Mesoporous nickel-sulfide/nickel/N-doped carbon as HER and OER bifunctional electrocatalyst for water electrolysis

The development of non-precious metal-based highly active bi-functional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is critical factor for making water electrolysis a viable process for large-scale industrial applications. In this study, bi-functional water splitting electrocatalysts in the form of nickel-sulfide/nickel nanoparticles integrated into a three-dimensional N-doped porous carbon matrix, are prepared using NaCl as a porous structure-forming template. Microstructures of the catalytic materials are characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and N₂ adsorption-desorption analysis. The most active catalyst synthesized in this study exhibits a low HER overpotential of 70 mV at 10 mA cm⁻² and a low Tafel slope of 45 mV dec⁻¹. In OER, the optimized sample performs better than a state-of-the-art RuO₂ catalyst and produces an overpotential of 337 mV at 10 mA cm⁻², lower than that of RuO₂. The newly obtained materials are also used as HER/OER electrocatalysts in a specially assembled two-electrode water splitting cell. The cell demonstrates high activity and good stability in overall water splitting.     

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.     

Black phosphorous dots phosphatized bio-based carbon nanofibers/bimetallic organic framework as catalysts for oxygen evolution reaction

As a multi-step and more complex half-cell reaction than the hydrogen reverse evolution reaction (HER), the oxygen evolution reaction (OER) always requires a higher overpotential than HER. In order to minimize the associated energy loss as an overpotential, these electrochemical half-reactions of water splitting should be catalyzed by suitable materials. Due to the abundant exposed surface area and extensive active edge sites, black phosphorous quantum dots (BP QDs) have shown great potential in OER. Here, BP QDs was introduced to incorporate with bio-based carbon nanofibers (CNF) and Co–Ni bimetallic organic framework (CoNiMOF), preparing a novel catalyst for oxygen evolution reaction (OER) by a facile one-pot reaction (Scheme 1). The unique structures and greater BET surface areas of CoNiMOF-BP QDs/CNF could possibly supply a larger electrocatalytic surface, expose further active sites. The obtained CoNiMOF-BP QDs/CNF possesses excellent electrocatalytic activity in alkaline electrolyte (1 M KOH) with a low overpotential of 281 mV at 10 mA cm^?2 and a low Tafel slope of 111.9 mV dec^?1. The CoNiMOF-BP QDs/CNF can remain stable for 25,000 s under alkaline electrolyte, showing excellent stability. The increase of electrocatalyst activity is mainly attributed to the synergistic effect of excellent conductivity and enriched active sites arising from BP QDs. This work not only provides an effective strategy for the development of bimetallic MOFs derived electrocatalysts, but also puts forward a new insight for the application of BP QDs in water splitting.     

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.     

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.     

PBA derived FeCoP nanoparticles decorated on NCNFs as efficient electrocatalyst for water splitting

Transition metal phosphides have been known as promising electrocatalysts for hydrogen evolution and oxygen evolution reactions (HER and OER) due to their high catalytic activity. In this work, the FeCoP nanoparticles decorated on N-doped electrospun carbon nanofibers (FeCoP@NCNFs) was successfully synthesized through depositing Fe, Co-based Prussian blue analogue Co₃[Fe(CN)₆]₂·10H₂O (FeCo-PBA) onto the electrospun PVP/PAN nanofibers via layer-by-layer approach, followed by carbonization and phosphorization treatments. Benefiting from the high electrical conductivity, abundant catalytic active sites and the synergistic effect between FeCoP nanoparticles and N-doped carbon nanofibers network, the obtained FeCoP@NCNFs displays good bifunctional electrocatalytic activity. In 1 M KOH, the FeCoP@NCNFs achieves 10 mA cm^?2 at an overpotential of 290, 226 mV for OER and HER, respectively. Moreover, it demands overpotential of 196 mV to achieve 10 mA cm^?2 for HER in 0.5 M H₂SO₄. The FeCoP@NCNFs is used as both anode and cathode for overall water splitting, it requires a low voltage of 1.65 V to achieve a current density of 10 mA cm^?2 and maintains outstanding stability over 10 h. Herein, a strategy for preparing bifunctional electrocatalysts of compositing transition metal phosphides with carbon nanofibers is proposed, and the application of metal-organic framework in electrocatalytic field is further extended.     

