Pristine and cobalt doped copper sulfide microsphere particles for seawater splitting

In this work, copper sulfide particles are synthesized with different Co doping concentrations such as 0, 1 and 5% at 80 °C by optimizing synthesis times from 1 to 3 h. Copper sulfide particles possess two structural phases of covellite CuS and digenite Cu₉S₅. The increase in synthesis time from 1 to 3 h increases the Cu₉S₅ phase growth and changes the morphology from flower to microsphere. The CuS synthesized with 0, 1 and 5% Co dopant concentrations demonstrate flower consisting of agglomerated nanosheets, microsphere and flower like microsphere. The elemental investigation substantiates Co ions presence in CuS microspheres. The A_1g (LO) mode intensity is decreased with increase in Co dopant concentration confirming Co incorporation into CuS microsphere. The CuS synthesized with 0, 1, 5% Co dopants exhibit 322 mV, 305 mV and 289 mV to attain 100 mA/cm² in 1 M KOH seawater. The CuS synthesized with 5% Co dopant demonstrates higher double layer capacitance (C_dl) of 173.9 mFcm^?2 and lower charge transfer resistance (R_ct) of 6.07 Ω with 78.84% retention after 10 h continuous stability than that of the other pristine (118.3 mFcm^?2, 13.72 Ω) and 1% Co doped CuS microsphere (165.7 mFcm^?2, 8.55 Ω) indicating more surface active site and rapid charge carrier transport, respectively.     

Recent advances in electrocatalysts for seawater splitting in hydrogen evolution reaction

Electrocatalytic water splitting is an important method to produce green and renewable hydrogen (H₂). One of the hindrances for wide applications of electrocatalysis in H₂ production is the lack of freshwater resources. Comparatively, seawater splitting has become an effective approach for large-scale H₂ production due to its abundant reserves. However, the increased complexity of seawater content emerged more problems in electrocatalytic seawater splitting. Recently, various strategies have been reported on improving the performance of electrocatalysts applied in seawater. Herein, this review firstly analyzed the mechanisms and challenges of electrocatalytic seawater splitting to evolve H₂, and summarized the recent progress on H₂ production in electrocatalytic seawater splitting. Furthermore, suggestions for future work have been provided for guidance.     

Enhanced alkaline/seawater hydrogen evolution reaction performance of NiSe2 by ruthenium and tungsten bimetal doping

The exploration of high-efficiency and stable electrocatalysts for alkaline and seawater hydrogen evolution reaction (HER) is the key to realize energy conversion, but there is still a significant challenge owing to the slow HER kinetics in alkaline and seawater systems. In this study, we prepared nickel foamed-supported Ru, W co-doped NiSe₂ (Ru, W–NiSe₂/NF) by a brief two-step hydrothermal strategy and the prepared Ru, W–NiSe₂/NF displays exceptional HER property, requiring only a low overpotential of 100 and 353 mV to reach 10 mA cm⁻² in 1 M KOH and natural seawater, respectively, far superior to Ru–NiSe₂/NF, W–NiSe₂/NF and NiSe₂/NF. Electrochemical surface area (ECSA) and operando electrochemical impedance spectroscopy (EIS) verify the abundant active sites and superior electron transfer rate of Ru, W–NiSe₂, which optimized the HER kinetics in alkaline solution and natural seawater. The ECSA normalization and TOF results indicated that Ru, W co-doping increased the intrinsic activity of NiSe₂. This study revealed the impact of bimetallic doping on the intrinsic activity of NiSe₂, and provided a practical strategy for designing and developing the HER electrocatalysts with excellent performance.     

Co/Mo2C composites for efficient hydrogen and oxygen evolution reaction

Non-precious transition metal electrocatalysts with high catalytic performance and low cost enable the scalable and sustainable production of hydrogen energy through water splitting. In this work, based on the polymerization of CoMoO₄ nanorods and pyrrole monomer, a heterointerface of carbon-wrapped and Co/Mo₂C composites are obtained by thermal pyrolysis method. Co/Mo₂C composites show considerable performance for both hydrogen and oxygen evolution in alkaline media. In alkaline media, Co/Mo₂C composites show a small overpotential, low Tafel slope, and excellent stability for water splitting. Co/Mo₂C exhibits a small overpotential of 157 mV for hydrogen evolution reaction and 366 mV for oxygen evolution reaction at current density of 10 mA cm⁻², as well as a low Tafel slope of 109.2 mV dec⁻¹ and 59.1 mV dec⁻¹ for hydrogen evolution reaction and oxygen evolution reaction, respectively. Co/Mo₂C composites also exhibit an excellent stability, retaining 94% and 93% of initial current value for hydrogen evolution reaction and oxygen evolution reaction after 45,000 s, respectively. Overall water splitting via two-electrode water indicates Co/Mo₂C can hold 91% of its initial current after 40,000 s in 1 M KOH.     

