Organic electrosynthesis is particularly appealing for transformations that would otherwise be challenging because of its intrinsic ability to synthesize extremely reactive species under mild conditions via anodic oxidation or cathodic reduction. It has sparked much attention as an effective, environmentally friendly synthesis tool because it generates less waste, uses fewer chemicals, and often requires fewer reaction steps than previous procedures. The processes that underpin organic electrosynthesis include functional group interconversion and formation of C−C and C−heteroatom bonds (such as C−N, C−O, C−S, and C−H) through a controlled electrode potential. Some of the strategies mentioned as aiding the overall process optimization include the use of indirect electrosynthesis, paired electrochemical processes, and electrochemical microreactors. Furthermore, the use of electrochemical flow reactors has resulted in accurate reaction control and optimization. This review discusses strategic developments in organic electrosynthesis, focusing on fundamental concepts, novel approaches, and future directions for sustainable chemical manufacturing.

Upcycling of waste polyethylene into liquid fuels with a narrow molecular-weight distribution presents significant potential for advancing the circular economy. Compared to pyrolysis and catalytic cracking, hydrocracking using bifunctional catalysts offers distinct advantages such as lower reaction temperatures, higher product saturation, reduced CO₂ emissions, and effective heteroatom removal. These benefits position it as a highly promising route for plastic waste valorization. Nevertheless, the intricate reaction mechanisms have hindered the clear understanding on structure-performance relationship. Therefore, the rational design and synthesis of catalysts optimized for specific target products remain a critical challenge. This review focuses on the precise regulation of bifunctional catalyst microstructures (including metal dispersion, metal activity, acid activity, and metal-acid distance) in polyethylene hydrocracking, and further elucidates the structure-performance relationship between catalyst and product selectivity. To better understand the catalyst design strategies, hydrocracking mechanism over bifunctional catalysts is firstly introduced. Next, progress in research to understand the metal sites and acid sites of bifunctional catalysts will be presented. The hydrocracking activities of bifunctional catalysts will also be investigated to demonstrate the metal-acid balance. Finally, the current challenges and future perspectives on optimization, precise design, and practical application of the bifunctional catalysts in polyethylene hydrocracking system will be proposed.

Ru-based oxygen evolution reaction (OER) catalysts exhibit considerable promise for the replacement of Ir-based catalysts due to their high activity and relatively low cost. However, optimization of activity and stability of Ru-based OER catalysts in acidic environment is still a challenging task. Here, we present an optimized amorphous-rutile crystalline heterostructure Ru₃Mn₁O_x-250 catalyst could achieve OER activity with an overpotential of only 211 mV at 10 mA/cm² while maintaining stable operation for at least 1000 h in acidic electrolyte. When the catalyst was used as an anode material in a proton exchange membrane (PEM) electrolyzer, it could deliver an industrial current of 1 A/cm² at 1.65 V (80 °C), outperforming the commercial RuO₂ catalyst (1.82 V). The catalyst can even maintain stable operation at 1 A/cm² for 100 h, showcasing its high OER activity and stability. The experimental and theoretical studies revealed that Mn is atomically dispersed throughout the amorphous-crystalline phases mainly in form of low valence state Mn, forming asymmetric Ru-O-Mn bonds which leads to distorted Oh coordination geometry of Mn with Ru. Such unique microstructure leads to: (1) enhancement of OER activity by reduction of the d band center further away from the Fermi level, weakening the adsorption of oxygen intermediates and accelerating the rate-determining *OOH intermediate formation; (2) enhancement of the catalyst stability by increasing the energy barrier of *RuO(OH)₂ formation, which is the key intermediate for the catalyst dissolution via RuO₄^- formation. This work demonstrates that an amorphous-crystalline heterostructure design strategy is an effective way to overcome the activity-stability trade-off, offering a new approach for the development of efficient OER catalysts stable in acidic electrolyte.

Ruthenium (Ru) is a promising electrocatalyst for the alkaline hydrogen oxidation reaction (HOR), yet it suffers from deactivation at higher potentials due to excessive oxophilicity, which leads to hydroxyl adsorption poisoning. Here, we report a tri-phase heterostructured catalyst (Ru-P25-TiO₂) comprising Ru with anatase (A-) and rutile (R-)TiO₂. This catalyst exhibits remarkable HOR activity, delivering 0.82 mA μg_Ru^-1 along with superior electrochemical stability up to 0.9 V vs. RHE, positioning it as the state-of-the-art electrocatalyst for HOR. This enhanced performance is attributed to the optimized electron distribution and a tailored d band structure at the Ru surface, enabled by strong metal and support interaction, which weakens both hydrogen binding energy and hydroxyl binding energy. The highly oxyphilic P25-TiO₂ facilitates hydroxyl adsorption and establishes a continuous hydrogen-bond network at the catalyst/electrolyte interface, thereby promoting OH⁻ transport and alleviating competitive OH adsorption on the Ru surface. The synergistic interplay between anatase and rutile TiO₂ ideally endows Ru with both superior activity and excellent electrochemical stability. This work not only unravels the intrinsic role of biphasic TiO₂ in tailoring Ru electrocatalysis but also provides a generalizable synergistic heterostructure design strategy for developing efficient and durable electrocatalysts.

