Photocatalytic methane conversion offers a sustainable route to transform the most inert C1 molecule into valuable oxygenates and hydrocarbons under ambient conditions. Recent progress has been made in the selective formation of methanol, ethanol, acetic acid, and C2 hydrocarbons, with notable efficiency. However, limited product diversity and an incomplete mechanistic understanding remain major barriers to further progress. This outlook deconstructs photocatalytic methane conversion into three elementary steps: formation of reactive species, coupling of reactive species, and transformation of intermediate products. This stepwise perspective enables a clearer identification of the factors governing individual reaction pathways and overall selectivity. By adopting a pathway-centric framework, the outlook integrates disparate observations from the literature into a unified mechanistic picture, elucidating how control over reactive-species generation, coupling modes, and intermediate evolution dictates reaction outcomes. From this analysis, general design principles and recurring control motifs are distilled, providing practical guidelines for the rational design of photocatalysts and reaction architectures aimed at more efficient and selective methane utilization.

Designing low-cost, high-performance bifunctional electrocatalysts for the oxygen reduction and evolution reactions (ORR/OER) is critical for advancing rechargeable zinc-air batteries (ZABs); however, simultaneously optimizing both reactions within a single material system remains a significant challenge. Herein, a Cop/CoFe-NC@MWCNT catalyst is constructed by integrating multi-metal active sites into a conductive multi-walled carbon nanotube (MWCNT) network. Outperforming the commercial Pt/C and RuO2 benchmarks, the Cop/CoFe-NC@MWCNT catalyst delivers an ORR half-wave potential of 0.855 V and an OER overpotential of 310 mV at 10 mA cm-2 under alkaline conditions. The evolution of the active sites during both reactions is tracked by in situ Raman spectroscopy, providing mechanistic insights into the ORR and OER pathways. When assembled into ZABs, the Cop/CoFe-NC@MWCNT catalyst achieves peak power densities of 164.1 and 77.15 mW cm-2 in liquid and flexible configurations, respectively, with the liquid cell delivering a specific capacity of 688.37 mAh g-1 and the flexible device retaining exceptional stability over 48 h. At a current density of 5 mA cm-2, the Cop/CoFe-NC@MWCNT electrodes achieved a round-trip efficiency of 42.6%, higher than the 38.7% recorded for the benchmark Pt/C + RuO2. This work establishes an effective strategy for developing highly active bifunctional electrocatalysts using non-noble bifunctional electrocatalysts.

The efforts to increase the active surface area of catalysts led to reduction of metal particle size, down to single metal atoms. This results in increasing importance of support-metal interactions. We demonstrate the mechanisms through which the support influences catalytic activity of nanoclusters: the support electronics, described by the O 2p energy level, and the support surface chemistry, determined by the density of Lewis base sites. Using Ru nanoclusters, our study shows that these parameters can be effectively captured within a single catalyst support descriptor (CSD). The apparent activation energy and turnover frequency (TOF) for the ammonia synthesis correlates strongly with CSD measured for the series Ru/MgO, Ru/Sc2O3, Ru/CeO2, Ru/La2O3, and Ru/Y2O3. Furthermore, the study demonstrates that CSD correlates linearly with the binding strength of N-Ru in nanocluster, thereby providing a direct link between the catalyst's surface chemistry and the nature of the support. The catalyst support descriptor developed in this study serves as a simple yet powerful tool for selecting the optimal support material to maximise the activity of metal nanoclusters without altering the metal itself.

