A review of modulation strategies for improving the catalytic performance of transition metal sulfide self-supported electrodes for the hydrogen evolution reaction.

Electrocatalytic water splitting is considered to be one of the most promising technologies for large-scale sustained production of H2. Developing non-noble metal-based electrocatalytic materials with low cost, high activity and long life is the key to electrolysis of water. Transition metal sulfides (TMSs) with good electrical conductivity and a tunable electronic structure are potential candidates that are expected to replace noble metal electrocatalysts. In addition, self-supported electrodes have fast electron transfer and mass transport, resulting in enhanced kinetics and stability. In this paper, TMS self-supported electrocatalysts are taken as examples and their recent progress as hydrogen evolution reaction (HER) electrocatalysts is reviewed. The HER mechanism is first introduced. Then, based on optimizing the active sites, electrical conductivity, electronic structure and adsorption/dissociation energies of water and intermediates of the electrocatalysts, the article focuses on summarizing five modulation strategies to improve the activity and stability of TMS self-supported electrode electrocatalysts in recent years. Finally, the challenges and opportunities for the future development of TMS self-supported electrodes in the field of electrocatalytic water splitting are presented.

Molybdenum/selenium based heterostructure catalyst for efficient hydrogen evolution: Effects of ionic dissolution and repolymerization on catalytic performance.

Transition metal chalcogenides (TMCs) are recognized as highly efficient electrocatalysts and have wide applications in the field of hydrogen production by electrolysis of water, but the real catalytic substances and catalytic processes of these catalysts are not clear. The species evolution of Mo and Se during alkaline hydrogen evolution was investigated by constructing MoSe2@CoSe2 heterostructure. The real-time evolution of Mo and Se in MoSe2@CoSe2 was monitored using in situ Raman spectroscopy to determine the origin of the activity. Mo and Se in MoSe2@CoSe2 were dissolved in the form of MoO42- and SeO32-, respectively, and subsequently re-adsorbed and polymerized on the electrode surface to form new species Mo2O72- and SeO42-. Theoretical calculations show that adsorption of Mo2O72- and SeO42- can significantly enhance the HER catalytic activity of Co(OH)2. The addition of additional MoO42- and SeO32- to the electrolyte with Co(OH)2 electrodes both enhances its HER activity and promotes its durability. This study helps to deepen our insight into mechanisms involved in the structural changes of catalyst surfaces and offers a logical basis for revealing the mechanism of the influence of species evolution on catalytic performance.

High-density low-coordination Ni single atoms anchored on Ni-embedded nanoporous carbon nanotubes for boosted alkaline hydrogen evolution.

Modulating the coordination environment of single-atom catalysts is considered an effective way to boost the electrocatalytic activity of the hydrogen evolution reaction. Herein, a novel electrocatalyst comprising high-density low-coordination Ni single atoms anchored on Ni-embedded nanoporous carbon nanotubes (Ni-N-C/Ni@CNT-H) is constructed through a self-template assisted synthetic strategy. We demonstrate that the in situ generated AlN nanoparticles not only serve as the template for the formation of the nanoporous structure, but also contribute to the coordination between Ni and N atoms. Benefiting from the optimized charge distribution and hydrogen adsorption free energy of the unsaturated Ni-N2 active structure and nanoporous structure of the carbon nanotube substrate, the resultant Ni-N-C/Ni@CNT-H exhibited outstanding electrocatalytic hydrogen evolution activity with a low overpotential of 175 mV at a current density of 10 mA cm-2, and a long-term durability for over 160 h in continuous operation. This work provides a new insight and approach to the design and synthesis of efficient single-atom electrocatalysts toward hydrogen fuel production.

Reversible active bridging sulfur sites grafted on Ni3S2 nanobelt arrays for efficient hydrogen evolution reaction.

