Electrochemical synthesis of amides from carbon- and nitrogen-containing small molecules is alluring from the view of carbon neutrality. Previous works were mainly focused on electro-reduction coupling of C-N bond to prepare amides coupled with the useless oxygen evolution reaction on the anode. But, the competing hydrogen evolution reaction is more favorable in dynamics on the cathode, severely retarding the Faradaic efficiency of the amides. Very recently, electro-oxidation construction of C-N bond via coupling the cheap C- and N-containing small molecules to achieve high energy efficiency emerges as a rising star, while the big challenge lies in preventing the sole oxidation of feedstocks. In this perspective, we highlight the recent progress in anodic electro-oxidation synthesis of amides and the potential reaction mechanism. We also discuss the application potential and the development opportunities of the electro-oxidation strategy for amides synthesis from carbon- and nitrogen-containing small molecules.

Catalytic coupling of abundant CO₂ or renewable CH₃OH with nitrogenous small molecules, such as N₂, NH₃, and NO₃^-, has emerged as a promising strategy for synthesizing high-value organonitrogen compounds. However, conventional thermal catalysis for C-N bond formation often relies on external chemical reagents and energy-intensive conditions, raising concerns about process sustainability. Photocatalysis offers a sustainable alternative by utilizing sunlight to generate high-energy electron-hole pairs in semiconductors, which can activate inert chemical bonds (e.g., C=O and N≡N) for programmed coupling under ambient conditions. In this review, we dissect the fundamental activation mechanisms underlying photon-mediated C‒N coupling reactions, highlight key recent breakthroughs in the synthesis of urea, formamide, and amino acids, and analyze persistent challenges alongside emerging opportunities. This work aims to deepen the understanding of photocatalytic C-N coupling reactions and inspire research interest in sustainable nitrogen fixation and carbon utilization.

Green hydrogen (H₂) energy plays an important role in combating climate change, promoting energy transition, and fostering sustainable development. Solar-driven plastic photoreforming afford an attractive solution, it overcomes the limitation of the slow oxygen evolution half-reaction in overall water splitting while tackling environmental pollution and resource waste caused by plastics. However, this technology still rests on the experimental stage, and the transition from laboratory to realistic application remains lacking systematic view. In this review, key components for plastic photoreforming, including plastic pretreatment routes, photocatalysts exploration, basic photocatalytic modules for the realistic application, and feasibility, are investigated. Finally, outlook in this area is discussed.

In recent decades, the unabated consumption of fossil fuels has resulted in a sustained increase in carbon dioxide emissions, exacerbating environmental challenges typified by the greenhouse effect, which has underscored the urgent imperative to develop highly efficient carbon dioxide capture and utilization technologies. The electrocatalytic carbon dioxide reduction reaction (eCO₂RR) has emerged as a promising strategy for the conversion of CO₂ into high-value-added chemical commodities. Recent investigations have demonstrated that alkali cations played a pivotal role in eCO₂RR, encompassing enhancements in catalytic activity and modulations of product selectivity. Despite these advancements, how exactly the alkali cations affect the electrocatalytic reaction process and the key determinants of alkali cation effects remain subjects of ongoing debate. We analyzed current research on the effects of alkali cations, in which the concentration and type of alkali cations were generally correlated with eCO₂RR performance. However, the distribution of alkali cations at the electrode interface is often overlooked. In this study, we first conclude recent advancements in electric double layer theory and elucidate three distinct modes of alkali cation distribution at the electrode-electrolyte interface. Subsequently, we systematically summarize the specific mechanisms through which these cations operate in different electrolyte systems. Furthermore, we propose fundamental perspectives for future investigations into alkali cation effects, aiming to provide guiding principles for the rational design of next-generation advanced eCO₂RR electrolysis systems.

