Facile construction of porous and heterostructured molybdenum nitride/carbide nanobelt arrays for large current hydrogen evolution reaction

The development of cost-effective, highly efficient and stable electrocatalysts for alkaline water electrolysis at a large current density has attracted considerable attention. Herein, we reported a one-dimensional (1D) porous Mo₂C/Mo₂N heterostructured electrocatalyst on carbon cloth as robust electrode for large current hydrogen evolution reaction (HER). The MoO₃ nanobelt arrays and urea were used as the metal and non-metal sources to fabricate the electrocatalyst by one-step thermal reaction. Due to the in-situ formed abundant high active interfaces and porous structure, the Mo₂C/Mo₂N electrocatalyst shows enhanced HER activity and kinetics, as exemplified by low overpotentials of 54, 73, and 96 mV at a current density of 10 mA cm^?2 and small Tafel slopes of 48, 59 and 60 mV dec^?1 in alkaline, neutral and acid media, respectively. Furthermore, the optimal Mo₂C/Mo₂N catalyst only requires a low overpotential of 290 mV to reach a large current density of 500 mA cm^?2 in alkaline media, which is superior to commercial Pt/C catalyst (368 mV) and better than those of recently reported Mo-based electrocatalysts. This work paves a facile strategy to construct highly efficient and low-cost electrocatalyst for water splitting, which could be extended to fabricate other heterostructured electrocatalyst for electrocatalysis and energy conversion.     

Amorphous-crystalline cobalt-molybdenum bimetallic phosphide heterostructured nanosheets as Janus electrocatalyst for efficient water splitting

Efficient and sustainable Janus catalysts toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are highly desirable for future hydrogen production via water electrolysis. Herein we report an active Janus electrocatalyst of amorphous-crystalline cobalt-molybdenum bimetallic phosphide heterostructured nanosheets on nickel foam (CoMoP/CoP/NF) for efficient electrolysis of alkaline water. As-reported CoMoP/CoP/NF consists of amorphous bimetal phosphide nanosheets doped with crystalline CoMoP/CoP heterostructured nanoparticles on NF. It can efficiently catalyze both HER (η = 127 mV@100 mA cm^?2) and OER (η = 308 mV@100 mA cm^?2) in alkaline electrolyte with long-term durability. Serving as anode and cathode of water electrolyzer, CoMoP/CoP/NF generates electrolytic current of 10, 50 and 100 mA cm^?2 at low voltage of 1.50, 1.59, and 1.67 V, respectively.     

Bimetallic NiCo–NiCoO2 nano-heterostructures embedded on copper foam as a self-supported bifunctional electrode for water oxidation and hydrogen production in alkaline media

Earth-abundant, non-precious metal-based bifunctional electrocatalysts with efficient water splitting activity are of valuable importance in the limitation of energy losses in an alkaline environment. Herein, we report NiCo–NiCoO₂ nano-heterostructures embedded on the oxidized surface of copper foam (NiCo–NiCoO₂@Cu₂O@CF) as an efficient bifunctional electrocatalyst for overall water splitting in 1 M KOH electrolyte solution. In this study, metallic Ni and Co interlinkage with NiCoO₂ nanoparticles (NPs) are suggested to form by thermal decomposition of nickel-cobalt hydroxide precursors embedding on copper foam under a nitrogen environment. Bimetallic thin layered nano-heterostructures of NiCo–NiCoO₂@Cu₂O@CF exhibits a synergic effect of doubly active metals Ni and Co to achieve remarkable small overpotentials of 133 and 327 mV to achieve a current density of 10 mA cm^?2 for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The influential synergetic and structural effects have been extensively discussed to understand the overall water splitting for designing an efficient electrocatalyst. Hence, this phenomenon for surface modification of conductive substrate (CF) with a suitable combination of metal/metal oxide alloying as catalytic material helps us to design and synthesize low cost, highly efficient, non-precious metal-based electrocatalysts for overall water splitting.     

