Metal exsolution from inorganic compounds is a promising strategy to obtain dispersed nanoparticles stabilized through strong metal-support interactions. In this work, exsolution of Ni from NiAl-layered double hydroxide (LDH) produces a well-defined family of Ni/Al2O3 catalysts for the steam reforming of methane (SRM) to hydrogen. Increasing the calcination temperature of 40 wt% NiAl-LDH from 400-900 degrees C (prior to a common reduction protocol) resulted in exsolved Ni nanoparticles of systematically increasing size from 4 to 18 nm diameter on an amorphous alumina support. In contrast, wet-impregnation of commercial alumina by Ni(NO3)(2) resulted in similar to 39 nm Ni nanoparticles at a similar metal loading. SRM exhibited a strong structure-sensitivity, being favored over smaller particles with 80 % methane conversion and a high specific hydrogen productivity of 0.37 mmol.g(Ni)(-1).s(-1) for Ni particles <= 8 nm at 700 degrees C, falling to 40 % conversion and 0.08 mmol.g(Ni)(-1).s(-1) for 39 nm particles (for wet-impregnated Ni/Al2O3). Selectivity to H-2 versus CO/CO2 mirrored this structure-sensitivity, with smaller Ni particles delivering >= 75% selectivity >450 degrees C, falling to 65 % over large particles. Exsolved Ni particles derived by 500 degrees C calcination exhibited excellent stability for at least 24 h time-on-stream, with negligible coking, offering Earth-abundant catalysts for hydrogen production from simple precursors.

Electrocatalytic water splitting has emerged as the most promising source of renewable hydrogen to support energy conversion/storage and chemical manufacturing as a part of the global circular economy. However, overall water splitting to produce green H2 through the hydrogen evolution reaction (HER) is limited by the high overpotential and sluggish kinetics of the associated oxygen evolution reaction (OER). Control over electron spin at the electrode-electrolyte interface may lower the thermodynamic barriers, and hence improve the catalytic efficiency, of both reactions. We employ compositionally identical chiral and racemic hydrogen-bonded organocatalysts, comprised of (ionised) melamine and l-, d-, or dl-tartaric acid, to demonstrate chirality-enhanced organoelectrocatalysis. Chiral electrocatalysts promote both OER and HER compared to their racemic counterpart, as evidenced by lower overpotential (384 (L)/379 (D) mV vs. 483 mV (DL) for OER, and 143 mV (L)/144 mV (D) vs. 358 mV (DL) for HER), a change in the rate-determining step, and an approximately four-fold increase in current density. This work highlights the impact of catalyst chirality on enhancing electrocatalytic water splitting to hydrogen and oxygen, and the promising performance of inexpensive and environmentally benign organoelectrocatalysts.

Esters play a critical role in industrial chemistry, serving as key components in the production of fine chemicals, polymers, and liquid fuels. Although traditionally synthesised by acid esterification, esters can also be prepared by the direct oxidative esterification of diverse starting materials, including aldehydes, alcohols and olefins. Metal oxides are promising heterogeneous catalysts for oxidative esterification, and their use in conjunction with a support phase affords synergies that can promote performance. Carbon supports are ubiquitous in catalysis due to their tuneable porosity, acid–base properties, high conductivity and chemical stability. This review discusses recent advances in the oxidative esterification of alcohols, aldehydes, alkenes, and alkynes over carbon-supported catalysts, outlining the commercial importance of esters and traditional esterification methods, and potential advantages of oxidative esterification. Methods to synthesise carbon catalysts and bifunctional heteroatom-doped analogues are introduced, with resulting structure–activity relationships for oxidative esterification highlighted, including the role of radicals. The resulting insight helps to identify strategies to circumvent current challenges in oxidative esterification and future opportunities to apply this methodology.