Transition metal sulfides (TMSs) are promising electrocatalysts for the oxygen evolution reaction (OER) due to their tunable spin states, diverse metal-sulfur coordination environments, and controllable electronic structures. However, their structural instability under anodic conditions remains a critical challenge. In particular, the mechanisms governing active-phase formation and the identification of true catalytically active sites during surface reconstruction require further investigation. Herein, we report a cubic, self-assembled FeCoS₂/FeS₂ heterostructure catalysts. Through sulfur doping and electrochemical activation-induced surface reconstruction, the catalyst achieves 10 mA cm⁻² current density at an overpotential of only 287 mV in 1.0 mol L⁻¹ KOH after 1000 cycles. Experimental and in-situ spectroscopy analyses reveal that the heterogeneous interface enhances electron transfer, while dynamic reconstruction generates a highly active metal (oxy)hydroxide phase as the primary catalytically active species. This work provides mechanistic insights into the surface reconstruction of TMSs, and offers a viable strategy for designing efficient and durable non-noble metal electrocatalysts.

Developing highly efficient and robust Pt-based electrocatalysts for oxygen reduction reaction (ORR) remains a substantial challenge due to the sluggish kinetics of proton-coupled electron transfer (PCET) process. Herein, an effective innovation strategy involves the rational construction of supported high-entropy intermetallics (HEIs) Pt₄FeCoNiSn, and its coupling with the ionic liquid [MTBD]⁺ is developed to simultaneously facilitate PCET steps of ORR. The anchoring effect of the substrate Co-NC and the induction effect of Sn atom conspicuously promote the formation of ordered Pt₄FeCoNiSn intermetallics at lower temperature. The multiple electron effects of HEIs and strong metal-support interactions enable Pt₄FeCoNiSn/CoNC with the half-wave potential (E_1/2) of 0.906 V in 0.1 mol L^-1 HClO₄ solution and 0.958 V in 0.1 mol L^-1 KOH solution, and long-term stability over 70 K cycles. Further [MTBD]⁺ modification of electrocatalyst leads to the enhancement in ORR performance, where the [MTBD]⁺ promotes the accumulation of reaction intermediates and increases the proportion of weakly hydrogen-bonded water at the electrode-electrolyte interface, thereby accelerating proton transfer rate during the ORR process. The Zn-air battery assembled by Pt₄FeCoNiSn/CoNC as oxygen electrode exhibits a high maximal power density of 190.2 mW cm^-2 at current density of 279.4 mA cm^-2, superior to those of Pt/C.

The electrocatalytic CO₂ reduction reaction (CO₂RR) offers a promising sustainable route for producing high-value C₂₊ chemicals and fuels by using renewable electricity. However, boosting C₂₊ product yields has been significantly hindered by insufficient *CO intermediate generation in confined spaces and limited activity of sites for subsequent hydrogenation and C-C coupling processes. Herein, we introduce an efficient strategy that involves carbene dual-function bridging of Ag-Cu sites to enable *CO pooling and facilitate *COCHO coupling. As a result, a remarkable C₂₊ Faradaic efficiency of 80.3% at 400 mA cm^-2 was achieved. In-situ surface-enhanced Raman spectroscopy, in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy, and density functional theory calculations collectively uncover the underlying mechanism. Carbene facilitates CO spillover from Ag to Cu sites, modulates the electronic structure of Cu, stabilizes CO intermediates, and reduces the energy barrier for CO hydrogenation. These effects synergistically enhance C-C coupling, thereby improving the Faradaic efficiency for C₂₊ product formation.

