in the absence of H2 ). Overall, a tradeoff exists between the removal of H2 from the process and the production of low-molecular weight phenolics during RCF.

Propylene Metathesis over Molybdenum Silicate Microspheres with Dispersed Active Sites.

In this work, we demonstrate that amorphous and porous molybdenum silicate microspheres are highly active catalysts for heterogeneous propylene metathesis. Homogeneous molybdenum silicate microspheres and aluminum-doped molybdenum silicate microspheres were synthesized via a nonaqueous condensation of a hybrid molybdenum biphenyldicarboxylate-based precursor solution with (3-aminopropyl)triethoxysilane. The as-prepared hybrid metallosilicate products were calcined at 500 °C to obtain amorphous and porous molybdenum silicate and aluminum-doped molybdenum silicate microspheres with highly dispersed molybdate species inserted into the silicate matrix. These catalysts contain mainly highly dispersed MoOx species, which possess high catalytic activity in heterogeneous propylene metathesis to ethylene and butene. Compared to conventional silica-supported MoOx catalysts prepared via incipient wetness impregnation (MoIWI), the microspheres with low Mo content (1.5-3.6 wt %) exhibited nearly 2 orders of magnitude higher steady-state propylene metathesis rates at 200 °C, approaching site time yields of 0.11 s-1.

Multifunctional, Hybrid Materials Design via Spray-Drying: Much more than Just Drying.

Spray-drying is a popular and well-known "drying tool" for engineers. This perspective highlights that, beyond this application, spray-drying is a very interesting and powerful tool for materials chemists to enable the design of multifunctional and hybrid materials. Upon spray-drying, the confined space of a liquid droplet is narrowed down, and its ingredients are forced together upon "falling dry." As  detailed in this article, this enables the following material formation strategies either individually or even in combination: nanoparticles and/or molecules can be assembled; precipitation reactions as well as chemical syntheses can be performed; and templated materials can be designed. Beyond this, fragile moieties can be processed, or "precursor materials" be prepared. Post-treatment of spray-dried objects eventually enables the next level in the design of complex materials. Using spray-drying to design (particulate) materials comes with many advantages-but also with many challenges-all of which are outlined here. It is believed that multifunctional, hybrid materials, made via spray-drying, enable very unique property combinations that are particularly highly promising in myriad applications-of which catalysis, diagnostics, purification, storage, and information are highlighted.

Catalytic amination of lactic acid using Ru-zeolites.

In this work we investigate the synthesis of alanine from lactic acid, a biobased platform chemical, using ammonia as a nitrogen source and Ru/zeolite catalysts. We report a high alanine selectivity when using Ru/BEA of 80-93%. Reaction side products were identified as ethanol, propionic acid or propanamide and the reaction mechanism was investigated. We further optimised reaction conditions resulting in turn over numbers five times higher than previously reported and could reduce Ru leaching by 30-40%. However, leaching and catalyst stability remains a concern. Furthermore, we critically analyse the benefits of Ru/zeolites versus their stability under the basic, high temperature reaction conditions.

Hydrogen Borrowing: towards Aliphatic Tertiary Amines from Lignin Model Compounds Using a Supported Copper Catalyst.

Upcoming biorefineries, such as lignin-first provide renewable aromatics containing unique aliphatic alcohols. In this context, a Cu-ZrO2 catalyzed hydrogen borrowing approach was established to yield tertiary amine from the lignin model monomer 3-(3,4-dimethoxyphenyl)-1-propanol and the actual lignin-derived monomers, (3-(4-hydroxyphenyl)-1-propanol and dihydroconiferyl alcohol), with dimethylamine. Various industrial metal catalysts were evaluated, resulting in nearly quantitative mass balances for most catalysts. Identified intermediates, side and reaction products were placed into a corresponding reaction network, supported by kinetic evolution experiments. Cu-ZrO2 was selected as most suitable catalyst combining high alcohol conversion with respectable aliphatic tertiary amine selectivity. Low pressure H2 was key for high catalyst activity and tertiary amine selectivity, mainly by hindering undesired reactant dimethylamine disproportionation and alcohol amidation. Besides dimethylamine model, diverse secondary amine reactants were tested with moderate to high tertiary amine yields. As most active catalytic site, highly dispersed Cu species in strong contact with ZrO2 is suggested. ToF-SIMS, N2 O chemisorption, TGA and XPS of spent Cu-ZrO2 revealed that imperfect amine product desorption and declining surface Cu lowered the catalytic activity upon catalyst reuse, while thermal reduction readily restored the initial activity and selectivity demonstrating catalyst reuse.

High-Entropy-Alloy Nanocrystal Based Macro- and Mesoporous Materials.

