Non-noble Metal-based Electrocatalysts Research Articles

CuNi alloy anchored on dual-substrate TiOx/N-doped carbon nanofibers as a bifunctional electrocatalyst for rechargeable zinc-air batteries

Development of non-noble metal-based electrocatalysts to enhance the performance of zinc-air batteries (ZABs) is of great significance, but it remains a formidable challenge due to their poor stability and activity. Herein, a bifunctional CuNi-TiOx/NCNFS electrocatalyst, featuring with electron-rich copper-nickel (CuNi) alloy nanoparticles anchored on titanium oxide/N-doped carbon nanofibers (TiOx/NCNFS), is constructed by a dual-substrate loading strategy. The introduction of TiOx has led to a significant increase in the stability of the dual-substrate. The strong electronic interaction between CuNi and TiOx strengthens the anchoring of active metal sites, thus accelerating the electron transfer. Theoretical calculations unclose that NCNFS can regulate the charge distribution of TiOx, inducing the charge transfer from NCNFS → TiOx → CuNi, thereby reducing the d-band center of Cu and Ni, which is beneficial to the desorption of intermediate oxide species of the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Therefore, CuNi-TiOx/NCNFS delivers a remarkable bifunctional performance with a low OER overpotential of 258 mV at 10 mA cm−2 and an ORR half-wave potential of 0.85 V. When assembled into ZABs, CuNi-TiOx/NCNFS shows a low potential gap of 0.64 V, a higher power density of 149.6 mW cm−2 at 330 mA cm−2, and an outstanding stability for 250 h at 5mA cm−2. This study provides a novel approach by constructing dual-substrate to tune the electronic structure of active metal sites for efficient rechargeable ZABs.

Seamless construction of self-supporting nanoporous FeCoZn alloy as one highly efficient electrocatalyst for oxygen evolution reaction in alkaline media

Exploring high-efficient and economical electrocatalyst for oxygen evolution reaction (OER) is critical for the electrocatalytic water splitting technology to hydrogen production. Herein, we report a hierarchical nanoporous FeCoZn alloys with different Fe/Co atomic ratios in-situ constructed on bimodal porous NiZn intermetallic and Ni heterojunction over nickel foam (FeCoZn/NF) through a scalable electroplating-annealing-etching strategy. The synergistic effect between multi-elements, multiple interface coupling, and self-supporting seamless porous architecture is beneficial for enhancing the number of active sites but also promoting efficient mass transport and electron transfer. FeCoZn/NF exhibits the superior electrocatalytic activity toward OER with a low overpotential of 440 mV at 1004 mA cm−2 and small Tafel slope of 84.8 mV dec−1. The as-made sample also shows exceptional long-term catalytic stability in alkaline media with 1.0 M KOH of remained under the overpotential of 350 mV for 100 h. Besides, the combined FeCoZn/NF and Pt/C/NF for overall water splitting needs the cell potential of 1.481 V at 10 mA cm−2, along with long-term stability. This work provides implications for the design and preparation of highly active non-noble metal-based multiple alloy electrocatalysts.

A Bifunctional Electrocatalyst of Flower-Like Cr-Doped CoP/Fe2P Microsphere for Efficient Overall Water Splitting

Developing efficient, low-price non-noble metal-based electrocatalysts for overall water splitting in alkaline medium remains a formidable challenge. In our work, Cr-doped CoP/Fe2P (Cr-CoP/Fe2P) flower-like microsphere was synthesized through a simple hydrothermal and phosphating process. The resulting Cr-CoP/Fe2P electrocatalyst shows significantly enhanced oxygen evolution reaction performance (262 mV @ 10 mA cm−2) and has a satisfactory hydrogen evolution reaction performance (114 mV @ 10 mA cm−2), coupled with favorable stability in an alkaline medium. Furthermore, when assembling Cr-CoP/Fe2P into an electrolytic cell, the two-electrode system can provide a current density of 10 mA cm−2 at a voltage of 1.61 V. At high current density, the performance of the electrolytic cell composed of Cr-CoP/Fe2P is superior to that of noble metal catalyst electrode pair. Electronic structure analysis and various characterizations confirm that Cr doping and the formation of CoP/Fe2P heterogeneous interfaces redistribute the electron densities of the active sites, enlarge the specific surface area, and enhance the aerophobicity of the catalysts, thereby improving the electrocatalytic property. This work provides a referable method for engineering highly efficient and stable non-noble polymetallic phosphides, which serve as bifunctional electrocatalyst for overall water splitting.