AuPd nanoalloys are shown to offer significantly enhanced catalytic performance for both the direct synthesis of hydrogen peroxide (H2O2) and the in-situ oxidative degradation of phenol. Under conditions where limited phenol conversion is observed using commercial H2O2, the bimetallic Au–Pd system facilitates efficient in-situ generation of H2O2 and associated reactive oxygen species (ROS), enabling phenol conversion rates exceeding 70

Covalent organic framework materials have recently garnered significant interest from the scientific community due to their fascinating properties that include highly ordered porosity, structural versatility, high chemical and thermal stabilities, and facile surface modification. Herein, for the first time, we present the design and fabrication of a self-powered blue-light photodetector based on boronate-ester-linked 2D covalent organic framework (COF-5) film, synthesized using hexahydroxytriphenylene and 1,4-phenylenediboronic acid organic linkers. Specifically, we have developed a COF-5/n-Si photodetector that exhibits an ultra-short rise response time of 41 µs and a decay response time of 222 µs under 0 V bias. Our work integrated rapid response times and the distinctive benefit of self-powering, setting it apart from existing COF-based photodetectors.

Carbon-neutral hydrogen production is of key importance for the chemical industry of the future. We demonstrate a new thermal catalytic route for the partial reforming of ethanol into hydrogen and acetic acid with near-zero carbon dioxide emissions. This reaction is enabled by a catalyst containing a high density of atomic Pt1 and Ir1 species supported on a reactive alpha-molybdenum carbide substrate, achieving a hydrogen production rate of 331.3 millimoles of hydrogen per gram catalyst per hour and an acetic acid selectivity of 84.5% at 270°C, and is therefore more energy-efficient compared with standard reforming. Techno-economic analysis of partial ethanol reforming demonstrates the potential profitability for operation at an industrial scale, presenting the opportunity to produce hydrogen and acetic acid with a substantially reduced carbon dioxide footprint.

Catalytic methane decomposition is a highly promising CO2-free hydrogen production technology with carbon material generation; however, developing catalysts that can efficiently decompose methane at moderate temperatures remains challenging. In this study, we develop a series of NiMn-Bi molten alloy catalysts with various Ni:Mn ratios for catalyzing methane decomposition. The Mn-modified Ni-Bi alloy exhibits a CH4 conversion of 15.3% at 850 °C, and the corresponding hydrogen production rate increases by 112% compared with Ni-Bi. The ternary alloy catalyst also demonstrates stability at this production rate for up to 80 h. Molecular dynamics simulations show that the introduction of Mn significantly reduces the strong interaction between the active metal Ni and the solvent metal Bi, thereby accelerating the methane dissociation rate. More importantly, among the theoretically calculated binding energy, interfacial energy, Ni-Bi interaction, and mean-square displacement, interfacial energy, a comprehensive demonstration of surface energy and atomic interactions, is proposed as a potential descriptor for predicating and estimating the catalytic performance of the molten alloy-based catalysts.

Atomic-scale changes can significantly impact heterogeneous catalysis, yet their atomic mechanisms are challenging to establish using conventional analysis methods. By using identical location scanning transmission electron microscopy (IL-STEM), which provides quantitative information at the single-particle level, we investigated the mechanisms of atomic evolution of Ru nanoclusters during the ammonia decomposition reaction. Nanometre-sized disordered nanoclusters transform into truncated nano-pyramids with stepped edges, leading to increased hydrogen production from ammonia. IL-STEM imaging demonstrated coalescence and Ostwald ripening as mechanisms of nanocluster pyramidalization during the activation stage, with coalescence becoming the primary mechanism under the reaction conditions. Single Ru atoms, a co-product of the catalyst activation, become absorbed by the nano-pyramids, improving their atomic ordering. Ru nano-pyramids with a 2-3 nm2 footprint consisting of 3-5 atomic layers, ensure the maximum concentration of active sites necessary for the rate-determining step. Importantly, the growth of truncated pyramids typically does not exceed a footprint of approximately 4 nm2 even after 12 hours of the reaction, indicating their high stability and explaining ruthenium's superior activity on nanotextured graphitic carbon compared to other support materials. The structural evolution of nanometer-sized metal clusters with a large fraction of surface atoms is qualitatively different from traditional several-nm nanoparticles, where surface atoms are a minority, and it offers a blueprint for the design of active and sustainable catalysts necessary for hydrogen production from ammonia, which is becoming one of the critical reactions for net-zero technologies.

