Salt precipitation remains a persistent barrier to industrial CO₂ electrolysis. This Perspective analyzes transformative breakthroughs in acidic systems, elegantly connecting Sargent’s cation-focused interface engineering, Xia’s robust catalyst/reactor design, and Wang’s revolutionary acid humidification strategy into a cohesive industrial pathway. Based on this, we propose that integrating these approaches, combining acid-humidified feeds with durable catalysts and reactor designs, could establish a scalable route to industrial CO₂ electrolysis deployment powered by renewable electricity.

Photoelectrochemical (PEC) water splitting efficiently produces chemical fuels, yet persistent efficiency bottlenecks impede widespread deployment despite documented advances. In recent years, the introduction of external physical fields has emerged as a promising technique to remarkably improve the PEC performances of semiconductors both internally and externally. This review presents an in-depth exploration of the mechanisms underlying the utilization of thermal field (photothermal, pyroelectric effect), piezoelectric field (strain piezoelectricity, ferroelectric polarization), magnetic field (negative magnetoresistive effect, lorentz forces, spin polarization), and coupled fields in enhancing the synergistic effects of PEC water splitting, and subsequently analyzes their influence on the performance of PEC systems. It particularly emphasizes the underlying mechanisms that facilitate the strengthening of external fields on the excitation, transfer, and separation of carriers, as well as the enhancement of surface reactions. Additionally, we delve into the expansive prospects of externally assisted PEC water splitting, examining both its fundamental research implications and practical applications. Finally, we discuss the challenges encountered in its development and offer insights into potential future directions.

Iron-group transition metal chalcogenides (IGTMCs) have emerged as promising electrocatalysts due to their tailorable electronic structures through composition engineering. This review summarizes the recent advancements in multi-component regulatory strategies employed in advanced IGTMC electrocatalysts, including anion substitution, cation doping, and the incorporation of zero-valent elements. Particular emphasis is placed on the roles of secondary and tertiary doping configurations, and chalcogen modulation in enhancing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) of IGTMC electrocatalysts. Thus, regulating the electronic structure and optimizing the adsorption strengths on this family of materials are strategies to boost catalytic kinetics. Notably, dynamic surface reconstruction (e.g., oxidation) of IGTMC electrocatalysts during the OER has recently attracted significant attention. Advanced in-situ/operando characterization insights into reconstruction phenomenon of IGTMC electrocatalysts for OER process are critically analyzed. Finally, the challenges and prospects of IGTMC electrocatalysts for ORR/OER electrocatalysis are outlined.

Selective hydrogenation is crucial in various chemical processes and environmental applications, where precise control of reactivity and selectivity is essential for the efficient production of high-purity products. Single-atom catalysts (SACs), with atomically dispersed metal sites, could bridge homogeneous and heterogeneous catalysis and have emerged as a transformative platform for highly efficient selective hydrogenation with minimal use of critical raw materials as catalysts. This review explores the latest advancements in this cutting-edge area. Specifically, we analyze the structure-activity relationships, such as catalytic properties and mechanisms that determine the reactivity and selectivity of such catalytic systems. Furthermore, we discuss challenges, including stability, synthesis scalability, coordination environment tuning, atomistic modeling, and mechanistic insights, while identifying research opportunities for optimizing SACs performance. If these challenges are addressed, SACs hold the potential to revolutionize selective hydrogenation processes, offering sustainable and highly efficient catalytic solutions for industrial applications.

The severe hazard of volatile organic compounds (VOCs) makes their decomposition technology a key topic research. Catalytic oxidation is an efficient and environmentally friendly strategy for removing VOCs. The metal oxide catalysts dominate VOCs oxidation reactions, owing to their cost-effectiveness, robust redox properties, tunable crystal structures, and excellent operational stability. Thus, designing high-performance metal oxide catalysts is important. This review systematically summarized the recent advances in constructing highly efficient active metal oxides, with emphasis on representative preparation method, the structure performance relationship, and the reaction mechanism of different types VOCs. Finally, the remaining challenges for creating metal oxide catalysts in practical applications are discussed.