High-entropy-alloy (HEA) nanoparticles are attractive for several applications in catalysis and energy. Great efforts are currently devoted to establish composition-property relationships to improve catalytic activity or selectivity. Equally importantly, developing practical fabrication methods for shaping HEA-based materials into complex architectures is a key requirement for their utilization in catalysis. However, shaping nano-HEAs into hierarchical structures avoiding demixing or collapse remains a great challenge. Herein, we overcome this issue by introducing a simple soft-chemistry route to fabricate ordered macro- and mesoporous materials based on HEA nanoparticles, with high surface area, thermal stability, and catalytic activity toward CO oxidation. The process is based on spray-drying from an aqueous solution containing five different noble metal precursors and polymer latex beads. Upon annealing, the polymer plays a double role: templating and reducing agent enabling formation of HEA nanoparticle-based porous networks at only 350 °C. The formation mechanism and the stability of the macro- and mesoporous materials were investigated by a set of in situ characterization techniques; notably, in situ transmission electron microscopy unveiled that the porous structure is stable up to 800 °C. Importantly, this process is green, scalable, and versatile and could be potentially extended to other classes of HEA materials.

Hybrid chemoenzymatic heterogeneous catalyst prepared in one step from zeolite nanocrystals and enzyme-polyelectrolyte complexes.

The combination of inorganic heterogeneous catalysts and enzymes, in so-called hybrid chemoenzymatic heterogeneous catalysts (HCEHCs), is an attractive strategy to effectively run chemoenzymatic reactions. Yet, the preparation of such bifunctional materials remains challenging because both the inorganic and the biological moieties must be integrated in the same solid, while preserving their intrinsic activity. Combining an enzyme and a zeolite, for example, is complicated because the pores of the zeolite are too small to accommodate the enzyme and a covalent anchorage on the surface is often ineffective. Herein, we developed a new pathway to prepare a nanostructured hybrid catalyst built from glucose oxidase and TS-1 zeolite. Such hybrid material can catalyse the in situ biocatalytic formation of H2O2, which is subsequently used by the zeolite to trigger the epoxidation of allylic alcohol. Starting from an enzymatic solution and a suspension of zeolite nanocrystals, the hybrid catalyst is obtained in one step, using a continuous spray drying method. While enzymes are expectedly unable to resist the conditions used in spray drying (temperature, shear stress, etc.), we leverage on the preparation of "enzyme-polyelectrolyte complexes" (EPCs) to increase the enzyme stability. Interestingly, the use of EPCs also prevents enzyme leaching and appears to stabilize the enzyme against pH changes. We show that the one-pot preparation by spray drying gives access to hybrid chemoenzymatic heterogeneous catalysts with unprecedented performance in the targeted chemoenzymatic reaction. The bifunctional catalyst performs much better than the two catalysts operating as separate entities. We anticipate that this strategy could be used as an adaptable method to prepare other types of multifunctional materials starting from a library of functional nanobuilding blocks and biomolecules.

Correction: Hybrid chemoenzymatic heterogeneous catalyst prepared in one step from zeolite nanocrystals and enzyme-polyelectrolyte complexes.

[This corrects the article DOI: 10.1039/D0NA00834F.].

CO2 Hydrogenation to Methanol with Ga- and Zn-Doped Mesoporous Cu/SiO2 Catalysts Prepared by the Aerosol-Assisted Sol-Gel Process*.

The preparation of copper-based heterogeneous catalysts dedicated to the hydrogenation of CO2 to methanol typically relies on multi-step procedures carried out in batch. These steps are precisely tailored to introduce the active phase (Cu) and the promoters (e. g., zinc, gallium) onto a preformed support to maximize catalyst performance. However, each process step can be associated with the formation of waste and with the consumption of energy, thereby negatively impacting the environmental performance of the overall catalyst preparation procedure. Here, a direct and continuous production process is proposed for the synthesis of efficient catalysts for the CO2 -to-methanol reaction. Gallium- and zinc-promoted mesoporous Cu-SiO2 catalysts were prepared in one step by the aerosol-assisted sol-gel process. The catalysts consisted of spherical microparticles and featured high specific surface area and pore volume, with interconnected pores of about 6 nm. A strong promoting effect of Ga and Zn was highlighted, boosting the selectivity for methanol at the expense of CO. Upon calcination, it was shown that Cu species (initially trapped in the silica matrix) underwent a migration towards the catalyst surface and a progressive sintering. After optimization, the catalysts obtained via such direct, continuous, simple, and scalable route could compete with the best catalysts reported in the literature and obtained via multi-step approaches.

Exploring, tuning, and exploiting the basicity of hydrotalcites for applications in heterogeneous catalysis.

Basic catalysis! The basic properties of hydrotalcites (see picture) make them attractive for numerous catalytic applications. Probing the basicity of the catalysts is crucial to understand the base-catalysed processes and to optimise the catalyst preparation. Various parameters can be employed to tune the basic properties of hydrotalcite-based catalysts towards the basicity demanded by each target chemical reaction.Hydrotalcites offer unique basic properties that make them very attractive for catalytic applications. It is of primary interest to make use of accurate tools for probing the basicity of hydrotalcite-based catalysts for the purpose of 1) fundamental understanding of base-catalysed processes with hydrotalcites and 2) optimisation of the catalytic performance achieved in reactions of industrial interest. Techniques based on probe molecules, titration techniques and test reactions along with physicochemical characterisation are overviewed in the first part of this review. The aim is to provide the tools for understanding how series of parameters involved in the preparation of hydrotalcite-based catalytic materials can be employed to control and adapt the basic properties of the catalyst towards the basicity demanded by each target chemical reaction. An overview of recent and significant achievements in that perspective is presented in the second part of the paper.