Metal-organic frameworks (MOFs) with mononuclear metal ion nodes have garnered significant attention in the electrocatalytic field owing to their high surface area and tunable structures, but their development is critically hindered by the limitation of active site availability. In contrast, multinuclear MOFs exhibit notable advantages by offering multi-metal active sites, constructing complex structures, enhancing structural and thermal stability, and coupling with in-depth studies on catalytic mechanisms, endowing them great application potential in complex multi-electron reactions. This work provides a comprehensive review on the precise construction, in-situ characterizations, reaction mechanisms, modulation strategies, and electrocatalytic applications of multinuclear MOFs, underlying their role in electrocatalytic processes with a focus on adsorption, active sites, and electron transfer. The effects of spin, polarization, orbital coupling, and pore confinement on catalytic performance are systematically elucidated. Furthermore, the unique tuning strategies of multinuclear MOFs are summarized to guide the precise construction, including adjusting the type and number of metal cores, optimizing electronic structures, and manipulating defects. Lastly, the future trends in the development of multinuclear MOFs for electrocatalysis are envisioned, laying a solid foundation for their practical applications.

The clinical efficacy of mRNA-based therapeutics is critically dependent on the structural integrity of the mRNA molecule, which in turn is governed by the efficiency and robustness of its manufacturing process. Unlike conventional small-molecule synthesis, mRNA manufacturing relies on complex enzymatic cascades involving biomacromolecules with dynamic conformations as templates, intermediates, and catalysts. Key enzymatic modules, including plasmid linearization for DNA template preparation (Module 1), in vitro transcription (IVT) synthesis (Module 2), capping modification (Module 3) of mRNA, and different nucleases-aided removal of impurities (Module 4), are highly interdependent, each with specific catalytic enzymes and auxiliary cofactors. These modules present major engineering challenges of low efficiency and lack of modular compatibility across the multi-step enzymatic processes. Moreover, traditional approaches such as multienzyme immobilization or compartmentalization often fail to meet the demands of high-throughput, continuous and scalable manufacturing. This review systematically summarizes recent advances in the engineering of enzymatic modules for mRNA manufacturing, emphasizing challenges in catalytic regulation, module integration and process intensification. The potential strategies for improving reaction compatibility and enabling process integration and intensification are discussed, providing insights into future directions for engineering mRNA synthesis at scale.

To address persistent challenge of charge recombination in semiconductor photocatalysis, we engineered an S-scheme heterojunction via covalent β-ketoenamine bridges between zirconium-based MOFs and triazine-COFs (Zr-BTB-COF). This dual-functional system pioneered a "one-photon, two-value" strategy for simultaneous CO₂-to-CO reduction and 4-methoxybenzyl alcohol-to-anisaldehyde oxidation, enabling solar-driven carbon refineries. Synergistic in-situ XPS analysis and density functional theory calculations unambiguously validated the S-scheme charge transfer mechanism. The covalent interface overcame lattice mismatch constraints while Fermi-level alignment generated an enhanced built-in electric field (9.8 times stronger than pristine Zr-BTB-NH₂), achieving ultrafast charge separation. Low-energy carrier recombination through the β-ketoenamine bridge preserved high-potential carriers (-1.61 V for CO₂ reduction; +2.22 V for alcohol oxidation). Critically, this architecture reduced the activation energy barrier for the rate-limiting *COOH → *CO step to ΔG = 0.65 eV, a 42% reduction versus isolated Zr-BTB-NH₂. Through concerted thermodynamic and kinetic optimization, the covalent Zr-BTB-COF achieved high CO and anisaldehyde yields (71.9 and 44.7 μmol·g^-1·h^-1) with internal quantum efficiency of 3.75% (365 nm). This bond-resolved interface engineering paradigm establishes a new design framework for synchronizing carbon-neutral cycles with high-value chemical synthesis.

Photocatalysis is deemed a green approach to sustainable energy conversion with great promise for addressing future energy challenges. However, traditional photocatalytic systems are often inhibited by rapid recombination of photogenerated electron-hole pairs and low light-harvesting efficiency. To overcome these challenges, an S-scheme heterojunction integrating Zn_xCd_1-xS_y (ZCS) nanocrystals with FePS₃ (FPS) nanosheets was designed to facilitate both photocatalytic hydrogen evolution and the conversion of benzyl alcohol to benzaldehyde (BAD). The obtained ZCS/FPS-15 (ZCSF-15) heterostructure exhibits remarkable visible-light-harvesting enhancement and charge separation efficiency, delivering a hydrogen evolution rate of 73.06 mmol g^-1 h^-1 and a BAD production rate of 46.68 mmol g^-1 h^-1, corresponding to 22.34- and 53.65-fold performance enhancements, respectively, compared with that of bare ZCS. To reveal the charge transfer dynamics and clarify the reaction mechanisms, in-situ diffuse-reflectance Fourier-transform infrared spectroscopy was used to identify key oxidation intermediates, coupled with interfacial charge transfer dynamics probed using in-situ X-ray photoelectron spectroscopy and atomic force microscopy-Kelvin probe force microscopy. This work establishes a dual-function heterojunction model, offering valuable insights into how to design S-scheme heterojunctions for simultaneous green fuel generation and selective organic synthesis.