With the continuous advancement of the industrialized methanol-to-olefins (MTO) process and a profound understanding of its mechanism, designing MTO catalysts to enhance light olefin yields and flexibly regulate product distribution has emerged as a significant challenge. Data-driven modeling allows chemists to anticipate reaction trends and outcomes. However, for models to be instructive for specific chemical issues, chemists must collect experimental data, encode the relevant variables and retrain specialized models. In this work, we demonstrate how to use a machine learning (ML) workflow to discover a potential MTO zeolite catalyst. An MTO database was built, on which over 20 types of ML models were trained, followed by their evaluation and experimental validation. The decision rules for high selectivity were extracted, facilitating the targeting of potential MTO catalysts and the understanding of MTO reaction mechanism. A rapid prediction of optimal MTO evaluation conditions and results for a given zeolite catalyst was also realized, greatly saving the cost of trial and error. In particular, a special MTO catalyst with high initial ethene selectivity over 60% was found, demonstrating the effectiveness and capability of ML techniques.

Precisely controlling acid center position in zeolites is still challenging. Pentene monomolecular cracking offers an ideal route to maximize ethylene and propylene yields simultaneously. To reveal the relationship between acid site distribution in FER-zeolite and pentene monomolecular cracking activity, this study proposes a novel strategy integrating pyridine pre-adsorption with K⁺ exchange modification to selectively shield acid sites within FER cages, while phosphorus modification is employed to selectively passivate acid sites in 10-MR channels and on the external surface. Adsorption infrared (IR) spectroscopy (CD₃CN-IR, Py-IR, and 2,6-DMPy-IR), and OH-IR characterization verified the selectivity and efficiency of these modification process. FER zeolites with distinct acid site distributions exhibit typical monomolecular cracking characteristics in pentene cracking, where the pentene cracking activity is linearly related to the acid density in the 10-MR channel and independent of the FER cage acidity. This result identifies 10-MR channel as primary pentene monomolecular cracking reaction position for the first time, providing a theoretical basis for designing zeolite catalysts that maximize ethylene and propylene production. The synergistic application of the pre-adsorption-K⁺ exchange modification strategy using different size basic molecules and phosphorus modification will provide an effective approach for precise control of acid site locations in zeolites with diverse pore/cavities architectures.

Electric fields play a pivotal role in renewable energy technologies and are essential for enabling a sustainable future. However, the regulation of macroscale catalytic behavior by electric fields has not been well digitally understood yet, as conventional computational models rely on reaction energy profiles that overlook the nonlinear effects of electric fields on elementary reaction steps. Here, we use advanced constant-potential microkinetic simulations to revisit the electrochemical nitrogen reduction reaction (eNRR) under operating conditions, which makes it possible to explicitly integrate both electrochemical and chemical steps and quantitatively predict the effects of electric fields on eNRR macroscale performance. The theoretical activity trends for different metals were successfully reproduced with our model, which are in good qualitative agreement with experimental observations. Furthermore, we propose a new theoretical protocol for eNRR catalyst screening, where an optimal catalyst should exhibit overwhelming N₂ adsorption ability over a wide potential range to sufficiently facilitate eNRR at high potentials. Interestingly, the rate-determining step undergoes dynamic evolution with potential variations, with chemical steps imposing fundamental constraints on practical ammonia (NH₃) electrosynthesis. Microkinetic simulations demonstrate that incorporating ^*NH₃ desorption steps can alter reaction rates by orders of magnitude, highlighting their critical yet often overlooked role. This work establishes a quantitative framework for achieving accurate, physically realistic theoretical simulations in heterogeneous electrochemistry.

