Single-atom catalysts (SACs) suffer from sluggish desorption-charge transfer processes during complex multi-atomic molecule oxidation (e.g., C/H/O-containing species) due to simple active sites and tedious carbonyl/C─H bond tandem oxidation pathways. Herein, we propose a new atomically dispersed Ir-N4/Pt-N4 catalyst (Ir1-Pt1 NC) to construct efficient dual-pathway reactions as directional parallel reactions, namely, Pt activates H adsorption while adjacent Ir sites specifically bind carbonyl groups (C═O) under the over-boiling point environment. The confirmed Ir-N4/Pt-N4 dual-isolated coordination structure modulates the d-band center to achieve greatly reduced energy barrier and form a new parallel dual-pathway mechanism, significantly improving catalytic kinetics and boosting the charge transfer process. The molecular dynamics (MD) simulations reveal that strong hydrogen bond networks in formic acid (FA) solutions impede molecular diffusion, where over-boiling point operation significantly weakens the hydrogen bonding of FA molecules, thus realizing a "double × double" enhancement effect. The "dual-atomic catalyst with over-boiling point hydrogen bond dissociation" strategy achieve an unprecedented catalytic performance, that is, a mass activity of 125.9 A mg-1, far exceeding those of the state-of-the-art single atomic catalysts (10-30 A mg-1) and the commercial iridium-carbon (Ir/C) catalyst (0.1 A mg-1), and building a new universal "structure + environment" dual-regulation for formic acid oxidation (FAOR) and the rapid degradation of other small organic molecules.

Electrocatalytic conversion of nitrate to ammonia via the nitrate reduction reaction (NO3RR) is a sustainable method for ammonia production with simultaneous electricity generation. The electrocatalytic NO3RR is not only a versatile and scalable method but also a strategic option for next-generation electric vehicles. Herein, we report the development of palladium-decorated copper (Pd@Cu) composite microspheres via pulsed laser irradiation in liquid, and their application as electrocatalysts for the NO3RR. The Pd@Cu-3 composite achieved a maximum NH3 yield rate of 13100 mu g h-1 cm-2 and a Faradaic efficiency of 92.5 % at-0.4 V vs. the reversible hydrogen electrode. In-depth analysis of the NO3RR kinetics using in situ micro-Raman, ex situ XRD, and ex situ Fourier transform infrared spectroscopy revealed information on reaction intermediates and confirmed the excellent electrochemical activity of the Pd@Cu-3 composite. A Zn-nitrate battery assembled with a Pd@Cu-3 composite as the cathode and a zinc plate as the anode exhibits an open-circuit voltage of 1.33 V and an ultralong cycling stability of 100 hat 10 mA cm-2. The high NH3 yield rate and excellent stability of the Pd@Cu-3 composite demonstrate its potential for real-world applications.

The electrocatalytic hydrogen evolution reaction (HER) is one of the prominent reactions involved in the generation of green hydrogen. A catalyst for the HER reaction should be highly electroactive and stable, as well as cost-effective. Being a zero-dimensional nanomaterial, graphene quantum dots (GQDs) possessed excellent structural and electronic features, rendering them as efficient materials for the HER process. Unlike previous reviews that predominantly focus on general synthesis strategies, optical properties, or broad applications of GQDs, the present review provides a focused and critical analysis of GQD-based electrocatalysts for HER. In particular, this review summarizes the important physicochemical properties of GQDs for the HER process, including the roles played by quantum dimension and edge configurations for H-atom adsorption. Further, different approaches for GQD material designing, such as modifying it by integrating dopant atoms or defects or hybridizing it with metals, their compounds, and carbonaceous carbon materials, are discussed based on their respective structure-function property relationship. In addition, special emphasis has been placed on the electronic modulation effect, synergistic effects, and HER mechanistic support by theoretical simulations, which could possibly lead to an understanding of the catalytic mechanisms of GQD-based materials. Finally, the discussion covers the challenges and future ideas for creating GQD-based materials for electrocatalytic reactions, focusing on problems like stability, scalability, and improving their electronic properties for better performance.

To enhance oxygen reduction reaction (ORR) kinetics of metallophthalocyanine catalysts, electronic structure modulation via support engineering is investigated using density functional theory. Herein, iron phthalocyanine (FePc) supported on pristine, N-doped, B-doped, and N,B-co-doped graphene is systematically examined. Electronic structure analyses reveal that N,B co-doping induces significant charge redistribution and strengthens Fe-support coupling, leading to optimized Fe-N bonding and favorable orbital alignment near the Fermi level. These modifications regulate the adsorption of key ORR intermediates (*OOH, *O, *OH). Free-energy calculations show that FePc@N,B-doped graphene exhibits balanced intermediate binding and delivers the lowest theoretical overpotential of 0.41 V, outperforming FePc supported on pristine (0.61 V), N-doped (0.54 V), and Bdoped graphene (0.64 V). The enhanced activity originates from moderated adsorption energetics governed by dband center modulation. This study provides mechanistic insight into heteroatom co-doping effects and guides the design of efficient noble-metal-free ORR electrocatalysts.