Abstracr: The synergistic coupling of photocatalytic hydrogen peroxide (H₂O₂) production and green organic synthesis not only optimizes utilization of photogenerated electron-hole pairs but also circumvents kinetically sluggish water oxidation reaction. In this study, an efficient composite photocatalyst was developed through in-situ growth of irregular TpPa-Cl blocks on the surface of boron-doped TiO₂, which boasts a large specific surface area. Boron doping enhances light absorption range and inhibits recombination of charge carriers. Additionally, deep integration of porous TiO₂ with TpPa-Cl improves the contact between the reactants and the photocatalyst, extends the carrier lifetime, and provides more active sites. In the absence of a co-catalyst, the yield of H₂O₂ reached 2082.6 μmol g^-1 h^-1, with a furfuryl alcohol conversion rate of 94%. In-situ XPS and density functional theory calculations confirmed S-scheme charge transfer mechanism, which enhances carrier separation and transfer efficiency while retaining photogenerated electrons and holes with strong redox properties. Quenching experiments, electron paramagnetic resonance, and in-situ diffuse reflectance infrared Fourier transformed spectroscopy demonstrated that H₂O₂ was primarily generated via a 2-electron oxygen reduction reaction with ·O₂^- and OOH^* as intermediates. Furthermore, furfuryl alcohol was oxidized to the radical ·C₅H₅O₂ by h⁺ and subsequently converted to furfural or furoic acid through reactions with h⁺ or ·OH. This work presents a novel strategy for designing efficient composite photocatalysts for H₂O₂ production and green organic synthesis.

Developing sustainable, low-cost H₂S conversion technologies holds significant importance for the coal chemical and petrochemical industries. Herein, twinned Cd_0.5Zn_0.5S (T-CZS) homojunctions serve as model photocatalysts, with a Na₂S/NaH₂PO₂ solution simulating H₂S absorption to regulate S²⁻/HS⁻ transformation pathways for concurrent efficient H₂ evolution and desulfurization. Notably, at 3 mol∙L⁻¹ NaH₂PO₂ concentration, the H₂ evolution rate (r_H2) over T-CZS reaches 233.9 mmol∙g⁻¹∙h⁻¹—representing a 5.5-fold enhancement versus 0.1 mol∙L⁻¹ Na₂S alone. Mechanistic studies reveal that the two-step oxidation of H₂PO₂⁻ delivers four electrons for H⁺ reduction while simultaneously scavenging deleterious S₂²⁻ species. This dual function mitigates light-absorption competition, enhances interfacial electron density, and accelerates H₂-evolution kinetics. Further, Co₃(PO₄)₂/CoS_x loading boosts H₂ production to 292.1 mmol∙g⁻¹∙h⁻¹, primarily ascribed to suppressed bulk/interface charge recombination. Crucially, acidification of post-reaction solutions yields pure elemental sulfur (S) as a yellow solid. Practical viability was validated using H₂S preparation and absorption system, confirming robust catalyst performance and system efficacy for integrated high-efficiency H₂ production and S recovery. The critical role and significant potential of H₂PO₂⁻ in enhancing H₂ evolution in S²⁻/HS⁻ solutions were emphasized, offering potential strategies for efficient photocatalytic conversion of S²⁻/HS⁻. This work establishes a new paradigm for green, economical H₂S valorization.

