Porous Co2P film coated on carbon fiber as highly performance electrocatalyst toward overall water splitting

Designing porous active materials and enhancing their contact with conductive substrates is an effective strategy to improve electrolytic water splitting performance of noble metal-free catalysts. Herein, a facile nanostructured electrode, composed of porous Co₂P films coated on carbon fiber (CF@P–Co₂P), is designed and prepared. The unique three-dimensional interconnected pore structure of Co₂P and the close contact between porous Co₂P and CF not only increase specific surface areas to expose abundant catalytic sites but also stimulate the transport of electron, mass and gaseous products in catalytic process. Benefit from the reasonable electrode structure, the self-supported CF@P–Co₂P electrodes present perfect performance with only needing overpotentials of 107.7/175.5/141.8 mV for hydrogen evolution reaction (HER) in acidic/neutral/alkaline solution and 269.4 mV for oxygen evolution reaction (OER) in alkaline solution to get current density of 20 mA cm^?2. In addition, alkaline electrolyzer equipped with CF@P–Co₂P bifunctional electrodes only needs a cell voltage of 1.657 V to get water-splitting current density of 20 mA cm^?2. Even better, the electrolyzer can continuously electrolyze over 50 h with negligibly decreasing current density and the Faraday efficiency is close to 100% toward both HER and OER.     

Vacancies and phosphorus atoms assembled in amorphous urchin-like Co3O4 for highly efficient overall water splitting

Designing highly efficient and low-cost electrocatalysts is essential for water splitting. Herein, urchin-like Co₃O₄ microspheres are firstly grown on nickel foam by a hydrothermal method, then Oxygen vacancies, phosphorus doping are effectively assembled in Co₃O₄ electrocatalysts. The introduction of oxygen vacancies and phosphorus doping will adjust the electronic structure of Co which increase the intrinsic catalytic activity and improve the adsorption energy of intermediates, simultaneously, progressively transform the crystal into randomly arranged atoms structure with short range order resulting in more active sites participate in the catalytic reaction. Moreover, the catalyst of vacancies Co₃O₄-Ov and phosphorus doping Co₃O₄–P demonstrate excellent performance in oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline media, Co₃O₄-Ov sample served as anode while Co₃O₄–P as cathode to form an electrolytic cell needs only 1.58 V to reach 20 mA cm^?2 for overall water splitting.     

Engineering multiphase for activating electroactive sites for highly efficient hydrogen evolution: Experimental and theoretical investigation

An ideal electrocatalyst for the hydrogen evolution reaction of water splitting requires substantial active sites with high catalytic activity, fast electron and mass transfer, low gas adsorption energy, and high stability. However, a single component catalyst usually has only one of the many properties of an ideal electrocatalyst. Herein, for the first time, we synthesize Co_xSe/MoSe₂ micro-prisms on foam via a hydrothermal and selenization strategy. After selenization, a crystallized CoMoO₄ smooth prismatic structure can be converted into a Co_xSe/MoSe₂ prismatic structure with lamellar morphology. Such synergistic effects lead to Co_xSe/MoSe₂ superior electrochemical catalytic activity with a 109 mV over-potential at 10 mA cm⁻² and 204 mV over-potential at 100 mA cm⁻², an appropriate Tafel slope of 90 mV dec⁻¹, and remarkable long-term stability during 20 h of testing for the hydrogen evolution reaction in an alkaline medium. Density-functional calculations reveal the absorption energy of water and Gibbs free-energy of intermediate adsorb hydrogen of Co_xSe/MoSe₂ is more favorable for hydrogen evolution reaction than single component catalyst. Both experimental and theoretical calculation results reveal that synergistic effect can efficiently reduce energy barrier of both the initial water adsorption step and subsequent H₂ generation on binary catalysts, and improve catalytic activity.     

