Electrochemical synthesis of value-added chemicals represents a promising approach to address multidisciplinary demands. This technology establishes direct pathways for electricity-to-chemical conversion while significantly reducing the carbon footprint of chemical manufacturing. It simultaneously optimizes chemical energy storage and grid management, offering sustainable solutions for renewable energy utilization and overcoming geographical constraints in energy distribution. As a critical nexus between renewable energy and green chemistry, electrochemical synthesis serves dual roles in energy transformation and chemical production, emerging as a vital component in developing carbon-neutral circular economies. Focusing on key small molecules (H₂O, CO₂, N₂, O₂), this comment examines fundamental scientific challenges and practical barriers in electrocatalytic conversion processes, bridging laboratory innovations with industrial-scale implementation.

Fischer-Tropsch synthesis (FTS) and hydroformylation are pivotal chemical processes for converting syngas and olefins into valuable hydrocarbons and chemicals. Recent advancements in catalyst design, reaction mechanisms, and process optimization have significantly improved the efficiency, selectivity, and sustainability of these processes. This Account introduces the relevant research activities in the Research Center for Catalysis in Syngas Conversion and Fine Chemicals (DNL0805) of Dalian Institute of Chemical Physics (DICP), Chinese Academy of Sciences. The reactions of interests include FTS, heterogeneous hydroformylation of olefins, alcohol dehydration and oxidation, and α-olefin polymerization, with the emphasis on developing innovative catalysts and processes to address the challenges of traditional processes. Exemplified by the discovery of robust Co-Co₂C/AC for FTS and Rh₁/POPs-PPh₃ for heterogeneous hydroformylation of olefins, it demonstrates how lab-scale fundamental understandings on the active sites of catalysts leads to pilot-plant scale-up and finally commercial technologies. Perspectives on the challenges and directions for future developments in these exciting fields are provided.

The electrochemical CO₂ reduction (ECR) to hydrocarbon products is an attractive pathway to decrease CO₂ emission and advance a carbon-neutral process. Among the products of ECR, methane (CH₄) stands out due to its high calorific value, serving as the main component of natural gas. However, the development of ECR catalysts capable of producing CH₄ with both high activity and stability remains critically urgent. This review summarizes and explores the research progress and future application strategies for ECR toward CH₄ production. Combining experiments, in-situ characterizations, and theoretical calculations, this review examines mechanism of CH₄ formation in ECR. It then clarifies key factors affecting Cu-based catalysts for CH₄ production, including facet dependence, size effects, and valence states. Next, this review details emerging strategies such as sub-nanoscale catalysts, Cu/oxides interface engineering, and Cu surface modification. Finally, future directions highlight in-situ characterization, reactor design, and high-throughput screening, guiding industrial CH₄ production.

Against the backdrop of global energy and environmental crises, the technology of CO₂ hydrogenation to produce methanol is garnering widespread attention as an innovative carbon capture and utilization solution. Bimetallic oxide catalysts have emerged as the most promising research subject in the field due to their exceptional catalytic performance and stability. The performance of bimetallic oxide catalysts is influenced by multiple factors, including the selection of carrier materials, the addition of promoters, and the synthesis process. Different types of bimetallic oxide catalysts exhibit significant differences in microstructure, surface active sites, and electronic structure, which directly determine the yield and selectivity of methanol. Although bimetallic oxide catalysts offer significant advantages over traditional copper-based catalysts, they still encounter challenges related to activity and cost. In order to enhance catalyst performance, future investigations must delve into microstructure control, surface modification, and reaction kinetics.

Ethylene glycol (EG) is a biomass derivative of polyethylene terephthalate (PET), and its electrocatalytic conversion into high-value chemicals has sparked widespread interest. This study reviews the most recent research development in electrocatalysis-based EG to glycolic acid (GA) conversion. Firstly, the strategies and research results of modulating the electronic structure of catalysts for efficient selective GA production from EG are reviewed. Second, by reviewing the data of in-situ Fourier transform infrared spectroscopy and in-situ electrochemically attenuated total reflection surface enhanced infrared absorption spectroscopy, the reaction pathway and catalytic mechanism of EG partial oxidation to GA were clarified. Finally, the design and regulation of catalysts for selective oxidation of EG by electrocatalysis in the future are prospected.