Porous sunflower plate-like NiFe2O4/CoNi–S heterostructure as efficient electrocatalyst for overall water splitting

Constructing high-efficient and nonprecious electrocatalysts is of primary importance for improving the efficiency of water splitting. Herein, a novel sunflower plate-like NiFe₂O₄/CoNi–S nanosheet heterostructure was fabricated via facile hydrothermal and electrodeposition methods. The as-fabricated NiFe₂O₄/CoNi–S heterostructure array exhibits remarkable bifunctional catalytic activity and stability toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline media. It presents a small overpotential of 219 mV and 149 mV for OER and HER, respectively, to produce a current density of 10 mA cm^?2. More significantly, when the obtained electrodes are used as both the cathode and anode in an electrolyzer, a voltage of 1.57 V is gained at 10 mA cm^?2, with superior stability for 72 h. Such outstanding properties are ascribed to: the 3D porous network structure, which exposes more active sites and accelerates mass transfer and gas bubble emission; the high conductivity of CoNi–S, which provides faster charge transport and thus promotes the electrocatalytic reaction of the composites; and the effective interface engineering between NiFe₂O₄ (excellent performance for OER) and CoNi–S (high activity for HER), which leads to a shorter transport pathway and thus expedites electron transfer. This work provides a new strategy for designing efficient and inexpensive electrocatalysts for water splitting.     

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.     

Nickel foam-supported Fe,Ni-Polyporphyrin microparticles: Efficient bifunctional catalysts for overall water splitting in alkaline media

Developing highly active, stable and sustainable electrocatalysts for overall water splitting is of great importance to generate renewable H₂ for fuel cells. Herein, we report the synthesis of electrocatalytically active, nickel foam-supported, spherical core-shell Fe-poly(tetraphenylporphyrin)/Ni-poly(tetraphenylporphyrin) microparticles (FeTPP@NiTPP/NF). We also show that FeTPP@NiTPP/NF exhibits efficient bifunctional electrocatalytic properties toward both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). Electrochemical tests in KOH solution (1 M) reveal that FeTPP@NiTPP/NF electrocatalyzes the OER with 100 mA cm⁻² at an overpotential of 302 mV and the HER with 10 mA cm⁻² at an overpotential of 170 mV. Notably also, its catalytic performance for OER is better than that of RuO₂, the benchmark OER catalyst. Although its catalytic activity for HER is slightly lower than that of Pt/C (the benchmark HER electrocatalyst), it shows greater stability than the latter during the reaction. The material also exhibits electrocatalytic activity for overall water splitting reaction at a current density of 10 mA cm⁻² with a cell voltage of 1.58 V, along with a good recovery property. Additionally, the work demonstrates a new synthetic strategy to an efficient, noble metal-free-coordinated covalent organic framework (COF)-based, bifunctional electrocatalyst for water splitting.     

Strategies for improving Co/Ni-based bimetal-organic framework to water splitting

The preparation of high-efficiency, stable, and low-cost oxygen evolution reactions (OER) and hydrogen evolution reactions (HER) electrocatalysts remains a challenge for new energy systems. In this study, three-dimensional (3D) cobalt-nickel bimetal MOFs were used as precursors to synthesize catalysts through thermal decomposition, carbonization, nitriding, oxidation, phosphating, sulfurizing, and selenization, respectively. In 1.0 M KOH electrolyte, the overpotential of Co/Ni-MOFs@Se for OER was 238 mV and the that of Co/Ni-MOFs@P for HER was 194 mV at a current density of 10 mA cm⁻². Based on the excellent OER and HER performances of Co/Ni-MOFs@Se and Co/Ni-MOFs@P, these two materials were further assembled into electrodes for overall water splitting. Results showed that a potential of only 1.59 V was required to provide a current density of 10 mA cm⁻². The electrodes also exhibited long-term durability in a 2000 min stability test without significant changes in the catalytic performances. According to the difference in the doped non-metal elements, an electrode pair with a suitable matching degree was constructed, thereby improving the overall water splitting performance. Thus, the controllable modification of the metal-organic frameworks (MOFs)-derived carbon materials (CMs) effectively improved the materials’ catalytic water splitting performance. It was possible to further develop an efficient, inexpensive, and low-cost assembled electrode pair.     