Two-dimensional flake Co/Co2N0.67 modified by molybdenum oxides achieves enhancement of bifunctional hydrogen electrocatalysis

To address the urgent need for non-precious metal-based catalysts in the industrial preparation and application of hydrogen energy, we present a secondary hydrothermal strategy to prepare a Mo-modified cobalt carbonate precursor, resulting in the Mo–Co/Co2N0.67 catalyst. The cobalt-based materials exhibit a layered flake structure due to molybdenum modification, exposing more active sites, while molybdenum oxide modification enhances hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). In alkaline HER measurements, Mo–Co/Co2N0.67 achieves a remarkable current density of 10 mA cm−2 at only 27 mV. The overall water splitting of Mo–Co/Co2N0.67 + RuO2 can reach 10 mA cm−2 at 1.52 V voltage. In alkaline HOR measurements, it exhibits the current density of 2.92 mA cm−2@0.1 V vs. RHE and an exchange current density (J0) of 2.96 mA cm−2. This work highlights the effective regulation of non-noble metal-based electrocatalysts through Mo modification, providing valuable insights for the development of efficient non-precious metal-based hydrogen electrocatalysis within the context of anion exchange membrane unitized reversible fuel cells (AEM-URFC).

Directed Surface Reconstruction of Fe Modified Co2VO4 Spinel Oxides for Water Oxidation Catalysts Experiencing Self-Terminating Surface Deterioration.

Affordable highly efficient catalysts for electrochemical oxygen evolution reaction (OER) play pivotal roles in green hydrogen production via water electrolysis. Regarding the non-noble metal-based electrocatalysts, considerable efforts are made to decipher the cation leaching and surface reconstruction; yet, little attention is focused on correlating them with catalytical activity and stability. Herein, in situ reconstruction of Fe-modified Co2VO4 precursor catalyst to form a highly active (Fe,V)-doped CoOOH phase for OER is reported, during which partial leaching of V accelerates the surface reconstruction and the V reserved in the reconstructed CoOOH layer in the form of alkali-resistant V2O3 serves for dynamic charge compensation and prevention of excessive loss of lattice oxygen and Co dissolution. Fe substitution facilitates Co pre-oxidation and endows the catalysts with structural flexibility by elevating O 2p band level; hence, encouraging participation of lattice oxygen in OER. The optimized Co2Fe0.25V0.75O4 electrode can afford current densities of 10 and 500 mA cm-2 at low overpotentials of 205 and 320 mV, respectively, with satisfactory stability over 600 h. By coupling with Pt/C cathode, the assembled alkaline electrolyzer can deliver 500 mA cm-2 at a low cell voltage of 1.798 V, better than that of commercial RuO2 (+) || Pt/C (-).

Effect of the synthesis route and Co Coverage on Co / Ti3C2Tx materials for the oxygen evolution reaction

Green hydrogen resulting from water electrolysis is a key component for the transition to a renewable energy economy. However, it's success highly depends on active and stable electrocatalysts for the oxygen evolution reaction (OER) which is the bottleneck reaction of water electrolysis. Herein we assess the OER performance of non-noble metal-based electrocatalysts comprising Co oxide/hydroxide and delaminated 2D transition metal carbide sheets, Ti3C2Tx MXene. The catalytically active sites are provided by Co oxide/hydroxide, while the MXene contributes exceptional electrical conductivity. Our comprehensive electrochemical evaluation of their OER performance reveals that the chemical functionalization of Co on MXene sheets outperforms the pure Co or MXene alone, as well as physically mixed materials, across all tested performance metrics. From the materials characterisation, the chemical functionalized Co/Ti3C2Tx materials exhibit increased formation of layered double hydroxide (LDH) Co(OH)2 structures compared to the pure Co and physically mixed materials which may result in the improved OER activity observed for these materials. These findings emphasize the potential of anchoring transition metal oxides/hydroxides on MXene as a superior OER electrocatalyst for advancing sustainable green hydrogen production.

In Situ-Generated Hollow CoFe-LDH/Co-MOF Heterostructure Nanorod Arrays for Oxygen Evolution Reaction.