Photoelectrocatalysis (PEC) is extensively applied in diverse redox reactions. However, the traditional oxygen evolution reaction (OER) occurring at the (photo)anode is hindered by high thermodynamic demands and sluggish kinetics, resulting in excessive energy consumption and limited economic value of the O₂ produced, thereby impeding the practical application of PEC reactions. To overcome these limitations, advanced anodic-cathodic coupling systems, as an emerging energy conversion technology, have garnered significant research interest. These systems substitute OER with lower potential, valuable oxidation reactions, significantly enhancing energy conversion efficiency, yielding high-value chemicals, while reducing energy consumption and environmental pollution. More importantly, by designing and optimizing photoelectrodes to generate sufficient photovoltage under illumination, meeting the thermodynamic and kinetic potential requirements of the reactions, and by tuning the voltage to match the current densities of the cathode and anode, coupling reactions can be achieved under bias-free conditions. In this review, we provide an overview of the mechanisms of PEC coupling reactions and summarize photoelectrode catalysts along with their synthesis methods. We further explore advanced catalyst modification strategies and highlight the latest development in advanced PEC coupling systems, including photocathodic CO₂ reduction, nitrate reduction, oxygen reduction, enzyme activation, coupled with photoanodic organic oxidation, biomass oxidation, and pollutant degradation. Additionally, advanced in situ characterization techniques for elucidating reaction mechanisms are discussed. Finally, we propose the challenges in catalyst design, reaction systems, and large-scale applications, while offering future perspectives for PEC coupling system. This work underscores the tremendous potential of PEC coupling systems in energy conversion and environmental remediation, and provides valuable insights for the future design of such coupling systems.

Herein, we present a copper-catalyzed carbonylative cross-coupling of unactivated alkyl bromides with aryl boronates under CO atmosphere which enabling the efficient synthesis of C(sp³)-C(sp²) ketones with extensive functional group compatibility. This strategy represents a significant advance in copper-catalyzed carbonylation involving alkyl bromides and C(sp²)-nucleophiles. The protocol addresses key challenges commonly encountered in the coupling of C(sp³)-alkyl halides with aryl boron reagents, such as sluggish oxidative addition of alkyl halides, competing Suzuki-Miyaura cross-coupling, undesired dehalogenation and so on. Distinguished by its broad substrate scope and high functional group tolerance, this approach offers a robust and versatile platform for the streamlined synthesis of alkyl aryl ketones.

The facets effect on the catalytic properties of inorganic compounds and metal-organic frameworks (MOFs) has been widely demonstrated, but the intrinsic facets effect free of interference of capping agents has not been discussed. Here we give a proof-of-concept illustration on the intrinsic facets effect by employing the popularly investigated NH₂-MIL-125(Ti) MOFs with {001}, {111} and {100} facets controllably exposed as model photocatalysts, which were synthesized via a simple supersaturation strategy free of any capping agents. Compared to conventional synthetic routes with capping agents employed, the NH₂-MIL-125(Ti) MOFs obtained in this work exhibit remarkably different physical and chemical properties such as surface wettability, charge separation as well as trend of facets effect on photocatalytic water splitting performance. The main reason has been unraveled to originate from unavoidable residue/influence of capping agents during the conventional facets-controlled synthetic routes leading to changed local surface structural environment as well as distinct charge separation property. Our results demonstrate the importance and feasibility of facets-controllable synthesis free of capping agents in getting insight into the intrinsic facets effect of MOFs-related materials.

The development of chemical technologies, which involves a multistage process covering laboratory research, scale-up to industrial deployment, and necessitates interdisciplinary collaboration, is often accompanied by substantial time and economic costs. To address these challenges, in this work, we report ChemELLM, a domain-specific large language model (LLM) with 70 billion parameters for chemical engineering. ChemELLM demonstrates state-of-the-art performance across critical tasks ranging from foundational understanding to professional problem-solving. It outperforms mainstream LLMs (e.g., O1-Preview, GPT-4o, and DeepSeek-R1) on ChemEBench, the first multidimensional benchmark for chemical engineering, which encompasses 15 dimensions across 101 distinct essential tasks. To support robust model development, we curated ChemEData, a purpose-built dataset containing 19 billion tokens for pre-training and 1 billion tokens for fine-tuning. This work establishes a new paradigm for artificial intelligence-driven innovation, bridging the gap between laboratory‐scale innovation and industrial‐scale implementation, thus accelerating technological advancement in chemical engineering. ChemELLM is publicly available at https://chemindustry.iflytek.com/chat.

