Adsorption Of Intermediates Research Articles

Direct parallel electrosynthesis of high-value chemicals from atmospheric components on symmetry-breaking indium sites

To tackle significant environmental and energy challenges from increased greenhouse gas emissions in the atmosphere, we propose a method that synergistically combines cost-efficient integrated systems with parallel catalysis to produce high-value chemicals from CO2, NO, and other gases. We employed asymmetrically stretched InO5S with symmetry-breaking indium sites as a highly efficient trifunctional catalysts for NO reduction, CO2 reduction, and O2 reduction. Mechanistic studies reveal that the symmetry-breaking at indium sites substantially improves d-band center interactions and adsorption of intermediates, thereby enhancing trifunctional catalytic activity. Employed in a flow electrolysis system, the catalyst achieves continuous and flexible production of NH3, HCOO-, and H2O2, maintaining over 90% Faradaic efficiency at industrial scales. Notably, the parallel electrolysis device reported in this study effectively produces high-value products like NH4COOH directly from greenhouse gases in pure water, offering an economically efficient solution for small molecule synthesis and unique insights for the sustainable conversion of inexhaustible gases into valuable products. Therefore, this work possesses considerable potential for future practical applications in sustainable industrial processes.

Crystalline/Amorphous Interface Engineering and d-sp Orbital Hybridization Synergistically Boosting the Electrocatalytic Performance of PdCu Bimetallene toward Formic Acid-Assisted Overall Water Splitting.

Advanced electrocatalysts capable of bifunctional catalysis for formic acid oxidation (FAOR) and hydrogen evolution reaction (HER) have garnered significant attention due to their exceptional energy efficiency. In this research, we have meticulously designed a PdCu bimetallene characterized by numerous crystalline/amorphous (c/a) interfaces and robust d-sp orbital hybridization, achieved by integrating the p-block metalloid boron within the PdCu matrix (B-PdCu-c/a). The B-PdCu-c/a bimetallene revealed a multitude of surface atoms and unsaturated defect sites, offering abundant catalytic active sites and an optimized electronic structure. The B2-PdCu-c/a exhibited the best performance in FAOR and HER, achieving a mass activity of 1106 mA mgcat-1 and an overpotential of 52 mV, respectively. Significantly, the two-electrode configuration of B2-PdCu-c/a∥B2-PdCu-c/a attained a low cell voltage of 0.19 V at 10 mA cm-2 during formic acid-assisted overall water splitting. Density functional theory (DFT) calculations indicated that c/a interface engineering and d-sp orbital hybridization synergistically optimized the electronic configuration of pristine PdCu bimetallene. This led to an elevation of the d-band center and an accumulation of charge at the c/a interface, which enhanced the adsorption of intermediates, facilitated C-H bond cleavage, and balanced the adsorption-desorption of hydrogen, thereby improving electrocatalytic activities for FAOR and HER, respectively. This study not only presents a viable strategy for effectively tuning the electronic configuration of bimetallene but also offers valuable insights into the development of electrocatalysts.

Low-Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation.

Electrocatalytic water splitting is long constrained by the sluggish kinetics of anodic oxygen evolution reaction (OER), and rational spin-state manipulation holds great promise to break through this bottleneck. Low-spin Fe3+ (LS, t2g 5eg 0) species are identified as highly active sites for OER in theory, whereas it is still a formidable challenge to construct experimentally. Herein, a new strategy is demonstrated for the effective construction of LS Fe3+ in NiFe-layered double hydroxide (NiFe-LDH) by introducing multiple defects, which induce coordination unsaturation over Fe sites and thus enlarge their d orbital splitting energy. The as-obtained catalyst exhibits extraordinary OER performance with an ultra-low overpotential of 244 mV at the industrially required current density of 500 mA cm-2, which is 110 mV lower than that of the conventional NiFe-LDH with high-spin Fe3+ (HS, t2g 3eg 2) and superior to most previously reported NiFe-based catalysts. Comprehensive experimental and theoretical studies reveal that LS Fe3+ configuration effectively reduces the adsorption strength of the O* intermediate compared with that of the HS case, thereby altering the rate-determining step from (O* → OOH*) to (OH* → O*) of OER and lowering its reaction energy barrier. This work paves a new avenue for developing efficient spin-dependent electrocatalysts for OER and beyond.