In order to attain high catalytic activity and long-term stability in the oxygen evolution reaction (OER), it is essential to design catalysts with hollow structures that integrate both the adsorbate evolution mechanism (AEM) and the lattice oxygen mechanism (LOM). Based on the above issues, we developed a novel templating method and, for the first time, synthesized double-shelled hollow nanospheres of ZIF-67. Utilizing the inherent hollow structure and chemical activity of ZIF-67, and through Cu-Mo co-doping, we prepared a CuCo₂S₄/MoS₂ OER catalyst with dual mechanisms. The Jahn-Teller effect of copper activates lattice oxygen, facilitating LOM in OER. The cooperative interaction between copper and molybdenum atoms induces surface reconstruction in the catalyst, accelerates the deprotonation step in LOM, and aids in the formation of *OOH in AEM, thus reducing energy barriers and optimizing the adsorption of reaction intermediates. The addition of molybdenum further boosts catalytic performance by enhancing both mechanisms, owing to the spatial disparity between Cu and Mo atoms. Due to the compatibility of the dual mechanisms, the catalyst demonstrates outstanding electrochemical performance in alkaline media (320 mV at 100 mA cm⁻²) and maintains a stable catalytic current in a commercial water-splitting device (500 mA cm⁻² for 300 h). This study presents an innovative strategy for designing oxygen evolution reaction catalysts that integrate both AEM and LOM mechanisms. Considering the widespread applications of ZIF-67 in electrocatalysis and electrochemical energy storage, CuCo-G@ZIF-67 not only serves as a versatile precursor for the synthesis of various catalysts but also paves the way for the development of novel transition metal catalysts and multi-shell energy storage materials.

Rational energy band engineering and the exposure of catalytically active sites critically enhance the efficiency of the hydrogen evolution reaction. In this study, TAPT-TFPT-COF/Mn_0.2Cd_0.8S composite photocatalysts were prepared by wet impregnation. The energy bands of non-precious-metal sulfide nanorods and a covalent organic framework (COF) were interleaved for effective heterojunction construction, enabling a three-fold enhancement in hydrogen evolution compared to that of the pure Mn_0.2Cd_0.8S catalyst. The enhanced catalyst performance is attributed to the construction of heterojunctions and the synergistic photothermal dynamics of the flexible monomers under illumination, which facilitates localized charge carrier migration. Furthermore, the hydrogen evolution mechanism in the Mn_0.2Cd_0.8S/COF composites was elucidated through photoelectrochemical experiments, in-situ irradiation X-ray photoelectron spectroscopy, surface photovoltage measurements, and density functional theory. The loaded organic semiconductor materials were combined with non-precious-metal semiconductors to construct S-scheme heterojunctions with increased hydrophilicity, and the tight combination of Mn_0.2Cd_0.8S and COF optimized the photogenerated electron utilization efficiency.

The deliberate integration and precise arrangement of electron donor (D) and acceptor (A) moieties within the crystalline lattices of covalent organic frameworks (COFs) represent a sophisticated strategy to optimize charge separation and electron transfer processes, thereby enhancing photocatalytic efficiency. Herein, we report the rational design and synthesis of two novel bisoxazole-based D-A type COFs, designated as Bpy-COF and Bph-COF. These frameworks incorporate identical acceptor units but are distinguished by their unique donor motifs, enabling a comparative evaluation of their structural and functional properties. The results reveal that Bpy-COF, which incorporates bipyridyl (Bpy) donor moieties, exhibits superior photocatalytic H₂O₂ production performance compared to Bph-COF, potentially related to its broader light response range and increased availability of reactive sites. Furthermore, the coplanar and conjugated nature of the Bpy groups facilitates efficient charge separation and migration, thereby accelerating the two-electron oxygen reduction reaction critical to H₂O₂ synthesis. This study affirms the effectiveness of manipulating the structural components of COF photocatalysts, propelling new insights for the design and synthesis of high-performance catalysts.