Cooperative coupling of photocatalytic hydrogen generation with oxidative organic synthesis is promising in simultaneously producing sustainable energy and value-added chemicals. However, the photocatalytic activity is constrained by restricted redox potentials and insufficient photocarrier separation and transfer. Herein, we construct S-scheme heterojunctions based on metal-doped ZnIn₂S₄ and covalent organic frameworks, denoted as M-ZIS/TpPa-1 (M = Ni or Mo). Theoretical calculations demonstrated that Mo-ZIS possess optimum H adsorption Gibbs free energies, deeper downshift of sulfur p-band center and higher integrated crystal orbital Hamilton population (ICOHP) value than Ni-ZIS and ZIS to optimize H adsorption/desorption dynamics. Besides, metal-doping reasonably enhanced the interfacial charge transfer in heterostructures, identifying the enlarged internal electric field (IEF) in Mo-ZIS/TpPa-1 than Ni-ZIS/TpPa-1 and ZIS/TpPa-1. Moreover, experimental explorations of photoelectrochemical measurements, femtosecond transient absorption spectroscopy, in-situ irradiated X-ray photoelectron spectroscopy and electron paramagnetic resonance verified the facilitated photocarrier separation and migration in metal-doped S-scheme heterojunctions. Ultimately, Mo_0.01-ZIS/TpPa-1 exhibited visible-light driven H₂ evolution rate of 1648 μmol g⁻¹ h⁻¹ and N-benzylidenebenzylamine formation rate of 1812 μmol g⁻¹ h⁻¹, better than Ni_0.048-ZIS/TpPa-1, and superior to parent ZIS/TpPa-1. This work might provide insights into the modulation of H adsorption/desorption behavior and IEF within S-scheme heterostructures via rational metal-doping strategy for efficient dual-functional photocatalysis.

The pursuit of an efficient photocatalytic pathway for hydrogen peroxide (H₂O₂) synthesis from pure water without adding additional sacrifice agents poses a formidable research endeavor and remains a pivotal challenge. Herein, we demonstrate that incorporating hexaketocyclohexane-derived carbon dots (H-CDs) and S vacancies into ZnIn₂S₄ weakens the exciton effect, leading to the dissociation into free carriers that participate in the dual pathways of oxygen reduction reaction and water oxidation reaction, thereby achieving efficient photocatalytic H₂O₂ production with a high H₂O₂ yield of 17.8 mM/g/h under visible light in pure water. Experimental results combined with theoretical calculations clearly illustrate that the presence of H-CDs and S vacancies modulates the local charge density of ZnIn₂S₄, markedly diminishing the exciton binding energy and facilitating the occurrence of exciton dissociation. Moreover, S vacancies and H-CDs effectively capture free electrons and extract free holes, respectively, significantly inhibiting the recombination of photogenerated electron-hole pairs. By optimizing the electronic structure and optical properties of ZnIn₂S₄, they thermodynamically satisfy the conditions for oxygen reduction and water oxidation reactions. Additionally, the synergy between H-CDs and S vacancies in ZnIn₂S₄ enhances the adsorption of oxygen and intermediate products, increasing their participation in the reaction and facilitating the conversion to H₂O₂. This work offers novel insights into catalyst design from the perspective of excitons dissociation, and underscores the distinct roles that free charge carriers play in various pathways for photocatalytic H₂O₂ production.

The direct conversion of methane into methanol under mild conditions represents a highly appealing pathway. Regulating the generation of hydroxyl radicals (•OH) is a representative method, but excessive release of •OH will inevitably lead to the over-oxidation of CH₃OH. Here, we design AgPd alloy and Co₃O₄ cascade active sites on the TiO₂ surface (AgPd-Co/TiO₂) to control the release rate of •OH to improve the selectivity of CH₃OH. By incorporating Co₃O₄ as a hole buffer and storage center, the kinetics of •OH generation at the TiO₂ interface can be effectively modulated. This confines the spatial distribution of •OH to the active sites of the AgPd alloy, thus facilitating the directional combination of •CH₃ and •OH. The optimal AgPd-Co/TiO₂ photocatalyst demonstrates outstanding catalytic performance with the selectivity of CH₃OH reaching up to 93% in the liquid phase. AgPd-Co/TiO₂ exhibited significantly enhanced selectivity relative to reported TiO₂-based photocatalytic systems, while simultaneously achieving comparable methanol yields. This research offers valuable insights for the precise design of composite photocatalysts to achieve highly selective methane oxidation.