One-step synthesis of Ni3S2 nanowires at low temperature as efficient electrocatalyst for hydrogen evolution reaction

Ni₃S₂ is an emerging cost-effective catalyst for hydrogen generation. However, a large amount of reported Ni₃S₂ was synthesized via multi-step approaches and few were fabricated based on the one-step strategies. Herein, we report a facile one-step low-temperature synthesis of Ni₃S₂ nanowires (NWs). In this strategy, a resin containing sulfur element is recommended as a sulfur resource to form Ni₃S₂ NWs. It presents a plausible explanation on the vapor–solid–solid (VSS) growth mechanism according to the results of this experiment and reported in literature that has been published. The Ni₃S₂ NW exhibits a potential ∼199 mV at 10 mA cm⁻² and the long-term durability over 30 h at 20 mA cm⁻² HER operation, better than other reported Ni₃S₂. More importantly, according to replace transition metal foam as the initial metal, other transition metal sulfide can be readily synthesized via this original approach.     

Electrocatalytic performance of ReS2 nanosheets in hydrogen evolution reaction

Two-dimensional layered rhenium disulfide (ReS₂) is regarded as an ideal high-performance catalyst for the hydrogen evolution reaction (HER) due to its distorted 1T crystalline structure, extremely weak interlayer coupling and unique Re–Re σ bond in the basal plane. However, relatively slow HER kinetics still restrict the further use of ReS₂. In this work, ReS₂ nanosheets were grown on a carbon cloth (CC) substrate by a hydrothermal method using a precursor solution of CS(NH₂)₂, NH₄ReO₄ and deionized water. With a decreasing CS(NH₂)₂ to NH₄ReO₄ molar ratio in the precursor solution, the ReS₂ nanosheet distribution density on the CC substrate gradually decreases, resulting in a decline in HER activity. A ReS₂ nanosheets/CC catalyst prepared with a CS(NH₂)₂ to NH₄ReO₄ molar ratio of 10:1 shows the optimal HER activity. It exhibits a low overpotential of 99 mV at 10 mAcm^?2, a small Tafel slope of 222 mVdec^?1, a large electrochemical surface area (ECSA) of 3375 cm² and very high durability. From the variation of ECSA with the distribution density and growth time, we deduce that the active sites for the 2D ReS₂ nanosheets exist on both the edge sites and basal planes. The active sites in the basal planes are ascribed to Re vacancies and defects.     

S-doping induced phase engineering of MoSe2 for hydrogen evolution reaction

MoSe₂ is a promising electrocatalyst for hydrogen evolution reaction (HER). It is confirmed that 1T-MoSe₂ shows better activity for HER compared with 2H-MoSe₂ since of wider interlayer spacing, higher conductivity and better hydrophilicity of 1T-MoSe₂. Realization of 1T-MoSe₂ is still a thorny issue due to its high formation barrier and thermodynamic metastable. Herein, considering the microstrain induced by atomic size mismatch through the substitution of Se by S, the MoSe_2-2xS_2x is prepared via one-pot hydrothermal synthesis, resulting in 70.3% high-purity 1T phase. Additionally, the MoSe_2-2xS_2x shows a low overpotential of 167 mV at 10 mA cm^?2, Tafel slope of 54 mV dec^?1, high double layer capacitance (C_dl) of 13.43 mF cm^?2 and superior cycle stability. The results are ascribed to larger interlayer spacing, high conductivity and good hydrophilicity of 1T phase MoSe_2-2xS_2x. This study provides a simple and feasible route to achieve high-purity TMDs for promoting HER application.     