Advancing highly efficient electrocatalysts is crucial for facilitating the widespread implementation of water splitting technologies. Two-dimensional (2D) materials have garnered significant attention among developing material platforms because of their adjustable electrical architectures and high surface-to-volume ratios. MXenes, a category of 2D materials, are distinguished by their intrinsic metallic conductivity, hydrophilic surfaces, and chemically modifiable terminations. However, their efficient catalytic performance is limited by a low density of intrinsic active sites, vulnerability to surface oxidation, and a significant tendency for restacking, which collectively impede mass and charge transport. The strategic design of 2D MXene-based electrocatalysts by electronic manipulation and customized interfacial interactions has proven to be an effective remedy for these limitations. This review article thoroughly elucidates recent developments in MXene-based electrocatalysts for water splitting. It initially outlines the fundamental chemistry of MXenes, as well as their electrical and electrochemical properties. The synthesis strategies of MXenes and MXene-based heterostructures are thoroughly discussed for their advanced and controlled nature. Furthermore, this review highlights defect engineering, surface termination, composite architectures, and single-atom/heterostructure strategies to optimize MXene electrocatalytic water-splitting performance. Finally, critical challenges and prospective research directions are examined to inform the systematic design of next-generation MXene-based catalysts that exhibit improved activity, stability, and durability for effective water splitting applications.

Electrocatalytic conversion of nitrite (NO2-) to ammonia (NH3) via the NO2- reduction reaction (eNO2RR) presents a promising approach. Prussian blue analog (PBA)-based electrocatalysts are potential candidates for eNO2RR owing to their good activity and selectivity. Herein, to the best of our knowledge, for the first time, we report a facile synthesis of a flower-like copper (Cu)-cobalt (Co) PBA sulfide (CuCoPBA-S) using pulsed laser irradiation in liquid and investigate its formation mechanism using acoustic levitation coupled with in situ Raman spectroscopy. This approach enables contaminant-free, rapid, and cost-effective synthesis of electrocatalysts. The sulfurization process is shown to be time-dependent in the formation of ordered/disordered flower-like CuCoPBA-S structures. CuCoPBA-S considerably influences the eNO2RR, achieving a NH3 faradaic efficiency (FE) of 80.91% and an NH3 yield rate of 3394.1 mu g h-1 cm-2 at a fixed potential of -0.5 V vs. the reversible hydrogen electrode (RHE). Moreover, density functional theory analysis validates the eNO2RR pathway facilitated by CuCoPBA-S during the electrocatalytic conversion of NO2- to NH3, and the rate-determining step in the pathway is the hydrogenation of *NH2O to *NH2OH.Keywords: Prussian blue analog; Acoustic levitation; Nitrite reduction; Electrocatalysis; Ammonia synthesis.

Precise regulation of metal-metal proximity in dual-atom catalysts is critical for overcoming the intrinsic kinetic limitations of the oxygen reduction reaction (ORR). Herein, the density functional theory calculations are employed to systematically investigate four Fe-Co dual-metal configurations embedded in N-doped carbon matrix, N2Fe-CoN2 (Model 1), N3Fe-CoN3 (Model 2), a shared-N bridged FeN4/CoN4 (Model 3), and spatially isolated FeN4 and CoN4 moieties (Model 4). The electron localization function, density of states, charge density difference, and frontier orbitals studies demonstrated that direct Fe-Co coupling and symmetric nitrogen coordination induced strong electronic delocalization and optimal charge redistribution. The ORR investigations demonstrated that Models 1-3 uniquely stabilized a cis-bridged Fe-O-O-Co adduct, enabling direct O-O bond activation and spontaneous cleavage into Fe-O and Co-O species. This two-site synergy enhanced the O-O bond dissociation and subsequent proton-electron transfer steps towards forming OH- and regenerating the active site significantly. In contrast, Model-4 preferred an end-on binding configuration, enforcing less O-O bond dissociation and an unfavourable associative pathway, thereby displaying higher ORR overpotential. The free-energy analysis reveals N3Fe-CoN3 (Model 2) to be the best catalytic motif with an extremely low ORR overpotential of 0.35 eV compared to Model 1 (0.52 eV), Model 3 (0.68 eV), and Model 4 (0.81 eV). This work establishes a metal-metal proximity, enabled cis-bridged-peroxo activation as a decisive descriptor for ORR activity, and further gives a robust theoretical blueprint toward the rational design of Fe-Co dual-atom electrocatalysts with high performance.