Elaborate and rational design of cost-effective and high-efficiency non-noble metal electrocatalysts for pushing forward the sustainable hydrogen fuel production is of great significance. Herein, a novel VS4 nanoparticle decorated Ni3S2 nanobelt array in-situ grown on nickel foam (VS4/Ni3S2/NF NBs) was prepared by a self-templated synthesis strategy. Benefitting from the unique nanobelt array structure, abundant highly active bridge S22- sites and strong electronic interaction between VS4 and Ni3S2 on the heterointerface, the integrated VS4/Ni3S2/NF NBs exhibited excellent electrocatalytic hydrogen evolution activity and robust stability. The density functional theory (DFT) further revealed the reversible conversion catalysis mechanism of bridging S22- sites in VS4/Ni3S2/NF NBs during HER process. Notably, bidentate bridging SS bonds as the predominant catalytically active centers can spontaneously open once H adsorbed its surface, leading to the aggregation of negative charges on S atoms and thus facilitating the generation of H* intermediates, and spontaneously close when H* desorption is going to form H2. Our work provides fresh insights for developing potential polysulfides as high-performance hydrogen-evolving electrocatalysts for prospective clean energy production from water splitting.

V-doped Ni2P nanoparticle grafted g-C3N4 nanosheets for enhanced photocatalytic hydrogen evolution performance under visible light.

Exploring low-cost and highly active photocatalysts with noble metal-free cocatalysts is of great significance for photocatalytic hydrogen evolution under simulated sunlight irradiation. In this work, a novel V-doped Ni2P nanoparticle loaded g-C3N4 nanosheet is reported as a highly efficient photocatalyst for H2 evolution under visible light irradiation. The results demonstrate that the optimized 7.8 wt% V-Ni2P/g-C3N4 photocatalyst exhibits a high hydrogen evolution rate of 271.5 µmol g-1 h-1, which is comparable to that of the 1 wt% Pt/g-C3N4 photocatalyst (279 µmol g-1 h-1), and shows favorable hydrogen evolution stability for five successive runs within 20 h. The remarkable photocatalytic hydrogen evolution performance of V-Ni2P/g-C3N4 is mainly due to the enhanced visible light absorption ability, the facilitated separation of photo-generated electron-hole pairs, the prolonged lifetime of photo-generated carriers and the fast transmission ability of electrons.

Heterogeneous Ni3P/Ni nanoparticles with optimized Ni active sites anchored in N-doped mesoporous nanofibers for boosting pH-universal hydrogen evolution.

Developing low-cost, environmentally friendly and efficient non-precious metal electrocatalysts as alternatives to noble metals for the hydrogen evolution reaction (HER) is highly essential for the sustainable advancement of green hydrogen energy. Herein, a novel heterostructured Ni3P/Ni nanoparticle anchored in nitrogen-doped mesoporous carbon nanofibers (Ni3P/Ni@N-CNFs) is prepared by a facile solid-phase calcination protocol. The results demonstrated that benefiting from the intensive electronic coupling effect at the interface of the Ni3P/Ni heterostructure, the electron configuration of the Ni active site is optimized and thus the favorable HER activity. Furthermore, the N-doped carbon nanofiber scaffold with an extensive mesoporous structure endows Ni3P/Ni@N-CNFs with abundant electrochemically active sites together with excellent conductivity and stability, contributing to fast electron/mass transport. As expected, the resultant Ni3P/Ni@N-CNF electrocatalyst exhibited exceptional HER catalytic properties under universal pH conditions, driving a current density of 10 mA cm-2 at pretty low overpotentials of 121 mV, 145 mV and 187 mV in acidic, basic and neutral solutions, respectively, and retaining the catalytic stability for over 60 h. This intriguing work represents a fresh perspective for designing and exploiting highly advanced phosphide electrocatalysts for green hydrogen fuel production.

Mo-Doped Cu2S Multilayer Nanosheets Grown In Situ on Copper Foam for Efficient Hydrogen Evolution Reaction.

