Aqueous zinc ion batteries hold great promise for large scale energy storage owing to their high safety and low cost. However, their commercialization is hindered by interfacial issues on the zinc anode, including dendrite growth, corrosion, and the hydrogen evolution reaction. In this study, a multifunctional composite protective layer was fabricated on a zinc foil surface via a simple blade coating method. The coating consists of zinc based montmorillonite (Zn-MMT) intertwined with cellulose nanofibers (CNF), forming a three dimensional (3D) architecture that integrates ion conductive channels with a hydrophilic network. Experimental results demonstrate that the composite coating significantly reduces the activation energy for zinc deposition and the nucleation overpotential, while enhancing the zinc ion transference number. Consequently, it effectively guides uniform zinc deposition and suppresses side reactions. Benefiting from these advantages, the Zn-MMT@Zn symmetric cell achieves an ultrastable cycling life of 2780 h at 5 mA cm−2. Furthermore, the assembled Zn-MMT@Zn||VO2 full cell exhibits excellent rate capability and cycling stability. This work provides a new strategy for constructing high performance, long life zinc metal anodes through interfacial engineering.

The electrocatalytic CO2 reduction reaction (CO2RR) in acidic media effectively circumvents the carbonate precipitation commonly encountered in neutral and alkaline systems. As the CO2RR typically occurs at the gas-liquid-solid three-phase interface, regulating the local microenvironment around the catalytic center is crucial for enhancing reaction activity. This review systematically summarizes recent progress in microenvironment engineering for acidic CO2RR interfacial reactions. Firstly, the concept of the interface reaction microenvironment is elaborated, and the core elements of the CO2RR interface reaction microenvironment under acidic conditions are summarized, including in situ local (interfacial) pH evolution, interface water structure, and double-layer electric field distribution. From the perspective of catalyst design, microenvironment regulation strategies based on confinement effects, surface wettability modulation, and interfacial electric field construction are discussed in detail. Subsequently, from the viewpoint of electrolyte engineering, advances in solution pH control, buffer system design, and alkali metal cation regulation are reviewed. Finally, the opportunities and challenges facing interfacial reaction microenvironment engineering in the development of the acidic CO2RR are discussed.

Recent studies on the electrocatalytic oxygen transfer from water to organic compounds have gained significant attention due to their sustainability and selectivity. However, the direct coactivation of inert hydrocarbons and water typically requires high oxidation potentials, leading to oxygen evolution reactions and low Faradaic efficiencies. Herein, a Ni-activated tungsten-oxygen covalency anode is designed for the efficient oxygen transfer from water to benzylic C(sp(3))-H bonds via a Ni-regulated interfacial water structure between the anode and electrolyte. Both experimental and theoretical results reveal the critical role of W-O covalency sites with Ni-heteroatoms for boosting efficient oxygen transfer via breaking the dense interfacial hydrogen bond network and inhibiting the undesired oxygen evolution reactions, facilitating the coactivation of oxygen species and C(sp(3))-H bonds. Thus, a Faradaic efficiency of > 56% in a water-involved system has been achieved. This work provides important insight into designing electrocatalytic systems for inert C-H oxidation.

Despite the development of the Haber-Bosch process, ammonia synthesis under mild conditions remains challenging due to the high bond energy (945 kJ mol(-)1) of the N equivalent to N triple bond. Both thermal- and photocatalytic processes often suffer from the intrinsic scaling relationship between N2 activation and NH3 desorption efficiencies. Here we report that the photocatalytic process over an AlFe nanoalloy catalyst provides a promising solution through a photoinduced nitrogen spillover reaction mechanism. Fe acts as the primary active site for N2 adsorption and dissociation. The transferred photoexcited electrons from Al to Fe enhance N2 activation. Al serves as a secondary active site, facilitating N spillover from Fe to Al sites under photoexcitation, promoting NH3 desorption. This dual-site strategy enables an ammonia synthesis rate of 8.6 mmol gcat-1 h-1 at 4.28 W cm-2 without additional thermal input under ambient pressure. The performance surpasses that of conventional industrial Fe catalysts under thermocatalytic conditions. This study proposes a photoassisted active site modulation strategy for efficient ammonia synthesis catalyst to circumvent scaling relationships.