Selective synthesis of value-added xylenes and para-xylene (PX) by CO₂ hydrogenation reduces the dependence on fossil resource and relieves the environment burden derived from the greenhouse gas CO₂. Herein, modified MCM-22 zeolite combined with ZnCeZrO_x solid solution is reported to catalyze the tandem CO₂ hydrogenation and toluene methylation reaction at a relatively low temperature (< 603 K), showing xylene selectivity of 92.4% and PX selectivity of 62% (PX/X, 67%) in total aromatics at a CO₂ conversion of 7.7%, toluene conversion of 23.6% and low CO selectivity of 11.6%, as well as giving high STY of xylene (302.0 mg·h^-1·g_cat^-1) and PX (201.6 mg·h^-1·g_cat^-1). The outstanding catalytic performances are closely related to decreased pore sizes and eliminated external surface acid sites in modified MCM-22, which promoted zeolite shape-selectivity and suppressed secondary reactions.

Single-atom catalysts (SACs) offer a promising approach for maximizing noble metals utilization in catalytic processes. However, their performance in CO₂ hydrogenation is often constrained by the nature of metal-support interactions. In this study, we synthesized TiO₂ supported Pt SACs (Pt₁/TiO₂), with Pt single atoms dispersed on rutile (Pt₁/R) and anatase (Pt₁/A) phases of TiO₂ for the reverse water-gas shift (RWGS) reaction. While both catalysts maintained 100% CO selectivity over time, Pt₁/A achieved a CO₂ conversion of 7.5%, significantly outperforming Pt₁/R (3.6%). In situ diffuse reflectance infrared Fourier-transform spectroscopy and X-ray photoelectron spectroscopy revealed distinct reaction pathways: the COOH pathway was dominant on Pt₁/A, whereas the -OH + HCO pathway was more competitive on Pt₁/R. Analysis of electron metal-support interactions and energy barrier calculations indicated that Pt₁/A better stabilized metallic Pt species and facilitates more favorable reaction pathways with lower energy barriers. These findings provide valuable insights for the design of more efficient SAC systems in CO₂ hydrogenation processes.

Electrochemical reduction of carbon dioxide (CO₂RR) is a promising approach to complete the carbon cycle and potentially convert CO₂ into valuable chemicals and fuels. Cu is unique among transition metals in its ability to catalyze the CO₂RR and produce multi-carbon products. However, achieving high selectivity for C₂₊ products is challenging for copper-based catalysts, as C-C coupling reactions proceed slowly. Herein, a surface modification strategy involving grafting long alkyl chains onto copper nanowires (Cu NWs) has been proposed to regulate the electronic structure of Cu surface, which facilitates *CO-*CO coupling in the CO₂RR. The hydrophobicity of the catalysts increases greatly after the introduction of long alkyl chains, therefore the hydrogen evolution reaction (HER) has been inhibited effectively. Such surface modification approach proves to be highly efficient and universal, with the Faradaic efficiency (FE) of C₂H₄ up to 53% for the optimized Cu-SH catalyst, representing a significant enhancement compared to the pristine Cu NWs (30%). In-situ characterizations and theoretical calculations demonstrate that the different terminal groups of the grafted octadecyl chains can effectively regulate the charge density of Cu NWs interface and change the adsorption configuration of *CO intermediate. The top-adsorbed *CO intermediates (*CO_top) on Cu-SH catalytic interface endow Cu-SH with the highest charge density, which effectively lowers the reaction energy barrier for *CO-*CO coupling, promoting the formation of the *OCCO intermediate, thereby enhancing the selectivity towards C₂H₄. This study provides a promising method for designing efficient Cu-based catalysts with high catalytic activity and selectivity towards C₂H₄.