Producing high-purity hydrogen through water electrolysis offers a promising eco-friendly alternative to fossil fuels. However, the anodic oxygen evolution reaction (OER) poses significant challenges in practical applications due to its sluggish kinetics. In contrast, the hydrazine oxidation reaction (HzOR), which operates at a much lower theoretical potential (−0.33 V vs. RHE) compared to OER (1.23 V vs. RHE), has emerged as an attractive substitute for more energy-efficient hydrogen production. Developing efficient bifunctional electrocatalysts for both HzOR and hydrogen evolution reaction (HER) is critical for scaling up energy-efficient hydrazine-hydrate-assisted hydrogen production. Nevertheless, the lack of viable catalyst design strategies has hindered their widespread applications. In this study, comprehensive density functional theory calculations were employed to explore the catalytic potential of defect-engineered and Pt-doped CoX (X = P, S, As, Se) materials. Our results reveal that several modified CoX materials exhibit exceptional catalytic activity for HzOR. Notably, CoSe-v-Pt stands out with an ultralow ΔG_PDS of 0.24 eV for HzOR along with excellent HER performance, demonstrating its potential as a highly effective bifunctional catalyst. The enhanced catalytic activity is attributed to electronic reconfiguration induced by structural modification, which optimizes the adsorption and reaction dynamics of N₂H_y intermediates and hydrogen at the Co active sites. This study provides a new avenue for designing high-performance HzOR and HER catalysts, paving the way for an energy-efficient, environmentally friendly, and highly effective electrocatalytic hydrogen production.

Operating hydrocarbons on protonic ceramic fuel cells (PCFCs) is promising and attractive, on account of their high energy conversion efficiency and potential for low carbon emissions compared to traditional thermal power generation. However, poor coking tolerance and insufficient catalytic activity at intermediate temperatures greatly hinder the development of PCFCs on hydrocarbons. Exploring a catalytic layer with high activity and durability is an effective way to achieve high-performance PCFCs on hydrocarbon fuels. Herein, we report an anode catalytic layer (ACL) with an optimized formula of Pd_0.01Ni_0.09Ce_1.9O_2-δ (P1NC). Pd-Ni alloy nanoparticles are exsolved from the ACL under a hydrogen atmosphere. The high oxygen vacancy concentration in P1NC has shown a positive effect on the oxygen storage capacity, which may facilitate carbon gasification, thereby reducing performance degradation during PCFC operation, as supported by the Raman and scanning electron microscopy observations. PCFCs with this ACL achieved a decent peak power density (P_max) of 1.20 W cm^-2 and stably operated at 0.2 A cm^-2 at 650 °C on CH₄. In addition, the cells with P1NC ACL exhibited encouraging P_max of 1.00 and 0.87 W cm^-2 at 650 °C on liquid fuels such as methanol and ethanol, respectively, exhibiting good fuel flexibility.

Electrocatalytic N₂ reduction reaction (eNRR) is a green and sustainable approach for producing ammonia. Herein, we synthesized a Ag_2-Ag_NPs@C catalyst by coupling dual-atom Ag sites (Ag₂) and Ag nanoparticle (Ag_NPs) on the carbon support, which exhibits excellent eNRR performance, with a high NH₃ yield rate of 139.9 μg h^-1 mg^-1_cat. and an outstanding Faradaic Efficiency of 74.2%, which are superior to those of most reported eNRR catalysts. Density functional thoery calculations and in-situ infrared spectroscopy analysis demonstrate that in Ag₂-Ag_NPs@C catalyst, Ag_NPs facilitate water dissociation to produce H* intermediate that supplies to adsorbed *N₂ on the Ag₂ site for promoting the formation of *NNH key intermediate, thus lowering the Gibbs free energy of rate-determining step and substantially enhancing the eNRR performance. This work opens up new avenues for developing efficient electrocatalytic nitrogen reduction catalysts via synergistic effect.

The rational design of high-performance electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is significant to the widespread commercialization of alkaline exchange membrane fuel cells. However, precise regulation of proton adsorption states and interfacial transfer kinetics at the catalytic interface remains a significant challenge in advancing HOR under alkaline conditions. Herein, we demonstrate that construction of phosphorus-doped carbon-coated nickel (Ni) catalyst (Ni@PC) featuring the bridging oxygen structures (Ni-O-C/P) enables rapid desorption of adsorbed hydrogen species and dynamic reconstruction of interfacial hydrogen-bond network. Density functional theory calculations reveal that the Ni-O-P configuration induces a downward shift in the d-band center of Ni, thereby weakening hydrogen binding energy (HBE). Furthermore, the bridging oxygen atoms facilitate the formation of hydrogen bonds with interfacial water molecules, optimizing the proton transfer pathway. In-situ surface-enhanced infrared absorption spectroscopy confirms that the Ni-O-P structure effectively converts weakly hydrogen-bonded water into strongly hydrogen-bonded water, enhancing the connectivity of hydrogen-bond network and facilitating efficient proton transfer. This work successfully achieves optimization of proton dynamics during the alkaline HOR progress, while also providing a strategic framework for the rational design of advanced carbon-coated electrocatalysts.