Electrospun prussian blue analogue derived NiCo@N-doped carbon nanofibers as efficient and highly stable electrocatalysts for neutral overall water splitting

Herein, we demonstrate an effective strategy to improve the catalytic stability and efficiency of inexpensive bifunctional electrocatalysts via using electrospun Prussian blue analogue derived NiCo alloy nanoparticles encapsulated in nitrogen-doped carbon nanofibers (NiCo@NC) for neutral overall water splitting. The optimal NiCo@NC-900 exhibits the best electrocatalytic activity toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in 1 M phosphate-buffered saline (PBS, pH 7), respectively. More importantly, a neutral electrolyzer using NiCo@NC-900 as both HER and OER electrodes achieves high stability with over 140 h and requires a low cell voltage of 1.75 V at 10 mA cm^?2. The remarkable stability and superior activity origin form the unique hierarchically porous and encapsulated structure, large surface area, abundant exposing active sites, and synergistic effect between the highly catalytic active NiCo alloy nanoparticles and high-conductivity N-doped carbon nanofibers, as demonstrated by the detailed analysis before and after HER and OER testing.     

FeOOH–CoS composite catalyst with high catalytic performances for oxygen evolution reaction at high current density

Water electrolysis is an efficient approach for high-purity hydrogen production. However, the anodic sluggish oxygen evolution reaction (OER) always needs high overpotential and thus brings about superfluous electricity cost of water electrolysis. Therefore, exploiting highly efficient OER electrocatalysts with small overpotential especially at high current density will undoubtedly boost the development of industrial water electrolysis. Herein, we used a simple hydrothermal method to prepare a novel FeOOH–CoS nanocomposite on nickel foam (NF). The as-prepared FeOOH–CoS/NF catalyst displays an excellent OER performance with extremely low overpotentials of 306 and 329 mV at 500 and 1000 mA cm⁻² in 1.0 M KOH, respectively. In addition, the FeOOH–CoS/NF catalyst can maintain excellent catalytic stability for more than 50 h, and the OER catalytic activity shows almost no attenuation no matter after 1000 repeated CV cycles or 50 h of stability test. The high catalytic activity and stability have exceeded most non-noble metal electrocatalysts reported in literature, which makes the FeOOH–CoS/NF composite catalyst have promising applications in the industrial water electrolysis.     

Carbon nanorod supported metal alloy nanocubes using polydopamine as location reagent for water splitting

Transition metal catalysts were supposed to be the most likely substitute for commercial noble metal catalysts, and the development of highly active and long-term catalyst for water splitting are the future trend. Herein, Ni rectangular nitrogen doped carbon nanorods@Fe–Co nanocubes (Ni-CNRs@Fe–Co cubes) were fabricated via a facile template-free method. This simple strategy not only realizes the structure tailoring, but also achieves high-quality nitrogen-doping. Specifically, nickel dimethylglyoxime [Ni(dmg)₂] with rectangular rodlike structure was firstly synthesized by solution method, then metal-organic frameworks Fe–Co nanocube with different contents were loaded on rectangular carbon nanorods with polydopamine as the locating and the connecting agent, and finally Ni-CNRs@xFe-Co cubes were obtained by a one-step calcination. A series of electrochemical tests were researched on materials with different metal contents in the 1 M KOH solution. The Ni-CNRs@Fe–Co cubes show excellent electrocatalytic activity in the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). For HER and OER, the Tafel slopes were 83.3 mV dec⁻¹ and 71 mV dec⁻¹, the onset potential were −167 mV and 1.62 V, and reached the current densities of 10 mA cm⁻², the overpotential just needed 196 mV and 433 mV, respectively. This novel synthetic strategy will provide a template-free way for cheap electrocatalysts of non-precious metal for OER and HER.     