The application of thiolate-protected gold nanoclusters (NCs) for the electrochemical CO₂ reduction reaction (CO₂RR) has received widespread attentions. In this work, three types of atomically precise [Au₂₅(SR)₁₈]^‒ NCs protected by 2-phenylethanethiol (PET), 1-hexanethiol (C6T), and 1-dodecanethiol (C12T), respectively, are employed as model catalysts for CO₂RR, where the molecular configuration and length of thiolate ligands are varied. The electrochemical results demonstrate that the [Au₂₅(C12T)₁₈]^‒ NC possesses lower activity and selectivity towards CO formation than [Au₂₅(PET)₁₈]^‒ and [Au₂₅(C6T)₁₈]^‒ NCs. Owing to their identical gold kernels, the differences in electrocatalytic CO₂RR performance of these three Au₂₅ NCs can be fully attributed to their distinctions in tail group structure. Density functional theory (DFT) calculations exclude the possible effects on the electronic structures of the active sites exerted by the distinctions in tail group structure, while molecular dynamics (MD) calculations reveal that different orientation modes of tail groups in aqueous solution affect the diffusion of the reactants to active sites. Overall, this work provides a unique perspective on the structure-property relationships for ligand-protected NCs in electrocatalytic CO₂RR.

Imidazolium-based ionic liquids (ILs) exhibit great potential in promoting electrochemical CO₂ reduction reaction (CO₂RR) by reducing overpotential reduction and enhancing catalytic efficiency. However, the regulatory role of ILs structure in the local physicochemical region at the electrode/electrolyte interface and in reaction kinetics remain unclear. In this study, we designed imidazolium-based ILs with tunable cation alkyl chain length and systematically revealed the dynamic interfacial regulation mechanism controlled by cation structure, based on in-situ infrared spectroscopy and molecular dynamics simulations. The commercial Ag electrodes in electrolytes with critical chain length exhibit nearly 100% Faradaic efficiency for CO production while maintaining high current density. Imidazolium cations with critical chain length effectively regulate the electric double layer at the Ag electrode/electrolyte interface: they notably balance a range of positive and negative factors, including hydrophobicity, CO₂ absorption, conductivity, viscosity, and hydrogen evolution reaction, etc. Collectively, these effects synergistically shape an optimized interfacial local physicochemical region, enhancing the rate of CO₂ catalytic reactions. This work elucidates the mechanistic framework of interfacial regulation in CO₂RR and delivers molecular design principles for engineering IL-based electrolytes toward enhanced catalytic selectivity.

The photocatalytic carbon dioxide reduction represents a promising route for solar-to-chemical energy conversion, enabling the sustainable production of carbon-neutral fuels. Achieving high selectivity toward specific products remains a major challenge due to the complex multi-electron transfer pathways and competing reaction intermediates. Herein, the Mn-doped Co₃O₄ (MMC) photocatalysts are synthesized based on an “impregnation-pyrolysis” strategy using in situ synthesized Mn-doped ZIF-67 as a precursor. The MOF-templated approach enables uniform Mn incorporation into the Co₃O₄ lattice while preserving a hierarchical porous architecture, thereby enhancing active-site accessibility and modulating the electronic environment of catalyst. The introduction of guest Mn effectively suppresses the competing hydrogen evolution reaction. As a result, the optimized 2MMC catalyst shows a 12.8-fold increase in CO production over undoped Co₃O₄ and enables selective CO₂ conversion in pure water with diluted CO₂. Photoelectrochemical characterizations reveal that guest Mn doping accelerates charge separation dynamics. In-situ irradiated X-ray photoelectron spectroscopy, in-situ Fourier transformed infrared spectra, and theoretical calculations unveil a Mn-mediated pathway that selectively promotes the formation of *CO₂ and *CO intermediates. This work provides new atomic-level insights into the selective photocatalytic conversion of CO₂ under green and sustainable conditions.