The role of TiO2, ZnO, and ZnTiO3 as supports for rhodium has been investigated for the CO2 hydrogenation. Rh/TiO2 demonstrated a high selectivity for CH4, which is typical for Rh catalysts; however, Rh/ZnO and Rh/ZnTiO3 shifted the product selectivity to CO almost exclusively. The difference in behavior is attributed to the modulation of strong metal-support interactions (SMSIs) by the supports. Detailed characterization revealed the formation of a distinct metallic Zn overlayer covering the RhZnx alloyed nanoparticle in Rh/ZnO, altering the electronic states of Rh, and a RhTix overlayer in Rh/ZnTiO3, suppressing the CO adsorption on Rh in bridged and tilted geometry and polarizing the CO bond. These structural features significantly modify the CO adsorption strength and mode, together with the intermediate hydrogenation behavior, influencing product formation. The study highlights the potential of tailoring SMSI states by modifying the support composition and interfacial coupling with metal nanoparticles, enabling improved CO-selective hydrogenation. These findings offer deeper insights into engineering metal-support interactions, with broad implications for advancing industrial processes involving CO, including Fischer-Tropsch synthesis, the water-gas shift reaction, and methanol synthesis.

Carbon dioxide is not only a greenhouse gas but also a valuable feedstock for producing chemicals and fuels, especially methanol, which serves as an energy storage medium and a precursor for olefins and gasoline. Herein, we show that a clean, atomically defined interface between a Pd catalyst and a ZnO support allows for the direct production of methanol from CO2 without any catalyst activation or induction period. Using magnetron sputtering, Pd atoms are directly deposited onto the ZnO surface, self-assembling into Pd nanoclusters with a high fraction of surface atoms, driven solely by the surface chemistry of ZnO, eliminating the need for solvents, reagents, or ligands. This atomically defined Pd/ZnO interface facilitates Pd-Zn alloying in situ during the reaction, achieving an impressive methanol production rate of 16.4 mol h-1 mol-1 Pd, outperforming catalysts prepared by other methods. By eliminating interfacial impurities and the consequent need for pretreatment, our work establishes magnetron sputtering as a transformative method for fabricating high-performance catalysts.

The selective oxidation of alcohol to the corresponding aldehydes via in situ H 2 O 2 (and associated ROS) production offers an exciting, environmentally friendly alternative to the use of stoichiometric oxidants.

ABSTRACT Advanced oxygen carrier plays a pivotal role in various chemical looping processes, such as CO 2 splitting. However, oxygen carriers have been restricted by deactivation and inferior oxygen transferability at low temperatures. Herein, we design an Fe–O v –Ce–triggered phase‐reversible CeO 2− x ·Fe·CaO ↔ CeO 2 ·Ca 2 Fe 2 O 5 oxygen carrier with strong electron‐donating ability, which activates CO 2 at low temperatures and promotes oxygen transformation. Results reveal that the maximum CO 2 conversion and CO yield obtained with 50 mol% CeO 2− x ·Fe·CaO are, respectively, 426% and 53.6 times higher than those of Fe·CaO at 700°C. This unique multiphase material also retains exceptional redox durability, with no obvious deactivation after 100 splitting cycles. The addition of Ce promotes the formation of the Fe–O v –Ce structure, which acts as an activator, triggers CO 2 splitting, and lowers the energy barrier of C═O dissociation. The metallic Fe plays a role in consuming O 2− lattice transformed from Fe–O v –Ce, whereas CaO acts as a structure promoter that enables phase‐reversible Fe 0 ↔ Fe 3+ looping.