The development of functional interfacial microenvironments via polymer coating modification offers a promising strategy for enhancing electrocatalytic reactions. However, conventional polymer modification typically relies on physical approaches such as drop-coating or spraying, which often suffer from issues such as uneven distribution and limited controllability. In this study, we introduce a novel approach that leverages the direct metal-catalyzed cleavage of diazo compounds to initiate carbene polymerization, enabling the in-situ growth of functional polymers on the Cu surface. By employing this method with three different diazo monomers, we fabricated distinct carbene polymer (CP) modification layers on a Cu electrode surface and investigated their influence on the electrocatalytic CO₂ reduction reaction. Our findings demonstrate that Cu electrodes modified with CP derived from phenyl diazo compounds exhibit a substantial improvement in C₂₊ production (primarily ethylene). In-situ Raman spectroscopy analysis revealed that CP modification effectively reduced the interfacial H₂O content and increased the *CO intermediate coverage, thereby facilitating C-C coupling and enhancing ethylene production. This study highlights the potential of surface polymerization for constructing functional interfacial microenvironments to control electrocatalytic reactions.

This study developed a lattice-matching engineering strategy to construct atomic-level coherent interfaces in hexagonal WO₃/TiO₂ S-scheme heterojunctions to boost photoelectrocatalytic glycerol (Gly) valorization. Through precise annealing control, hexagonal WO₃/TiO₂ achieved an ultra-low lattice mismatch (m) of 0.027%, significantly lower than the 2.30% mismatch of its monoclinic counterparts, thus inducing a strong built-in electric field (3.71 eV) and optimized S-scheme charge transfer. These features resulted in 90% suppressed carrier recombination, 2.64-fold extended carrier lifetime, and enhanced secondary hydroxyl adsorption affinity (1.854 eV), collectively steering Gly oxidation toward high-value dihydroxyacetone with 35% selectivity (1.9-fold higher than that of monoclinic systems). The heterojunction also delivered a 21% Gly conversion rate (40% higher than its monoclinic counterparts), while maintaining > 85% total C3-product selectivity and stability over 40 h. This study identified the atomic-scale interface coherence as a critical factor for synchronizing charge dynamics and surface reactions in biomass upgrading.

Enhancing the carrier separation efficiency and charge transport properties of polymeric carbon nitride (PCN) has been a major focus of research. Extensive interest has been directed toward its modification and functionalization. In this study, a molten-salt approach was employed to simultaneously introduce cationic (K⁺) and anionic (-C≡N) species, enabling the one-step synthesis of highly crystalline PCN with significantly improved carrier separation and charge transport efficiencies. Comprehensive experimental characterization and theoretical calculations reveal that the coupling interaction between the cations and anions substantially increased the localized charge distribution, thereby facilitating exciton dissociation. Moreover, the incorporation of -C≡N and K⁺ ion pairs enhanced the adsorption and activation of O₂, driving the two-electron oxygen reduction reaction (2e^- ORR) to produce H₂O₂, exhibiting a remarkable 46.6-fold increase over unmodified PCN. This work provided valuable insights into the critical role of cation-anion pairs in enhancing exciton dissociation, paving the cost-effective way for photocatalysts toward efficient solar energy conversion and high-value-added chemicals artificial photosynthesis.

Heterogeneous Fenton-like systems provide sustainable water-purification solutions; however, improving their catalytic efficiency and recyclability remains challenging. We developed a facile strategy to prepare an FeNi nanoparticle (NPs)-coupled single-atom site catalyst ((FeNi)_NPs,SAs-N-C)), which exhibits a strong synergy between FeNi NPs and monodisperse Fe/Ni active sites. This catalyst effectively activates peroxymonosulfate (PMS) at low concentrations (0.2 mmol/L), generating abundant reactive oxygen species. Under the condition of continuous flow, the optimized system achieved over 99% sulfamethazine degradation within 3000 min, with a kinetic rate constant (k = 1.5758 min^-1) that is 16, 17, and 7 times higher than those of MIL-88B(Fe), MIL-88B(Fe,Ni) and Fe_NPs,SAs-N-C, respectively. Mechanistic studies showed that PMS activation occurs via a nonradical pathway dominated by singlet oxygen (¹O₂) and direct electron transfer, enhancing the resistance to interference from inorganic anions and natural organic matter. Density functional theory calculations showed that FeNi NPs donated electrons to affect the d-orbitals in Fe single-atom sites, enhancing their interaction with PMS to produce ¹O₂ and enable electron transfer. This study presents a viable method for creating efficient NPs coupled with single-atom site catalysts for environmental clean-up.