Solar-driven CO₂ conversion and pollutant removal with an S-scheme heterojunction provides promising approach to alleviate energy shortage and environmental crisis, yet the comprehensive regulation of the charge separation and the activation sites of reactant molecules remains challenging. Herein, a dual-active groups regulated S-scheme heterojunction for hydroxy-regulated BiOBr modified amino-functionalized g-C₃N₄ (labeled as HBOB/ACN) was designed by spatially separated dual sites with hydroxyl group (OH) and amino group (NH₂) toward simultaneously photocatalytic CO₂ reduction and ciprofloxacin (CIP) oxidation. The optimized HBOB/ACN delivers around 2.74-fold CO yield rate and 1.61-times CIP removal rate in comparison to BiOBr/g-C₃N₄ (BOB/CN) without surface groups, which chiefly ascribed the synergistic effect of OH and NH₂ group. A series of experiments and theoretical calculation unveiled that the OH and NH₂ group trapped holes and electrons to participate in CIP oxidation and CO₂ reduction, respectively. Besides, dual-functional coupled reaction system realized the complete utilization of carriers. This work affords deep insights for dual-group modified S-scheme heterojunctions with redox active sites toward dual-functional coupled reaction system for environment purification and solar fuel production.

Direct conversion of syngas to light olefins (STO) on bifunctional catalysts has garnered significant attention, yet a comprehensive understanding of the reaction pathway and reaction kinetics remains elusive. Herein, we theoretically addressed the kinetics of the direct STO reaction on typical ZnAl₂O₄/zeolite catalysts by establishing a complete reaction network, consisting of methanol synthesis and conversion, water gas shift (WGS) reaction, olefin hydrogenation, and other relevant steps. The WGS reaction occurs very readily on ZnAl₂O₄ surface whereas which is less active towards alkane formation via olefin hydrogenation, and the latter can be attributed to the characteristics of the H₂ heterolytic activation and the weak polarity of olefins. The driving effect of zeolite component towards CO conversion was demonstrated by microkinetic simulations, which is sensitive to reaction conditions like space velocity and reaction temperature. Under a fixed ratio of active sites between oxide and zeolite components, the concept of the “impossible trinity” of high CO conversion, high olefin selectivity, and high space velocity can thus be manifested. This work thus provides a comprehensive kinetic picture on the direct STO conversion, offering valuable insights for the design of each component of bifunctional catalysts and the optimization of reaction conditions.

Molybdenum carbide has shown great potential in various hydrogenation reactions, and serves as a primary active species for synthesis of ethanol from dimethyl oxalate hydrogenation process which is a crucial step in the efficient utilization of coal resources. In this study, a molybdenum carbide catalyst with a three-dimensional mesh-like hollow structure and lattice defects was carefully designed. The MoO₃ precursor with abundant oxygen vacancies and defects was prepared by flame spray pyrolysis, and a structural modifier, Cu, was introduced by sputtering. The Cu deposited by sputtering affected the carburization and phase evolution processes. A three-dimensional mesh-like hollow structure composed of defective molybdenum carbide is formed, with the β-Mo₂C exhibiting lattice distortions and defects. This defective β-Mo₂C exhibits high reactivity, and facilitates the C=O hydrogenation process, showing a high reactivity of 83.1% yield in the hydrogenation of dimethyl oxalate. This work provides a new approach to the design and application of molybdenum carbide catalysts.

In recent years, photocatalytic CO₂ reduction reaction has been recognized as a crucial approach to solve the greenhouse effect. However, the low concentration of CO₂ in the atmosphere necessitates a catalyst with excellent CO₂ enrichment capability. Herein, we designed and synthesized a series of NiO nanosheets featuring oxygen vacancies. Under the condition of pure CO₂ and photosensitizer [Ru(bpy)₃]Cl₂, the yield of CO reaches 16.8 μmol/h with a selectivity of 96%. Through characterization and theoretical calculations, we demonstrate that the presence of oxygen vacancies not only enhances the adsorption capacity of catalysts but also induces lattice distortion in NiO, leading to an increased dipole moment and formation of an internal electric field that facilitates photogenerated carrier separation. Furthermore, we conducted CO₂ reduction reactions under atmospheric condition and surprisingly observed a changing of selectivity from CO to CO and CH₄. A series of control experiments showed that [Ru(bpy)₃]Cl₂ acts as a reduction reaction site due to the presence of O₂ in the atmosphere. Simultaneously, oxygen promotes water splitting, which results in abundant proton generation and subsequent changes in carbon products.