The CO₂ photoreduction reaction (CO₂RR) into C₂H₄ represents a highly promising technology for converting greenhouse gases into value-added chemicals. However, this technology faces challenges such as a high energy barrier in the C-C coupling process and a slow electron supply efficiency. In this study, we constructed Ti₃C₂ MXene-derived TiO₂/CoNiO₂ S-scheme heterojunction (MTC-X) by a simple in-situ growth process. The Co-Ni dual-site provided the structural foundation for C-C coupling, effectively reducing the energy barrier of the *CO-*COH intermediate coupling step. Meanwhile, the S-scheme heterojunction ensured the rapid supply of electrons and protons during the CO₂RR, thereby enabling the efficient conversion of CO₂ to C₂H₄. Notably, the MTC-2 sample exhibited the C₂H₄ production rate of 25.2 μmol·g^-1·h^-1, which was 23 times higher than that of the pure CoNiO₂. In summary, by combining in-situ X-ray photoelectron spectroscopy, in-situ Kelvin probe force microscopy, femtosecond transient absorption spectroscopy and difference charge density calculation, confirmed the formation of the TiO₂/CoNiO₂ S-scheme heterojunction. Further, by photoelectrochemical tests, in-situ Fourier transform infrared spectroscopy, Gibbs free-energy calculations, elucidated the mechanism by which the Co-Ni dual-site structure and S-scheme heterojunction synergistically enhance the C-C coupling kinetic process. This provides new experimental reference and theoretical basis for the selective conversion of CO₂ to C₂H₄.

Oxygen vacancies (Ov) play a pivotal role in enhancing photocatalytic C-H bond oxidation, yet their susceptibility to depletion under oxidative conditions significantly compromises catalyst stability. To address this challenge, we developed a surface engineering strategy through in-situ growth of a Bi-MOF layer on oxygen vacancy-rich Bi₂WO₆ (Bi₂WO_6-x@Bi-MOF). This interfacial Bi-O interaction not only constructed a built-in charge transfer channel to boost electron migration from Bi₂WO_6-x to Bi-MOF, but also shifted the Bi p-band center closer to the Fermi level (E_f) to facilitate the adsorption of oxygen molecules and toluene. This surface engineering strategy preferentially adsorbs O₂ on Bi-MOF and prevents its direct interaction with the Bi₂WO_6-x host, thereby mitigating oxygen vacancy depletion and enhancing catalyst stability. The optimized photocatalyst achieves 96% toluene conversion and 80% benzaldehyde selectivity within 2 h of light irradiation and maintains excellent structural stability and catalytic performance over ten consecutive cycles. This study offers a new design strategy for constructing robust and efficient Ov-based photocatalytic systems and expands the potential application of MOF materials in complex interfacial reactions.

The photocatalytic double-electron oxygen reduction pathway has become a strategic approach for the production of hydrogen peroxide (H₂O₂). In many heterojunction systems, indium zinc sulfide (ZnIn₂S₄) has received increasing attention, but it is limited by its slow REDOX kinetics and the lack of sufficient double-electron oxygen reduction active sites. In this study, low-cost CN-NH₄ fragments were loaded onto flower-like indium zinc sulfide (ZnIn₂S₄) to construct a compact S-scheme, in order to achieve environmentally friendly hydrogen peroxide photosynthesis. The H₂O₂ yield of the ZnIn₂S₄/CN-NH₄ photocatalyst was 2031 µmol g^-1 h^-1, which was 2.84 and 21.39 times that of ZnIn₂S₄ and CN-NH₄, respectively. This is attributed to the contact between ZnIn₂S₄ and CN-NH₄, providing a fast migration channel for electrons, forming a strong internal electric field at the interface, and effectively prolonging the migration lifetime of photogenerated carriers. The introduction of CN-NH₄ enhances the absorption of oxygen by ZnIn₂S₄ and simultaneously reduces the energy barrier of its two-electron oxygen reduction reaction. This study provides a new approach for constructing S-scheme heterojunction materials that can efficiently generate H₂O₂ under solar irradiation.