The selective activation and cleavage of C-O bonds through directional hydrogenation play a critical role in numerous industrial catalytic applications. Traditional noble metal catalysts often face challenges due to their strong propensity for active H₂ dissociation, leading to active site occupation by hydrogen atoms and subsequently hindering the efficiency of selective C-O bond cleavage. Furthermore, achieving selective cleavage of high-bond-energy C-O bonds while preserving lower-energy ones remains a significant challenge requiring further exploration. Herein, we present the design of a Rh single-atom catalyst anchored on Co for the selective cleavage of the high-bond-energy C2-O bond in furfural, serving as a model reaction. Through combined experimental investigations and density functional theory calculations, we demonstrate that Rh1Co single-atom alloys effectively lower the activation barrier for furfural hydrogenation, converting the C-O bond cleavage process from an endothermic reaction to an exothermic one. This catalytic behavior is notably absent in conventional Rh catalysts. The strong interactions within the Rh1Co alloy enhance the surface basicity and oxygen vacancies concentration, significantly promoting the hydrogenolysis of the C2-O bond and achieving a 1,5-pentanediol yield of 60.3%, surpassing most previously reported catalysts. Most importantly, Co sites facilitate H2 activation, while isolated Rh sites serve as the centers for C-O bond cleavage, introducing a reverse hydrogen spillover mechanism distinct from traditional hydrogenation processes. This reverse hydrogen spillover mechanism addresses the issue of hydrogen-induced deactivation of precious metal active sites, offering a promising pathway for broader application across diverse catalytic hydrogenation systems.

Antimicrobial resistance (AMR) poses a critical challenge to global health, as pathogenic microorganisms increasingly evade traditional therapies. Addressing this, we report an antimicrobial nanocomposite, prepared by atomic layer deposition (ALD) of a high area, conformal ZnO ultrathin film over mesoporous silica (SBA-15). Photophysical characterisation of the ZnO/SBA-15 composite revealed well-defined mesopores, a high surface area of 790 m2 g- 1, and an optical band gap of 3.25 eV, suitable for light-responsive applications. Antimicrobial efficacy of ZnO/SBA-15 was tested against Escherichia coli 0157, a common Gram-negative bacterium found in water systems and resistant to standard antibiotics. ZnO/SBA-15 showed a 0.51 log reduction in bacterial colony counts in 1 h at a ZnO concentration of 2 mg/mL under UV light, significantly outperforming ZnO nanoparticles and SBA-15 alone by 47 and 33 %, respectively. This enhanced bacteriostatic activity is attributed to efficient reactive oxygen species generation facilitated by the ZnO ultrathin film, demonstrating the utility of ALD to coat complex 3D architectures to combat AMR in water treatment or biomedical applications.

Developing an efficient photocatalyst is the key to realize the practical application of photocatalysis. The S-scheme heterojunction has great potential in photocatalysis due to its unique charge-carrier migration pathway, effective light absorption and high redox capacity. However, further enhancing the built-in electric field of the S-scheme, accelerating carrier separation, and achieving higher photocatalytic performance remain unresolved challenges. Herein, based on the continuously adjustable band structure of continuous solid-solution, a novel 0D/2D all solid-solution S-scheme heterojunction with adjustable internal electric field was designed and fabricated by employing a solid-solution of ZnxCd1-xS and Bi2MoyW1-yO6 respectively as reduction and oxidation semiconductors. The synergistic optimization of effective light absorption, fast photogenerated carrier separation, and high redox potential leads can be tuned to promote photocatalytic activity. Under visible light, the S-scheme system constructed by Zn0.4Cd0.6S quantum dot (QDs) and Bi2Mo0.2W0.8O6 monolayer exhibits a high rate for photocatalytic degradation C2H4 (150.6 x 10-3 min-1), which is 16.5 times higher than that of pure Zn0.4Cd0.6S (9.1 x 10-3 min-1) and 53.8 times higher than pure Bi2Mo0.2W0.8O6 (2.8 x 10-3 min-1). Due to the unique charge-carrier migration pathway, photo-corrosion of ZnxCd1-xS is further inhibited simultaneously. In-situ irradiation X-ray photoelectron spectroscopy, photoluminescence spectroscopy, time-resolved photoluminescence, transient absorption spectroscopy and electron paramagnetic resonance provide compelling evidence for interfacial charge transfer via S-scheme pathways, while in-situ diffuse reflectance infrared Fourier transform spectroscopy identifies the reaction pathway for C2H4 degradation. This novel S-scheme photocatalysts demonstrates excellent performance and potential for the practical application of the fruits and vegetables preservation at room temperatures. (c) 2025, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Furfural is an important platform chemical for producing value-added biobased molecules and materials as alternatives to fossil-derived chemical building blocks. Furfuryl alcohol (FALC) is one such valuable product, whose sustainable synthesis requires the catalytic reduction of furfural over Earth-abundant elements under mild conditions. Here, we report the liquid-phase hydrogenation of furfural over Ni nanoparticles prepared by either wet impregnation of alumina or exsolution from a NiAl layered double hydroxide (LDH). Exsolved and calcined Ni nanoparticles (NPs) spanned 11-18 nm, whereas the wet impregnation of [gamma+delta]Al2O3 yielded large Ni particles (24-101 nm) indicative of weak metal-support interactions. All catalysts exhibited moderate acid loadings (0.3-0.9 mmolg-1) and weak basicity. Furfural conversion at 10 bar H2 and 165 degrees C is inversely proportional to Ni particle size and structure-insensitive. Ni metal is the active site for furfural hydrogenation to FALC (specific activity of 84 mmol.g(Ni) -1h-1 for NiAl-LDH, six times faster than Al2O3-supported Ni analogues with similar loading, and superior to many precious metal catalysts). FALC was the primary product at isoconversion with 60% selectivity but prone to secondary reactions at high furfural conversion, notably hydrogenolysis to 2-methylfuran (2-MF) or ring hydrogenation to tetrahydrofuryl alcohol (THFA). THFA was itself susceptible to hydrodeoxygenation over small Ni NPs at 10 bar H2 in the presence of an acidic support to form 2-methyltetrahydrofuran (2-MTHF) via a previously unreported pathway. Higher hydrogen pressures favored FALC ring hydrogenation to THFA. Furfural hydrogenation to FALC was structure-insensitive for Ni NPs spanning 11-101 nm; however, secondary reactions of FALC were structure-sensitive. LDH-derived catalysts with 11 nm Ni NPs achieved a high yield of 2-MTHF (73%), a green solvent, liquid electrolyte, and high-density fuel additive. Furfural inhibited ring hydrogenation of reactively formed FALC (versus its hydrogenolysis or HDO), suppressing THFA and 2-MTHF production. However, ring hydrogenation of reactively formed FALC is favored at 25 bar H2, albeit with THFA, the dominant product.