Self-template synthesis of lychee like Mn-doped Co2P yolk-shell spheres for enhanced hydrogen evolution reaction activity

Designing an electrocatalyst for hydrogen production from water splitting that is highly efficient, stable, and free of noble metals is necessary but challenging. The phosphorus compound is considered a viable candidate for producing hydrogen from water split, but its electrocatalytic performance needs further improvement. Herein, we present an easy and straightforward method for constructing Mn-doped Co₂P yolk-shell lychee spheres. The Co nano prisms are used as a self-sacrificing template to conduct an ion exchange reaction with manganese ions, constructing Co oxide yolk-shell spheres with Mn–Co hydroxide nano-blocks. After in-suit phosphating at low temperature, Mn-doped Co₂P with yolk-shell structure and lychee morphology is formed. The Mn-doped Co₂P with an optimized Mn and Co molar ratio (0.125) exhibits excellent hydrogen evolution performance in alkaline and acidic electrolyte. The overpotentials can reach 10 mA cm^?2 at 98 mV and 72 mV, respectively, and the Mn–Co₂P-0.125 catalyst has faster electron transfer efficiency and larger electrochemically active surface area. The experimental results ascertain that doping an appropriate amount of Mn significantly changes the morphology and structure, thereby affecting the exposure of active sites, and modulating the electronic structure around Co₂P. Under the dual regulation of morphology and electronic structure, the electrocatalytic process is accelerated, enhancing its catalytic activity.     

Iron doped mesoporous cobalt phosphide with optimized electronic structure for enhanced hydrogen evolution

We report a self-supporting electrode fabricated by covering iron doped mesoporous cobalt phosphide film on carbon cloth substrate (meso-Fe_xCo_1-xP/CC) for hydrogen evolution reaction (HER). In acidic and alkaline electrolytes, the electrode exhibited excellent catalytic activity and fast kinetics towards the HER, only requiring small overpotentials of 61 mV and 67 mV to drive 10 mA cm^?2, respectively. The superior electrocatalytic activity is attributed to the mesoporous structure with high specific surface area (147.5 m² g^?1) and doping of Fe atom. The mesoporous structure grown on the conductive carbon cloth substrate enables the fully exposure of active sites and the rapid penetration of electrolyte. Additionally, density functional theory (DFT) calculation reveals that the doping of Fe enhances the adsorption of H atoms by shifting the d-band center of Co. Meanwhile, the introduction of Fe lowers the energy barrier for water dissociation, which accelerates the catalytic kinetics in alkaline electrolyte.     

Phosphatizing engineering of heterostructured Rh2P/Rh nanoparticles on doped graphene for efficient hydrogen evolution in alkaline and acidic media

A wide diversity of phosphides of platinum-group metal including Rh, Ru and Ir exhibit intriguing electrocatalytic activity toward hydrogen evolution reaction (HER). The phosphidation degree, namely the P dosage in these phosphides shows pronounced influence on the catalytic performance but is hard to control. In this work we developed a reliable strategy to synthesize Rh₂P-based nanoparticles with controlled phosphidation degree, and investigated the influence of phosphidation degree on HER. It is found that the heterostructured Rh₂P/Rh nanoparticle, i.e., the P-deficient composite with mixed metallic and phosphide phases, outperforms either the metallic Rh or pure Rh₂P nanoparticles. As-synthesized Rh₂P/Rh nanoparticles supported on P/N co-doped graphene (denoted as Rh₂P/Rh-G) display remarkable HER activity with tiny overpotential of 17 and 19 mV at 10 mA cm^?2 current density in alkaline and acid, efficiently surpassing its Rh-based rivals and benchmark Pt/C catalyst. Meanwhile it illustrates a large mass-specific activity (3.23 and 6.26 A mg^?1 @50 mV overpotential in alkaline and acid, respectively) due to its high activity and low metal loading. Density functional theory (DFT) calculation indicates that the Rh₂P/Rh heterostructured interface possesses the optimal close-to-zero value of hydrogen adsorption energy and water dissociation process is accelerated, and thus boosts HER activity.     

Accelerating water dissociation kinetic in Co9S8 electrocatalyst by mn/N Co-doping toward efficient alkaline hydrogen evolution

Electrocatalytic hydrogen evolution under alkaline media holds great promising in hydrogen energy production. Transition-metal sulfides (TMSs) are attractive for electrocatalytic alkaline hydrogen evolution, yet their catalytic performance is unsatisfactory owing to the sluggish water dissociation kinetics. Herein, a Mn/N co-doping strategy is proposed to regulate the water dissociation kinetics of Co₉S₈ nanowires array grown on nickel foam thus improve the activity of hydrogen evolution reaction (HER). The optimal Mn/N co-doping Co₉S₈ (Mn–N–Co₉S₈) catalyst achieves low overpotentials of 102 and 238 mV at 10 and 100 mA cm^?2 in the 1 M KOH solution, respectively, remarkably higher than the single-doping Mn–Co₉S₈ and N–Co₉S₈ as well as superior to many reported Co₉S₈-based HER electrocatalysts. Density functional theory (DFT) calculation results confirm that the water dissociation barrier of the Mn–N–Co₉S₈ is reduced significantly owing to the synergistic co-doping of Mn and N, which accounts for the enhanced alkaline HER performance. This study offers an effective strategy to enhance the alkaline HER activity of TMSs by accelerating water dissociation kinetic via the cation and anion co-doping strategy.     