Small pore zeolites have been reported to show salient performance in methane oxidation reactions. Among them, the synthesis of AEI zeolite is highly dependent on organic structure-directing agents (OSDA). The isomer OSDAs have been informed to influence the crystallization rate and spatial Al distribution on the crystalline particle of AEI zeolite. Still, its impact on the framework Al distribution of the AEI zeolite is not well known, which significantly impacts the subsequent loading of metal cations and thus active sites available for catalytic reactions. We herein report the impact of the isomer OSDA for synthesizing AEI-type aluminosilicate zeolite on the Al distribution. The discrepancy of Al distribution in as-synthesized AEI zeolites directed by trans and cis-rich OSDAs was identified by ²⁷Al MQMAS/MAS NMR and density functional theory (DFT). The cis-OSDA gave a higher intensity of bands at 60-63 ppm as the shoulder of tetracoordinated Al. The trans-rich OSDA guided to a slightly higher Al content and a slightly higher proportion of Al pairs than the cis-one. The DFT calculation indicated that trans- and cis-OSDAs preferentially led to the Al atoms at the T3 and T1 sites, respectively. The exchanged Cu/AEI zeolites with varied Cu content were applied in the direct and continuous oxidation of methane reaction and exhibited different activities. Given the results, we report here the methane activation properties of the Cu/AEI zeolites and how the isomer identity of the OSDA impacts the activity of Cu/AEI in methane oxidation to methanol. This work highlighted that isomer OSDA influenced the Al distribution as well as crystallization kinetics and gave an insight into the design of the OSDA for zeolite synthesis.

The concept of liquid-solid hybrid catalyst that featuring a truly homogeneous liquid microenvironment together with insoluble solid characteristics has been established recently by our group, which enables us to conveniently bridge the gap between homo- and heterogeneous catalysis. In this study, we extend this general concept to the confinement of molecular rhodium phosphine complexes, including Rh-TPPTS, Rh-TPPMS and Rh-SXP, for olefin hydroformylation reactions. A series of hybrid catalyst materials consisting a modulated liquid interior ([BMIM]NTf₂, [BMIM]PF₆, [BMIM]BF₄ or H₂O) and a permeable silica crust were fabricated through our developed Pickering emulsion-based method, showing 9.4-24.2-fold activity enhancement and significantly improved aldehyde selectivity (from 72.2%, 61.8% to 86.6%) compared to their biphasic counterparts or traditional supported liquid phase system in the hydroformylation of 1-dodecene. Interestingly, the catalytic efficiency was demonstrated to be tunable by rationally engineering the thickness of porous crust and dimensions of the liquid pool. The thus-attained hybrid catalyst could also successfully catalyze the hydroformylation of a variety of olefin substrates and be recycled without a significant loss of activity for at least seven times.

Hydrogen evolution reaction (HER) is unavoidable in many electrochemical synthesis systems, such as CO₂ reduction, N₂ reduction, and H₂O₂ synthesis. It makes those electrochemical reactions with multiple electron-proton transfers more complex when determining kinetics and mass transfer information. Understanding how HER competes with other electrochemical reduction reactions is crucial for both fundamental studies and system performance improvements. In this study, we employed the oxygen reduction reaction (ORR) as a model reaction to investigate HER competition on a polycrystalline-Au surface, using a rotating ring and disk electrode. It’s proved that water molecules serve as the proton source for ORR in alkaline, neutral, and even acidic electrolytes, and a 4-electron process can be achieved when the overpotential is sufficiently high. The competition from H⁺ reduction becomes noticeable at the H⁺ concentration higher than 2 mmol L^-1 and intensifies as the H⁺ concentration increases. Based on the electrochemical results, we obtained an equivalent circuit diagram for the ORR system with competition from the H⁺ reduction reaction, showing that these reactions occur in parallel and compete with each other. Electrochemical impedance spectroscopy measurements further confirm this argument. Additionally, we discover that the contribution of H⁺ mass transfer to the total H⁺ reduction current is significant and comparable to the kinetic current. We believe this work will deepen our understanding of HER and its competition in electrochemical reduction systems.