CO2 assisted synthesis of silk fibroin driven robust N-doped carbon aerogels coupled with nickel–cobalt particles as highly active electrocatalysts for HER

Hydrogen evolution reaction (HER), has been considered as an ideal alternative energy system to alleviate the global energy crisis. Unfortunately, the rational design of a cost-effective, highly active and stable electrocatalyst remains a tough challenge. In this work, a CO₂ assisted synthesis of N- doped carbon aerogel derived from silk fibroin (SFCA) without any additives was used to anchor Nickel–Cobalt (NiCo) nanoparticles as an HER electrocatalyst in basic medium (1 M KOH). The obtained SFCA-NiCo electrocatalyst demonstrated outstanding electrochemical performance having an onset potential of 52 mV and a low overpotential of 179 mV at current density of 10 mA cm^?2, whilst exhibiting long term stability when tested for 24 h. The outstanding electrocatalytic performance marks SFCA-NiCo as a favourable electrocatalyst for HER and the synthesis strategy paves way for constructing novel catalysts even for other areas.     

High throughput preparation of Ni–Mo alloy thin films as efficient bifunctional electrocatalysts for water splitting

The synthesis of cost-effective and high-performance electrocatalysts for water splitting is the main challenge in electrochemical hydrogen production. In this study, we adopted a high throughput method to prepare bi-metallic catalysts for oxygen/hydrogen evolution reactions (OER/HER). A series of Ni–Mo alloy electrocatalysts with tunable compositions were prepared by a simple co-sputtering method. Due to the synergistic effect between Ni and Mo, the intrinsic electrocatalytic activity of the Ni–Mo alloy electrocatalysts is improved, resulting in excellent HER and OER performances. The Ni₉₀Mo₁₀ electrocatalyst shows the best HER performance, with an extremely low overpotential of 58 mV at 10 mA cm^?2, while the Ni₄₀Mo₆₀ electrocatalyst shows an overpotential of 258 mV at 10 mA cm^?2 in OER. More significantly, the assembled Ni₄₀Mo₆₀//Ni₉₀Mo₁₀ electrolyzer only needs a cell voltage of 1.57 V to reach 10 mA cm^?2 for overall water splitting.     

Metal-organic frameworks derived self-supported Ni2P nanorod arrays for electrocatalytic hydrogen evolution

The development of efficient and low-cost electrocatalysts for hydrogen evolution reaction (HER) is of importance. Herein, we demonstrate a self-supported Ni₂P nanostructure with nanorod arrays morphology, fabricated by directly growing metal-organic frameworks (MOFs) on the commercial nickel foam prior to phosphorization treatment, as an electrocatalyst for HER. This electrocatalyst exhibits remarkable electrocatalytic HER activity in an alkaline electrolyte, affording current densities of 10 and 100 mA cm^?2 at the overpotentials of 120 and 168 mV, respectively, accompanied with a low Tafel slope of 37 mV dec^?1. Furthermore, this electrocatalyst shows a current density of 105 mA cm^?2, and this current density can be retained for more than 20 h, suggesting its superior stability. This remarkable HER performance is believed a result of superiority for its structural integrality and mechanical stability.     

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.     

Heterostructured CoP/MoO2 as high efficient electrocatalysts for hydrogen evolution reaction over all pH values

Delicate design and rapid development of low-cost, highly active, and perdurable pH-universal heterogenveous hydrogen evolution reaction (HER) electrocatalysts are demanding challenge in energy-conversion technologies. Herein, heterostructured CoP/MoO₂ electrocatalyst was synthesized by employing MoO₂ nanorods as framework for the growth of CoP nanoparticles. Owing to the fact that the effective interface of heterostructure can enhance electron transfer/mass diffusion and expose ample active sites, the CoP/MoO₂ reveals eminent HER activities with favorable long-term stability in all pH electrolytes, overpotentials of 69, 78, and 165 mV in 0.5 M H₂SO₄, 1.0 M KOH, and 1.0 M PBS (phosphate-buffered solution) electrolytes were required for CoP/MoO₂ to reach the current density of 10 mA cm^?2. This work emphasizes that strategy of electronic structure engineering holds great promises in pH-universal HER electrocatalysts for energy storage and conversion.     