Breaking Activity‐Durability Inverse Relationship via Electrode Engineering by Utilizing β‐MnO2/RuO2 Heterostructures for Efficient Seawater Electrolysis

AbstractSignificant efforts are underway to enhance the efficiency of water electrolysis for sustainable hydrogen production. Approaches that were explored are the design of an efficient anode, engineering of electrolytes, and application of diffusion protective layer over the catalyst to protect it from corrosive reactions. Here we are exploring the engineering of electrode fabrication to enhance the efficacy of anode catalysts by ensuring that the materials are carefully selected. β‐MnO2 has been used to develop a cost‐effective method for electrode fabrication that establish a Schottky junction at heterostructure interface. This method transforms commercial RuO2, which is considered to be less active and stable, highly selective for chlorine oxidative reactions, into a highly active, stable, and OER‐selective in alkaline medium and surrogate seawater. With the help of thorough electrochemical techniques, we found that this engineering significantly improves the effective electrochemical surface area, and higher kinetics and conversion per unit site, profoundly affecting the charge transfer mechanism and optimizing the adsorption of OER intermediates, resulting in much‐increased mass activity. It is observed that the selectivity of the OER was enhanced due to the Lewis acid repercussions of β‐MnO2.

Demystifying Synergistic Multifunctional Electrocatalysis of N-Doped Graphene/WS2 Heterostructure with Single-Atom Catalysts for Water Splitting and Fuel Cells.

As the demand for sustainable energy continues to rise, electrocatalysis has become increasingly prominent in the advancement of clean energy technologies. By scrutinizing the material to function as a multifunctional catalyst, the effectiveness of energy conversion processes is significantly enhanced. This study focuses on harnessing graphene/WS2 van der Waals heterostructures for overall water splitting and fuel cell applications, using transition metals (TMs) from Sc-Zn as single-atom catalysts (SACs). Additionally, the research explores the synergistic effect of nitrogen doping combined with SACs to modify the material into multifunctional catalysts. The stability of all TMs as SACs in the vdW heterostructure (TM@GW) and nitrogen-doped TM@GW (TM@NGW) is validated with negative cohesive and formation energies, and thermodynamic stability is also corroborated with ab initio molecular dynamics (AIMD) analysis at both 300 and 500 K for 5 ps. The observed electrocatalytic performance of TM@GW and TM@NGW depicts that the Ni@NGW system exhibits trifunctional property with the lowest overpotentials {ηHER; ηOER; ηORR = 0.21; 0.42; 0.27 V}. Additionally, the Cr@NGW material displays bifunctional catalytic activity for the OER and ORR, with overpotentials of 0.53 and 0.37 V, respectively. The synergistic effect between N doping and SACs is further studied with the d, p band centers and density of states calculations. Furthermore, the scaling relation between the adsorption of intermediates and reaction kinetics is studied, which validates the coaction of N and SACs in the TM@NGW heterostructure. This study demonstrates that the inclusion of SACs and nitrogen atoms in the GW heterostructure significantly enhances the catalytic performance by approximately 26%, effectively transforming the system into a multifunctional catalyst. These findings emphasize the role of SACs in vdW heterostructures and N doping effects, providing valuable insights to guide the design of advanced catalysts for water splitting and fuel cell applications.

Structural Modulation of Nanographenes Enabled by Defects, Size and Doping for Oxygen Reduction Reaction

Nanographenes are among the fastest‐growing materials used for the oxygen reduction reaction (ORR) thanks to their low cost, environmental friendliness, excellent electrical conductivity, and scalable synthesis. The perspective of replacing precious metal‐based electrocatalysts with functionalized graphene is highly desirable for reducing costs in energy conversion and storage systems. Generally, the enhanced ORR activity of the nanographenes is typically deemed to originate from the heteroatom doping effect, size effect, defects effect, and/or their synergistic effect. All these factors can efficiently modify the charge distribution on the sp2‐conjugated carbon framework, bringing about optimized intermediate adsorption and accelerated electron transfer steps during ORR. In this review, the fundamental chemical and physical properties of nanographenes are first discussed about ORR applications. Afterward, the role of doping, size, defects, and their combined influence in boosting nanographenes’ ORR performance is introduced. Finally, significant challenges and essential perspectives of nanographenes as advanced ORR electrocatalysts are highlighted.