Assembling a heterostructure is an effective strategy for enhancing the electrocatalytic activity of hybrid materials. Herein, CoFe-layered double hydroxide and Co-metal-organic framework (CoFe-LDH/Co-MOF) hollow heterostructure nanorod arrays are synthesized. First, [Co(DIPL)(H3BTC)(H2O)2]n [named as Co-MOF, DIPL = 2,6-di(pyrid-4-yl)-4-phenylpyridine, H3BTC = 1,3,5-benzenetricarboxylic acid] crystalline materials with a uniform hollow structure were prepared on the nickel foam. The CoFe-LDH/Co-MOF composite perfectly inherits the original hollow nanorod array morphology after the subsequent electrodeposition process. Optimized CoFe-LDH/Co-MOF hollow heterostructure nanorod arrays display excellent performance in oxygen evolution reaction (OER) with ultralow overpotentials of 215 mV to deliver current densities of 10 mA cm-2 and maintain the electrocatalytic activity for a duration as long as 220 h, ranking it one of the non-noble metal-based electrocatalysts for OER. Density functional theory calculations validate the reduction in free energy for the rate-determining step by the synergistic effect of Co-MOF and CoFe-LDH, with the increased charge density and noticeable electron transfer at the Co-O site, which highlights the capability of Co-MOF to finely adjust the electronic structure and facilitate the creation of active sites. This work establishes an experimental and theoretical basis for promoting efficient water splitting through the design of heterostructures in catalysts.

Ru Single Atoms Integrated into Cobalt Oxide Spinel Structure with Interstitial Carbon for Enhanced Electrocatalytic Water Oxidation.

Oxygen evolution reaction (OER) plays a critical role in energy conversion technologies. Significant progress has been made in alkaline conditions. In contrast, it remains a challenge to develop stable OER electrocatalysts in acidic conditions. Herein, a new strategy is reported to stabilize single atoms integrated into cobalt oxide spinel structure with interstitial carbon (Ru0.27Co2.73O4), where the optimized Ru0.27Co2.73O4 exhibits a low overpotential of 265, 326, and 367mV to reach a current density of 10, 50, and 100mA cm2, respectively. More importantly, Ru0.27Co2.73O4 has long-term stability of up to 100h, representing one of the most stable OER electrocatalysts. X-ray adsorption spectroscopy (XAS) characterization and density functional theory (DFT) calculations jointly demonstrate that the significant catalytic performance of Ru0.27Co2.73O4 is due to the synergistic effect between the Ru and Co sites and the bridging O ligands, as well as the significant reduction of the OER energy barrier. This work provides a new perspective for designing and constructing efficient non-noble metal-based electrocatalysts for water splitting.

Non-Noble Transition Metal-Based Electrocatalysts for Green Hydrogen Production from Anion Exchange Membrane (AEM) Seawater Electrolyzer

As water-scarce is increasing rapidly all over the world, water electrolysis might not be a practical approach for sustainable hydrogen production in the long term. Fortunately, hydrogen production from the anion exchange membrane (AEM) seawater electrolysis enables to achieve of sustainability and durability. But still, suitable electrocatalysts for hydrogen and oxygen evolution reactions in seawater are not figured out yet. Here we report non-noble transition metal-based electrocatalysts for hydrogen and oxygen evolution reaction in seawater electrolysis. The synthesized electrocatalysts were in-situ characterized in X-ray diffraction (XRD), scanning electron microscopy (SEM), Transition electron microscopy (TEM), Raman spectroscopy, and ex-situ characterized in linear sweep voltammetry (LSV), Chronopotentiometry, and impedance studies. Further, the electrocatalysts were investigated in a single-cell anion exchange membrane electrolyzer, and polarization curves, stability tests, and efficiency calculations were carried out. These research findings will be further investigated until attains the industrially required parameters of 1 A cm-2 at a low overpotential of 1.8 V.

MOF-derived CoS2/WS2 electrocatalysts with sulfurized interface for high-efficiency hydrogen evolution reaction: Synthesis, characterization and DFT calculations

Developing high-efficiency, economical and non-noble-metal electrocatalysts is of great importance to produce hydrogen through hydrogen evolution reaction (HER) in water splitting. Transition metal dichalcogenide has received increasing interests in the application in efficient catalysis, energy conversion and storage. Now, a unique bimetallic sulfide composite (CoS2/WS2) has been prepared by calcination and one-pot hydrothermal method using metal–organic frameworks (MOFs) as precursors. The presence of suitable thioacetamide (TAA) plays a great role in forming the best sulfide interface between CoS2 and WS2 to enhance HER performance. Herein, the overpotential and Tafel slope of as-synthesized CoS2/WS2 at 10 mA cm−2 in 0.5 M H2SO4 medium are obtained as 79 mV and 52 mV dec–1, respectively, which are much lower than those of most non-noble metal-based electrocatalysts. Density Functional Theory (DFT) calculations verify that the bimetallic configuration through the sulfide interface changes the electronic structure, enhances the electrical conductivity and reduces the hydrogen adsorption energy (ΔGH*), effectively accelerating the Heyrovsky step in the HER process. Meanwhile, CoS2/WS2 shows excellent stability in durability tests. The method proposed in this work provides a feasible solution for synthesizing low-cost electrocatalysts.