Boosting activity and stability by coupling Pt–Ni nanoparticles with La-modified flexible carbon nanofibers for hydrogen evolution reaction

Platinum (Pt) is considered as the most efficient catalyst for hydrogen evolution reaction (HER) with a nearly zero overpotential, but it is limited by the high cost and poor stability. Herein, we report an efficient electrocatalyst of Pt–Ni alloy nanoparticles (NPs) supported on the La-modified flexible carbon nanocomposite fibers (PtNi@La-CNFs) for HER. The rare earth metal oxide in the catalyst has a structure-effect relationship with the carbon fibers to form a flexible fiber membrane. Experimental results show that the macroscopic and microscopic properties of carbon nanocomposite fibers can be optimized by doping La₂O₃, and the Pt–Ni NPs can be anchored effectively. The Pt₁Ni₁@La-CNFs electrocatalyst exhibits a small overpotential of 32 mV to achieve current density of 10 mA cm^?2 with a low Tafel slope of 51 mV dec^?1 in alkaline medium, outperforming that of Pt@La-CNFs and the commercial Pt/C catalyst. This study reveals that the multiple coupling effect of rare earth compound, precious metal, and transition metal in composite catalyst can tailor its the electronic configuration, and results in an enhanced HER performance. This work opens up a novel approach to design high active and low cost Pt-based HER catalysts.     

Bifunctional nanoporous ruthenium-nickel alloy nanowire electrocatalysts towards oxygen/hydrogen evolution reaction

A class of ruthenium-nickel alloy catalysts featured with nanoporous nanowires (NPNWs) were synthesized by a strategy combining rapid solidification with two-step dealloying. RuNi NPNWs exhibit excellent electrocatalytic activity and stability for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in which the RuNi-2500 NPNWs catalyst shows an OER overpotential of 327 mV to deliver a current density of 10 mA cm^?2 and the RuNi-0 NPNWs catalyst requires the overpotential of 69 mV at 10 mA cm^?2 showing the best HER activity in alkaline media. Moreover, the RuNi-1500 NPNWs catalyst was used as the bifunctional electrocatalyst in a two-electrode alkaline electrolyzer for water splitting, which exhibits a low cell voltage of 1.553 V and a long-term stability of 24 h at 10 mA cm^?2, demonstrating that the RuNi NPNWs catalysts can be considered as promising bifunctional alkaline electrocatalysts.     

One-pot solvothermal synthesis of Co2P nanoparticles: An efficient HER and OER electrocatalysts

Development of an inexpensive electrocatalyst for hydrogen evolution (HER) and oxygen evolution reactions (OER) receives much traction recently. Herein, we report a facile one-pot ethyleneglycol (EG) mediated solvothermal synthesis of orthorhombic Co₂P with particle size ~20–30 nm as an efficient HER and OER catalysts. Synthesis parameters like various solvents, temperatures, precursors ratios, and reaction time influences the formation of phase pure Co₂P. Investigation of Co₂P as an electrocatalyst for HER in acidic (0.5 M H₂SO₄) and alkaline medium (1.0 M KOH), furnishes low overpotential of 178 mV and 190 mV, respectively to achieve a 10 mA cm^?2 current density with a long term stability and durability. As an OER catalyst in 1.0 M KOH, Co₂P shows an overpotential of 364 mV at 10 mA cm^?2 current density. Investigation of Co₂P NP by XPS analysis after OER stability test under alkaline medium confirms the formation of amorphous cobalt oxyhydroxide (CoOOH) as an intermediate during OER process.     

Facile fabrication of a binary NiCo phosphide with hierarchical architecture for efficient hydrogen evolution reactions

Exploring and designing efficient non-noble catalysts formed by element doping and nanostructure modification for the hydrogen evolution reaction (HER) is of critical importance with respect to sustainable resources. Herein, we have prepared a three-dimensional binary NiCo phosphide with hierarchical architecture (HA) composed of NiCoP nanosheets and nanowires grown on carbon cloth (CC) via a facile hydrothermal method followed by oxidation and phosphorization. Due to its unique hierarchical nanostructure, the NiCoP HA/CC electrocatalyst exhibits excellent performance and good working stability for the HER in both acidic and alkaline conditions. The obtained NiCoP HA/CC shows excellent HER activity with a low potential of 74 and 89 mV at 10 mA cm⁻², a small Tafel slope of 77.2 and 99.8 mV dec⁻¹ and long-term stability up to 24 h in acidic and alkaline electrolyte, respectively. NiCoP HA/CC, a non-noble metal material, is a promising electrocatalyst to replace noble metal-based electrocatalysts for the HER.     