Structural Modulation of Nanographenes Enabled by Defects, Size and Doping for Oxygen Reduction Reaction.

Nanographenes are among the fastest-growing materials used for the oxygen reduction reaction (ORR) thanks to their low cost, environmental friendliness, excellent electrical conductivity, and scalable synthesis. The perspective of replacing precious metal-based electrocatalysts with functionalized graphene is highly desirable for reducing costs in energy conversion and storage systems. Generally, the enhanced ORR activity of the nanographenes is typically deemed to originate from the heteroatom doping effect, size effect, defects effect, and/or their synergistic effect. All these factors can efficiently modify the charge distribution on the sp2-conjugated carbon framework, bringing about optimized intermediate adsorption and accelerated electron transfer steps during ORR. In this review, the fundamental chemical and physical properties of nanographenes are first discussed about ORR applications. Afterward, the role of doping, size, defects, and their combined influence in boosting nanographenes' ORR performance is introduced. Finally, significant challenges and essential perspectives of nanographenes as advanced ORR electrocatalysts are highlighted.

Machine-Learning-Assisted Screening of Nanocluster Electrocatalysts: Mapping and Reshaping the Activity Volcano for the Oxygen Reduction Reaction.

In computational heterogeneous catalysis, Sabatier's principle-based activity volcano plots provide an intuitive guide to catalyst design but impose a fundamental constraint on the maximum achievable catalytic performance. Recently, subnano clusters have emerged as an exciting platform, offering high noble metal utilization and superior performance for various reactions compared to extended surfaces, reflecting a complex structure-activity relationship in the non-scalable regime. However, understanding their non-monotonic catalytic activity, attributed to the large configurational space and their fluxional identity, poses a formidable challenge. Here, we present a machine learning (ML) framework that captures the non-monotonic trends in oxygen reduction reaction (ORR) activity at the subnanometer scale, attributed to their dynamic fluxional characteristics. We demonstrate a size-dependent shifting and reshaping of the ORR activity volcano, with Au replacing Pt at the peak. Leveraging only upon the non-ab initio geometric and electronic properties, our trained ML model accurately captures the site-specific adsorption energies of intermediates at the subnanometer regime. To account for the inconsistent trend in activity, we analyzed the correlation between electronic and geometric properties. Our findings reveal that the d-filling and coupling matrix of the neighboring metal atom significantly influences the intermediate adsorption on the local chemical environment compared to the d-band center. Following this analysis, we utilized ML to map the catalyst distribution in the activity volcano and identified the five best sub-nano electrocatalysts, demonstrating overpotential values lower than or comparable to the Pt(111) surface for the ORR. This study provides intuitive guidelines for the rational designing of highly efficient electrocatalysts for fuel cell applications while modifying the activity volcano plots for electrocatalysts at the subnanometer regime.

Ru‐MnO Heterostructure Clusters Toward Efficient and CO‐Tolerant Alkaline Hydrogen Oxidation Reaction

AbstractDesigning efficient and CO‐tolerant catalysts for hydrogen oxidation reaction (HOR) in anode is one of the challenges for alkaline exchange membrane fuel cells in practical application. Herein, Ru‐MnO heterostructure with two adjacent clusters supported on commercial carbon (BP 2000) (denoted as Ru‐MnO/C) is designed to accelerate the sluggish kinetics of alkaline HOR. The cluster–cluster heterostructure interface modifies the electronic structure of Ru sites with electron transfer from Ru to MnO, then optimizes the adsorption of intermediates on Ru sites. Consequently, this catalyst exhibits high catalytic HOR activities in alkaline media with high exchange current density (3.71 mA cm−2) and mass activity (0.78 A mgRu−1). Meanwhile, the alkaline exchange membrane fuel cell delivers a specific peak power density (PPD) of 7.0 W mg−1Ru under H2/O2 condition, which is higher than that of most reported catalysts. More importantly, the catalyst also demonstrates the remarkable stability and CO‐tolerance. This work presents the superiority of cluster–cluster heterostructure interface toward efficient HOR, which is expected to further enlighten the design of advanced catalysts for electrocatalysis.