Conjugated porous polymers have been extensively studied as photocatalysts for hydrogen generation. However, the photocatalytic efficiency is often hindered by the inefficient charge separation and rapid recombination of photo-induced charge carriers, both are strongly affected by the electronic structure of the co-monomers in polymer photocatalysts. In this study, we design three conjugated porous polymers with distinct electronic architectures by combining dibenzo[g,p]chrysene (DBC) and benzene with different substituted groups. The results demonstrate that the combination of DBC and the unsubstituted benzene forms a donor-donor (D-D) structure due to their similar energy levels, while the introduction of methoxy enhances the electron-donating ability of benzene ring, leading to a reinforced D-D structure between DBC and the methoxy-substituted benzene unit, which suppresses the charges separation. In contrast, the introduction of electron-withdrawing cyano group significantly enhances the electron receptivity of the benzene unit, leading to the formation of donor-acceptor (D-A) structure between DBC and the cyano-substituted benzene unit, promoting charges transfer and separation of light-induced electrons and holes. As a result, the D-A polymer DBC-BCN achieves an impressive hydrogen evolution rate (HER) of 20.67 mmol h^-1 g^-1 under UV-Vis light irradiation, outperforming the D-D polymers of DBC-BMO (2.13 mmol h^-1 g^-1) and DBC-B (13.10 mmol h^-1 g^-1). This study underscores the importance of the electronic structure matching of building blocks in polymer photocatalysts to enhance the photocatalytic activity.

CO₂-free H₂ refers to H₂ production process without CO₂ emission, which is a promising clean energy in the future. Catalytic decomposition of methane (CDM) is a competitive technology to produce CO₂-free H₂ with large-scale. However, CDM reaction is highly endothermic and is kinetically and thermodynamically unfavorable, which typically requires a harsh reaction temperature above 800 °C. In this work, solar-driven photothermal catalytic decomposition of methane was firstly introduced to produce CO₂-free H₂ relying solely on solar energy as the driving force. A high H₂ yield of 204.6 mmol g^-1 h^-1 was observed over Ni-CeO₂ interface under photothermal conditions, along with above 87% reduction in the apparent activation energy (11.2 vs. 87.3 kJ mol^-1) when comparing with the traditional thermal catalysis. Further studies suggested that Ni/CeO₂ catalyst enhanced optical absorption in visible-infrared region to ensure the heat energy for methane decomposition. The generated electrons and holes participated in the redox process of photo-driven CDM reaction with enhanced separation ability of hot carriers excited by ultraviolet-visible light, which lowered activation energy and improved the photothermal catalytic activity. This work provides a promising photothermal catalytic strategy to produce CO₂-free H₂ under mild conditions.

Photocatalytic hydrogen peroxide (H₂O₂) production offers a sustainable route to convert water and oxygen into H₂O₂ using solar energy. However, achieving long-term stability in photocatalysts remains a critical challenge due to mismatched kinetics between oxygen reduction (ORR) and water oxidation (WOR), which leads to hole accumulation and oxidative degradation. Here, we report a redox-mediated strategy to address this bottleneck by designing a hydroquinone-embedded covalent organic framework (Tz-QH-COF) that enables reversible hole buffering and kinetic balance. The hydroquinone (QH) units act as dynamic hole reservoirs, capturing excess holes during ORR and converting to benzoquinone (Q), which is regenerated to QH via WOR, thereby preventing oxidative decomposition. This reversible QH/Q cycle, directly visualized through in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy, ensures unmatched stability, achieving continuous H₂O₂ production for 528 h (22 d) with an accumulated yield of 18.6 mmol L^-1—the highest reported duration for organic photocatalysts. Density functional theory calculations reveal that the QH units exhibit a strong oxygen adsorption energy and favorable two-electron ORR/WOR pathways with low energy barriers. The synergy between experimental and theoretical insights elucidates a redox-mediated charge-balance mechanism, advancing the design of robust photocatalysts for solar-driven H₂O₂ synthesis.