Covalent organic frameworks (COFs) have garnered significant attention in photocatalysis owing to their exceptional light absorption capacities, tunable band structures, and high specific surface areas. However, the rapid recombination of photogenerated carriers in COFs remains a critical bottleneck limiting their practical application. In this study, a novel S-scheme heterojunction was constructed by integrating a Ni-doped zeolitic imidazolate framework-8 (Ni-ZIF-8) with Py-COF, effectively addressing this challenge. Through precisely controlled synthesis, the heterojunction achieves efficient and stable material combination, which not only significantly enhances photogenerated charge separation efficiency and markedly reduces recombination rates, but also demonstrates outstanding catalytic performance (162.77 mmol·h^-1·g^-1) and cycling stability in hydrogen evolution reaction. This study provides new insights into the design of efficient ZIF/COF-based heterojunction catalysts. This study provides an important theoretical foundation for the design of high-performance photocatalytic materials with broad application prospects.

Symmetry-broken single-atom catalysts (SACs) are pivotal due to their asymmetric electronic environments, which enhance the activity of the hydrogen evolution reaction (HER). This study investigated how symmetry breaking in SACs affects HER performance using density functional theory (DFT) and variable selection machine learning (ML). The study revealed a nearly volcano-shaped correlation between the degree of spin density symmetry breaking (D_asym) and HER activity, with catalysts at the base of the volcano showing enhanced HER activity. Spin density symmetry breaking facilitates the enrichment of unpaired electrons on the active sites and reduces HER energy barriers, resulting in up to a 40-fold enhancement in HER performance of symmetry-broken SACs compared to symmetric SACs. The ML model accurately identified key descriptors, such as symmetry breaking and electronic transfer effects, allowing spin density symmetry breaking on M-N3C-SWCNTs to be further condensed into an effect term with a structure-property relationship. A weaker symmetry breaking effect and a stronger electron transfer enhance HER performance. ML-guided analysis highlighted a spin selection-related Volmer-Heyrovsky pathway with a dual activation mechanism involving surface atom displacement and para-activation. These findings offer critical insights into the design of advanced HER catalysts by elucidating the interplay between symmetry-breaking properties and catalytic behavior.

Photoelectrochemical (PEC) CH₃OH oxidation provides a promising path to HCHO synthesis instead of thermal catalytic method. However, it suffers the low conversion rate and selectivity. Here, surface fluorinated BiVO₄ photoanodes were fabricated by combined immersion method and PEC treatment for selective CH₃OH oxidation into HCHO. The surface fluorination simultaneously improved the reaction kinetics and selectivity for HCHO synthesis on BiVO₄ photoanode, where the formation of metal‒F bonds promoted the CH₃OH molecules adsorption, O‒H bond stretching, C‒H bond activation, and eventually HCHO desorption, resulting in excellent HCHO production with high selectivity. The optimal photoanode BVO-F2 obtained a photocurrent density of 3.24 mA cm^-2 at 1.2 V_RHE, which is about twice that of the bulk BVO photoanode (1.66 mA cm^-2). In addition, at 0.8V_RHE, the Faraday efficiency of BVO-F2 PEC CH₃OH oxidation for HCHO synthesis reached 90.7%, and maintained relatively stable performance in continuous oxidation for 5 h, and finally accumulated 98.12 µmol HCHO. This work illustrates the potential of surface functionalization in PEC conversion of small molecules, as well as in regulating charge dynamics and catalytic reaction thermodynamics.

Bi-based catalysts are known to promote the electrochemical reduction of CO₂ to formic acid (HCOOH) or formate (HCOO^-). However, their implementation presents challenges: the first H⁺/e^- pair transfer to form the key *OCHO intermediate on a Bi surface is a slow, kinetically sluggish endergonic process, resulting in a large overpotential and narrow potential window for high HCOOH/HCOO^- selectivity. Altering the localized p-orbital electron states of Bi to change intermediate binding behaviors is difficult. We addressed this problem by using an in-situ polymerization method to obtain a polyaniline-Bi hybrid (PANI-Bi) with Bi surrounded by PANI chains. Combined experimental and computational studies indicate that the polyaniline acted as an “electron pump” that facilitated charge transfer from the PANI backbone to the Bi surface and changed the p-orbital electrons of the Bi active sites. This lowered the energy barrier for the adsorption of intermediates and facilitated *OCHO formation. Consequently, a significant increase in formate production was observed, achieving a single-pass carbon efficiency exceeding 48.7% at 800 mA cm^-2. This organic functionalization strategy, aimed at modifying the electronic structure of heterogeneous catalysts, offers a promising approach for achieving highly selective electroreduction of CO₂ at a high current density.