Strain Effects and Crystalline-Amorphous Interface of NiFe-LDH@S-NiFeOx/NF with Heterogeneous Structure for Enhancing Electrocatalytic Oxygen Evolution Reaction of Water-Electrolysis.

Electrochemical water-electrolysis for hydrogen generation often requires more energy due to the sluggish oxygen evolution reaction (OER). This work introduces a double-layered nanoflower catalyst, NiFe-LDH@S-NiFeOx/NF, featuring a crystalline NiFe-LDH coating on amorphous S-NiFeOx on nickel foam. Strategically integrating a crystalline-amorphous (c-a) heterostructure leverages strain engineering to enhance OER activity with low overpotentials (η100 = 220 and η500 = 245mV) and stability (135 h at η100 and 80 h at η500). Theoretical density functional theory (DFT) calculations reveal that the compressive strain can optimize the adsorption of oxygen-containing intermediates to reduce the reaction energy barrier, thus improving the reaction kinetics and performance of OER. Moreover, its phosphated derivative, NiFeP@S-NiFeOx/NF, exhibits high hydrogen evolution reaction (HER) performance (η10 = 64mV, η100 = 187mV). An alkaline water-electrolysis cell of NiFeP@S-NiFeOx/NF(-)||NiFe-LDH@S-NiFeOx/NF(+) requires only a cell voltage of 1.77V at 100 mA cm-2, demonstrating excellent stability over 110 h (at both 10 and 100mA cm-2). This work highlights the benefits of integrating crystal-amorphous interfaces and strain effects, offering insights into the understanding and optimizing catalytic OER mechanism and advancing water-electrolysis technology.

Modulating Built‐In Electronic Configuration via Variable Al Doping for Robust Oxygen Evolution Reaction

Transition metal‐based electrocatalysts play a crucial role in the oxygen evolution reaction (OER). However, their heavy reliance on free electrons at the <i>d</i>‐band significantly limits the screening of potentially efficient, earth‐abundant alternatives. Despite extensive exploration of catalyst engineering through multi‐metal cooperation to modulate electron configuration by introducing additional transition metals, practical success remains elusive. Here, we present a straightforward electrodeposition method for preparing amorphous FeCoAl hydroxide catalysts. The introduction of Al contributes external free electrons, enabling a well‐defined electron configuration for intermediate adsorption. Al doping also adjusts the <i>d</i>‐band position of adjacent Co atoms, bringing them closer to the Fermi level and significantly enhancing intrinsic activity at the active sites. Furthermore, Al dopants facilitate rapid mass and charge transfer near the catalyst layer, promoting faster reaction kinetics. Leveraging these properties, the FeCoAl hydroxide catalyst achieves a large current density of 100 mA cm <sup>‐2</sup> at an overpotential of 340 mV, with a small Tafel slope of 29.1 mV dec <sup>‐1</sup>. Our work provides valuable insights for designing efficient electrocatalysts by leveraging free electron‐rich metal doping and expanding the parameter space for catalyst engineering.

D‐Band Center Modulation of Metallic Co‐Incorporated Co7Fe3 Alloy Heterostructure for Regulating Polysulfides in Highly Efficient Lithium‐Sulfur Batteries