Hydrogen peroxide (H₂O₂), a versatile green oxidant and energy carrier, faces production challenges due to the energy-intensive anthraquinone process. Photocatalytic H₂O₂ synthesis via the two-electron oxygen reduction reaction (2e^- ORR) offers a sustainable alternative, but its efficiency is limited by sluggish charge transfer and insufficient active sites. Here, we design a dual-modulation strategy that combines defect-induced electronic tuning with piezoelectric polarization to enhance surface catalytic processes. Specifically, anchoring Au nanoparticles on N-deficient graphitic carbon nitride (CNNv-Au) allows N vacancies to modulate the electronic structure of the Au nanoparticles, increasing the proportion of electron-deficient Au^δ+ sites and enhancing Au-O₂ interactions, while the piezoelectric field simultaneously facilitates charge separation and directs electrons toward the adsorbed O₂ molecules. In-situ X-ray photoelectron spectroscopy (XPS) under simulated catalytic conditions revealed a 0.5 eV Au 4f shift toward higher binding energy, confirming enhanced electron transfer from Au^δ+ sites to adsorbed O₂ under light irradiation. Synergistic effects of these modifications elevate the H₂O₂ production rate from 247.0 to 1788.5 μmol g^-1 h^-1, a 7.2-fold enhancement. Combined XPS, electron paramagnetic resonance, density functional theory, and in-situ diffuse reflectance infrared Fourier transformed spectroscopy analyses confirm that N vacancies induce local polarization of Au sites, optimizing O₂ activation and intermediate stabilization. This work demonstrates a dual modulation strategy, defect-induced electronic tuning and piezoelectric polarization, to enhance surface catalytic processes, providing a blueprint for efficient photocatalytic H₂O₂ generation.

The development of high-performance all-organic heterojunction photocatalytic systems and the elucidation of their charge carrier excitation and interface migration dynamics have attracted significant research interest. Herein, poly (barbituric acid)/g-C₃N₄ (PBA/UCN) all-organic heterojunctions were prepared by exploiting multiple intermolecular interactions to induce fast interface charge-carrier transfer with a lifetime of approximately 5.05 ps, as was directly verified by in-situ Kelvin probe force microscopy and in-situ irradiation X-ray photoelectron spectroscopy. Moreover, the dynamics and lifetimes of charge carriers were studied by fitting the decay curves of excited-state absorption signals at 600 nm and ground-state bleaching signals at 495 nm obtained by femtosecond transient absorption spectroscopy to further reveal the diffusion, relaxation, and transfer processes of PBA/UCN. The as-prepared PBA/UCN all-organic molecular heterojunction with optimal redox ability exhibits an excellent H₂ evolution rate of 12.55 mmol h^-1 g^-1 and an apparent quantum efficiency of 17.12% at 420 ± 15 nm. In particular, we demonstrate that PBA, which is a promising oxidizing organic semiconductor, can be coupled with various reducing organic photocatalytic materials such as poly(triazine imide), poly(heptazine imide), perylene-3,4,9,10- tetracarboxylic acid, and covalent triazine-based frameworks to obtain a series of efficient all-organic heterojunction photocatalysts.

S-scheme heterojunctions can offer an effective strategy for spatially separating photogenerated charge carriers, thereby sigFnificantly enhancing photocatalytic performance. In this study, cadmium sulfide (CdS)/copper tungstate (CFuWO₄) (CdS/CW) S-scheme heterojunction photocatalysts with adjustable components were fabricated by decorating CdS nanorods with CuWO₄ nanoparticles. The optimal hydrogen evolution rate (2725.91 μmol g^-1 h^-1) of CdS/CW-10% with excellent cycling stability under visible light is 10.1-fold higher than pure CdS. Density functional theory calculations and photoelectrochemical analyses confirmed that the S-scheme charge-transfer mechanism from CdS to CuWO₄ is responsible for the enhanced photocatalytic performance by promoting charge separation. Additionally, the photothermal effect of CuWO₄ increased the local temperature of the photocatalyst, further accelerating the reaction kinetics. This study highlights a dual-enhancement approach based on interfacial charge modulation by constructing an S-scheme heterojunction and photothermal activation, providing valuable insights into the design of high-efficiency S-scheme photocatalysts for solar-driven hydrogen production.