Electrospinning derivative fabrication of sandwich-structured CNF/Co3S4/MoS2 as self-supported electrodes to accelerate electron transport in HER

The substitution of noble metal catalysts with earth abundant TMs as electrocatalysts for hydrogen production is of great significance. One biggest bottleneck for high-efficiency water electrolysis in TM catalysts is the sluggish reaction kinetics or electron transport efficiency. The electrical coupling between the substrate and the catalytic material can accelerate the electron transport, enhancing the charge transfer kinetics, and thereby improve the catalytic performance of the catalyst. Herein, we report a sandwich-structured CNF/Co₃S₄/MoS₂, MoS₂ grown in-situ on N-doped nanofibers with Co₃S₄ nanoparticles via electrospinning, carbonization and hydrothermal process, as self-supported electrodes for hydrogen evolution reaction. The sandwich structure is comprised of CNFs/Co₃S₄/MoS₂ as substrate/accelerator/catalyst. Thereinto, the three-dimensional CNF framework, intrinsically doped by nitrogen, can open accessible channels for reactants and served as substrates for the in-situ growth of Co₃S₄ and MoS₂ nanocrystals with high conductivity and massive active sites. Hence, the CNF/Co₃S₄/MoS₂ shows outstanding catalytical performance in water electrospinning, only 80 mV required to drive 10 mA cm^?2 current density with the Tafel slope of 99.2 mV dec^?1 in alkaline media. Besides, the performance can be maintained for at least 40 h with negligible decline. This experiment can provide a new idea for the design of efficient and stable self-supporting electrodes.     

Noble metal interlayer-doping enhances the catalytic activity of 2H–MoS2 from first-principles investigations

Recent studies show that the interlayers regulatory can be used as an approach to increase catalytic activity of 2H–MoS₂ for hydrogen evolution reaction. Although the noble metals are better catalyst, the effect of noble metal interlayer doping on 2H–MoS₂ is unclear. To this end, we apply first-principles method to investigate the structural stability of the noble metal interlayer doped 2H–MoS₂. In particular, we investigate the influence of noble metal interlay doping on the catalytic hydrogen evolution activity of 2H–MoS₂. The result shows that the noble metal interlayer doping is beneficial to improve the electronic transport near Fermi level. Moreover, it is found that the Ru-doped 2H–MoS₂ has better thermodynamic stability compared to the Au-doping, Pd-doping and Pt-doping. Importantly, the noble metal interlayer doping strengthens the interaction between single layers in comparison with the weak van der Waals force between single layers of the pristine 2H–MoS₂. Finally, it is found that four noble metals interlayer doping increase the catalytic hydrogen evolution activity of 2H–MoS₂. In particular, the Ru-doped 2H–MoS₂ has better catalytic activity because the transfer of the Ru-4d state from low energy region to high energy region, which weakens the interaction between Mo and S.     

Effect of cobalt on the microstructure and hydrogen sorption performances of TiFe0.8Mn0.2 alloy

The microstructures and the hydrogen sorption performances of TiFe_0.8Mn_0.2Co_x (x = 0, 0.05, 0.10, 0.15) and TiFe_0.8Mn_0.2-yCo_y (y = 0.05, 0.10) alloys have been investigated. For TiFe_0.8Mn_0.2Co_x alloys, the lattice parameters of TiFe phase decreased and the Laves phase contents increased with the addition of Co. With the increase of Co content in TiFe_0.8Mn_0.2Co_x alloys, the maximum hydrogen storage capacities of TiFe_0.8Mn_0.2Co_0.05 and TiFe_0.8Mn_0.2Co_0.10 alloys decreased, but the effective hydrogen capacities increased, which is ascribed to the improved flatness of the α-β desorption plateau. Substitution of Co for Mn in TiFe_0.8Mn_0.2-yCo_y alloys can effectively lead to single phase of TiFe alloys. Therefore, TiFe_0.8Mn_0.2-yCo_y alloy showed a deteriorated activation property, but its effective hydrogen capacity increased remarkably due to the obviously improved flatness of the α-β desorption plateau. The addition of Co might adjust the change of the octahedral intersitial environment caused by Mn doping in TiFe phase, which contributes to the improved flatness of the α-β desorption plateau and hence the increased effective hydrogen capacity.     