AbstractLithium‐sulfur (Li‐S) batteries, with their high theoretical energy density and cost‐effectiveness, have become one of the most promising next‐generation energy storage devices. However, they still face challenges such as the “shuttle effect” caused by the dissolution of polysulfide intermediates and the slow sulfur conversion kinetics. In this study, based on the Co7Fe3 alloy catalyst, additional Co metal is introduced to form a Co7Fe3Co catalyst with a heterostructure through a simple heat treatment process. This catalyst is incorporated into Ketjenblack (KB) to form a sulfur‐infused cathode material (designated as S/KB/Co7Fe3Co). Li‐S batteries using S/KB/Co7Fe3Co as the cathode demonstrate outstanding electrochemical performance, maintaining a reversible specific capacity of over 500 mAh g−1 after 1000 cycles at a current density of 1 C, with a capacity decay rate of 0.046% per cycle. DFT theoretical calculations and experimental results both reveal that the introduction of additional Co effectively regulates the d‐band center of the material, enhancing the adsorption of polysulfide intermediates by Co7Fe3Co and promoting bidirectional catalytic sulfur conversion. This work highlights the importance of the simple construction of heterostructured catalytic materials and their role in improving the performance of Li‐S batteries.

Iron and nickel based alloy nanoparticles anchored on phosphorus-modified carbon-nitrogen plane enhances electrochemical nitrate reduction to ammonia

The catalysts of iron and nickel nanoparticles anchored on carbon–nitrogen plane (FeNi-CN) are considered as the potential candidates for promising electrochemical nitrate reduction to ammonia (ENO3RR). However, the high d-orbital energy levels of iron and nickel sites coordinated with nitrogen atoms often lead to overly strong adsorption of reaction intermediates on active sites, severely limiting the improvement of catalytic performance. Herein, a catalyst FeNi3@P-NC consisting FeNi3 alloy nanoparticles confined in phosphorus (P)-modified carbon–nitrogen plane is successfully fabricated, where the electron withdrawal effect induced by P on the carbon–nitrogen plane decreases the d-orbital energy, and optimizes the d-band center of FeNi alloy, thus weakening the overly strong adsorption of intermediates at the metal-N sites and thereby improving NO3RR activity. The prepared FeNi3@P-NC catalyst exhibits exceptional NO3RR performance with a 93 ± 4.5 % Faradaic efficiency of NH3 production (FENH3) and a high NH3 yield rate (YNH3) of 9633 ± 227.3 μg h−1 cm−2 at −0.7 V versus Reversible Hydrogen Electrode (vs. RHE) under alkaline medium. Importantly, FeNi3@P-NC also demonstrates superior catalytic stability and durability, which maintains stability over twenty-five successive electrochemical cycles and for 50 h of continuous electrolysis at 100 mA cm−2.

Boosting multi-carbon products selectivity of carbon dioxide reduction via bifunctional cyclodextrin-modification on copper/copper(I) oxide electrocatalysts

Electrochemical carbon dioxide reduction to multi-carbon (C2+) products presents a significant opportunity for converting greenhouse gases into valuable fuels and feedstocks. The development of highly active and stable catalysts remains a critical challenge. In this study, we report the design and synthesis of cyclodextrin-modified Cu/Cu2O electrocatalysts, which exhibit remarkable efficiency in driving the CO2 electroreduction process towards C2+ products. Our optimized catalyst achieves a C2+ Faradaic efficiency exceeding 50 % at a high current density of over 200 mA cm−2. Experimental findings, supported by density functional theory (DFT) calculations, reveal that cyclodextrin plays a dual role in stabilizing Cu+ and increasing the surface density of hydroxyl radicals. This dual function greatly benefits for enhancing *CO intermediate adsorption and promotes *CHO formation, thereby facilitating the crucial dimerization step for the formation of C2+ products. This work provides valuable insights into the development of highly active and selective electrocatalysts by carefully tuning the local catalytic environment, potentially opening new avenues for functionalizing electrocatalysts for future research in this area.

Regulating N-doped biochar with Fe-Mo heterojunctions as cathode in long-life zinc-air battery

Carbonaceous electrode loaded nano Mo2C-Fe3N@NCF was synthesized by solvothermal and pyrolysis from soybean straw for high-performance zinc-air batteries (ZABs). The empowered ZAB achieved 1.51 V open-circuit voltage, 88.40 mW cm−2 power density and over 1150 h cycle life. Density functional theory analysis indicates that charge transfer from Mo2C-Fe3N heterogeneous structure to N-doped biochar can significantly reduce the reaction barrier for oxygen reduction/evolution reactions, enhancing the adsorption of oxygen intermediates. Cellulose-derived carbon provides a large specific surface area, and N-doping enhances the conductivity of the resultant biochar, which both play a crucial role in the efficient loading of Fe and Mo active sites. This work inspires the design and application of interfacial engineering on low-cost biochar carriers.