The electrocatalytic nitrogen reduction reaction (NRR) has emerged as a viable substitute to the energy-intensive Haber-Bosch process for ambient ammonia (NH3) synthesis, but its practical implementation is limited by low NH3 yields and inadequate Faradaic efficiency under ambient circumstances. Recent advancements indicate that rare-earth (RE) elements, which contain multiple oxidation states, significant redox flexibility, a tendency to create oxygen vacancies, and multiple accessible active sites, make them suitable candidates for effective electrocatalytic NRR. Electrocatalysts are critical prerequisites for improving electrochemical efficiency and maximizing product yield. A comprehensive analysis of rare earth-based materials in influencing the electronic characteristics of NRR catalysts, alongside the structure-performance correlation in electrocatalytic activities, is summarized systematically. This review offers a timely and thorough overview of the advancements in the utilization of RE-based micro/nanomaterials and presents plausible forecasts for the future electrocatalytic NRR. Finally, challenges, perspectives, rational design, and development of highly efficient RE-based catalysts are articulated with particular focus on diverse metal-based electrocatalysts for N2 fixation.

A new one-dimensional Cu(II) coordination polymer, formulated as [Cu2(mu-pyridine-4-carboxylato)(1,10-phenanthroline)Cl]n & sdot;DMSO ([Cu2(mu-4-pyCOO)(phen)Cl]n & sdot;DMSO), has been synthesized and comprehensively characterized to elucidate its structural, physicochemical, and biological properties. Single-crystal X-ray diffraction reveals that the polymer crystallizes as a catena-type architecture in which Cu(II) centres adopt distorted octahedral geometries, bridged by mu-pyridine-4-carboxylate ligands and stabilized by chelating 1,10-phenanthroline units. The extended polymeric chains are further reinforced by an extensive network of C-H & ctdot;O, C-H & ctdot;Cl, and C-H & ctdot;N hydrogen bonds, together with significant it-it stacking and C-H ... it interactions, giving rise to a robust supramolecular assembly. Spectroscopic investigations using FT-IR, Raman, and UV-Vis techniques confirm effective metal-ligand coordination and provide insight into ligand binding modes and electronic transitions. Thermal analysis demonstrates a multistep decomposition process, indicating good thermal robustness of the coordination framework prior to ligand degradation. SEM-EDS and XRF analyses confirm homogeneous elemental distribution and agreement with the proposed stoichiometry. The antifungal activity of the coordination polymer was evaluated against three agriculturally important phytopathogens, Fusarium oxysporum, Fusarium solani, and Fusarium graminearum. The polymer exhibits significantly enhanced and time-dependent antifungal efficacy compared to the free ligands. Molecular docking studies further support the experimental findings, revealing favourable binding affinities and diverse noncovalent interactions with key fungal target proteins. These results highlight the potential of Cu-based coordination polymers as promising antifungal agents for agricultural applications.

The oxygen reduction reaction (ORR) is an important efficiency-determining process in fuel cells and metal-air batteries, requiring highly efficient and low-cost electrocatalysts. Single-atom catalysts (SACs) have recently emerged as a revolutionary type of catalyst for ORR reaction due to their optimized atom use, precise coordination environment, and controlled electronic structure. Theoretical simulations, especially density functional theory (DFT), have been highly influential in understanding mechanisms of ORR reaction and defining structure-activity relationships of SACs during the last few years. Nevertheless, a very substantial number of possible SAC compositions and structures represents an intrinsic difficulty of solely theoretical catalyst research. In this context, synergy of machine learning (ML) with DFT results has emerged a new paradigm with high potential for speeding up the rational design of SACs for ORR. This review presents a compilation of the latest results on the theory-guided and ML-assisted investigations on ORR active SACs. First, basic concepts of ORR, theory-based descriptors for ORR activity, selectivity, and stability at isolated metallic sites are reviewed. Next, the latest approaches based on ML, including supervised machine learning, descriptor-based approaches, high-throughput techniques, and generative modeling, which use DFT-based data to quickly estimate the ORR energetics of promising SAC structures. Particular attention is given to M–N–C catalysts, coordination asymmetry, axial ligation, frameworks described by dual descriptors, and the role of graph neural networks for the local chemical environments. Finally, we also payed special attention to the challenges, such as the lack of sufficient data, interpretability, and the aforementioned transferability and dynamic effects. Concluding, we provided future perspectives on closed-loop autonomous catalyst discovery, the theory, machine learning, and experimental validation for the development of the next generation ORR electrocatalysts.