A series of Ni-decorated Zn0.6Cd0.4S (Ni/ZCS) photocatalysts was prepared through electrostatic adsorption and evaluated for hydrogen generation driven by visible light. Microscopic characterization revealed that Ni nanoparticles were dispersed across the surface of the three-dimensional spiny Zn0.6Cd0.4S microspheres, establishing intimate interfacial contact between the two components. Compared with pristine ZCS, Ni modification improved light utilization and facilitated interfacial charge transport, while also lowering the kinetic barrier for hydrogen evolution. Among the samples investigated, the catalyst containing 0.5wt% Ni delivered the optimum hydrogen production rate obtained for 5284.2 μmol·h⁻¹·g⁻¹, corresponding to a 4.2-fold increase over bare Zn0.6Cd0.4S. This sample also achieved an apparent quantum yield of 14.76% under 400nm irradiation and retained its hydrogen-production performance during repeated cycling. The enhanced activity is caused by the formation of a Ni/ZCS Schottky interface. Owing to its higher work function, Ni can serve as an electron sink, promoting photogenerated electron extraction and suppressing recombination of electrons and holes. These results identify Ni as an inexpensive and readily accessible cocatalyst to promote the photocatalytic H2 production performance of Zn0.6Cd0.4S

A schematic diagram of interfacial reaction microenvironment engineering for promoting acidic CO 2 electrocatalytic reduction is provided.

Anode-free lithium metal batteries, containing no excess Li metal and utilizing only the cathode's Li inventory, promise extreme energy densities. Realization of practical anode-free Li batteries, however, is constrained by the poor reversibility of Li metal electrodeposition and rapid depletion of the Li inventory in the form of "dead" Li. To address these issues, conventional Cu current collectors were modified with ultrathin dual-layer coatings to construct a lithiophobic artificial solid electrolyte interface (ASEI) atop a lithiophilic metallic alloy layer. The lithophilic layer consisting of LixAu alloys reduced the Li nucleation overpotential, inducing continuous and homogenous Li deposition on the current collector. The lithiophobic ASEI composed of MgF2 conferred superior Li dendrite suppression stability due to its high interfacial energy, resulting in less Li penetration into the SEI. Conventional Cu current collectors coated with ultrathin Au and MgF2 films provided an enhanced Coulombic efficiency of 99.2 % over 350 cycles in a Li||Cu cell, compared to only similar to 98.4 % from baseline samples employing conventional, bare Cu current collectors. More importantly, when the coated copper current collectors were incorporated into anode-free LiFePO4 full cells, the average initial CE and capacity retention were improved by similar to 8.2 % and 30.1 %, respectively. The high energy density of the cell was maintained given the thinness of the layers (<50 nm in total). This ultrathin dual layer design provides a pathway to practical, reversible anode-free Li batteries while preserving extreme energy densities.

Aqueous zinc-ion batteries (AZIBs) are promising candidates for large-scale energy storage due to their high safety and low cost. However, the practical application of zinc metal anodes is hampered by parasitic reactions, including the hydrogen evolution reaction (HER) and dendrite growth. Herein, 4-chlorobenzenesulfonamide (CBS) is proposed as a novel and cost-effective electrolyte additive to achieve highly reversible zinc plating/stripping. Theoretical calculations and spectroscopic analyses reveal that the CBS molecules, featuring functional groups -SO2- and -NH2, effectively reconstruct the primary solvation sheath of Zn2+ by replacing water molecules, thereby reducing free water activity and suppressing the HER. Simultaneously, CBS preferentially adsorbs on the Zn surface, facilitating the formation of a robust solid electrolyte interphase (SEI) rich in ZnS, which guides uniform Zn deposition and inhibits dendrite formation. Consequently, the Zn parallel to Zn symmetric cell with the CBS-containing electrolyte achieves an ultralong cycling life of over 3000 hours at 0.25 mA cm-2 and 0.25 mAh cm-2. When paired with a MnO2 cathode, the full cell exhibits significantly enhanced cycling stability, retaining a capacity of 95.91 mAh g-1 after 600 cycles at 1 A g-1. This work provides a strategic approach to stabilizing zinc anodes through rational electrolyte engineering with multifunctional additives.