Enhanced ethanol synthesis via CO2 hydrogenation using La-Doped CuFeOx catalysts

CO2 hydrogenation is an effective solution for direct ethanol production as it realizes a high-value utilization of waste CO2. As it requires a synergistic multi-step process of CO2 activation, asymmetric hydrogenation of CO, and precise coupling of C-C bonds, the design of highly active and selective catalysts for such procedures remains challenging. In this study, we prepared a series of La-doped CuFe catalysts using a simple and green solvent-free ball milling method to accelerate the rate of CO2 hydrogenation to ethanol generation. HRTEM, in situ XRD, EPR, and CO2-TPD analyses indicated that the doping of moderate amounts of La can significantly improve the dispersion of the Cu and Fe species, enhance the interaction between the CuFe species, decrease the reduction temperatures of CuO and Fe2O3, promote the formation of oxygen vacancies during the reaction process, and enhance CO2 adsorption and activation ability. DFT calculations, XPS, in situ FTIR, and CO-TPSR-MS analyses indicated that the transfer of electrons from the Fe to La species decreased their electron cloud densities, weakened the bridge type adsorption of CO, enhanced the linear adsorption of CO, and optimized the ratio of the dissociative and non-dissociative adsorption of CO intermediates, which ultimately resulted in a better matching of the rates of generation of CHx* and C(H)O* intermediates. The occurrence of C-C coupling at the abundant Cu0-Fe5C2 interface promoted the highly efficient synthesis of ethanol, achieving yields as high as 13.5 % over the 5La-CuFeOx catalyst, ranking the top level among the reported catalysts in the literature. This study presents a feasible strategy for the targeted regulation of multicomponent active centers.

Unique electron-feeding mechanism in CoN3O for enhanced acidic oxygen reduction

Co-centered single-atom catalysts (SACs) have emerged as an increasingly promising non-platinum group candidate for acidic oxygen reduction reaction (ORR) due to their balanced activity and stability. However, the intrinsic ORR activity of present Co-centered SACs remains far below the commercial Pt/C. Herein, a CoN3O-structured SAC is successfully fabricated by a gas-phase strategy and achieves a peak power density of 492.6 mW cm−2 under the 1.0 bar H2/air condition, demonstrating its excellent application potential in practical fuel cells. Unique electron-feeding mechanism is revealed to account for the remarkably enhanced ORR activity inner CoN3O SAC. It is indicated that the electron interaction inner active site governed by both electronegativity in σ bond and d-p back-feeding in π bond reaches balance at CoN3O, thus optimized adsorption of oxygen-containing intermediates. Our work provides multiple insights into the orbital scale laws for higher-performance PGM-free ORR catalysts.

Interface engineering in Ni(OH)2/NiOOH heterojunction to enhance energy-efficient hydrogen production via urea electrolysis

Electrochemical urea electrolysis has merged as a promising alternative to conventional water splitting methods for hydrogen fuel production due to its cost-effectiveness and superior energy efficiency. The utilization of heterostructures has been proposed as a viable strategy to improve the efficiency of the urea oxidation reaction (UOR) by augmenting the quantity of active sites and optimizing the electronic structure. In this study, a Ni(OH)2/NiOOH heterojunction, referred to as H-Ni, was synthesized via a straightforward hydrothermal synthesis method. The notable performance of H-Ni in UOR is ascribed to the synergistic interaction between Ni(OH)2 and NiOOH, which constitute the principal components of the catalyst. Density functional theory (DFT) calculations reveal that the H-Ni composite is capable of modulating the d-band center, thereby enhancing the adsorption and desorption of reaction intermediates and decreasing the Gibbs free energy (ΔG) associated with the rate-determining step (RDS) of the UOR. Experimental results from catalytic performance tests indicate that the H-Ni-140 catalyst attains a current density of 10 mA·cm−2 in 1 a M KOH electrolyte containing 0.33 M urea at a relatively low potential of 1.341 V versus reversible hydrogen electrode (RHE), thereby highlighting its superior electrocatalytic performance. Furthermore, the catalyst requires only a cell voltage of 1.78 V to achieve a current density of 100 mA·cm−2, which is approximately 120 mV lower than that required for water electrolysis. This work presents a straightforward methodology for the cost-effective development of heterojunction catalysts.