Ammonia (NH₃) is seen to be promising hydrogen carrier, but its decomposition into hydrogen (H₂) has been plagued by high operating temperature (400‒700 °C) and long start-up time. Here, we present that directly electrochemical liquid NH₃ decomposition (ELADH) method could realize efficient onsite H₂ generation at room-temperature, whereas active and stable electrocatalytic system is challenging. Through rationally optimizing the electrolysis system with Ru catalysts, we achieved an active and durable ELADH into H₂ under ambient temperature. It was found that Ru nanoparticles (Ru NPs) with (101) facet could effectively promote the favorable N-H dissociation and hydrogen desorption, and thus accelerate the slow reaction kinetics. The as-prepared Ru NPs on nitrogen carbon exhibit lower potential of ‒1.01 V vs. NHE at ‒10 mA cm^‒2 and larger current density of ‒910 mA cm^‒2 at ‒1.47 V vs. NHE, superior to Ru single atoms and commercial Pt/C. Importantly, this system affords stable H₂ evolution under 100 h continuous electrolysis without apparent degradation, far beyond the reported catalysts. This work paves the new way of room-temperature onsite H₂ production and presents insightful understanding of the electrochemical liquid ammonia splitting process.

Zinc air batteries (ZABs) are a low-cost, high-energy density, and green sustainable energy storage device. At present, the main challenge in achieving large-scale application of ZABs is to develop low-cost and high-performance bifunctional catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Compared with monometallic single-atom catalyst, the bimetallic single-atoms catalyst can effectively improve ORR/OER bifunctional activity, realize rapid charge transfer, and play a significant role in regulating the adsorption of oxygen intermediates. In this study, we design the novel Fe and Co bimetallic single-atoms coordinated by Te and N anchoring on N-doped carbon (NC) (denoted as FeN_xTe_y/CoN_xTe_y@NC) for the first time, serving as a bifunctional catalyst for ZABs. This innovative catalyst exhibits excellent bifunctional ORR/OER catalytic performance under alkaline conditions, achieving a high half-wave potential of 0.912 V for ORR and a low overpotential of 305 mV for OER at 10 mA cm^-2. The FeN_xTe_y/CoN_xTe_y@NC-based ZABs realizes a high peak power density of 306.1 mW cm^-2 and a large specific energy density of 773.2 mAh g^-1. The experimental data show that the N-doped can achieve precise regulation of the structure and high-density distribution of atomic active sites in FeN_xTe_y/CoN_xTe_y@NC (idealized theoretical model is FeCoN₆Te). The density functional theory calculations show that when the FeN₄/CoN₄ models (the synthesized catalyst denoted as FeN_x/CoN_x@NC) transforms into FeCoN₆Te models, Te atoms regulate the local charge densities of Fe and Co on FeCoN₆Te models and further promote the charge transfer between Fe and Co on FeCoN₆Te models, which optimizes the adsorption energies of ORR/OER intermediates. The findings in this study will pave the way for the development of high-performance bimetallic single-atom catalysts for practical energy conversion applications.

Reversible protonic ceramic cells (R-PCCs) represent a highly promising energy conversion and storage technology, offering high efficiency at intermediate temperatures (400-700 °C). However, their commercialization is significantly impeded by the sluggish oxygen reaction kinetics on air electrodes. This work reports a Mn-doped PrBa_0.8Ca_0.2Co₂O_5+δ air electrode with a nominal composition of PrBa_0.8Ca_0.2Co_1.5Mn_0.5O_5+δ, which primarily segregates into a deficient double perovskite Pr_1.25Ba_0.5Ca_0.25Co_1.58Mn_0.42O_5+δ phase and a minor BaCo_0.6Mn_0.4O_3-δ hexagonal perovskite phase, as suggested by the X-ray diffraction refinement. The formation of Mn-doped nanocomposites substantially enhances the activities of oxygen reduction/evolution reactions, attributed to elevated oxygen vacancy concentrations and improved oxygen surface exchange and bulk diffusion capabilities, relative to the undoped PrBa_0.8Ca_0.2Co₂O_5+δ. The synergistic effect between the two phases may enhance electrochemical performance. Single cells incorporating these nanocomposite air electrodes achieve exceptional electrochemical performance at 700 °C: peak power density of 2.05 W cm^-2 in fuel cell (FC) mode and current density of -3.78 A cm^-2 at 1.3 V in electrolysis (EL) mode. Furthermore, promising durability is demonstrated during a FC test (100 h), an EL test (100 h), and a FC-EL cycling test (120 h) at 600 °C. This Mn-doping approach establishes an effective strategy for developing advanced air electrode materials.