The In Situ Construction of NiFeS on Stainless Steel Mesh as an Efficient Electrocatalyst for UOR

Urea can be used as an effective hydrogen energy carrier, the development of efficient and stable anodic electrocatalysts for urea oxidation reaction (UOR) was crucial for achieved energy-saving hydrogen-production. Nanoflower like structures electrocatalysts have attracted increasing research interests due to its structural advantages. In this article, NiFeS/SSM with two dimensions (2D) nanosflower like structures in situ growth on three dimensions (3D) stainless steel mesh (SSM) is prepared by step-wise hydrothermal method. NiFeS/SSM was derived from NiFe layered double hydroxides, and the as-prepared electrode was directly served as a electrocatalysts for UOR. Benefiting from the electronic effect between Ni and Fe components which promotes the formation of the high valence Ni species in the NiFeS/SSM catalyst, the tuning effect from the in situ generated sulfate and its open 3D porous structure for SSM basement. The electrode displayed excellent catalytic activities towards UOR, the overpotential for UOR are 1.08 V in alkaline electrolyte at 50 mA·cm−2. This work not only illustrated that non-noble metal-based electrocatalysts have tremendous potential applications for electrocatalytic electrolysis of urea but also provided a feasible strategy to prepare high-efficiency and stable non-precious metal UOR anode catalysts in alkaline medium.

MXene based electrocatalyst: CoS2@Ti3C2Tx composite for hydrogen evolution reaction in alkaline media

The worldwide need for hydrogen (H2) fuel generation through electrolysis is significant. The challenge of selecting a suitable electrocatalytic material, on the other hand, is highly complicated, since it involves discovering a stable, cost-effective choice that is widely accessible. Non-noble metal-based electrocatalysts are being studied for their potential to display attractive electrochemical water splitting (EWS) behaviour especially in alkaline media. Researchers are evaluating their ability to provide increased electrical conductivity, reduced overpotential, and greater density, which are all required for practical implementation. Herein, we present wet chemical-based synthesized MXene (Ti3C2Tx) incorporated cobalt-sulfide (CoS2) electrocatalyst for hydrogen evolution reaction (HER) in alkaline medium. As-prepared catalyst shows; very low overpotential value (286 mV) to reach 20 mA/cm2 current density, lower Tafel slope value of 78 mV/dec, higher electrochemical surface area (ECSA) 495 cm2, as well as a lower charge transfer resistance (Rct) value of 115 Ω. Such electrochemical features support this composition as a novel and robust electrocatalyst for HER toward its practical usage for energy storage and conversion systems.

Interface engineering of NiS/NiCo2S4 heterostructure with charge redistribution for boosting overall water splitting

Developing highly efficient bifunctional non-noble metal-based electrocatalysts is pivotal to fulfilling practical water electrolysis. In this work, NiS/NiCo2S4 heterostructured electrocatalysts are prepared through a simply controlling sulfurization process by employing a one-pot solvothermal strategy. The alteration of cobalt addition amount can affect the crystalline phase, morphology, and catalytic activity of the resulting heterostructured materials. The successful integration of NiS with NiCo2S4 is realized by deliberately tuning the cobalt addition amount. The resulting Co-Ni-S5:1 delivers high activity with low overpotentials of 198 and 259 mV to attain 10 mA cm−2 when used as electrocatalysts toward hydrogen evolution reaction and oxygen evolution reaction, respectively. Experimental and theoretical calculations evidence the strong interface coupling between NiS and NiCo2S4 leads to increased electronic conductivity, electron migration near lattice-matched interface and interfacial charge redistribution, thereof enhancing the reaction kinetics rate and activity. Moreover, the potential application is demonstrated by employing Co-Ni-S5:1 in a two-electrode electrolyzer which can efficiently catalyze water electrolysis and work stably for 100 h. This work not only provides highly efficient bifunctional heterostructured electrocatalysts by simply regulating the metal components in sulfides but also further broadens the application of interface engineering.