MOF-Derived Nitrogen-Rich Hollow Nanocages as a Sulfur Carrier for High-Voltage Aluminum Sulfur Batteries.

Aluminum-sulfur batteries (ASBs) are emerging as promising energy storage systems due to their safety, low cost, and high theoretical capacity. However, it remains a challenge to overcome voltage hysteresis and short cycle life in the sulfur/Al2S3 conversion reaction, which hinders the development of ASBs. Here, we studied a high-voltage ASB system based on sulfur oxidation in an AlCl3/urea electrolyte. Nitrogen-doped hollow nanocages (HNCs) synthesized from MOF precursors were rationally designed as sulfur/carbon composite electrodes (S@HNC), and the impact of the nitrogen species on the electrochemical performance of sulfur electrodes was systematically investigated. The S@HNC-900 achieved efficient conversion at 1.9 V, delivering a stable capacity of 197.3 mA h g-1 and a Coulombic efficiency of 93.28% after 100 cycles. Furthermore, the S@HNC-900 electrode exhibited exceptional rate capacity and 800th long-term cycling stability, retaining a capacity of 87.1 mA h g-1 at 500 mA g-1. Ex situ XPS and XRD characterizations elucidated the redox mechanism, revealing a four-electron transfer process (S/AlSCl7) at the S@HNC-900 electrode. Density functional theory calculations demonstrated that pyridinic nitrogen-enriched HNC-900 significantly enhanced the sulfur conversion reaction and facilitated the adsorption of sulfur intermediates (SCl3+) on the carbon interface. This work provides critical insights into the high-voltage sulfur redox mechanism and establishes a foundation for the rational design of carbon-based electrocatalysts for the enhancement of ASB performance.

Surface Corrosion‐Resistant and Multi‐Scenario MoNiP Electrode for Efficient Industrial‐Scale Seawater Splitting

AbstractThe construction of efficient and durable multifunctional electrodes for industrial‐scale hydrogen production presents a main challenge. Herein, molybdenum‐modulated phosphorus‐based catalytic electrodes (Mo‐NiP@NF) are prepared via mild electroless plating. Heteroatoms doping or heterostructures construction can reconfigure the intrinsic electronic structure of the pre‐catalyst and optimizes the key intermediates adsorption. Moreover, the (hypo/meta‐)phosphite anions (POxδ−) and molybdate ions (MoOxδ−) on the electrode surface of Mo‐NiP@NF afford resistance to chloride (Cl−) corrosion. Mo‐NiP@NF exhibits ultralow overpotentials of 278/550 and 282/590 mV at 1 A cm−2 during the hydrogen/oxygen evolution reaction (HER/OER) in alkaline simulated and real seawater, respectively, whereas catalytic overall seawater splitting (OWS) reach 1 A cm−2 at 1.96 and 1.97 Vcell. Remarkably, Mo‐NiP@NF maintains stable operation for 1500 h in OWS. The scalability of Mo‐NiP@NF allowing the assembly of proton exchange membrane (PEM) electrolyzer powered by photovoltaic energy, simulating a portable hydrogen‐oxygen respirator provides an oxygen/hydrogen flows of 160/320 mL min−1. Expanding further, the trace ruthenium‐loaded Mo‐NiP@NF catalyst sodium borohydride (NaBH4) hydrolysis achieving a hydrogen generation rate (HGR) of 11049.2 mL min−1 g−1. This work provides strategic innovations and optimization solutions for the economical and mild construction of multi‐scenario durable green energy conversion materials at industrial‐scale application.