Photoelectrochemical (PEC) synthesis presents a transformative strategy for the sustainable production of value-added chemicals by synergistically utilizing light and electrical energy. This approach overcomes critical limitations of standalone photocatalysis and electrocatalysis. The strategic shift from PEC water splitting to synthesizing high-value chemicals (e.g., fuels, pharmaceuticals, polymers) addresses economic viability and environmental challenges. Key advantages include precise control over reaction pathways via bias/light tuning, enhanced selectivity, and the potential to utilize earth-abundant materials. Despite significant advances in materials and understanding, challenges remain in efficiency, stability, achieving high selectivity in complex reactions, and system scalability. This review discusses the current state of PEC synthesis and the progress needed to advance this technology toward industrial-scale green chemical manufacturing.

The activation and catalytic conversion of resource-abundant small molecules (e.g., H 2 O, N 2 , O 2 , CO 2 , and CH 4 ) hold transformative potential for synthesizing value-added chemicals and improving energy conversion/storage efficiency. However, these processes remain challenging owing to the high bond dissociation energy and low reaction selectivity of these molecules, making the development of advanced catalytic materials essential. In this perspective, we systematically review and summarize the small-molecule activation mechanisms on Mott–Schottky heterojunctions and intermetallic compounds, while discussing the critical role of small-molecule activation in energy storage applications. We also highlight the emerging impact of artificial intelligence in accelerating catalyst design and unraveling reaction mechanisms. Finally, we offer our perspectives on the key factors and future directions for advancing research in small-molecule activation.

Oxygen reduction reaction (ORR) performance of platinum can be improved through alloying transition metals, with L10-PtCo emerging as a standout option due to its balanced catalytic performance, durability, and manufacturability. However, traditional carbon supports often fail to stabilize nanoparticles, leading to performance degradation. This study introduces a mesoporous Co-N-C supported ordered L10-PtCo catalyst to overcome the above limitations. The CoN4 sites in the mesoporous Co-N-C (MS-CoNC) support create a strong synergy with L10-PtCo clusters, preventing nanoparticle aggregation during high-temperature synthesis. X-ray absorption spectroscopy reveals a unique shortened Pt-Pt bond length in L10-PtCo/MS-CoNC, which contributes to a mass activity of 0.54 A mg-1, 6.3 times that of commercial carbon-supported PtCo catalysts. Rationalised by density functional theory, L10-PtCo/MS-CoNC optimizes its d-band centre for enhancing ORR intermediate adsorption-desorption. Membrane electrode assemblies test deliver remarkably improved peak power density while with only 60 µgPt cm-2 of Pt. The mesoporous structure of the Co-N-C support further reduces mass transport losses, enhancing oxygen diffusion and stability. Durability testing shows minimal performance loss after 30 000 voltage cycles, showcasing the catalyst's robustness under harsh PEMFC conditions. This work demonstrates the synergistic advantages of mesoporous Co-N-C supports and L10-PtCo catalysts, paving the way for high-performance, low-Pt fuel cell technologies.

Electrocatalytic synthesis of ammonia from nitrogen, as a novel approach to environmentally friendly NH3 production, still faces challenges in developing efficient electrocatalysts. In this work, we fabricated a FeS2/Bi2S3 heterojunction by integrating bismuth compound with iron compound using an interfacial engineering approach. The strong interfacial coupling between the two phases of this heterojunction not only generates abundant interfacial defects and enhances the material's nitrogen adsorption capacity but also promotes the construction of the built-in electric field. This accelerates the migration of electrons and facilitates the upward migration of the d-band centers of the catalysts, optimizing the adsorption of the NRR (nitrogen reduction reaction) intermediates and significantly improving the NRR performance of the catalysts. As a result, the FeS2/Bi2S3 heterojunction achieved excellent NRR performance with an ammonia production rate of 15.95 mu g & sdot;h- 1 & sdot;mg- 1 cat and a Faraday efficiency of 30.91 %. The synergistic effect of bimetallic Fe/Bi and the strong interfacial coupling enabled the FeS2/Bi2S3 heterojunction to achieve an optimal balance between ammonia production rate and Faraday efficiency. This work provides new insights for the selection and design of NRR catalysts.