Photocatalytic hydrogen peroxide (H₂O₂) production offers a green alternative to the traditional anthraquinone process but remains limited by inefficient charge separation and underutilized photogenerated holes. Herein, we present a spatially resolved coordination strategy to couple efficient H₂O₂ generation with selective oxidation of biomass-derived hydroxy acids. Anisotropic Au-modified BiVO₄ photocatalysts were constructed, where Au nanoparticles on the (010) facet promoted H₂O₂ formation, while undercoordinated Bi atoms on the (110) facet selectively oxidized citric acid (CA). A five-membered chelate ring formed between β-hydroxyl and carboxyl groups of CA and surface Bi atoms, enabling directional coordination that enhanced hole extraction and guided a selective decarboxylation pathway to produce acetone dicarboxylic acid with 99% selectivity. This dual-functional design achieved a high H₂O₂ production rate (~0.6 mmol L^-1 h^-1) and exhibited broad applicability to other hydroxy acids. This work provides mechanistic insights into photocatalyst-substrate interactions and establishes a generalizable strategy for integrating H₂O₂ photosynthesis with value-added chemical production under solar irradiation.

Cleavage and reassembly of C-C bonds is a fascinating and challenging strategy to forge complex high-value molecules in an atom- and step-efficient manner. Herein, we disclose a photoredox-catalyzed four-atom skeletal editing strategy, enabling highly selective reassembly of 1,3-diketones into architecturally distinct acylated 1,5-ketoalcohols with excellent atom, step, and redox economy. Notably, this propoxy insertion unit (i.e., three sp³-hybridized carbons and one oxygen atom) is derived from the other two simple and readily available starting materials (i.e., alkene and aldehyde). Experimental studies have elucidated the key intermediate (lactol) and reaction mechanism (radical-radical crossover cyclization/rearrangement), which are distinct from classical De Mayo reaction. More importantly, the rapid construction of high-value-added product γ,δ-unsaturated ketones and dihydropyrans is also achieved via photocatalytic synthesis of acylated 1,5-ketoalcohols/Lewis acid-promoted Wagner-Meerwein rearrangement cascade and photocatalytic formal [2+2+2] annulation/MsCl-promoted elimination cascade, respectively.

Sluggish Fe(III)/Fe(II) cycling and inefficient two-electron H₂O₂ production severely limit the practicality of conventional photocatalytic Fenton systems. In this study, we present a metal-free pyridine-based covalent organic framework (TpBpy-COF) that enables a highly efficient and self-sustaining photo-Fenton process. The system is designed to integrate dual-path H₂O₂ production—through oxygen reduction reaction (ORR) and water oxidation reaction (WOR), along with interfacial Fe(III) reduction. Electron-rich dual-pyridinic nitrogen (μ-N,N) bridging sites facilitate Fe(III)/Fe(II) redox cycling and direct 2e^- ORR, while β-ketoenamine-linked benzene units promote 2e^- WOR, working synergistically to enable continuous in situ H₂O₂ generation. This cooperative mechanism leads to outstanding water purification performance, including rapid degradation of pharmaceuticals (e.g., caffeine), complete microbial inactivation, and robust stability across diverse real water matrices. In-situ spectroscopy and density functional theory calculations elucidate the atomic-scale synergy: pyridinic-N sites selectively reduce Fe(III) and activate O₂, while β-ketoenamine-linked benzene units oxidize water via spatially decoupled charge transfer, collectively enabling autonomous Fenton cycles. This work pioneers a self-sustained Fenton paradigm through a metal-free COF architecture that synergizes dual-path H₂O₂ generation and autonomous Fe(III)/Fe(II) cycling, offering a solar-driven platform for eco-adaptive water purification with negligible reliance on exogenous reagents or energy inputs.

Achieving efficient photocatalytic CO₂ reduction using H₂O as a hydrogen source requires the synergistic optimization of both charge and proton transfer between CO₂ reduction and H₂O oxidation half-reactions. However, conventional studies mostly focused on enhancing these half-reactions independently, overlooking the intrinsic interdependence between them. Herein, this work develops a photothermal catalyst (denoted as Pd_1+c/3DOM-In₂O₃) through engineering synergistic Pd single atoms (Pd₁) and Pd clusters (Pd_c) in three-dimensional ordered macroporous (3DOM) In₂O₃ framework. The mechanistic study reveals that the coexistence of Pd single atoms and clusters not only offers synergistic active sites to promote the reaction of CO₂ and H₂O, but also substantially improves the separation and transfer efficiencies of photogenerated electrons and holes. The Pd clusters facilitate H₂O dissociation to ensure an adequate supply of active hydrogen species as well as synergistically enhance the adsorption and activation of CO₂ at Pd single-atom sites. Furthermore, the enhanced photoabsorption in visible and near-infrared regions, attributed to the localized surface plasmon resonance of Pd clusters, leads to a significant increase in catalyst temperature under simulated solar irradiation. The integration of photocatalysis with the photothermal effect affords an intensified driving force for the selective conversion of CO₂ and H₂O into CO, thereby accelerating the reaction kinetics of the overall photocatalytic CO₂ reduction process. As a result, the Pd_1+c/3DOM-In₂O₃ catalyst exhibits excellent performance for solar-driven CO₂ reduction with H₂O vapor, achieving a remarkable CO production rate of 192.52 μmol g^-1 h^-1, which is 19.8-fold and 12.2-fold higher than those of pure 3DOM-In₂O₃ and Pd₁/3DOM-In₂O₃, respectively. This study provides valuable insights into the synergistic effect of metal single atoms and clusters toward both efficient photocatalysis and photothermal effect for solar-driven CO₂ reduction.