Controlling Surface Chemical Inhomogeneity of Ni2 P/MoNiP2 /MoP Heterostructure Electrocatalysts for Efficient Hydrogen Evolution Reaction.

Crystalline/amorphous phase engineering is demonstrated as a powerful strategy for electrochemical performance optimization. However, it is still a considerable challenge to prepare transition metal-based crystalline/amorphous heterostructures because of the low redox potential of transition metal ions. Herein, a facile H2 -assisted method is developed to prepare ternary Ni2 P/MoNiP2 /MoP crystalline/amorphous heterostructure nanowires on the conductive substrate. The characterization results show that the content of the MoNiP2 phase and the crystallinity of the MoP phase can be tuned by simply controlling the H2 concentration. The obtained electrocatalyst exhibits a superior alkaline hydrogen evolution reaction performance, delivering overpotentials of 20 and 76mV to reach current densities of 10 and 100mA cm-2 with a Tafel slope of 30.6mV dec-1 , respectively. The catalysts also reveal excellent stability under a constant 100h operation, higher than most previously reported electrocatalysts. These striking performances are ascribed to the optimized hydrogen binding energy and favorable hydrogen adsorption/desorption kinetics. This work not only exhibits the potential application of ternary Ni2 P/MoNiP2 /MoP crystalline/amorphous heterostructure nanowires catalysts for practical electrochemical water splitting, but also paves the way to prepare non-noble transition metal-based electrocatalysts with optimized crystalline/amorphous heterostructures.

Energy-Efficient Ammonia Synthesis from Nitrate via CoNi Alloys Incorporated in Carbon Frameworks

As a nitrogen-containing source, nitrate is regarded as a promising precursor for generating ammonia (NH3) through electrochemical processes that can potentially mitigate the problem of groundwater contamination and the hydrogen-carrier energy crisis. Herein, we report a cobalt zeolitic imidazolate framework (ZIF-67)-derived catalyst of CoNi alloys incorporated in N-doped carbon frameworks for nitrate electroreduction. Computational results obtained using the density functional theory give a deep insight that the structure of CoNi alloys embedded in the N-doped carbon skeleton can inhibit the production of hydrogen and facilitate the hydrogenation of *NO intermediates. The enriched active sites from the ZIF-67-derived structure and the introduction of Ni in the catalyst afford desirable electrocatalytic performance. Finally, the optimized CoNi@NC hybrid can achieve an ammonia production of 168 mmol gcat–1 h–1 and a Faradaic efficiency of ∼93% at a potential as low as −0.1 V vs reversible hydrogen electrode (RHE). The highest yield rate of 1254 mmol gcat–1 h–1 can be detected at −0.6 V vs RHE. This study can inspire further development of non-noble metal-based hybrid electrocatalysts for nitrate reduction and also anticipation into sustainable synthesis of carbon-related fuels from CO2 reduction.

Active sites and intermediates adsorption regulation of Ni5P4 porous nanosheets arrays through Ce doping toward efficient electrocatalytic overall water splitting

The development of non-noble metal-based bifunctional electrocatalysts toward overall water splitting is urgent recently. However, their catalytic activity is still limited by the insufficient active sites and unsatisfactory adsorption toward reaction intermediates. Here, a self-supported rare earth Ce-doped Ni5P4 porous nanosheets array is designed as an efficient bifunctional electrocatalyst, which requires a competitive overall water splitting potential of 1.56 V to drive the current density of 10 mA/cm2 under alkaline condition. It is shown that the introduction of Ce can greatly reduce the charge transfer resistance and increase the active sites of Ni5P4, which promotes fast charge transfer and facilitates the kinetics to maintain high catalytic activity. Especially, systematic DFT theoretical calculation is further conducted to study the electrocatalytic process, and it is shown that Ce doping can regulate the center of the d band and adsorption of reaction intermediates, thus reducing the overall speed-decisive step of water splitting reaction. This work demonstrates an efficient strategy for enhancing the overall water splitting properties of bifunctional electrocatalysts through rare earth Ce doping, which also has guiding significance for the study of electrocatalytic mechanism in atomic scale.