Aligned Co3O4–CoOOH heterostructure nanosheet arrays grown on carbon paper with oxygen vacancies for enhanced and robust oxygen evolution

Developing efficient and stable non-noble metal oxygen evolution reaction (OER) electrocatalysts for sustainable overall water-splitting is extremely desirable but still a great challenge. Herein, we developed a facile strategy to fabricate Co₃O₄–CoOOH heterostructure nanosheet arrays with oxygen vacancies grown on carbon paper (Co₃O₄–CoOOH/CP). Benefiting from the unique 3D architecture, large surface area, synergistic effects between Co₃O₄, CoOOH and oxygen vacancies, the obtained self-supporting Co₃O₄–CoOOH/CP presents excellent electrocatalytic OER activity (low overpotentials of 245 and 390 mV at 10 and 100 mA cm⁻²) and robust long-term stability in alkaline condition. The present strategy provides the opportunities for the future rational design and discovery of high-performance non-noble metal based electrocatalysts for advanced water oxidation and beyond.     

Embedding Co2P nanoparticles into co-doped carbon hollow polyhedron as a bifunctional electrocatalyst for efficient overall water splitting

The reasonable design and construction of non-precious metal electrocatalysts with low cost and high performance is critical for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, a facile polymerization-pyrolysis method is proposed to encapsulate Co₂P nanoparticles in co-doped hollow carbon shell by using ZIF-67 and P-containing polymers as precursor. The unique construction not only effectively prevents nanoparticles from detaching, showing good stability after long-term testing, but also provides abundant active sites, large surface areas and large pore volumes, enabling the electrolyte and electrode material to full contact. As expected, the Co₂P/NPSC-800 performs superior HER performance with low overpotential of 173 mV at 10 mA cm⁻² and excellent stability of 88% retention for 35 h and OER performance with low overpotential of 320 mV at 10 mA cm⁻², which endows Co₂P/NPSC-800 with good catalytic activity in overall water splitting. Furthermore, density functional theory (DFT) calculations reveal that the metallic property and the decreased reaction barriers of Co₂P can promote the catalytic reactions. This work offers an effective route in synthesizing other transition metal phosphides with high catalytic properties.     

Heterostructured Co3O4/VO2 nanosheet array catalysts on carbon cloth for hydrogen evolution reaction

Developing highly efficient, low-cost, and robust water splitting hydrogen production catalysts is critical for hydrogen energy applications. This study presents the synthesis of Co₃O₄/VO₂ heterogeneous nanosheet structures on carbon cloth (Co₃O₄/VO₂/CC). The obtained Co₃O₄/VO₂/CC hybrid catalyst has a low overpotential of 108 mV at a current density of 10 mA cm^?2, a Tafel slope of 98 mV dec^?1, and high stability in 1.0 M KOH for 10 h. The experimental results and density functional theory (DFT) calculations results also show that Co₃O₄ coupled with VO₂ in Co₃O₄/VO₂/CC can optimize hydrogen adsorption energy and facilitate electron transport, thereby accelerating the catalytic kinetics for hydrogen evolution reaction (HER). This work also provided an alternative method to design and construct non-noble metal oxide-based catalysts for alkaline hydrogen production.     

Influence of cobalt dopant in NiFe2-xCoxO4 (0≤x≤2) on electrochemical catalytic properties