Metal–organic framework derived CoS2/FeS-MOF with abundant heterogeneous interface as bifunctional electrocatalyst for electrolysis of water

Highly active and stable non-precious metal dual-functional electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are very important for the industrialization of water electrolysis. Herein, a three-dimensional (3D) porous CoS₂/FeS-MOF with adjustable Co/Fe molar ratio are in-stiu grown on a nickel foam (NF) to get a binder-free electrocatalyst electrode for HER and OER (CoS₂/FeS-MOF@NF). It should be emphasized that the MOFs precursor forms abundant heterogeneous interfaces through in-situ sulfidation. Moreover, the open skeleton and ordered porous structure of MOFs will not be destroyed due to the low temperature. The redistribution of electrons at the heterogeneous interfaces will produce more catalytic active centers, providing more active sites for reactant molecules or intermediates, thus availably promoting the electrocatalytic activity of the composite. Therefore, the optimized catalyst CoS₂/FeS-MOF@NF-1 displays high OER activity. The overpotential is only 136 mV at 10 mA cm^?2. At the same time, the CoS₂/FeS-MOF@NF-1 also shows good HER catalytic activity. Therefore, the assembled corresponding symmetric electrolyzer CoS₂/FeS-MOF@NF-1||CoS₂/FeS-MOF@NF-1 achieves a low cell voltage of 1.5 V at 10 mA cm^?2 with long time stability for 24 h. This work provides a simple and convenient strategy for the synthesis of transition metal sulfides dual-function electrocatalysts.     

Pomegranate-like Ni-doped cobalt boride implanted in B,N-doped carbon nanocages for enhanced electrochemical oxygen evolution

The development of efficient and stable transition metal boride electrocatalysts for oxygen evolution reaction (OER) is critical for energy conversion and environmental protection. Herein, we synthesized B, N-doped carbon layer encapsulated the Ni-doped Co_xB nanocages electrocatalyst (denoted as Ni-Co_xB@BNC) via a high-temperature boronizing, derived from Ni-doped cobalt-based zeolite imidazole frame (NiCo-ZIF), toward enhanced electrochemical alkaline oxygen evolution reaction. The Ni-Co_xB@BNC electrocatalyst synthesized at 550 °C exhibits excellent OER activity with a low overpotential of 274 mV and a Tafel slope of 80 mV dec⁻¹ at a current density of 10 mA cm⁻², which is better than precious metal RuO₂. The synergistic effect between B, N-doped carbon layer and Ni-doped Co_xB in Ni-Co_xB@BNC leads to higher OER catalytic activity. The B, N-doped carbon layer provides additional active sites, which accelerates charge transport and enhances the conductivity of Ni-Co_xB@BNC during OER. In addition, it also protects the pomegranate seed-like Ni-Co_xB nanoparticles inside, improving the stability of the Ni-Co_xB@BNC material. This work unambiguously elucidates the design and preparation strategy of transition metal boride implanted B, N-doped carbon nanocage electrocatalysts derived from controlled bimetallic ZIF precursor.     

Tailor-designed bimetallic Co/Ni macroporous electrocatalyst for efficient glycerol oxidation and water electrolysis

Water electrolysis is broadly considered one of the most promising technologies for green hydrogen production. However, the oxygen evolution reaction (OER) is thermodynamically unfavorable and requires large overpotentials to proceed with an adequate rate. Herein, we introduce key structural and compositional parameters controlling the hydrogen evolution reaction (HER) performance of a representative family of bimetallic CoNi porous electrocatalysts and highlight a simple strategy for replacing the OER with glycerol oxidation reaction (GOR) to reduce the input cell voltage. The structural, morphological, and electrochemical characterizations of a series of electrocatalysts, prepared by the dynamic hydrogen bubble template technique (DHBT), were fully studied which reveals that changing of Co: Ni ratio affects HER activity. Optimization of this ratio leads to enhancement in both intrinsic and mass activity besides the high density of accessible active sites. This, in turn, leads to an efficient electrocatalyst achieving a low overpotential of ?67 mV at a current density of 10 mA/cm² during HER. As a bifunctional electrocatalyst, it requires only 1.65 V to deliver the same current density with excellent stability for more than 20 h of continuous water electrolysis in alkaline medium. Moreover, the input cell voltage drops by at least 0.2 V during glycerol electrolysis with concurrent production of both hydrogen and value-added chemicals especially hydroxy pyruvate ion.     