Tunably fabricated nanotremella-like Bi2S3/MoS2: An excellent and highly stable electrocatalyst for alkaline hydrogen evolution reaction

Reasonable design of efficient and stable catalysts with low cost and abundant natural reserves is vital for electrocatalytic water splitting. Herein, novel nanotremella-like Bi₂S₃/MoS₂ composites with different mass ratios between Bi₂S₃ and MoS₂ have been successfully prepared through a hydrothermal approach and further applied to hydrogen evolution reaction (HER) in 1.0 M KOH electrolyte for the first time. When the mass ratio of Bi₂S₃ and MoS₂ is 5:5, as-prepared nanotremella-like Bi₂S₃/MoS₂ (marked as BMS-5) manifests favorable HER catalytic activity with overpotential of 124 mV at current density of 10 mA cm⁻² and relatively low Tafel slope of 123 mV dec⁻¹. Moreover, it exhibits an extraordinary durability for uninterrupted hydrogen generation. The enhanced HER performances are ascribed to the synergistic effects between Bi₂S₃ and MoS₂, giving rise to large electrocatalytic active area and fast HER kinetics. The results pave a new path to design and construct excellent Bi₂S₃/MoS₂ nanomaterials for electrocatalytic hydrogen generation.     

Flower-like CoS2/MoS2 nanocomposite with enhanced electrocatalytic activity for hydrogen evolution reaction

Molybdenum sulfide (MoS₂) has received tremendous attracts for its promising performance in the aspects of hydrogen evolution reaction (HER). To improve the HER activity of MoS₂, we designed a flower-shaped CoS₂/MoS₂ nanocomposite with enhanced HER electroactivity compared with MoS₂ nanosheets by a simple one-step hydrothermal method. The facile approach brings about distinct transformation of the morphology from nanosheets to nanoflower structures. The introduction of Co element into MoS₂ results in the larger active surface area, more edge-terminated structures, and higher conductivity of the CoS₂/MoS₂ nanocomposite, which are good for improving the HER electroactivity. In brief, the optimized catalyst exhibits the low overpotential of 154 mV at 10 mA cm^?2, small Tafel slope of 61 mV dec^?1, and excellent stability in acidic solution.     

Recent advances on electrocatalytic and photocatalytic seawater splitting for hydrogen evolution

Hydrogen is a clean and renewable energy source, which has aroused increasing attentions. Water splitting can effectively evolve hydrogen. Since freshwater is scarce, the direct exploitation of seawater as the feedstock to produce hydrogen has become a hotspot. Such direct exploitation can lower the cost of hydrogen produce and facilitate the rational exploitation of seawater resources. Over the past few years, advanced technologies (e.g. photocatalysis, electrocatalysis and photoelectrocatalysis) have been introduced into seawater splitting and have showed significant potentials. In this study, representative reports on photo-electro-catalytic seawater splitting to produce hydrogen were comprehensively reviewed. Besides, advancements and defects of each process were discussed. Furthermore, recommendations for subsequent study in this research field have been proposed.     

Facile hydrothermal synthesis of combined MoSe2PS nanostructures on nickel foam with superior electrocatalytic properties for hydrogen evolution reaction

Producing an efficient and inexpensive electrocatalyst for use in the water electrolysis process is the most efficient and logical way to industrialize this method to produce hydrogen as a clean and alternative fuel for fossil fuels. In this study, combined and unique MoSe₂PS nanostructures are synthesized on nickel foam by three steps hydrothermal process. Microstructural observations reveal the unique morphology of the petals covered by the elongated nano-blades. A high electrocatalytic performance is attained with this nanostructure in hydrogen evolution reaction, so that the 90 mV overpotential is achieved at a current density of ?10 mA/cm². The near-platinum activity is due to the unique and combined nanostructure due to the synergistic properties of S and P on MoSe₂ as well as the high electrochemical active sites in the specimen. Additionally, excellent stability of the synthesized electrocatalyst is observed in the alkaline medium for 30 h, which confirms its potential application in relevant industries such as fuel cells and transportation.     