The design of highly efficient, stable, and nonprecious-metal-based electrocatalysts for the oxygen evolution reaction (OER) has been a major research topic in the field of hydrogen production from electrolytic water splitting. In this work, a novel hierarchical hollow NiCo layered double hydroxide (NiCo LDH) with Cu-TCPP (TCPP = tetrakis(4-carboxyphenyl)-porphyrin) intercalation (denoted as X-CT/LR, where X is the amount of Cu-TCPP addition) was successfully fabricated by using zeolite imidazole framework-67 (ZIF-67) as a template. Among them, 1-CT/LR has superior OER activity and stability, requiring only a low overpotential of 204 mV to reach a current density of 10 mA/cm2. The experimental results show that the introduced Cu-TCPP, in addition to being an active center itself, also acts as an electron transfer medium in the interlayer to enhance the conductivity of the material. Meanwhile, the hierarchical hollow structure and interlayer domain-limiting effect of NiCo LDH also ensure the dispersion and stabilization of Cu-TCPP, which is favorable to give full play to the synergistic catalytic effect of the two components. This work provides a facile strategy to obtain a nonprecious-metal-based OER electrocatalyst for water splitting.

The development of solid acid catalysts with highly active sites for the mass production of fine chemicals, oil refining, and biomass conversions is a powerful alternative to highly toxic and polluting mineral acids. However, the as-generated water from acid-catalyzed industry-scale esterification, dehydration, ketalization, and condensation reactions leads to unwanted deactivation of the acid sites. The key challenge is to design durable solid acids that strike a balance between a high density of accessible acid sites and resistance to water-induced degradation. Here, we introduce a heterojunction-type solid acid catalyst, MX/pCN, capable of generating both Lewis and Br & oslash;nsted acid sites. The as-formed dual-acid systems continuously catalyze the solvent-free acetal reaction of various benzaldehydes with high selectivity. Compared with conventional acid catalysis, our MX/pCN-based catalytic system does not suffer from acid site loss and poisoning and thus can be well maintained for multiple and long-term uses.

Alkylamines are essential intermediates in pharmaceuticals, agrochemicals, and fine chemicals, with annual global consumption reaching up to 6 million tons. Conventional N-alkylation via a hydrogen borrowing pathway from alcohols and amines typically requires harsh conditions, solvents, and additives. Electrochemical strategies offer a more sustainable alternative, but existing methods are largely limited to products with unsaturated bonds and rely on liquid electrolytes. Herein, we reported a proton borrowing pathway-based electrolyzer that enables N-alkylation of pure alcohols and amines under ambient condition. The electrolyzer employs a Pdδ-/NC cathode, which accelerates proton transfer through the cathodic substrate molecular network and selectively returns protons to the C═N bonds of imines, thereby achieving dibenzylamine production with a Faradaic efficiency of 53%. In addition, the system exhibits robust operational stability, broad substrate tolerance, and sustained alkylamine synthesis at currents up to 200 mA, delivering yield rates as high as 0.21 mmol h-1 cm-2 based on electrode area. This work underscores the pivotal role of catalyst design in proton transfer and return processes and provides new insights into decoupling redox processes via electrochemical pathways.

Hydrogen fuel cells, which use hydrogen as fuel to generate electricity, hold great promises as future energy conversion devices for heavy-duty transport, due to their zero CO2 emissions, high energy conversion efficiency, and high power density. However, the adoption of hydrogen fuel cells has been slow due to their reliance on large amounts of costly and scarce platinum (Pt) for the oxygen reduction reaction. The replacement of Pt with Earth-abundant transition metals such as Fe, Co, Mn, and Sn with oxygen reduction reaction affinity has thus been a holy grail of electrocatalysis research. Pt-free catalysts must combine both high power density and high stability in hydrogen fuel cells to be considered viable alternatives to Pt. Despite promising progress on both fronts, a trade-off has emerged: Pt-free catalysts either achieve high power densities (≥1.5 W cm-2) but suffer from low stabilities (≥70% loss after 25 h) or more recently demonstrate improved stability (≤25% loss after 150 h), while delivering considerably lower power densities (<1 W cm-2) in hydrogen fuel cells. Herein, we summarize the recent progress in the synthesis of high power density M-N-C catalysts for hydrogen fuel cells and highlight the critical importance of uncovering the underlying mechanisms using operando methods. We then discuss the primary causes of catalyst degradation in hydrogen fuel cells and the most promising strategies to enhance the stability of the M-N-C catalysts. Finally, a roadmap is proposed to overcome the activity stability trade-off for Pt-free catalysts in hydrogen fuel cells.