Heterometallic doping can modulate the electron distribution of a catalyst, thereby influencing its intrinsic activity. In this study, we pioneer zinc doping within copper hydroxy oxides (CuO_xH_y) to alter the electronic structure and geometry, unlocking a distinct proton-coupled dynamic catalysis mechanism and significantly improving electrochemical CO₂ reduction reaction (CO₂RR) pathway selectivity toward formate. The Cu_0.4Zn_0.6O_xH_y catalyst, synthesized via a template co-precipitation method, exhibits a 4.1-fold enhancement of Faraday efficiency of formate over pristine CuO_xH_y at ‒1.1 V vs. RHE. In-situ Raman and X-ray photoelectron spectroscopy results confirm that the Cu_0.4Zn_0.6O_xH_y catalyst undergoes surface electron reconfiguration while maintaining bulk structural integrity with sustained Cu redox cycling, preserving the key active sites that sustain performance during CO₂RR. Density functional theory calculations show that Zn doping effectively modulates the d-band center of Cu, enhances interfacial charge transfer with the *HCOO adsorbate, and lowers the energy barrier of the limiting step (CO₂ → *HCOO), thereby boosting CO₂RR performance. This work establishes a design principle for modulating the electronic structure of Cu-based hydroxides by zinc doping, highlighting dopant-induced electronic redistribution as a critical factor for achieving high formate selectivity.

Protic ionic liquid (IL) modification has been demonstrated to be a promising approach for improving the oxygen reduction reaction (ORR) activity and electrochemical stability of catalysts. However, its fundamental mechanism remains largely elusive and controversial, and the possible roles of electrocatalytic interface microenvironment has been ignored so far. Herein, taking the well-structured iron phthalocyanine (FePc) as a model catalyst, it is found that the ORR activity evolution behavior induced by the protic IL modification exhibits a striking pH-dependence, that is, ORR is promoted in acid while slightly inhibited in alkaline. Integrating the electrokinetic analyses, ab initio molecular dynamics simulation and in situ surface-enhanced infrared absorption spectroscopy, we show that the discrepancy in activity evolution arises from the regulation of IL modification on the vastly dissimilar electrochemical interfacial structures under acid and alkaline ORR conditions. Such mechanistic picture can be further supported by the fact that the protic IL with a lower pK_a renders a higher acid ORR activity. This study provides a unique interfacial perspective for understanding the IL modifiers-modulated ORR performance and highlights opportunities for developing cost-effective and high-efficiency proton exchange membrane fuel cells through the functional modulation of electrocatalytic interfaces.

Tandem electrocatalysis offers considerable potential for selectively converting nitrate ions (NO₃^-) to ammonia (NH₃) via electrochemical reduction, yet its practical application is often hampered by sluggish nitrite ions (NO₂^-) intermediate transfer between spatially separated active sites and mismatched reaction potentials, which together constrain conversion efficiency and limit high Faradaic efficiency (FE) to a narrow operating window. Herein, we report a rationally designed dual-phase Cu-doped Co/CoO (Cu-Co/CoO) heterojunction, featuring spatially distinct yet synergistic active sites and abundant atomic-scale heterointerfaces that enable accelerated tandem catalysis. Mechanistic investigations reveal that the Cu-doped CoO domain predominantly catalyzes the reduction of NO₃^- to NO₂^-, which is rapidly transferred across the heterointerface to the Cu-doped Co domain for further hydrogenation to NH₃. As a result, the Cu-Co/CoO catalyst achieves a high FE exceeding 85% and sustains high NH₃ yields across a broad potential range. Notably, the catalyst achieves a remarkable NH₃ yield of 27.3 mmol h^-1 mg_cat^-1 and an NH₃ partial current density of 0.58 A cm^-2 at -0.8 V (vs. RHE). Integration into a Zn-NO₃^- battery system further enables simultaneous high-rate NH₃ production and power output. This work establishes a viable methodology for engineering high-performance tandem electrocatalysts and offers new insights into interfacial engineering for renewable NH₃ synthesis.