A new bimetallic coordination polymer, poly[μ-ethylenediaminetetraacetato-diaqua-cobalt(II)-sodium(I)] ([CoNa(EDTA)(H2O)2]ₙ), was synthesized and structurally characterized. Single-crystal X-ray diffraction revealed that the compound crystallizes in the monoclinic space group P21, forming a three-dimensional coordination framework in which low-spin Co(III) adopts a slightly distorted octahedral geometry and Na(I) ions propagate the polymeric structure through carboxylate bridges. Spectroscopic analyses, bond valence sum (BVS) calculations, and elemental analysis further confirmed the coordination environment and oxidation state of the cobalt centre. Hirshfeld surface analysis showed that H···O/O···H (59.1

The review provides a comprehensive overview of the transition from batch to continuous-flow synthesis of metal nanowires, covering a wide variety of materials, including silver, cobalt, copper, gold, nickel, palladium, platinum, aluminum, bismuth, scandium, titanium, zirconium, vanadium, niobium, molybdenum, tungsten, rhenium, iron, ruthenium, rhodium, iridium, zinc, cadmium, and gallium, and heterostructure nanowires. Their scalability and flexibility have attracted significant interest in large-scale production. Over the past few decades, flow chemistry has proven highly effective for producing nanomaterials, enabling scalable, high-throughput, and reproducible manufacturing. Continuous flow synthesis enhances the quality of NWs for applications in solar cells, sensors, batteries, electrocatalytic reactions, electrochromic window, heaters and optomechanical detection by significantly reducing agglomeration problems in large-scale production. It prevents oxidation and adds stability but requires precise control over the reducing conditions and metal ion concentration to ensure large-scale effectiveness. The various formulations of metal nanowire ink used in this research are critically analyzed to identify performance at reduced metal content. The engineering requirements necessary for designing continuous-flow reactors are presented in the context of challenges associated with large-scale synthesis and related process issues. Concurrently, the biomedical potential of MNWs is explored, with a focus on their use in biosensing, targeted drug delivery, and tissue engineering.

Industrial-level alkaline water electrolysis requires high-efficiency catalysts to achieve rapid water dissociation and hydrogen intermediate migration at an ampere-level current density. However, conventional alloy catalysts lack spatially organized, abundant site functions, resulting in poor coupling between alkaline electrolysis steps. Here, we report a new NiCoFeCuMoW high-entropy alloy (HEA) catalyst prepared by pulse electrodeposition, featuring efficient mass and charge transport. The catalyst features a three-dimensional hierarchically porous framework with tailored surface atomic configurations and chemically differentiated multimetallic motifs, enabling abundant accessible active sites, accelerated transport, and cooperative regulation of reaction intermediates. Density functional theory (DFT) calculations show that Mo/W-richdomains preferentially facilitate H2O dissociation, whereas adjacent NiCoFeCuMoW ensembles optimize hydrogen diffusion and intermediate stabilization via regulated d-band states, thereby establishing an efficient dissociation-diffusion cascade. The NiCoFeCuMoW HEA delivers overpotentials of only 36 mV within the hydrogen evolution reaction (HER) while exhibiting 226 mV in the oxygen evolution reaction (OER) operating in alkaline electrolytes at 10 mA cm-2. Amazingly, the cell delivers an ultra-low electrolyte potential of 1.57 V at 120 °C and 1 A cm-2, owing to greatly enhanced charge-mass transport and perturbed hydrogen-bond networks in the over-boiling environment, providing a scalable HEA design strategy for ampere-level industrial water splitting.

Abstract Organic molecular oxidation reactions are ideally regarded to be energy-saving alternative to replace oxygen evolution reaction (OER) for lowering the oxidation overpotential during green hydrogen production. However, the vast scale of hydrogen production is far beyond the fine chemical processes, inevitably resulting in substantial oxygen release. Here, we propose another type of coupled oxidation reactions to stably accommodate with high-current density hydrogen production, accompanied by easy separation. As taking benzylamine oxidation reaction (BOR) as a probe without other side reactions, we propose a bubble-assisted strategy by activating OER and utilizing the generated oxygen bubbles to timely take the insoluble product benzonitrile away from electrode surface, and effectively overcome the electrode poisoning issue. The assembled prototype water electrolyzer achieves a typical current density of 200 mA/cm 2 and faradaic efficiency of 55% at 1.65 V for over 40 hours, diversify high-value chemical outputs. Such hybrid electrolysis within bubble-assisted strategy endows system flexibility for next-generation integrated electrochemical energy platforms.