Sustainable biomanufacturing depending on CO₂ conversion contributes to mitigate global dependence on fossil fuels and accelerate a future green economy. However, CO₂ conversion is limited by inefficient CO₂ fixation pathways, deficient capacity for regenerating reducing power and energy, and narrow product scope. Here, a light-powered CO₂ fixation biosystem (LCFB) was developed by coupling a new-to-nature Pyruvate decarboxylase/Malic enzyme (PM) cycle for CO₂ fixation with natural thylakoid membranes for regenerating energy and reducing power. This synthetic LCFB was able to convert CO₂ to organic molecules at a rate of 2.37 nmol min^-1 mg^-1 proteins comparable to that of natural CO₂ fixation system. Further, LCFB was programmed to extend the length of carbon chain for outputting multi-carbon chemicals by designing and constructing multiple anaplerosis CO₂ fixation pathways in a plug-and-play fashion. Finally, the programmed LCFB powered by light facilitated the direct biosynthesis of multi-carbon chemicals from CO₂, such as alcohols, aldehydes, organic acids and amino acids. This study presented here brings a potential avenue for developing a carbon-negative versatile platform to widen the applicability of LCFB and advancing sustainable biomanufacturing in the future.

Cocatalyst loading has been extensively adopted in photocatalysis for enhancing photocatalytic performance. However, the sluggish interfacial charge dynamics between cocatalyst and photocatalyst has restricted the wide applications of such a strategy. Herein, we introduce the Ni-N interfacial bonds between lamellar nitrogen-vacancy-rich g-C₃N₄/CoNi₂S₄ nanoparticles (CN-V_N/CoNi₂S₄) composite material to bridge the photogenerated charge carrier separation at their interface. Specifically, extended X-ray absorption fine structure analysis reveals that these Ni-N interfacial bonds are originated from the bonding of CoNi₂S₄ with the nitrogen atoms adjacent to the nitrogen vacancies (V_N) in g-C₃N₄. Experimental evidence and theoretical calculations reveal that Ni-N interfacial bonds cannot only cause an intimate contact interface between CN-V_N/CoNi₂S₄, but also modulate the charge distribution on the CN-V_N and CoNi₂S₄, further boosting the photogenerated charge carrier separation. More interestingly, this tailored interfacial microenvironment significantly reduces the energy barrier for key intermediates formation while modulates the rate-determining step from *COOH generation to CO desorption, enabling efficient and controllable CO production. This work establishes a methodological framework for engineering advanced photocatalysts, enabling high-efficiency conversion of solar energy into clean fuels.

The green photocatalytic synthesis of hydrogen peroxide (H₂O₂) has attracted considerable attention as an environmentally friendly approach for H₂O₂ production. However, the rapid recombination of photogenerated charge carriers, reliance on sacrificial agents, and low activity and selectivity of photocatalytic H₂O₂ remain major challenges for the further development of this process. In this study, we synthesized an S-scheme composite photocatalyst composed of N-vacancy-tailored, sulfur-modified graphitic carbon nitride (Vr-CNS) and Zn₂In₂S₅ (ZIS) that enabled solar-driven H₂O₂ synthesis, achieving a rate of 475.6 μmol g^-1 h^-1 in pure water and air without sacrificial agents. This represents a five-fold enhancement over pristine graphitic carbon nitride (g-C₃N₄). S-doping mainly altered the electronic structure of g-C₃N₄, resulting in bandgap narrowing and a redshift of the absorption edge. N vacancies (N_V) not only promoted charge separation and reduced charge transfer resistance, but also accelerated surface reactions. Moreover, N_V lowered the energy barrier due to O₂ adsorption, which is the rate-determining step, thereby accelerating the reaction. The S-scheme Vr-CNS/ZIS heterojunction retained the strong reduction ability of Vr-CNS and robust oxidation capability of ZIS. The presence of N_V strengthened the electronic coupling between Vr-CNS and ZIS after heterojunction contact. The synergistic effect of defect engineering (sulfur doping coupled with nitrogen vacancies) and the S-scheme accelerated the reaction kinetics, promoting the migration and separation of the photogenerated carriers. This study provides an effective strategy for the design of multifunctional photocatalysts by exploiting the synergy between defect engineering and S-scheme heterojunctions.