The sluggish kinetics of the oxygen reduction reaction (ORR) and high over potential of oxygen evolution reaction (OER) are big challenges in the development of high-performance zinc-air batteries (ZABs) and fuel cells. In this work, we report a rational design and a simple fabrication strategy of a photo-enhanced Co single-atom catalyst (SAC) comprising g-C₃N₄ coupled with cobalt-nitrogen-doped hierarchical mesoporous carbon (Co-N/MPC), forming a staggered p-n heterojunction that effectively improves charge separation and enhances electrocatalytic activity. The incorporation of Co SACs and g-C₃N₄ synergistically optimizes the photogenerated electron-hole pair separation, significantly boosting the intrinsic ORR-OER duplex activity. Under illumination, g-C₃N₄@Co-N/MPC exhibits an outstanding ORR half-wave potential (E_1/2) of 0.841 V (vs. RHE) in 0.1 mol L^-1 KOH and a low OER overpotential of 497.4 mV (vs. RHE) at 10 mA cm^-2 in 1 mol L^-1 KOH. Notably, the catalyst achieves an exceptional peak power density of 850.7 mW cm^-2 in ZABs and of 411 mW cm^-2 even in H₂-air fuel cell. In addition, g-C₃N₄@Co-N/MPC-based ZABs also show remarkable cycling stability exceeding 250 h. The advanced photo-induced charge separation at the p-n heterojunction facilitates faster electron transfer kinetics, and the mass transport owing to hierarchical mesoporous structure of Co-N-C, thereby reducing the overpotential and enhancing the overall energy conversion efficiency. This work provides a new perspective on designing next-generation of single-atom dispersed oxygen reaction catalysts, paving the way for high-performance photo-enhanced energy storage and conversion systems.

The rigorous operating condition of proton exchange membrane fuel cells (PEMFCs) poses a substantial hurdle for the long-term stability of Pt-based alloy catalysts; thus, the development of Pt-alloy catalysts with unique morphologies is crucial for enhancing the stability of PEMFCs. In this study, we synthesized a novel PtCu nano-dendrite (PtCuND) catalyst through a facile, one-step solvothermal process. The sub-nanometer particles and nanopores within this catalyst facilitate enhanced mass transport. In PEM single-cell tests, the PtCuND catalyst displays high activity and robust stability, achieving a mass activity of 0.65 A mg_Pt^-1. Notably, after accelerated durability tests, the mass activity and the voltage at 0.8 A cm^-2 of PtCuND exhibits only minimal decreases of 18.5% and 9 mV, respectively. The combined experimental results and theoretical calculations conclusively illustrate the optimized adsorption of oxygen species and the impact of compressive strain on the catalyst surface. The enhanced durability can be attributed to the maintained nano-dendritic morphology and the strengthened interaction within the Pt-Cu bonds. This work not only enhances the stability of PEMFCs but also provides a robust foundation for the future scaling up of catalyst production, paving the way for widespread application in sustainable energy systems.

Asymmetric single-atom catalysts (ASACs) have attracted much attention owing to their excellent catalytic properties. However, the relationship between asymmetric coordination and the spin states of metal sites remains unclear. Additionally, the modulation of reactive oxygen species in Fenton-like reactions remains challenging. Herein, a novel strategy is reported for the rational design of highly loaded Co ASACs (CoN₁C₂/C₂N) immobilized on three-dimensional flower-like C₂N using an in situ-generated carbon defect method. In particular, the asymmetrically tricoordinated CoN₁C₂/C₂N exhibited excellent catalytic activity for sulfachloropyridazine degradation, with a turnover frequency of 36.8 min^-1. Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration (t_2g⁶e_g¹) to the high-spin configuration (t_2g⁵e_g²) owing to asymmetric coordination. The high-spin Co 3d orbital in CoN₁C₂/C₂N possessed more unpaired electrons and therefore, had a strong ability to gain electrons from the O 2p orbitals of HSO₅^-, boosting d-p orbital hybridization. More importantly, the spin-electron filling in the σ* orbital of high-spin Co 3d−O 2p accelerated the desorption of ^*SO₅^•−, which acted as a rate-limiting step in the reaction, thus facilitating more ¹O₂ generation. This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state, paving the way for advancements in environmental remediation and energy conversion applications.