Ultrafast Thermal Synthesis of Non-Noble Metal-Based Electrocatalysts for Overall Water Splitting

Non-noble metal-based electrocatalysts have attracted extensive interest due to their low-cost, earth-abundance, and highly efficient catalytic performance as alternatives to noble metal counterparts. However, conventional approaches to synthesize electrocatalysts can endure overlong synthesis time with throughput degradation. Here, we demonstrate an ultrafast thermal method to synthesize non-noble metal-based electrocatalysts for overall water splitting. The method can be extensively used for metal-based catalysts, including metal oxides, metal carbides, alloys, and their composites. Among them, we select two outstanding electrocatalysts as examples for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The hybrid structure of nickel oxides and molybdenum carbides on activated carbon felt (Ni–Mo@ACF) for HER shows remarkable catalytic activity with a low overpotential of 87 mV and an excellent durability for 48 h at a current density of 10 mA cm–2. The NiFe alloy nanosheets on activated carbon felt (NiFe@ACF) for OER show superb catalytic activity with a low overpotential of 270 mV and great durability for 48 h at a current density of 10 mA cm–2. Consequently, an overall water splitter assembled with Ni–Mo@ACF as the cathode and NiFe@ACF as the anode only requires a low cell voltage of 1.60 V to drive a current density of 10 mA cm–2 with excellent durability for 36 h, which is the best among non-noble metal-based electrocatalysts reported so far. This work offers an approach for the ultrafast and facile synthesis of non-noble metal-based electrocatalysts for water splitting and other applications.

CoS2 particles loaded on MOF-derived hollow carbon spheres with enhanced overall water splitting

Electrocatalytic water splitting is a promising method for producing high-purity hydrogen. Metal-organic frameworks (MOFs) have recently emerged as unique electrocatalysts for overall water splitting. With their large specific surface area, high porosity, adjustable composition, and diversified structure, MOFs are widely used as precursors for preparing non-noble metal-based electrocatalysts. This paper presents the preparation of CoS2 particles loaded on carbon spheres derived from Co-MOF microspheres by calcination and sulfide reaction with sulfur. The optimized CoS2–600 particles demonstrate excellent OER and HER electrocatalytic performance in 1 M KOH solution. The MOF does not act as a catalyst, but rather adjusts the phase of the catalytic active material, changes the intermediate adsorbent, and increases the number of catalytic sites. The morphology and physical phases of the CoS2–600 particles were analyzed after cycling to identify the real active components during hydrogen and oxygen evolution.

High-Density Cationic Defects Coupling with Local Alkaline-Enriched Environment for Efficient and Stable Water Oxidation.

The inferior activity and stability of non-noble metal-based electrocatalysts for oxygen evolution reaction (OER) seriously limit their practical applications in various electrochemical energy conversion systems. Here we report, a drastic nonequilibrium precipitation approach to construct a highly disordered crystal structure of layered double hydroxides as a model OER catalyst. The unconventional crystal structure contains high-density cationic defects coupled with a local alkaline-enriched environment, enabling ultrafast diffusion of OH- ions and thus avoiding the formation of a local acidic environment and dissolution of active sites during OER. An integrated experimental and theoretical study reveals that high-density cationic defects, especially di-cationic and multi-cationic defects, serve as highly active and durable catalytic sites. This work showcases a promising strategy of crystal structure engineering to construct robust active sites for high-performance oxygen evolution in an alkaline solution.

Anion assisted completely reconfigured manganese oxides with optimal proton adsorption for boosting acidic hydrogen evolution reaction

The optimal proton adsorption design of non-noble metal based catalysts is critical to the realization of efficient hydrogen evolution reactions (HER) in acidic media, but it is also challenging. Herein, sulfur anion-assisted completely reconfigured MnOx (R-S-MnOx-CC) with self-supported nanostructure was prepared on carbon cloth by in situ phase transformation method. The reconfiguration process results in spinel-structured Mn3O4 which can enhance charge transport and expose more active sites through charge disproportionation. The theoretical calculation indicates that the reconfiguration can increase the electron state density of the Mn d band near the Fermi level, promote the right shift of the d-band center, enhance the electron transport capacity of the catalyst to achieve the optimal H+ adsorption. The R-S-MnOx-CC catalyst has excellent acidic HER performance with an overpotential of only 43 mV and 234 mV at 10 mA cm−2 and 400 mA cm−2, respectively, a low charge transfer resistance Rct (0.29 Ω) and stably maintained for 100 h without decay (∼300 mA cm−2). This strategy provides a feasible way to design efficient and stable non-noble metal-based electrocatalysts for the HER industrialization of proton exchange membrane (PEM) water electrolyzers.