Heterostructured two dimensional materials of MXene and graphene by hydrothermal method for efficient hydrogen production and HER activities

Recent development on two-dimensional (2D) heterostructured graphene and MXene materials were explored for electrochemical water splitting hydrogen evolution reaction (HER) activity. The hybrid MXene/reduced graphene oxides as two-dimensional (2D) hybrid structures were prepared by facile hydrothermal techniques at 150 °C with MXene and RG hybrid layered composites. As-prepared electrocatalytic active materials have been confirmed through structural and surface morphological studies such as XRD, RAMAN, FT-IR and SEM analysis. The prepared 2D materials were carried out for HER activities due to attractive conductivity and mass transfer process. HER performance were tested from linear sweep voltammetry (LSV) cures. The prepared MX, RG and MX@RG hybrid electrocatalyst exhibited overpotential values as observed as 220 mV, 193 mV, 121 mV respectively at 10 mAcm^?2 cathodic on set. MX@RG hybrid heterostructure exhibited enhanced HER action with lowest overpotential (η = 121 mV) and good H₂ productions as an active future electrocatalyst for energy storage and conversion applications.     

Synergistic regulation of hydrogen adsorption/desorption via dual interfaces of Cu/Ni/Ni(OH)2 toward efficient hydrogen evolution reaction

Nickel-based catalysts have attracted tremendous attention as alternatives to precious metal-based catalysts for electrocatalytic hydrogen evolution reaction (HER) in virtue of their conspicuous advantages such as abundant reserves and high electrochemical activity. Nevertheless, a great challenge for Ni-based electrocatalyst is that nickel sites possess too strong adsorption for key intermediates H1, which severely suppresses the hydrogen-production activities. Herein, we report a hierarchical architecture Cu/Ni/Ni(OH)₂ consisting of dual interfaces as a high-efficient electrocatalyst for HER. The Cu nanowire backbone could provide geometric spaces for loading plenty of Ni sites and the formed Ni/Cu interface could effectively weakened the adsorption intensity of H1 intermediates on the catalyst surface. Moreover, the H1 adsorption could be further controlled to appropriate states by in-situ formed Ni(OH)₂/Ni interface, which simultaneously promotes water adsorption and activation, thus both Heyrovsky and Volmer steps in HER could be obviously accelerated. Experimental and theoretical results confirm that this interface structure can promote water dissociation and optimize H1 adsorption. Consequently, the Cu/Ni/Ni(OH)₂ electrocatalyst exhibits a low overpotential of 20 mV at 10 mA cm^?2 and an ultralow Tafel slope of 30 mV dec^?1 in 1.0 M KOH, surpassing those of reported transition-metal-based electrocatalysts and even the prevailing commercial Pt/C.     

Flower-like HEA/MoS2/MoP heterostructure based on interface engineering for efficient overall water splitting

The development of cheap, efficient, and active non-noble metal electrocatalysts for total hydrolysis of water (oxygen evolution reaction (OER) and hydrogen evolution reaction (HER)) is of great significance to promote the application of water splitting. Herein, a heterogeneous structured electrode based on FeAlCrMoV high-entropy alloy (HEA) was synthesized as a cost-effective electrocatalyst for hydrogen and oxygen evolution reactions in alkaline media. In combination of the interfacial synergistic effect and the high-entropy coordination environment, flower-like HEA/MoS₂/MoP exhibited the excellent HER and OER electrocatalytic performance. It showed a low overpotential of 230 mV at the current density of 10 mA cm⁻² for OER and 148 mV for HER in alkaline electrolyte, respectively. Furthermore, HEA/MoS₂/MoP as both anode and cathode also exhibited an overpotential of 1.60 V for overall water splitting. This work provides a new strategy for heterogeneous structure construction and overall water splitting based on high-entropy alloys.     

NiCoP nanoarchitectures: One-step controlled electrodeposition and their application as efficient electrocatalysts for boosting hydrogen evolution reaction

Designing non-precious and long-lasting electrocatalysts with enhanced catalytic properties for hydrogen evolution reaction (HER) is a fundamental approach to address the needs for hydrogen industry and overcome the current challenges in sustainable energy generation. Herein, we present ternary NiCoP nanostructures synthesized through a direct and controlled electrochemical deposition at room temperature as highly efficient electrocatalysts for HER. Different Ni/Co ratios in the alloy were investigated resulting in different nanoarchitectured morphologies, chemical compositions and HER performances, in turn. The NiCoP–I alloy exhibited a nanoparticulated morphology comprising well-defined nanoparticles of ～20–30 nm which evolved to nanoparticulated caps at prolonged electrodeposition times presenting a large electrochemical surface area of 526 cm². The NiCoP–I electrocatalyst demonstrated a small Tafel slope of 49 mV dec^?1 and an ultra-low overpotential of 68 mV vs. RHE at ?10 mA cm^?2 in alkaline solution which well rivals to that of Pt foil and outmatches its binary alloy counterparts.     