In recent years growing interest has been placed on the role of dopant concentrations of tertiary precious and base metals in modifying the performance of supported AuPd nanoalloys towards the direct synthesis of H2O2. Within this contribution, we expand on these earlier studies, with a focus on Fe-containing systems. Through rational catalyst design, an optimal 0.5%Au-0.5%Pd-0.02%Fe/TiO2 formulation has been developed, which not only outperforms the parent bimetallic analogue but also offers increased reactivity compared to alternative trimetallic formulations previously reported, including those which incorporate Pt. Such observations may be surprising given the propensity for Fe to decompose H2O2via Fenton pathways. However, detailed analysis by CO-DRFITS and XPS reveals that the enhanced activity can be attributed to the electronic modification of Pd and the formation of domains of mixed Pd2+/Pd0 oxidation state, upon Fe introduction. Notably, the resulting improvement in catalytic performance which results from dopant Fe incorporation, is seen to result from an increase in H2 utilisation, rather than improved catalytic selectivity towards H2O2.

The formation of C-C bonds through coupling reactions is an important industrial process. The ability of Au to catalyze such reactions has been reported, with both homogeneous and heterogeneous catalyst examples. Previous work has shown that carbon-supported cationic and nanoparticulate Au are active for the homocoupling of phenylboronic acid to biphenyl. However, the stability of supported cationic Au is short-lived, and the formed nanoparticles were suggested to be the active species. Through the synthesis of two types of supported cationic Au catalysts, utilizing either aqua regia or acetone solvents, we show that both catalysts develop nanoparticulate Au species early in the reaction; however, only the aqua regia prepared catalyst is active. We ascribe the activity of the aqua regia prepared Au catalyst to excess Cl and the presence of C-Cl surface species in combination with Au. Carbon treated with aqua regia was inactive; however, when used as a support for Au deposited with acetone or via a sol immobilization method, activity was comparable to the aqua regia prepared catalyst. The role of C-Cl and Au nanoparticles is discussed with respect to their correlation to the biphenyl yield, which is shown to be significant only when the C-Cl species are present on the catalyst.

The development of titianosilicates is considered a major milestone in oxidative catalysis due to the ability of framework Ti sites to co-ordinate hydrogen peroxide/peroxy species. Herein, we demonstrate that interfacial Ti sites can be constructed through the vertical intergrowth of two MFI-type zeolite surfaces along [100] and [010] projections, with the assistance of UV-induced hydroxyl radicals. The application of these intergrown titanosilicalites as supports for Au species are observed to simultaneously offer a 2.1-fold and 3.0-fold increase in propene oxide (PO) formation rate and Au efficiency, respectively, when compared to standard Au/TS-1 catalysts. Mechanistic studies reveal that the intergrown interface Ti sites allow for lower-energy epoxidation pathways with more efficient activation of key oxygen-transfer intermediates. These results provide insights into the development of zeolite intergrown interface sites (e.g., titanosilicalite/silicalite-1/ZSM-5) and may allow for further advancements in the epoxidation of a range of key feedstocks.

Within this contribution, the combination of supported AuPd nanoalloys with horseradish peroxidase is demonstrated to offer high efficacy towards the one-pot oxidative polymerisation of the model wastewater contaminant phenol, via the chemo-catalytic supply of in-situ generated H2O2. Notably, the utilisation of AuPd alloyed formulations offered considerably improved cascade efficiencies, compared to that observed over monometallic analogues, with the optimal 0.5%Au-0.5%Pd/TiO2 catalyst achieving total conversion of phenol within 15 minutes when used in conjunction with the enzyme. Importantly, the in-situ chemo-enzymatic system was shown to offer good stability over successive reactions, and outperforms analogous approaches reliant on the use of preformed H2O2, while also avoiding the proprietary stabilising agents present in the commercial oxidant.