Electrocatalytic oxidation of cyclohexanone (KOR) to adipic acid provides a sustainable and value-added pathway for coupled hydrogen evolution (HER). However, the weak adsorption of the reactants and intermediates leads to poor reaction kinetics and product yield. Herein, we synthesized MoNi₄/MoO₂ heterostructures via phase conversion to engineer a large work function difference that optimizes the Ni electronic structure. This design enhances cyclohexanone adsorption and regulates intermediates, achieving 85% Faradaic efficiency for production of adipic acid and a 2 mmol h^-1 cm^-2 production rate, along with an ampere-level current. In a membrane electrode assembly electrolyzer for KOR-assisted HER, this catalyst displays 1 A current with 12.1 mol adipic acid production and 3.34 L H₂ generation over 8 h, maintaining stability for 56 h at 3 A. Optimized Ni electronic structure achieved through heterojunction-induced charge redistribution strengthens cyclohexanone adsorption and lowers the energy barriers for key intermediates (C₆H₁₀O₂^* and C₆H₁₀O₃^*), boosting oxidation activity. This study presents a novel heterojunction engineering strategy that synergistically enhances reactant adsorption and optimizes intermediate reaction kinetics, offering a tailored approach for efficient catalytic systems.

Enzymatic catalysis within surface- and volume-confined environments is common in biological cells or industrial applications. Despite their prevalence both in vivo and in vitro, a comprehensive mechanistic understanding of how these confinements tune the intrinsic activity of enzymes has remained elusive. Herein, we explore the role of confinement in shaping the activity of enzymes. Experiments show that the confinements induced by macromolecular crowding enhance lipase activity. To uncover the origin of the activity enhancement, thermodynamic activation parameters of lipase catalysis were calculated through extensive molecular dynamics (MD) and empirical valence bond (EVB) simulations. The EVB approach has proven to be an efficient method, enabling extensive sampling via MD and the evaluation of thermodynamic activation parameters for enzyme catalysis. Our findings reveal that confinement applied at the loop regions of lipase leads to higher intrinsic activities, and this effect depends on the degree of confinement. The lower free energy of activation originates from the gain of both enthalpy and entropy. Better preorganization of the active site and greater conformational space overlap between initial and transition states enhance lipase catalysis. We observe that the catalytic enhancement due to surface confinement is not exclusive to lipase but extends to PETase, highlighting its potential universality as a principle for enzyme design and engineering.

Polyvinyl chloride (PVC) tarpaulins reinforced with poly(ethylene terephthalate) (PET) fibers are widely used in various industrial applications. However, the increasing demand for recycling PVC tarpaulin waste poses challenges because of the difficulty in separating the two different plastics. In this study, we investigated the possibility of recycling PVC and PET through the glycolysis of PET. The milled PVC tarpaulin underwent a glycolysis process, selectively depolymerizing the PET fibers into water-soluble bis(2-hydroxyethyl) terephthalate (BHET), while the PVC was removed by filtration. The PET fibers were selectively depolymerized by 77.6% after reacting at 190 °C for 2 h in the presence of 0.5% (w/w) betaine as a catalyst, quantitatively yielding BHET. During glycolysis, the physical appearance of the PVC changed because of leaching of the plasticizer, however, no dechlorination or shortening of the PVC polymer was observed. Interestingly, additives in PVC, such as CaCO₃ and CZ-stabilizer, act as catalysts for glycolysis, thereby enhancing PET depolymerization. The recovered PVC, when blended into a PVC formulation, maintained its mechanical properties and appearance up to 40 parts per hundred resins in roll-mill-processed sheets. In addition, ethylene glycol, which is used as a solvent in glycolysis, can be reused up to three times without the additional removal of BHET. This study demonstrated an industrially applicable method for simultaneously recycling PVC and PET from widely used tarpaulins.