Metal sulfide electrocatalyst is developed as a cost-effective and promising candidate for hydrogen evolution reaction (HER). In this work, we report a novel Mo-doped Cu2S self-supported electrocatalyst grown in situ on three-dimensional copper foam via a facile sulfurization treatment method. Interestingly, Mo-Cu2S nanosheet structure increases the electrochemically active area, and the large fleecy multilayer flower structure assembled by small nanosheet facilitates the flow of electrolyte in and out. More broadly, the introduction of Mo can adjust the electronic structure, significantly increase the volmer step rate, and accelerate the reaction kinetics. As compared to the pure Cu2S self-supported electrocatalyst, the Mo-Cu2S/CF show much better alkaline HER performance with lower overpotential (18 mV at 10 mA cm-2, 322 mV at 100 mA cm-2) and long-term durability. Our work constructs a novel copper based in-situ metal sulfide electrocatalysts and provides a new idea to adjust the morphology and electronic structure by doping for promoting HER performance.

In situ construction of superhydrophilic crystalline Ni3S2@amorphous VOx heterostructure nanorod arrays for the hydrogen evolution reaction with industry-compatible current density.

The synergistic effect of a highly active surface/interface and an optimized electronic structure of electrocatalysts is of great significance to improve the performance of the hydrogen evolution reaction. Herein, a superhydrophilic core@shell heterostructure nanorod-integrated electrode composed of an amorphous VOx nanoshell (3-7 nm) and a crystalline Ni3S2 core supported on Ni foam (CS-NS/NF) was prepared by an in situ conversion method. We prove that the amorphous VOx not only helps to kinetically decouple the adsorption/dissociation of hydroxyl/water, but also enriches the active sites, thereby significantly enhancing the electron transfer efficiency and electrocatalytic activity toward the hydrogen evolution reaction (HER). The optimized CS-NS/NF has excellent hydrogen production performance, with overpotentials of 335 and 394 mV at current densities of 500 and 1000 mA cm-2, respectively, as well as superior durability for over 68 h in 1 M KOH.

Establishing historical 90Sr activity in seawater of the China seas from 1963 to 2018.

Historical 90Sr activity in seawater was established in the China seas from 1963 to 2018. Based on the exponential decrease in 90Sr activity in seawater, the effective half-life (EHL) of 90Sr was quantified to be 11.5 ± 1.6 a, 16.5 ± 2.4 a, 27.2 ± 6.2 a, and 26.7 ± 4.3 a in the Bohai Sea, Yellow Sea, East China Sea, and South China Sea, respectively. We found contrasting patterns in the EHL of 90Sr and 137Cs in the marginal seas and open oceans that were closely related to the subtly different pathways of 90Sr and 137Cs in marine environment. Additionally, we demonstrated that Fukushima-derived 90Sr (<0.01 Bq/m3) would be difficult to identify in the China seas. Our study not only provided the key parameter of the EHL in marine models for predicting the 90Sr activity in the China seas in the post-Fukushima era but also enhanced our understanding of 90Sr behavior and its fate in marine environments.

Fe2P encapsulated in carbon nanowalls decorated with well-dispersed Fe3C nanodots for efficient hydrogen evolution and oxygen reduction reactions.

The development of cost-effective, high-efficiency bifunctional electrocatalysts as alternatives to the state-of-the-art Pt-based materials toward the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) is of great significance but still challenging. Herein, an advanced bifunctional electrocatalyst is presented, composed of Fe2P encapsulated in carbon nanowalls decorated with well-dispersed Fe3C nanodots (denoted as Fe2P@Fe3C/CNTs), which is achieved by a novel "inside-out" gas-solid reaction protocol. When functioning as a cathodic catalyst for water splitting, the Fe2P@Fe3C/CNT catalyst needs an ultralow overpotential of 83 mV to deliver a current density of 10 mA cm-2, shows a small Tafel slope of 53 mV dec-1 and ensures long-term stability for over 200 h in an alkaline electrolyte. Notably, the Fe2P@Fe3C/CNT catalyst exhibits an extremely impressive ORR performance with an onset potential (Eonset) of 1.060 V and a half-wave potential (E1/2) of 0.930 V, excellent stability (≈94% activity retention after 36 000 s), and a strong methanol resistance ability, even far outperforming commercial Pt/C (Eonset = 0.955 V, E1/2 = 0.825 V, ≈75% activity retention after less than 3500 s). Such outstanding HER and ORR performances are mainly ascribed to the improved corrosion resistance of the unique Fe2P@C core-shell structures, the abundant catalytically active sites of ultrasmall Fe3C nanodots incorporated in carbon nanowalls, and the good electrical conductivity of 2D graphitic carbon nanotubes used as a support.