Decarbonisation of hard-to-abate liquid transport fuels, notably used in the aviation and shipping sectors, requires new catalytic routes to valorise waste feedstocks. Here we report a bifunctional Rh/Al-SBA-15 catalyst for the one-pot, two step cascade hydroformylation of 1-alkenes with CO/H2 to form linear and branched aldehydes, and their subsequent hydroxyalkylation (HAA) with 2-methylfuran to form oxygenated jet fuel precursors. A strong synergy between Rh and Al-SBA-15 is observed for hydroformylation, with the bifunctional catalyst significantly more active than Rh/SBA-15 for the first step of the cascade. Superior yields of desired HAA products are observed over Rh/Al-SBA-15 relative to a physical mixture of Rh/SBA-15 and Al-SBA-15. Under syngas (CO/H2) at 30 bar and 80 degrees C, alkenes undergo Rh catalysed hydroformylation to aldehydes, and in a subsequent step under N2, HAA of aldehydes over the solid acid sites of Al-SBA-15 gives an overall similar to 60% yield of fuel range precursors.

Catalytic dehydration of (bioderived) ethanol to ethylene or diethyl ether (DEE) offers an atom-efficient route to commodity chemicals and renewable aviation fuels. Here, the impact of silica support morphology and dispersion of H3PW12O40 (HPW) on the vapor-phase dehydration of ethanol to ethylene and DEE was investigated. Ethanol conversion at 175 degrees C and ambient pressure was inversely proportional to HPW dispersion over a fumed silica and mesoporous SBA-15 support, with specific activity directly proportional to the crystalline water content, highlighting the importance of catalysis within the pseudo-liquid phase. A common turnover frequency of similar to 2500 h(-1) was determined for HPW/SBA-15, with all acid sites participating. Catalyst deactivation at 175 degrees C could be suppressed by co-feeding 10 wt % water, likely by mitigating the loss of crystalline (acidic) water; higher reaction temperatures induce decomposition of the heteropolyanion to WO3 and could also be partially suppressed by co-fed water. In the presence of co-fed water, the optimum 50 wt % HPW/SBA-15 catalyst could be used for three consecutive reactions at 175 degrees C with minimal loss of activity or selectivity without any reactivation protocol. Ethanol dehydration was selective to DEE (similar to 80%) for reaction <225 degrees C, with higher temperatures inducing a switchover to ethylene (87% >= 300 degrees C) in accordance with thermodynamic predictions. Maximum steady-state DEE productivity was 600 mmolg(cat)(-1)h(-1) at 175 degrees C, and maximum steady-state ethylene productivity was 1800 mmolg(cat)(-1)h(-1) at 225 degrees C. In situ DRIFTS identified the protonated ethanol dimer (C2H5OH)(2)H+ as the reactive intermediate to DEE formation, with higher temperatures favoring the formation of protonated ethanol (C2H5OH)H+ and ethoxy intermediates to ethylene.