Iron molybdate catalysts have been extensively explored for the oxidation of methanol to formaldehyde. However, low surface area catalysts are typically formed, and iron-rich phases still exist from common preparation methods, leading to lower selectivity. The use of supercritical antisolvent precipitation to form novel precursors led to catalysts with improved productivity compared to alternative precipitation techniques. Using isoconversion studies, new structure-performance relationships have been uncovered. The novel iron molybdate catalysts provided an improved formaldehyde production of 42.5 mmolCH2O gcat-1 h-1 for the best performing catalyst, whilst specific productivity was used as a descriptor to probe intrinsic properties of the catalysts. Improved performance was achieved by increased agglomerate size and by phase purity, both controlled by the precursor structure. Both properties improve the supply of oxygen to the amorphous MoOx surface phase from the reducible crystalline phase.

Deuterated amine derivatives have emerged as valuable compounds in medicinal chemistry and materials science due to their enhanced metabolic stability and unique physicochemical properties, emphasizing the need for cost-effective and efficient deuteration catalysts; yet this topic has rarely been explored. In this work, we present an atomically dispersed Fe-P pair-site catalyst with high catalytic efficiency and regioselectivity in the deuteration of arenes and heteroarenes using D2O as the deuterated source. Remarkably, these metal-nonmetal Fe-P catalytic pairs with low Fe loading (0.15 wt %) achieve superior catalytic efficiency with a turnover frequency of 131.3 h-1, demonstrating activity up to 30 times higher than the state-of-the-art Fe nanoparticle catalyst (4.9 wt %, TOF: 4.5 h-1). Mechanistic investigations and density functional theory reveal that Fe-P pair sites play a key role in activating D2O and the substrate, enabling the regioselective deuteration of (hetero)-arenes. The investigation further demonstrates the remarkable performance of the phosphorus-doped Fe single-atom catalyst (SAC) across a diverse array of substrates, including various functional group-substituted anilines, nitrogen-containing heterocycles, phenol derivatives, and even complex drug molecules, yielding a total of 39 deuterated compounds. The scale-up synthesis of the Fe-P-C catalyst and subsequent stability tests further underscore the catalyst's potential for practical applications. This methodology introduces a promising direction for developing low-cost, non-noble metal SACs, offering significant potential for advancing the sustainable synthesis of fine chemicals.

Deuterated amines are key building blocks for drug synthesis and the identification of metabolites of new pharmaceuticals, which drives the search for general, efficient, and widely applicable methods for the selective synthesis of such compounds. Here, we describe a multifunctional phosphorus-doped carbon-supported Fe catalyst with highly dispersed isolated metal sites that allow for tandem reductive amination-deuteration sequences. The optimal phosphorus-modified Fe-based catalyst shows excellent performance in terms of both reactivity and regioselectivity for a wide range of deuterated anilines, amines, bioactive complexes, and drugs (>50 examples). Experiments on the gram scale and on catalyst recycling show the application potential of this method. Beyond the direct applicability of the developed method, the described approach opens a perspective for the development of multifunctional single-atom catalysts in other value-adding organic syntheses.

Electric plasma activation of methane opens up the possibility to produce ethene, an important platform chemical in industry, by using sustainable resources like biogas or hydrogenated carbon dioxide and electricity from renewable energies. The ethene stream of such pyrolysis plants contains much higher concentrations of acetylene (>= 15 vol.%) compared to ethene from conventional steam cracking of naphtha (<2 vol.%). In this study, silver-palladium catalysts in various compositions supported on alumina were synthesized via a sol-immobilization technique and investigated in the selective gas-phase hydrogenation of equally concentrated acetylene-ethene mixtures under industrially relevant pressures. A molar Pd concentration of around 10 % in the PdAg alloyed nanoparticles was identified as the optimum composition for simultaneous high activity and ethene selectivity under catalysis conditions. Higher temperatures seem to be crucial for the stability of the catalysts on-stream most likely via increased desorption of active site blocking and high-boiling oligomers from acetylene. The best performing Pd10Ag90 displayed an ethene, ethane and C4+ selectivity of 65%, 4%, and 14%, respectively, at 175 degrees C while being active for more than 200 min. The performance of the catalyst was compared with catalysts synthesized via a mechanochemical and a conventional wet-impregnation procedure.