The catalytic efficiency of natural enzymes depends on the precise electronic interactions between active centers and cofactors within a three-dimensional (3D) structure. Single-atom nanozymes (SAzymes) attempt to mimic this structure by modifying metal active sites with molecular ligands. However, SAzymes struggle to match the catalytic efficiency of natural enzymes due to constraints in active site proximity, quantity, and the inability to simulate electron transfer processes driven by internal electronic structures of natural enzymes. This study introduces a universal spatial engineering strategy in which molecular ligands are replaced with graphdiyne (GDY) to induce d-π orbital hybridization with copper nanoparticles (Cu NPs), leading to an asymmetric electron-rich distribution along the longitudinal axis that mimics the local electric field of natural laccase. Moreover, multiple sp bonds within GDY scaffold effectively anchor Cu NPs, facilitating the construction of 3D geometric structure similar to that of natural laccase. An enzymatic activity of 82.53 U mg −1 is achieved, 4.72 times higher than that of natural laccase. By reconstructing both 3D structures and local electric fields of natural enzymes through d-π orbital hybridization, this approach enhances electron interactions between cofactors, active centers, and substrates, and offers a versatile framework for biomimetic design of nanozymes.

Efficient oxidase-mediated oxidation is pivotal for environmental remediation and energy conversion application, yet natural enzymes require artificial alternatives due to inherent instability. Cofactors are essential in natural oxidase catalysis, interacting with the active centre to induce an electronic 'push effect' that propels the catalytic process. While efforts to mimic cofactors in nanozyme often involve sophisticated designs and complex synthesis. This study presents a scalable material engineering approach to mimic cofactor functionality using platinum nanoparticles (Pt NPs) supported on an ultrathin graphdiyne/graphene (GDY/G) composite (Pt/GDY/G), in which the sp-hybridized carbon (sp-C) in GDY induces a dual electronic 'push effect'. The unique sp-C structure in GDY imparts semiconductor characteristics and a low work function, this induces an interfacial electrostatic potential between GDY and Pt, which enables unidirectional electron transfer from GDY to Pt, thereby enhancing the electron density at Pt sites. Moreover, the sp-C sites in GDY act as oxygen (O2) adsorption centres, forming a spCOO-Pt bridge that facilitates electron transfer from GDY to O2. This sp-C induced dual electronic 'push effect' significantly reduces the energy barrier for OO bond cleavage, resulting in a 3.4-fold enhancement of the oxidase-like (OXD-like) activity of Pt/GDY/G compared to Pt NPs alone. This work provides mechanistic insights into the design of OXD-like nanozymes, offering a promising strategy to boost O2 activation and OO bond cleavage. The superior catalytic performance of Pt/GDY/G highlights its potential for dye and microplastics degradation, contributing to sustainable environmental remediation.

Deuterated organic compounds have gained significant attention due to their diverse applications, including reaction mechanism studies, probes for metabolism and pharmacokinetics, and raw materials for labeled compounds and polymers. Conventional reductive deuteration methods are limited by the high cost of deuterium sources (e.g., D₂ gas) and challenges in product separation and D₂O recycling. Electrochemical deuteration using D₂O is promising, but existing methods still suffer from low Faradaic efficiency (FE) and high separation costs. Herein, we report a deuterium ion diffusion-based all-solid electrolyser, featuring a RuO₂ anode for D+ generation from pure D2O and a Pd/nitrogen-doped carbon-based liquid diffusion cathode (Pdδ+/NC LDC) with tunable electron deficiencies Pdδ+/NC to enhance selective deuteration. This system achieves over 99% selectivity for deuterated benzyl alcohol with a FE of 72%, and demonstrates broad applicability for the deuteration of aldehydes, ketones, imines, and alkenes with high FE and selectivity. Moreover, the Pdδ+/NC-based electrolyser can achieve ten-gram-scale production of deuterated benzyl alcohol over 500 hours, showcasing its potential for high-throughput, solvent-free deuteration reactions in practical applications.