Enhanced Electrocatalytic Activity of Nickel Cobalt Phosphide Nanoparticles Anchored on Porous N-Doped Fullerene Nanorod for Efficient Overall Water Splitting.

Design and fabrication of bifunctional efficient and durable noble-metal-free electrocatalyst for hydrogen and oxygen evolution is highly desirable and challenging for overall water splitting. Herein, a novel hybrid nanostructure with Ni2P/CoP nanoparticles decorated on a porous N-doped fullerene nanorod (p-NFNR@Ni-Co-P) was developed as a bifunctional electrocatalyst. Benefiting from the electric current collector (ECC) effect of FNR for the active Ni2P/CoP nanoparticles, the p-NFNR@Ni-Co-P exhibited outstanding electrocatalytic performance for overall water splitting in alkaline medium. To deliver a current density of 10 mA cm-2, the electrolytic cell assembled by p-NFNR@Ni-Co-P merely required a potential as low as 1.62 V, superior to the benchmark noble-metal-based electrocatalyst. Experimental and theoretical results demonstrated that the surface engineered FNR serving as an ECC played a critical role in accelerating the charge transfer during the electrocatalytic reaction. The present work paves the way for fullerene nanostructures in the realm of energy conversion and storage.

Vanadium -mediated ultrafine Co/Co9S8 nanoparticles anchored on Co-N-doped porous carbon enable efficient hydrogen evolution and oxygen reduction reactions.

Developing cost-effective, highly-active and robust electrocatalysts is of vital importance to supersede noble-metal ones for both hydrogen evolution reactions (HERs) and oxygen reduction reactions (ORRs). Herein, a unique vanadium-mediated space confined strategy is reported to construct a composite structure involving Co/Co9S8 nanoparticles anchored on Co-N-doped porous carbon (VCS@NC) as bifunctional electrocatalysts toward HER and ORR. Benefitting from the ultrafine nanostructure, abundant Co-Nx active sites, large specific surface area and defect-rich carbon framework, the resultant VCS@NC exhibits unexceptionable HER catalytic activity, needing extremely low HER overpotentials in pH-universal media (alkaline: 117 mV, acid: 178 mV, neutral: 210 mV) at a current density of 10 mA cm-2, paralleling at least 100 h catalytic durability. Notably, the VCS@NC catalyst delivers high-efficiency ORR performance in alkaline solution, accompanied with a quite high half wave potential of 0.901 V, far overmatching the commercial Pt/C catalyst. Our research opens up novel insight into engineering highly-efficient multifunctional non-precious metal electrocatalysts by a metal-mediated space-confined strategy in energy storage and conversion system.

Fe, Ni-codoped W18O49 grown on nickel foam as a bifunctional electrocatalyst for boosted water splitting.

Designing cost-effective bifunctional catalysts with high-performance and durability is of great significance for renewable energy systems. Herein, typical Fe, Ni-codoped W18O49/NF was prepared via a simple solvothermal method. The incorporation of Fe ions enhanced the electronic interaction and enlarged the electrochemically active surface area. The increased W4+ leads to a high proportion of unsaturated W[double bond, length as m-dash]O bonds, thus enhancing the adsorption capacity of water. The valence configuration of nickel (Ni) sites in such dual-cation doping is well adjusted, realizing a high proportion of trivalent Ni ions (Ni3+). Due to the orbital interactions, the Fe3+/Ni3+ ions and OER reaction intermediates exhibit strong orbital overlap. The positions of the valence band and conduction band are well modulated. As a result, the Fe, Ni-codoped W18O49/NF shows improved electrocatalytic activity, and achieves a low decomposition voltage of 1.58 V at 10 mA cm-2 and retains long-time stability.

Formation of porous NiCoV-LTH nanosheet arrays by in situ etching of nickel foam for the hydrogen evolution reaction at large current density.

We report the in situ generation of NiCoV-LTH on nickel foam for the HER. Interestingly, the introduction of Co into NiV-LDH can induce the formation of porous nanosheets to expose a large number of active sites and change the electron density around Ni and V to promote the absorption of hydrogen species and thus accelerate the HER kinetics.