N-doped carbon wrapped CoFe alloy nanoparticles with MoS2 nanosheets as electrocatalyst for hydrogen and oxygen evolution reactions

Developing efficient and cost-effective transition metal-based electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial to generate clean and renewable hydrogen energy. The construction of hybrid catalysts with multiple active sites is an effective approach to promote catalytic performance. Herein, a molybdenum disulfide (MoS₂)-based hybrid with N-doped carbon wrapped CoFe alloy (MoS₂/CoFe@NC) was synthesized through a typical hydrothermal method. The MoS₂/CoFe@NC exhibits excellent electrocatalytic performance with overpotentials of 172 mV for HER and 337 mV for OER at 10 mA cm⁻², and long-term stability of 24-h electrolytic reaction in 1 M KOH solution. The chemical coupling between MoS₂ and CoFe@NC provides improved electronic structures and more accessible active sites. The CoFe@NC substrate accelerates the charge transfer to MoS₂ through a synergistic effect. This work demonstrates that the CoFe@NC is a promising substrate for depositing MoS₂ nanosheets (NSs) to achieve excellent catalytic performance for both HER and OER.     

Efficient overall water splitting using nickel boride-based electrocatalysts

Currently there is tremendous interest in the discovery of low cost and efficient electrocatalysts for the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). In this work, iron-doped nickel boride (Fe_xNi_1-xB) and nickel boride (NiB) were successfully grown on 3D self-supporting graphene (SSG) electrodes via a one-step reduction approach. The Fe_0.2Ni_0.8B/SSG electrode required a very low overpotential of only 263 mV for OER (the best OER activity achieved to date for a metal boride). NiB/SSG showed modest OER performance but excellent HER activity. A water electrolyzer comprising Fe_0.2Ni_0.8B/SSG and NiB/SSG delivered a current density of 10 mA cm⁻² at a voltage of only 1.62 V. Further, the Fe_0.2Ni_0.8B/SSG and NiB/SSG catalysts showed excellent stability with no deactivation observed over 14 h of testing. Results demonstrate that nickel boride-based electrocatalysts are promising lost cost alternatives to precious metal-based electrocatalysts for OER, HER and overall water splitting.     

Straightforward preparation of nickel selenide nanosheets supported on nickel foam as a highly efficient electrocatalyst for oxygen evolution reaction

The development of economical, durable, and efficient oxygen evolution reaction (OER) electrocatalysts is essential for large-scale industrial water electrolysis. Here, a straightforward strategy is proposed to synthesize a series of nickel selenide nanosheets supported on nickel foam (NiSe₂/NF) materials by directly selenizing nickel foam substrates at different temperatures under an inert atmosphere. When evaluated as electrocatalysts in OER, the optimal self-supported NiSe₂/NF-350 shows an excellent performance in 1.0 M KOH medium with an overpotential of 458 mV at 100 mA cm^?2, a small Tafel slope of 45.8 mV dec^?1, and a long-term stability for 36 h. Furthermore, the structural and compositional preservation for NiSe₂/NF-350 after stability test was also verified by various characterizations.     

Accessible active sites activated by nano cobalt antimony oxide @ carbon nanotube composite electrocatalyst for highly enhanced hydrogen evolution reaction

The electrochemical hydrogen evolution reaction (HER) was one of new energy development strategies with clean, efficient and renewable characteristics, and electrocatalysts play a crucial role in HER technology. Herein, a composite material (CSO@0.5CNT) derived from the combination of nano cobalt antimony oxide (CSO) with carbon nanotubes (CNT) through hydrothermal reaction, in which the nanoparticles of CSO were closely compounded on the surface of CNT, could be a highly efficient electrocatalyst for HER in 1 M KOH. The binary composite electrocatalyst of CSO and CNT reduced the internal resistance, promoted the charge transfer, exhibited a large electrochemical active area, and obtained the lower overpotential, with 155 mV at 10 mA/cm² current density. Moreover, such a CSO@0.5CNT electrocatalyst displayed a small Tafel slope of 86.5 mV dec^?1, excellent catalytic activity and extraordinary long-term structural stability after 30 h and 3000 CV cycles. Furthermore, the electrocatalytic mechanism revealed by Density Functional Theory (DFT) calculation proved that, the decomposition of H₂O molecules was the control step of the whole HER, and the superior electron transport ability of CNT was favorable to the improvement of electrocatalytic performance. Benefitting from accessible active sites on carbon nanotube (C atom) and CSO (Co atom), the composite electrocatalyst of CSO@0.5CNT displayed synergistic effect for electrocatalytic HER properties, and that was the main mechanism for significantly improving the electrocatalytic activities. Our work provides a novel strategy towards high-efficiency electrocatalysts for hydrogen evolution reaction.