Even though lead-containing halide perovskites have been deemed emerging materials. However, the presence of toxic and carcinogenic lead (Pb) metal, small surface area, low charge separation, and a high charge-carrier recombination rate mainly restrain their widespread utilization. To shake off these challenges, we designed a non-toxic lead-free halide perovskite (LFHPs: CsSnBr3) nanocatalyst, which possesses suitable energy band positions, efficient activities, and lower toxicity as compared to lead-containing halide perovskites (CsPbBr3, CsPbCl3, CsPbI3). To further shine the overall efficacy of LFHPs-CsSnBr3, we decorate it with a polyarylimide-based covalent organic framework. The resultant fabricated COF/CsSnBr3 hybrid nano catalysts possess appropriate band structures, low charge recombination rate, elevated charge separation, large surface area, active surface sites with high porosity, tuned energy band gaps, and improved visible light-harvesting capability compared to pristine CsSnBr3 and COF. The most active sample (5COF/CsSnBr3) delivered 4-time improved activities for photocatalytic CO2 conversion into C1 products (CO, CH4) and C2 products (C2H6, C2H5OH, C2H4). Our DFT calculations and simulation-based strategy give deeper insights and support for our experimental findings. Ultimately, our novel research work will unlock a new pathway for designing non-hazardous lead-free halide perovskite-based nanocatalysts for photocatalytic CO2 conversion, energy-rich fuels production, and achieving China's commitment to control CO2 emissions before 2030.

In this study, we introduce a rational design of pulsed laser irradiation in liquids -synthesized Pd nanoparticle-decorated Co nanodendrites (Pd/Co NDs), exhibiting high activity and selectivity toward the nitrate reduction reaction (NO3RR). The optimized Pd/Co ND-3 electrocatalyst achieves a maximum Faradaic efficiency (FE) of 92.35% at -0.1 V vs. RHE and a maximum NH3 yield rate of 9.03 mg h-1 cm-2 at -0.4 V vs RHE during NO3RR. Combined in situ and ex situ spectroscopic analyses reveal dynamic surface reconstruction processes occurring under reaction conditions. Specifically, the Pd/Co NDs undergo structural transformation into a Pd/CoOOH@Co structure during NO3RR, where the synergistic interaction within the reconstructed Pd/CoOOH@Co NDs remarkably enhances catalytic performance, as further supported by theoretical calculations. Furthermore, a Zn-NO3 - battery using Pd/Co NDs as the cathode achieves an open-circuit voltage of 1.506 V and the cathodic NO3RR FE of 68.78% at a current density of 4 mA cm-2, with long-term stability over 500 h. This study highlights the importance of surface reconstructions in the Pd/CoOOH@Co ND electrocatalysis for NO3RR and the performance of the Zn-NO3 - battery, providing valuable insights for designing advanced electrocatalysts aimed at sustainable NH3 synthesis from NO3 - pollutants.

Among emerging material platforms, two-dimensional (2D) semiconductors have attracted considerable interest due to their tunable electronic structures, high surface-active sites, and unique interfacial chemistry, which altogether contribute to the multifunctionality of the materials in energy applications. Despite various review articles dedicated to particular families of 2D semiconductors or to certain aspects of their electrochemistry, there is still an absence of a general understanding of the structure–electronic properties–performance relationships, which govern the performance of 2D semiconductors in energy conversion/storage devices. This review is intended to fill the gap by presenting structure–electronic properties–performance relationships of 2D semiconductors in terms of energy conversion and storage. The fundamental electronic descriptors, charge transport mechanisms, surface chemistry, and interface interactions responsible for catalytic performance are discussed herein. Particular emphasis is placed on atomically engineered approaches such as defect/vacancy engineering, phase tuning, heteroatom doping, strain engineering, heterostructure engineering, and machine learning-driven materials design for their significance in manipulating electronic structure and reaction mechanism. Recent advancements made in oxygen evolution, hydrogen evolution, oxygen reduction, CO2 reduction, N2 reduction, rechargeable battery, and supercapacitor applications is discussed comprehensively from a mechanistic standpoint. Finally, emerging opportunities involving artificial intelligence-guided materials discovery, adaptive semiconductor architectures, high-entropy systems, and sustainable manufacturing are discussed as future directions for intelligent energy materials. By integrating fundamental principles with recent technological advances, this review provides a comprehensive roadmap for the rational design of next-generation 2D semiconductor platforms for sustainable energy conversion and storage.