Environmental pollution has increased owing to the excessive consumption of fossil fuels. Thus, the combustion of which does not emit pollutants, has attracted attention for as an alternative fuel in various energy application systems. Using hydrogen energy has considered as an environmentally friendly solution to significantly reduce the dependency on fossil fuels and it can be produced by electrochemical water splitting. However, the sluggish kinetic reaction of the oxygen evolution reaction (OER) during electrochemical water splitting reduces the efficiency of hydrogen energy. Therefore, an excellent electrochemical catalyst with superior electrochemical activity in OER is required to increase the energy conversion efficiency. In this study, a NiFe_2-xCo_xO₄ (0 ≤ x ≤ 2) electrochemical catalyst was prepared by hydrothermal synthesis by controlling the amount of Co dopant. The influence of Co doping on the electrochemical catalytic activity of the prepared sample was evaluated by comparing the oxygen vacancies, bandgap, macroporosity and active surface area. Previous research have reported that abundant oxygen vacancies can improve the electrochemical catalytic activity. However, NiCo₂O₄ with the least number of oxygen vacancies exhibited excellent bifunctional catalytic activity for OER/oxygen reduction reaction (ORR) owing to the development of macropore, large active surface areas, and lower bandgap. Therefore, the bandgap and porosity such as macroporosity, large surface area, are an important factor that exert a greater influence than oxygen vacancies in electrochemical catalysts.     

Synthesis of Co2FeAl alloys as highly efficient electrocatalysts for alkaline hydrogen evolution reaction

The development of cost-effective non-precious metal electrocatalysts is a major challenge for water splitting applications, but it is important for the realization of renewable energy systems. Alloying has proved an effective way to design metal-based electrocatalysts, and by controlling the annealing temperature, the surface morphology and crystallinity of the alloy can be tuned to control the hydrogen evolution reaction (HER) performance. In this work, with a simple coprecipitation method, we have prepared Co₂FeAl alloys at different annealing temperatures (550 °C–670 °C), which exhibit excellent crystallinity and electrocatalytic performance for HER in alkaline solution. Among all conditions, the Co₂FeAl alloys prepared at 620 °C shows the better crystallinity and the higher purity, and it could achieve a low overpotential of 149 mV at 10 mA cm^?2 in alkaline solution. The overpotential demonstrates persistent stability with only 3 mV change after over 1000 cycles. Both density functional theory (DFT) calculations and experimental results revealed that alloying optimizes the electronic structure near the Fermi surface of the system, improving the electron transport efficiency and enhancing the catalytic activity. These Co₂FeAl alloys are appealing candidates for high-performance alkaline HER electrocatalytic electrodes in water electrolysis due to their outstanding electrocatalytic properties.     

WS2/NiSx heterojunction nanosheet clusters: A highly efficient electrocatalyst for hydrogen evolution reaction

The development of highly active and stable electrocatalysts is essential to solve energy and environmental problems and realize sustainable social and economic development. Herein, we synthesized a bimetallic sulfide material by a kinetically controlled low-temperature solid-phase reaction. The bimetallic sulfide improves the conductivity of the electrocatalysts by optimized electronic structure, and the coupling effect at the heterogeneous interface of WS₂ and NiS_x increases the charge density on the S site at W–S–Ni, making it easier for the electrocatalysts to trap the active material in solution. In addition, nanosheet clusters expose abundant catalytic sites, which together improve hydrogen evolution reaction (HER) for catalytic activity. Optimized WS₂/NiS_x composite show near-precious metal catalyst activity with an overpotential at 10 mA cm^?2 of only 72 mV in alkaline media, which exhibits excellent catalytic stability and outperforms most non-precious metal electrocatalysts.     

Highly active FexCo1-xP cocatalysts modified CdS for photocatalytic hydrogen production

In this paper, we report a ternary Fe_xCo_1−xP co-catalyst, which can greatly improve the photocatalytic performance of CdS photocatalyst for hydrogen production under visible light irradiation. The high efficiency of ternary Fe_xCo_1-xP loaded CdS is mainly due to the high electrochemical activity and efficient charge transfer between Fe_xCo_1-xP cocatalyst and CdS. Experimental results have shown that the substitution of Fe ions for some Co ions in CoP can change the electrochemical properties of Fe_xCo_1-xP. The electrocatalytic performance of Fe_xCo_1-xP and the photocatalytic activity of Fe_xCo_1-xP/CdS are both dependent on the molar concentration x of Fe. When x = 0.4 the hydrogen generation rate (18.27 mmol h⁻¹ g⁻¹) and the quantum efficiency (50.6% at 420 nm) for 0.5 wt% Fe_0.4Co_0.6P/CdS photocatalyst is 5.85 times higher than that of pure CdS and 1.35 times higher than that of 0.5 wt% CoP/CdS. This new noble-metal-free Fe_xCo_1-xP cocatalyst is beneficial for the solar hydrogen economy.     