Efficient CoMoRu0.25Ox/NF nanoplate architectures for overall electrochemical water splitting

The development of inexpensive electrocatalysts with excellent electrocatalytic activity for the hydrogen and oxygen evolution reactions (HER and OER, respectively) has been challenging. In this study, we synthesized cobalt molybdenum ruthenium oxide with porous, loosely-assembled nanoplate morphology. The CoMoRu_0.25O_x/NF electrocatalyst exhibited the highest electrocatalytic activity, requiring overpotentials of 230 and 78 mV for the OER and HER, respectively, to attain a current density of 10 mA cm^?2; moreover, its long-term stability was outstanding. The electrocatalyst required a cell voltage of only 1.51 V for overall water splitting in an alkaline medium, which was lower than that required by many CoMo-based catalysts.     

Synthesis of MoS2 nanoparticles embedded,N, S co-doped mesoporous carbon via molten salt method as hydrogen evolution electrocatalyst under alkaline and neutral conditions

We developed a salt-template strategy to prepare MoS₂ nanoparticles (NPs) embedded, N, S co-doped carbons via the solid-state process. The addition of the inorganic salt played two main roles in the synthetic proceeding. First, the salts could be utilized as the templates to produce the mesopores, which could be removed by simple washing process. Second, the salts could promote the formation of MoS₂ NPs. The as-received electrocatalyst, K-G4.0T2.0Mo1.0, possessed high BET surface area of 446 m² g^?1, in addition to high double layer capacitance of 24.5 mF cm^?2 in the alkaline media. When evaluated as the electrocatalyst for hydrogen evolution reaction (HER), K-G4.0T2.0Mo1.0 demonstrated excellent performance in the alkaline and neutral medias. In details, K-G4.0T2.0Mo1.0 showed a low overpotential of 173 and 358 mV to afford 10 mA cm^?2 under alkaline and neutral conditions, respectively, as well as outstanding durability.     

N-doped graphene supported W2C/WC as efficient electrocatalyst for hydrogen evolution reaction

Tungsten carbides (W₂C and WC) materials, as promising non-precious electrocatalysts, possess highly efficient activity for HER. Herein, N-doped graphene supported tungsten carbide (N–W₂C/WC) nanocomposite is synthesized by spray drying process followed with a two-step pyrolysis treatment, which exhibits a remarkable hydrogen evolution reaction (HER) activity and excellent stability in acidic solution and alkaline solution. N–W₂C/WC displays low overpotentials of 166 mV and 125 mV to achieve a current density of 10 mA cm^?2 and small Tafel slopes of 60.97 and 62.66 mV dec^?1 in 0.5 M H₂SO₄ and 1.0 M KOH, respectively. After 1000 cycles, the electrocatalytic activity of N–W₂C/WC is almost no change in acidic media but slightly decreases in alkaline media. This work might provide a new way to explore high comprehensive performance tungsten-based electrocatalyst for HER.     

A highly active composite electrocatalyst Ni–Fe–P–Nb2O5/NF for overall water splitting

This work demonstrates a facile Nb₂O₅-decorated electrocatalyst to prepare cost-effective Ni–Fe–P–Nb₂O₅/NF and compared HER & OER performance in alkaline media. The prepared electrocatalyst presented an outstanding electrocatalytic performance towards hydrogen evolution reaction, which required a quite low overpotential of 39.05 mV at the current density of ?10 mA cm^?2 in 1 M KOH electrolyte. Moreover, the Ni–Fe–P–Nb₂O₅/NF catalyst also has excellent oxygen evolution efficiency, which needs only 322 mV to reach the current density of 50 mA cm^?2. Furthermore, its electrocatalytic performance towards overall water splitting worked as both cathode and anode achieved a quite low potential of 1.56 V (10 mA cm^?2).