Catalytic decomposition of ozone is considered as one of the most effective, economically viable, and promising strategies for ozone abatement. In a number of oxide-supported Ag catalysts, manganese oxide-based catalysts have been identified with superior activities, but there are still challenges for Ag sintering and competitive adsorption of water under humid conditions, which strongly hinder their catalytic performances. Herein, we prepared a pure silica Beta zeolite supported Ag-Mn catalysts (Ag-Mn/Beta-Si), exhibiting excellent catalytic properties in the decomposition of ozone, which is reasonably attributed to the in-situ formed AgMnO₂ on the pure silica Beta zeolite, where the formed AgMnO₂ as a new active site prevents the sintering of Ag NPs and the hydrophobicity of the pure silica Beta zeolite is favorable for hindering water adsorption on the active sites under humid conditions. These hypotheses have been evidenced by theoretical simulations of the mean square displacement and diffusion coefficient of water molecules and experimental results of sample transmission electron microscopy images.

Zeolites are important components of catalysts for aromatics synthesis from methanol and CO/CO₂. Although generally attributed to their confinement effects, the key reaction steps and the role of methanol or other C1 intermediates remain unclear. Herein, extensive first principles calculations were performed to reveal the mechanism of aromatics formation from light olefins such as propene and methanol within H-ZSM-5 zeolites. Propene was found to undergo chain growth, ring formation, and ring methylation, resulting in various aromatics. Our calculations show that the above steps become increasingly more difficult, so aromatic ring methylation by methanol to form protonated polymethylbenzenes was the most challenging. This can largely be attributed to both the zeolite confinement effect due to the higher spatial demand for the methylation of the aromatic ring than that of the carbon chain by methanol, and the disruption of its aromaticity. Our prediction agrees with the experimentally observed delayed formation of aromatic species, and also explains the improved production of specific aromatics by co-feeding aromatic species to change the hydrocarbon pool composition and suppress the chain growth. Thus, theoretical insights can enable the rational design of better catalysts and processes for the valorization of C1 molecules.

Crystal plane engineering is a powerful tool to optimize catalytic efficiency in heterogeneous catalysis. However, there is a surprising dearth in the exploration of the support plane effect on glycerol hydrogenolysis to 1,3-propanediol (1,3-PDO). In this work, we synthesized prism-shaped rutile TiO₂ nanorods (RTNR-T) with tunable {110}/{111} exposure ratios by varying the hydrothermal temperature. The proportion of the {110} planes is identified to exhibit a volcano-like relationship with the hydrothermal temperature. The concentrations of oxygen vacancies and Ti³⁺ sites on both the RTNR-T nanorods and Pt-WO_x/RTNR-T catalysts are positively correlated with the proportion of the {110} planes. Coherently, the Pt dispersion and surface acidity on the catalysts are parallel to the proportion of the {110} planes, attributable to the high defect density that facilitates the anchorage of Pt and promotes WO_x-support interaction. In glycerol hydrogenolysis, the Pt-WO_x/RTNR-453 catalyst with the highest proportion of the {110} planes displayed the best catalytic performance, with glycerol conversion and 1,3-PDO selectivity of 96.7% and 60.6%, respectively, affording an outstanding 1,3-PDO yield of 58.6% and excellent recyclability. Density functional theory calculations demonstrated that the presence of defects markedly reduced the dissociation and diffusion barriers, which greatly boosts hydrogen spillover to WO_x for in-situ Brönsted acid site generation and oxocarbenium intermediate hydrogenation. This work offers a robust design principle based on the crystal plane-defect-activity correlation for high-performance glycerol hydrogenolysis catalysts.

Oxide supports are well known to significantly influence the structure and properties of active oxide overlayers through strong oxide-support interactions. However, the effect of oxide overlayers on the underlying active oxide substrates remains poorly understood. Here, we report the controllable formation of ceria (CeO₂) overlayers on a hematite (Fe₂O₃) surface (CeO₂/Fe₂O₃) via a melting-wetting method. Submonolayer CeO₂ patches facilitate the partial reduction of surrounding Fe₂O₃ to active magnetite (Fe₃O₄) while effectively suppress further reduction of Fe₃O₄ to inactive metallic iron (Fe⁰) under harsh high-temperature water-gas shift (HT-WGS) conditions. We demonstrate this stabilization effect of surface oxide patches (MO_x, M = Ce, Cr, Mn, Mg, Al and Zn) on surrounding active Fe oxide sites via creating a shielding zone around each oxide patch. As a result, Fe₂O₃ catalysts covered with a small amount of CeO₂ surface overlayers (~1.8 wt%) exhibit remarkable stability at 450 °C for over 100 h, in contrast to rapid deactivation observed in pure Fe₂O₃ and industrial iron-chromium (6.5 wt% Cr) catalysts. Building on these findings, we have developed an advanced HT-WGS process that utilizes Cr-free catalysts and significantly reduces steam consumption. This study highlights the critical role of surface oxide overlayers in modulating the redox behavior and reactivity of underlying active oxide substrates, developing an interface confinement strategy for the design of robust and efficient oxide catalysts.