Waste plastics present a significant threat to ecosystems and human health, necessitating efficient and cost-effective solutions for their conversion into high-value products. This study introduces a novel electrochemical reforming strategy to upgrade polyethylene terephthalate (PET) into valuable chemicals, primarily formic acid, while simultaneously generating hydrogen. A highly efficient electrocatalyst composed of nano-arrays of silver and NiFe layered double hydroxide (LDH) is synthesized via a hydrothermal and photo-precipitation process on a nickel foam substrate. This advanced catalyst achieves selective electrochemical conversion of ethylene glycol (EG) as PET hydrolysate to formate and glycolate with Faradaic efficiencies of 85% and 13% at 1.5 V vs. the reversible hydrogen electrode, with a stable and high current density. Density functional theory calculations reveal that the synergistic interaction between Ag and NiFe-LDH optimizes the adsorption and desorption of key intermediates on the catalytic sites, resulting in superior activity, selectivity, and stability for the electrochemical EG oxidation reaction. These findings highlight the potential of this catalyst for sustainable plastic waste valorization and renewable hydrogen production.

Single atomic iron-nitrogen-carbon (Fe-N-C) have emerged as promising catalysts for the oxygen reduction reaction (ORR), however, the insufficient activity and stability hindered their application in proton exchange membrane fuel cells (PEMFCs). Simultaneously regulating the coordination environments and local carbon structures of atomic Fe-N sites is essential to boost Fe-N-C’s ORR performance. In this study, a dual-site confinement strategy is proposed to precisely incorporate Mn single atoms at adjacent Fe sites to form active and stable FeMn-N catalytic structure within a graphitic carbon matrix, which is achieved via heat treatment of MnFe₂O₄ nanoparticles embedded ZIF-8. Experimental and theoretical calculations demonstrate that the incorporation of Mn atoms could effectively modulate the electronic structure of Fe atoms, enhance Fe-N bond stability and reduce Fe site dissolution. Moreover, in-situ Raman and in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy spectra suggest that Mn doping could suppress Fenton reactions by optimizing the ORR pathway through facilitating *OH intermediate desorption and circumventing *OOH intermediate formation. The synthesized FeMn-N-C exhibits better catalytic activity than commercial Pt/C catalysts (E_1/2 of 0.885 vs. 0.855 V) and maintains stable cycling operation over 20000 cycles with a small E_1/2 gap of 95 mV. When applied in PEMFCs, FeMn-N-C achieves a high peak power density of 899.9 mW cm^-2 and retains 66.4% of its initial performance after 20000 square-wave cycles, which is superior to Fe-N-C catalyst. This study provides an innovative design strategy for developing high-performance, long-lasting ORR catalysts for PEMFCs.

For achieving high-power and low-platinum direct methanol fuel cell (DMFC) under proton-exchange-membrane, we introduce the oxidation-state ruthenium species as H₂O-activation centers stabilized on PtZn NPs to boost methanol-oxidation reaction (MOR). The Zn-regulated Ru centers, approaching bivalent states, enhance interfacial H₂O-capture/dissociation and OH-transfer, enabling rapid CO* removal from adjacent Pt sites. It exhibits an outstanding mass activity of MOR at 2.71 A mg_Pt^-1 and powers a DMFC with 191.2 mW cm^-2 peak density (382.4 W g_Pt^-1) while maintaining 125-hour stability, higher than documented results to date, essentially different from traditional alloy catalysts. Combined ab initio molecular dynamics simulations and in-situ spectroscopy reveal a dense O-down water network around Ru centers, where intermediate RuO(OH)₂ structure significantly deceases the H₂O-dissociation barrier. Kinetic isotope effect tests (CH₃OH/H₂O vs. D₂O) show J_H2O/D2O = 4.2 for RuO_x-PtZn/C at 0.85 V_RHE, versus 16.2 for RuO_x-Pt/C, directly confirming superior water activation efficiency of RuO_x-PtZn/C. We envision that the comprehensive understanding of high-performance MOR on RuO_x-PtZn/C through experimental-theoretical approaches will contribute to the practical application of DMFC as early as possible.