A Li-doped Co3O4 oxygen evolution catalyst for non-precious metal alkaline anion exchange membrane water electrolysers

Li-doped Co₃O₄ (Li_xCo_3−xO₄, x = 0, 0.07, 0.21, 0.35, 0.49) spinel powders were prepared with a thermal decomposition method and characterized by XRD, SEM, TEM, and XPS. The Li_xCo_3−xO₄ samples were formed as tetragonal powders with a simple spinel structure and with particle sizes about 30–40 nm. All Li_xCo_3−xO₄ samples exhibited a 50 mV more negative onset potential for oxygen evolution reaction (OER) than Co₃O₄. The influence of Li-doping is discussed regarding cation distribution, electronic conductivity and oxygen binding energy. Li_0.21Co_2.79O₄ exhibited the highest OER activity amongst the five samples. A single cell, non-precious metal alkaline anion exchange membrane water electrolysers (AAEMWE) with Li_0.21Co_2.79O₄ anode exhibited a current density of 300 mA cm⁻² at a voltage 2.2 to 2.05 V at temperatures of 20–45 °C and the stability was examined with a continuous operation for 10 h at 300 mA cm⁻² and at 30 °C.     

Heterostructural Co/CeO2/Co2P/CoP@NC dodecahedrons derived from CeO2-inserted zeolitic imidazolate framework-67 as efficient bifunctional electrocatalysts for overall water splitting

The design and fabrication of highly active, robust and cost-efficient electrocatalysts for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is of great significance towards overall water splitting, but remains challenging as well. Herein, we report, for the first time, heterostructural Co/CeO₂/Co₂P/CoP@NC dodecahedrons as bifunctional electrocatalyst, in which abundant interfaces are formed between different components. Typical ZIF-67 (ZIF = zeolitic imidazolate framework) dodecahedrons with pre-inserted CeO₂ nanowires were selected as precursors to synthesize Co/CeO₂/Co₂P/CoP@NC via a direct carbonization process followed by phosphidation, simultaneously generating the strong coupled heterojunction interfaces through interactions between CeO₂ and Co_xP species. Abundant porous structure leads to the exposure of more active sites and the carbon encapsulation of nanodomains sustains the high robustness and conductivity and the synergistic effect between the multi-components heterostructure. Benefiting from the above collective advantages, the Co/CeO₂/Co₂P/CoP@NC electrocatalysts exhibit small overpotentials of 307 and 195 mV to derive 10 mA cm⁻² for OER and HER, respectively. Furthermore, an alkaline electrolyzer assembled by using Co/CeO₂/Co₂P/CoP@NC as both cathode and anode can achieve a current density of 10 mA cm⁻² at a low voltage of 1.76 V and work continuously for over 15 h. This work would provide a rational protocol for fabrication multi-phase interface enriched electrocatalysts toward highly efficient energy conversion.     

Electrochemical construction of S-doped MnOx/Mn integrated film on carbon paper in a choline chloride based deep eutectic solvent for enhanced electrochemical water oxidation

The rational design and synthesis of highly efficient, precious metal-free electrocatalysts in the promotion of electrochemical water oxidation is essential for the sustainable use of renewable energy. Herein, an integrated, S-doped MnO_x/Mn film developed on carbon paper (CP) formed by a two-step transformation approach that includes template-free electrodeposition and in-situ electrochemical oxidation is employed as an efficient oxygen evolution reaction (OER) electrocatalyst. The doping of S and in-situ electro-oxidation lead to a tailored electronic structure and phase composition, which endow the composite electrode with a significantly enhanced OER catalytic performance. This S-doped integrated electrode perfectly combines highly active MnO_x outer layers with conductive metallic Mn inner layers to offer abundant catalytic interfaces and electronic paths, leading to favorable reaction kinetics. As a result, the optimal S-doped MnO_x/Mn/CP offers a low overpotential of 435 mV at 10 mA cm^?2 with a Tafel slope of 89.97 mV dec^?1 as well as improved stability. Impressively, a highly intrinsic catalytic activity with a turnover frequency of 0.0112 s^?1 is obtained for S-doped MnO_x/Mn/CP, which is 4.2-fold higher than that of MnO_x/Mn/CP. S doping plays a critical role in stabilizing the Mn^IIIO_x active phase and is ultimately responsible for the enhanced catalytic performance. This work provides an integrated design concept and S doping approach suitable for boosting the OER catalytic performance of MnO_x.