CoS2 with carbon shell for efficient hydrogen evolution reaction

In this study, we demonstrated the active electrocatalysts of CoS₂ coated by N-doped carbon microspheres, CoS₂@NHCs-x (x = 600, 700, 800, and 900; x is pyrolysis temperature). Results show that the obtained electrocatalyst has good catalytic activity and cyclic stability for the reaction of hydrogen evolution (HER) when the pyrolysis temperature is 800 °C. At a current density of 10 mA cm⁻², the overpotential of CoS₂@NHCs-800 was only 98 mV in 0.5 M H₂SO₄, and 118 mV in 1 M KOH, respectively. In addition, CoS₂@NHCs-800 also revealed excellent electrochemical stability, with only 32.7% performance degradation after continuous reaction in 0.5 M H₂SO₄ for 20 h, and the later current density almost no longer deceased with time as the reaction process stabilized. The excellent HER catalytic performance of CoS₂@NHCs-800 is mainly attributed to the rich active sites of CoS₂, the unique porous core-shell structure, and the enhanced conductivity of the carbon carrier caused by N and S co-doping. This work opens up an opportunity for advanced CoS₂-based electrocatalysts for HER.     

Surfactant-assisted hydrothermal synthesis of nitrogen doped Mo2C@C composites as highly efficient electrocatalysts for hydrogen evolution reaction

We describe a facile surfactant-assisted hydrothermal route to synthesize nitrogen doped Mo₂C@C composites in the presence of cetyltrimethylammonium bromide (CTAB) as carbon source and structure guiding agent. The resulting Mo₂C@C composites consist of Mo₂C nanocrystals with sheet-like morphology and well-dispersed nitrogen element doping. Controllable experiments indicate that the additive amount of CTAB can efficiently tune porous structure and electrochemical activity of the as-prepared Mo₂C@C materials. This unique nitrogen doped Mo₂C@C composite provides several advantages for electrocatalytic applications: (1) nitrogen doped carbons can prevent the aggregation of Mo₂C nanocrystals and render it high conductivity; (2) the homogeneous dispersion of Mo₂C nanocrystals provides abundant active sites; (3) 2D morphology, the hierarchical porosity, and high surface areas allow large exposed field of active sites and facilitate mass transfer. As a result, the nitrogen doped Mo₂C@C composites deliver superior HER electrocatalytic activities with a low overpotential of only 100 mV and also a low Tafel slope of 53 mV/dec in alkaline condition. Such CTAB-assisted strategy may open up an opportunity towards synthesis of low cost and high performance Mo-based electrocatalysts for various applications, such as water splitting.     

Nitrogen-doped cobalt sulfide as an efficient electrocatalyst for hydrogen evolution reaction in alkaline and acidic media

The enhancement in intrinsic catalytic activity and material conductivity of an electrocatalyst can leads to promoting HER activity. Herein, a successful nitrogenation of CoS₂ (N–CoS₂) catalyst has been investigated through the facile hydrothermal process followed by N₂ annealing treatment. An optimized N–CoS₂ catalyst reveals an outstanding hydrogen evolution reaction (HER) performance in alkaline as well as acidic electrolyte media, exhibiting an infinitesimal overpotential of ?0.137 and ?0.097 V at a current density of ?10 mA/cm² (?0.309 and ?0.275 V at ?300 mA/cm²), corresponding respectively, with a modest Tafel slope of 117 and 101 mV/dec. Moreover, a static voltage response was observed at low and high current rates (?10 to ?100 mA/cm²) along with an excellent endurance up to 50 h even at ?100 mA/cm². The excellent catalytic HER performance is ascribed to improved electronic conductivity and enhanced electrochemically active sites, which is aroused from the synergy and mutual interaction between heteroatoms that might have varied the surface chemistry of an active catalyst.     

Electrochemically active and robust cobalt doped copper phosphosulfide electro-catalysts for hydrogen evolution reaction in electrolytic and photoelectrochemical water splitting