Machine learning has great potential to accelerate computational discovery of new materials and catalytic reactions but is challenging to implement with quantum chemical accuracy for diverse chemical systems. Here, we explore the pretrained foundation model MACE-MP-0, a machine-learned interatomic potential (MLIP) using the MACE architecture, as a low-cost computational method for structure relaxation prior to density functional theory (DFT) computations of furfural (FUR) adsorption over single-crystal copper surfaces. A data set of 240 adsorption configurations of FUR, including both trans- and cis-FUR rotamers, was created using an automated workflow to randomly orientate the bioderived platform chemical at heuristic adsorption sites on Cu(111), (100), and (110) surfaces. The performances of DFT alone versus a MACE+DFT approach were compared, with common local minima geometries identified through structure relaxation followed by hierarchical agglomerative clustering using the smooth overlap of atomic positions (SOAPs) as a descriptor of the chemical environment. New adsorption configurations were discovered for FUR on Cu(110). Combining MACE-MP-0 prerelaxation with agglomerative clustering to preselect energetically stable configurations for subsequent DFT relaxation eliminated human bias in the starting geometries and reduced the computational cost by 75%.

Biomass-derived diols are key chemical building blocks for the sustainable chemical manufacturing of textiles and plastics, however their synthesis by a selective, scalable process from holocellulose is challenging. Furfuryl alcohol (FALC) is a potential precursor to 1,5-pentanediol (1,5-PeD) through acid-catalysed hydrogenolysis, and hence the impact of oxide support acidity on this reaction over Pt nanoparticles was investigated under batch and continuous flow in toluene. Platinum dispersed over weakly acidic fumed silica and mesoporous SBA-15 supports was almost inactive towards furfuryl alcohol at 150 degrees C and 10 bar H2 and promoted decarbonylation and hydrodeoxygenation of FALC to furan and methyltetrahydrofuran, respectively. The introduction of Al3+ into silica supports, to form either an amorphous silica-aluminate (ASA) or mesoporous Al-SBA-15, selectively activated the cyclic ether bond at the C-2-O position, increasing the specific activity for FALC conversion in continuous flow from 20 mmol gPt(-1) h(-1) (Pt/SBA-15) to 295 mmol gPt(-1) h(-1) (Pt/ASA), and 1,5-PeD selectivity from similar to 25% (Pt/SBA-15) to 65% (Pt/ASA). This synergy between metal and acid sites resulted in a >25-fold enhancement in 1,5-PeD productivity, reaching 186 mmol gPt(-1) h(-1) for Pt/ASA, and was maintained for 7 h time-on-stream with negligible deactivation or metal leaching. A moderately acidic Pt/gamma-Al2O3 catalyst exhibited reactivity intermediate between that of the Pt/silica and Pt/aluminosilicate catalysts. The yield of 1,5-PeD was directly proportional to the support acid site loading, indicating a common reaction mechanism. These findings demonstrate the striking promotion of metal catalysed hydrogenation that can be achieved through judicious support selection, and its translation from batch to flow with similar reaction kinetics.

With the increasing global demand for clean energy, the rapid development of photovoltaic (PV) power generation has led to a growing issue of waste PV module disposal. Traditional recycling methods face challenges such as low efficiency, high energy consumption, and environmental pollution. Flash Joule heating (FJH) technology offers a promising alternative for upcycling waste PV cells. Here, FJH was adopted to produce silicon carbide (SiC) from waste crystalline silicon (c-Si) PV cells that were pulverized and mixed with conductive carbon black (CB). Optimal reaction efficiency was achieved with an input voltage of 130 V and a peak temperature of similar to 2200 degrees C during a single flash heating cycle of 0.5 s. Repeated FJH and regrinding steps resulted in high purity beta-SiC (similar to 96-98%) after removal of excess carbon through calcination; most inorganic impurity elements were removed by evaporation during the heating process. FJH consumes significantly less energy and emits fewer greenhouse gases than alternative chemical or thermal technologies, resulting in a notable cost reduction.