The metal-acid bifunctional catalyzed conversion of furfurals to linear ketones is crucial but challenging for sustainable chemical synthesis owing to the tendency for over hydrogenation and overacid-catalyzed reaction pathways over traditional catalysts. Herein, ruthenium-tungsten (RuW) alloy nanoparticle-supported catalysts (such as, RuW/SiO₂, RuW/Al₂O₃, RuW/C) were prepared via incipient wetness impregnation followed by H₂ reduction, showing a cascade hydrogenation-ring opening transformation of furfural to 5-hydroxy-2-pentanone with an unprecedented yield of 86.2% at a mild temperature of 80 °C. Catalytic mechanism studies confirmed that hydrogen spillover from RuW alloy sites to WO_x sites generated H⁺-H^- pairs in situ, which functioned as atypical active sites for the furfural hydrogenation step and offered Brönsted acidic sites for the ring opening of furan alcohol, thereby facilitating the facile preparation of 5-hydroxy-2-pentanone. Furthermore, the catalyst exhibited broad applicability for synthesizing linear ketones from various furfurals (i.e., 5-methyl furfural and 5-hydroxymethyl furfural). This study demonstrated interesting bifunctional catalysis through harnessing hydrogen spillover to form transient H⁺-H^- pairs, enabling a challenging cascade reaction pathway toward an efficient linear ketone synthesis.

Natural gas vehicles (NGVs) offer significant environmental advantages by reducing pollutant emissions, but effective exhaust treatment remains a challenge due to high methane emissions and catalyst deactivation over time. This study introduces a core-shell Pd@CeO₂/Al₂O₃ three-way catalyst (TWC) designed to enhance the efficiency and durability of NGV exhaust treatment. The core-shell structure significantly improves catalytic performance. The optimized Pd@Ce/Al (S-500) catalyst demonstrates excellent low-temperature activity, with T₅₀ values of 336 °C for CH₄ and 397 °C for NO. It also achieves remarkable reductions of 113 and 177 °C in the T₉₀ for CH₄ and NO conversion, respectively, compared to the non-core-shell counterpart, Pd-Ce/Al (S-500). Characterizations reveal enhanced metal-support interactions, increased oxygen vacancies, and optimized Pd-CeO₂ interfaces as key active sites. Density functional theory calculations further demonstrate that the core-shell structure facilitates electron transfer at Pd-CeO₂ interfaces and lowers energy barriers for three-way reactions, enhancing catalytic efficiency. Notably, the core-shell Pd@Ce/Al (S-500) catalyst maintains high conversion efficiency for CH₄ and NO, with only slight losses (5.5% and 6.6%, respectively) over a 100-h time-on-stream stability test, following 16 h of harsh hydrothermal aging at 800 °C, showcasing its long-term stability. These findings provide a deeper understanding of the role of the core-shell Pd@CeO₂ structure in Pd-based TWCs and offer valuable insights for designing durable and efficient catalysts to meet the stringent emission standards of NGVs.

NvfI, a 2-oxoglutarate (2OG)-dependent non-heme Fe(II) dioxygenase, catalyzes the formation of endoperoxide-containing fumigatonoid A, a key step in the biosynthesis of novofumigatonin. However, the molecular mechanism underlying these processes remains elusive. To address this, extensive MD simulations and QM/MM calculations were performed. Our computational study suggests that the nascent Fe(IV)-oxo species is not able to conduct the H-abstraction from the target C13-H directly. Instead, the Fe(IV)-oxo species performs the H-abstraction from the proximal C7′-H, and the resulting C7′-centered radical can serve as the radical relay for the further oxidation of the distal C13-H bond. Such radical relay mechanism not only remarkably reduces the barrier for the activation of the distal C13-H bond, but also efficiently prevents the undesired OH-rebound pathway. Regarding the final OH-rebound at the C3′ site, our study suggests that the dynamic reorganization of the active site reduces the distance between the substrate radical and the Fe(III)-OH, facilitating the efficient OH-rebound at the C3′ site. These computational findings offer valuable insights for NvfI-catalyzed biosynthesis of endoperoxide.