Direct synthesis of dimethyl carbonate (DMC) from CO₂ is critical for achieving carbon neutrality, yet the sluggish formation and conversion of the key *CH₃OCOO intermediate-due to the difficulty of C-O coupling-limit high DMC yields. Herein, we developed a boric acid-assisted recrystallization strategy to fabricate grain-boundary-rich CeO₂ hollow nanospheres, which serve as an efficient catalyst for CO₂ to DMC synthesis. The introduction of grain-boundary (GBs) induced the electron redistribution, which led a decrease in the electron density of bulk Ce ions and created a localized electron-rich region at homogeneous interface. This unique electronic landscape promoted reactive methoxy formation and stronger CO₂ adsorption, thereby enabling more efficient coupling of *CH₃O and *CO₂ to form the *CH₃OCOO. Concurrently, the enhanced CO₂ adsorption facilitated the dissociation of *CH₃OCOO and subsequent DMC formation. As a result, the 4%BCeO₂-GBs achieved an advantageous DMC yield of 19.8 mmol/g. In the assistance of dehydrating agent, the catalyst delivered a remarkable 264.2 mmol/g DMC yield and 7.12% methanol conversion, which was 32 times higher than commercial CeO₂. This study elucidated the intrinsic mechanisms governing *CH₃OCOO intermediate behavior and offers valuable guidance for CO₂ converting into high-value organic chemicals.

The direct synthesis of aromatic compounds from the reduction of CO₂ remains challenging due to harsh operating conditions, low aromatic yields, and catalyst deactivation. A comprehensive understanding of the distance-induced optimal activity is therefore essential for achieving a rational spatial arrangement of multifunctional active sites for the hydrogenation of CO₂ to generate aromatic compounds. In this study, a triple-bed catalyst system is reported, which directly converts CO₂ into aromatic compounds with low CO emission levels. At a CO₂ conversion of 50.3%, the hydrocarbon pool contained 73.6% aromatic compounds while maintaining a moderately low CO selectivity of 13.9%. The BTEX (benzene, toluene, xylene, and ethylbenzene) selectivity within the aromatic products reached 67.8% and remained stable over 125 h, with only a slight decline being observed beyond this time. Compared to the mortar- and granular-mixed configurations, the triple-bed system exhibited a superior catalytic stability, likely due to the suppression of Na-induced poisoning on the zeolite acid sites. Additionally, the close contact between Fe and the zeolite structure altered the Fe phase evolution process for the chain extension reaction, while also significantly degrading the structural integrity of the zeolite. Under 370 °C and 3.5 MPa conditions, the zeolite crystallinity in the mortar-mixed 11% Na-promoted FeAlO_x/Zn-HZSM-5@SiO₂ catalyst dropped below 12%, whereas the double- and triple-bed configurations retained crystallinities of ~65%, which likely contributed to the improved catalyst longevity. These results indicate that the triple-bed configuration provides a promising route for enhancing the stability and efficiency of the direct hydrogenation reaction to generate aromatic compounds from CO₂.

Methylcyclohexane (MCH) stands out as a leading liquid organic hydrogen carrier (LOHC) due to its favorable hydrogen storage capacity and transportability. Despite its potential, advancing catalysts that combine high efficiency, cost-effectiveness, and durability for MCH dehydrogenation to produce hydrogen remains a critical challenge hindering large-scale industrial deployment. Herein, we report the synthesis of highly dispersed and stable bimetallic Pt-MoO_x nanoparticles immobilized on γ-Al₂O₃. The introduction of MoO_x species significantly improves the stability of Pt and results in a high toluene (TOL) selectivity of 99.8 % with MCH conversion of 99.5% and a high hydrogen evolution rate of 470.5 mmol·g_Pt^-1·min^-1 at 340 °C. Moreover, the optimal catalyst exhibits a remarkable long-term stability, with no evident loss of activity in 140-h dehydrogenation reaction at a weight hourly space velocity of 11.7 h^-1. Through detailed in-situ structure analyses, it was revealed that the introduction of subnanometer MoO_x species facilitates the generation of ultrafine Pt nanoparticles with improved resistance to sintering, resulting in enhanced catalytic activity and durability of the noble metal. Furthermore, in-situ spectroscopic characterization demonstrates the positively charged Pt^δ+ species promote the rapid desorption of TOL products. The excellent catalytic performance including high conversion and selectivity and superior stability offers great opportunities for their practical applications in LOHC technologies.