Biofuels are critical drop-in replacement energy sources to support the decarbonisation of hard-to-abate sectors such as aviation and marine shipping. Transesterification of non-edible oils is a well-established route to biodiesel as a versatile liquid transport fuel, but is challenging to scale using existing homogeneous liquid base catalysts. In this work, we report the synthesis, characterisation, and application of silica-supported MgO solid base catalysts for triglyceride transesterification with methanol and highlight the impact of silica pore structure on performance. True liquid crystal templating enables the one-pot synthesis of mesoporous MgO/SBA-15 catalysts with variable Mg content, or hierarchical macroporous-mesoporous MgO/SBA-15 analogues through the addition of polystyrene nanospheres. Both MgO/SBA-15 families exhibit highly ordered pore networks; however, similar to 280 nm macropores stabilise Mg-O-Si interfacial species even at high Mg loading, in contrast to the mesoporous support that permits sintering of similar to 14 nm MgO nanocrystals. Hierarchical porous MgO/SBA-15 catalysts exhibit higher specific activity and conversion of tributyrin to methyl butyrate than their mesoporous analogues (3 mmol center dot h(-1)center dot g(-1) versus 2 mmol center dot h(-1)center dot g(-1) at 60 degrees C and 11 wt% Mg). The magnitude of this rate enhancement increases with triglyceride chain length, being approximately three-fold for trilaurin (C-12) transesterification at 90 degrees C, attributed to superior in-pore mass transport of bulky reactants through the hierarchical porous catalyst.

Plastic overproduction and improper disposal generates over 390 million tons of waste annually, severely polluting marine ecosystems. Polyglycolic acid (PGA) is widely used in biomedical and packaging fields. Here, this study introduces an electrochemical degradation strategy for PGA waste that couples its conversion with seawater-driven hydrogen evolution reaction (HER) using rosette-like high-entropy NiCoFeMnAlOx nanosheets (r-NCFMAO). The PGA-derived glycolic acid oxidation reaction (GAOR) achieves 100 mA cm-2 at 1.36 V versus RHE, benefiting from abundant hydroxyl species (OH*) that lower the required potential by over 190 mV compared to the oxygen evolution reaction. This method produces ≈90% CO3 2-, and subsequent Ca2+ precipitation recovers 77% of CaCO3, a valuable material in construction and papermaking. Electrochemical analysis, quasi in situ electron paramagnetic resonance, and in situ Raman spectroscopy reveal continuous OH- oxidation enhancing GAOR activity, while density functional theory confirms that OH* lowers the energy barrier for the rate-determining C─C bond cleavage and C─H bond activation. The integrated GAOR ‖ HER system sustains performance for over 300 h at industrial current densities and is applicable to upcycling various plastics. This work pioneers a synergistic approach for plastic waste valorization and hydrogen production, advancing circular carbon strategies.

The selective dehydration of glycerol to hydroxyacetone (acetol) was studied in a continuous flow fixed-bed reactor with CuO supported on monoclinic (m-) or tetragonal (t-) ZrO2 nanoparticles. Catalysts were characterised by ICP, N-2 physisorption, powder XRD, HR-TEM and SEM-EDS, N2O titration, and NH3- and CO2-TPD. Quasi-in situ XPS reveals the impact of zirconia phase on copper speciation, with m-ZrO2 preferentially stabilising Cu(I) species, whose presence correlates with enhanced catalytic performance. In situ FTIR of 1,2-propanediol and glycerol evidenced Cu(I) promote desorption of a CO containing intermediate. Solvent selection strongly influenced catalyst reactivity, with methanol less prone to competitive adsorption than water, and favouring the genesis of Cu(I) species. Cu/m-ZrO2 achieved 60% yield of the desired acetol at 240 degrees C, maintaining >= 50% yield over three consecutive regeneration cycles, being one of the most efficient catalysts based on earth abundant metals for continuous glycerol dehydration to acetol under the present conditions.

Biodiesel is a non-toxic, drop-in liquid transportation fuel that is amenable to continuous production from sustainable biomass resources using catalytic technologies. A diverse range of catalysts and reactor technologies have been experimentally investigated and computationally modelled, for producing biodiesel (fatty acid methyl esters) from oil feedstocks by their esterification or transesterification with short-chain alcohols. Solid-acid and base catalysts are attractive for biodiesel production from renewable oil feedstocks due to their ease of separation from the desired biodiesel and glycerol by-product, use of Earth’s abundant elements, and suitability in continuous processes. Here, we review the technical challenges and opportunities in designing catalytic reactor systems for biodiesel production.

Biomass valorisation through the selective oxidation of carbohydrate and lipid derivatives offers access to an array of platform chemicals through energy- and atom-efficient catalytic processes. Supported metal nanoparticles are promising catalysts for the aerobic selective oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), but typically require strong liquid base to achieve high selectivity. Here, we explore the utility of MgO as a solid base support for the Ru-catalysed aerobic oxidation of HMF, obtaining 68% FDCA yield at 160 degrees C and 1.5 MPa of O-2 using <1 mol-% metal.