The area of non-noble metals based electro-catalysts with electrochemical activity and stability similar or superior to that of noble metal electro-catalyst for efficient hydrogen production from electrolytic and photoelectrochemical (PEC) water splitting is a subject of intense research. In the current study, exploiting theoretical first principles study involving determination of hydrogen binding energy to the surface of the electro-catalyst, we have identified the (Cu_0.83Co_0.17)₃P: x at. % S system displaying excellent electrochemical activity for hydrogen evolution reaction (HER). Accordingly, we have experimentally synthesized (Cu_0.83Co_0.17)₃P: x at. % S (x = 10, 20, 30) demonstrating excellent electrochemical activity with an onset overpotential for HER similar to Pt/C in acidic, neutral as well as basic media. The highest electrochemical activity is exhibited by (Cu_0.83Co_0.17)₃P:30 at. % S nanoparticles (NPs) displaying overpotential to reach 100 mA cm^?2 in acidic, neutral and basic media similar to Pt/C. The (Cu_0.83Co_0.17)₃P:30 at. % S NPs also display excellent electrochemical stability in acidic media for long term electrolytic and PEC water splitting process [using our previously reported (Sn_0.95Nb_0.05) O₂: N-600 nanotubes (NTs) as the photoanode]. The applied bias photon-to-current efficiency obtained using (Cu_0.83Co_0.17)₃P:30 at. % S NPs as the cathode electro-catalyst for HER in an H-type PEC water splitting cell (～4%) is similar to that obtained using Pt/C (～4.1%) attesting to the promise of this exciting non-noble metal containing system.     

The effect of annealing temperature,reaction time,and cobalt precursor on the structural properties and catalytic performance of CoS2 for hydrogen evolution reaction

In this study, cobalt disulfide (CoS₂) nanostructures are synthesized using a simple hydrothermal method. The effects of experimental parameters including cobalt precursor, reaction times, and reaction temperatures are investigated on the structure, morphology and electrocatalytic properties of CoS₂ for hydrogen evolution reaction (HER). The characterization of as-prepared catalysts is performed using X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS). The HER efficiency of the catalysts is examined using linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) methods in 0.5 M H₂SO₄ solution. Furthermore, chronoamperometry (CA) is used for stability evaluation. The catalyst obtained from cobalt acetate precursor, within 24 h at 200 °C exhibits superior electrocatalytic activity with a low onset potential (139.3 mV), low overpotential (197.3 mV) at 10 mA. cm^?2 and a small Tafel slope of 29.9 mV dec^?1. This study is a step toward understanding the effect of experimental parameters of the hydrothermal method on HER performance and developing optimal design approaches for the synthesis of CoS₂ as a common electrocatalyst.     

A facile synthesis of metal ferrites (MFe2O4, M = Co,Ni, Zn,Cu) as effective electrocatalysts toward electrochemical hydrogen evolution reaction

Developing low-cost, stable, and robust electrocatalysts for hydrogen evolution reaction (HER) is highly desirable for large-scale application. In this study, a highly efficient electrocatalysts of metal ferrites (MFe₂O₄, M = Co, Ni, Zn, Cu) with superior activity and durability are successfully fabricated on copper substrate through a facile co-precipitation method followed by doctor-blading deposition. The electrocatalytic performance of CoFe₂O₄, NiFe₂O₄, ZnFe₂O₄ and CuFe₂O₄ electrodes for hydrogen evolution reaction is studied in alkaline media using polarization curves and electrochemical impedance spectroscopy (EIS). Among them, CoFe₂O₄ presented the best electrocatalytic activities for HER with extremely low overpotentials of 270 mV (vs. RHE) at a current density of 10 mA cm^?2 in 1 M KOH. The electrocatalytic activity of MFe₂O₄ (M = Co, Ni, Zn, Cu) for HER to generate current density of 10 mA cm^?2 with low overpotential followed the order of CoFe₂O₄ > CuFe₂O₄ > NiFe₂O₄ > ZnFe₂O₄. The highly improved HER performance of CoFe₂O₄ is mainly due to a large number of exposed active sites, high electrical conductivity and low apparent activation energy, which are confirmed by a remarkable electrochemically active surface area (ECSA = 53.17 cm²), Nyquist plots analysis and Arrhenius plots measurement, respectively. Moreover, the CoFe₂O₄ electrode showed outstanding electrocatalytic stability even after 1000 cyclic voltametry tests. These results provide a promising avenue for developing cost-effective and high-efficiency electrocatalysts based on earth-abundant transition metal ferrite as advanced electrodes for large-scale energy conversion processes.     