The electrochemical reduction of nitrate (NO₃⁻) to ammonia (NH₃) (NO₃RR) represents an environmentally sustainable strategy for NH₃ production while concurrently addressing water pollution challenges. Nevertheless, the intrinsic complexity of this multi-step reaction severely constrains both the selectivity and efficiency of NO₃RR. Copper-based electrocatalysts have been extensively investigated for NO₃RR but often suffer from nitrite (NO₂⁻) accumulation, which stems from insufficient NO₃⁻ adsorption strength. This limitation often leads to rapid catalyst deactivation, hindered hydrogenation pathways, and reduced overall efficiency. Herein, we report a one-step green chemical reduction method to synthesize PtCuSnCo quarternary alloy nanoparticles with homogeneously distributed elements. Under practical NO₃⁻ concentrations, the optimized catalyst exhibited an impressive Faradaic efficiency approaching 100% and an outstanding selectivity of 95.6 ± 2.9%. Mechanistic insights uncovered that SnCo sites robustly facilitated NO₃⁻ adsorption, complemented by the proficiency of PtCu sites in NO₃⁻ reduction. The synergistic spatial neighborhood effect between SnCo and PtCu sites efficiently stabilizes NO₃⁻ deoxygenation and suppresses NO₂⁻ accumulation. This tandem architecture achieves a finely tuned balance between adsorption strength and deoxygenation kinetics, enabling highly selective and efficient NO₃RR. Our findings emphasize the indispensable role of engineered multi-metallic catalysts in overcoming persistent challenges of NO₃RR, paving the way for advanced NH₃ synthesis and environmental remediation.

Nitrate pollution poses a significant environmental challenge, and photocatalytic nitrate reduction has garnered considerable attention due to its efficiency and environmental advantages. Among these, the development of Schottky junctions shows considerable potential for practical applications. However, the impact of metal nanoparticle size within Schottky junctions on photocatalytic nitrate reduction remains largely unexplored. In this study, we propose a novel method to modulate metal nanoparticle size within Schottky junctions by controlling light intensity during the photodeposition process. Smaller Au nanoparticles were found to enhance electron accumulation at active sites by promoting charge transfer from COF to Au, thereby improving internal electron transport. Additionally, the Schottky barrier effectively suppressed reverse electron transfer while enhancing NO₃^- adsorption and activation. The Au₂-COF exhibited remarkable nitrate reduction performance, achieving an ammonia yield of 382.48 μmol g^-1 h^-1, 5.7 times higher than that of pure COF. This work provides novel theoretical and practical insights into using controlled light intensity to regulate metal nanoparticle size within Schottky junctions, thereby enhancing photocatalytic nitrate reduction.

This study explores, for the first time, the influence of various C1 gases, such as methane (CH₄), carbon dioxide (CO₂), and biogas (CH₄ + CO₂), on catalytic pyrolysis of plastic waste (polypropylene) to evaluate their potential in producing aromatic hydrocarbons. Also, this study used the 0.5 wt%, 1 wt%, 3 wt%, and 5 wt% Ga-modified ZSM-5 catalyst and its reduction-oxidation processed catalysts owing to their promising catalytic properties. According to the results, the highest yield (39.5 wt%) of BTEX (benzene, toluene, xylene, and ethylbenzene) was achieved under CH₄ over RO-GHZ(1) catalyst among all tested conditions. The reduction-oxidation process not only promotes a significant reduction of the Ga-size but also induces its diffusion inside the pore, compared to GHZ(1). This leads to the formation of highly active GaO⁺ ionic species, balancing the Lewis/Brönsted ratio, thereby accelerating the aromatization reaction. The effect of Ga loading on the RO-GHZ catalyst was also evaluated systematically, which showed a negative impact on the BTEX yield owing to the lowering in the concentration of active GaO⁺ species. A detailed catalyst characterization supports the experimental results well.