Electrocatalysts for hydrogen evolution reaction

In addition to the historical importance of water electrolysis, hydrogen evolution reaction (HER) is the heart of various energy storage and conversation systems in the future of renewable energy. The HER electrocatalysis can be well conducted by Pt with a low overpotential close to zero and a Tafel slope around 30 mV dec^?1; however, the practical developments to satisfy the growing demands require cheaper electrocatalysts. Noble metals are still the promising candidates, though further improvement is needed to enhance the HER efficiency in performance. Three categories of non-noble metal electrocatalysts are under heavy investigations: (i) alloys, (ii) transition metal compounds, and (iii) carbonaceous nanomaterials. The most practical option, based on the electrocatalytic activity and electrochemical stability, seems to be the transition metal compounds MX (where M is Mo, W, Ni, Co, etc. and X is S, Se, P, C, N, etc.). Among these compounds, some like MoS₂ and WC can display metallic properties and a Pt-like electrocatalytic activity, but they still need serious modifications for the practical performance. In general, similar strategies have been employed to improve the HER performance of all of these materials such as doping (both cation and anion), controlling the crystallinity and amorphism, and increasing the active sites by changing the morphology. Another important issue is the chemical and physical structure of the carbon-based catalyst support, as carbon is normally a vital component even for the Pt electrocatalysts.     

Facile hydrothermal synthesis of rare earth phosphate for boosting hydrogen evolution reaction

The water electrolysis process has attracted great attention due to the production of high energy density pure hydrogen. However, the involved cell reactions in this process such as hydrogen and oxygen evolution reactions are kinetically sluggish and demands high input energy to accelerate the rate of these reactions. Therefore, the development and application of efficient electrocatalyst is essential for hydrogen evolution reaction (HER) as well as oxygen evolution reaction (OER). In the present work, we have successfully synthesized two rare earth phosphates through the hydrothermal route and used as a catalysts towards HER in an acidic medium. The rare earth phosphate PrPO₄ exhibits better catalytic activity than YPO₄ catalyst. The overpotential of PrPO₄, YPO₄ and standard Pt/C were found as 147, 484.3 and 58 mV vs. reversible hydrogen electrode, respectively, to reach current density 10 mA·cm^?2 and corresponding Tafel slopes were found as 107.58, 118.73 and 80.89 mV decade^?1, respectively in 0.5 M H₂SO₄. The catalytic activity of PrPO₄ (472.83 mA·cm^?2) overcome standard Pt/C (179.60 mA·cm^?2) at high overpotential 450 mV vs. reversible hydrogen electrode. The prepared PrPO₄ shows efficient electrocatalytic activity towards HER in acidic medium because it possess high BET surface area, large ECSA value and small charge transfer resistance than YPO₄.     

N,P-co-doped carbon coupled with CoP as superior electrocatalysts for hydrogen evolution reaction and overall water splitting

To achieve high activity and stability for both hydrogen and oxygen evolution reactions through the non-precious-metal based electrocatalysts is still facing the great challenge. Herein, we demonstrate a facile strategy to prepare CoP nanoparticles (NPs) loaded on N, P dual-doped carbon (NPC) electrocatalysts with high concentration N and P dopants through a pyrolysis-deposition-phosphidation process. The great bifunctional electrocatalytic activity for both HER (the overpotential of 98 mV and 86 mV at 10 mA cm⁻² in both 0.5 M H₂SO₄ and 1 M KOH electrolytes, respectively) and OER (the overpotential of 300 mV at 10  mA cm⁻² in 1 M KOH electrolyte) were achieved. When CoP@NPC hybrid was used as two electrodes in the 1 M KOH electrolyte system for overall water splitting, the needed cell potential for achieving the current density of 10 mA cm⁻² is 1.6 V, and it also showed superior stability for HER and OER after 10 h’ test with almost negligible decay. Experimental results revealed that the P atoms in CoP were the active sites for HER and the CoP@NPC hybrid showed excellent bifunctional electrocatalytic properties due to the synergistic effects between the high catalytic activity of CoP NPs and NPC, in which the doping of N and P in carbon led to a stronger polarization between Co and P in CoP, promoting the charge transfer from Co to P in CoP, enhancing the catalytic activity of P sites and Co sites in CoP for HER and OER, respectively. Specifically, the improvements could result from the changed charge state, the increased active specific surface area, and the facilitated reaction kinetics by N, P co-doping and admixture. This work provides a high-efficient, low-cost and stable electrocatalyst for overall water splitting, and throws light on rational designing high performance electrocatalysts.