Controlled Synthesis of V-Doped Heterogeneous Ni3S2/NiS Nanorod Arrays as Efficient Hydrogen Evolution Electrocatalysts.

The development of low-cost and high-efficient electrocatalysts toward hydrogen evolution reaction (HER) is highly desirable and challenging. Herein, the novel V-doped Ni3S2/NiS heterostructure nanorod arrays grown on nickel foam (VNS/NF-WM) are synthesized via a facile methanol-assisted hydrothermal method. We demonstrate that the morphology, phase composition, and crystallinity of VNS/NF are well modulated by tuning the ratios of water/methanol solvent. The optimized VNS/NF-WM-heterostructured nanorod (volume ratio of water/methanol is 3:1) exhibits superior HER electrocatalytic activity with low overpotentials of 85 and 218 mV to yield current density values of 10 and 100 mA cm-2, respectively, meanwhile sustaining an excellent stability with almost an unchanged current density of 10 mA cm-2 for 60 h. Our work offers fresh insights into the rational design of highly active and stable earth-abundant-heterostructured electrocatalysts for the hydrogen fuel production.

Generation of Ni3S2 nanorod arrays with high-density bridging S22- by introducing a small amount of Na3VO4·12H2O for superior hydrogen evolution reaction.

Bridging S22- moieties have been demonstrated to be highly active sites existing in metal polysulfides for the hydrogen evolution reaction (HER), thus the incorporation of high-density bridging S22- into a Ni3S2 material to improve its electrocatalytic HER performance is highly desirable and challenging. Herein, we report a novel Ni3S2 nanorod array decorated with (020)-oriented VS4 nanocrystals grown on nickel foam (Shig-NS-rod/NF) via a simple and facile solvothermal method. Results show that the in situ incorporation of VS4 not only triggers the formation of such a nanorod array structure, but also contributes to the uniform grafting of high-density and high catalytically active bridging S22- sites on the interface between Ni3S2 and VS4 for enhanced HER activity, and also promotes the absorption ability of OH- radicals and thus accelerates the HER Volmer step in alkaline media. As expected, the resultant Shig-NS-rod/NF material exhibits impressive catalytic performance toward the HER, with a much lower overpotential of 137 mV at 10 mA cm-2 and a long-term durability for at least 22 h, and is superior to Ni3S2 nanorod arrays with low-density bridging S22- (Slow-NS-rod/NF) and NS-film/NF counterparts (without VS4), even outperforming the NF-supported 20% Pt/C at a large current density of over 120 mA cm-2. Our findings put forward fresh insight into the rational design of highly efficient electrocatalysts toward the HER for green hydrogen fuel production.

Methanol-assisted synthesis of Ni3+-doped ultrathin NiZn-LDH nanomeshes for boosted alkaline water splitting.

The construction of nanoporous structure combined with the optimization of electronic structure toward electrocatalysts could be a promising and effective approach to boosting their catalytic performance. Herein, we rationally synthesized a novel Ni3+-doped ultrathin NiZn layered double hydroxide nanomesh supported on nickel foam (Ni(ii,iii)Zn-LDH/NF-nm) by a facile one-step methanol-assisted hydrothermal method. Results show that methanol can not only trigger the generation of ultrathin nanomesh structure, but adjust portion of Ni2+ to Ni3+ and thus to result in the Ni3+-doped NiZn-LDH nanomesh material. The nanoporous feature endows Ni(ii,iii)Zn-LDH/NF-nm with abundant exposed catalytic active sites and fast mass transfer for alkaline water electrolysis. More importantly, the Ni3+ doping can facilitate the available formation of highly active NiOOH phase on the surface for the oxygen evolution reaction (OER), accompanied by increased oxygen vacancies that can greatly enhance the electronic conductivity, leading to the improved intrinsic activity and the accelerated electrocatalytic OER reaction kinetics. As expected, the as-prepared Ni(ii,iii)Zn-LDH/NF-nm has relatively low overpotentials of 320 and 370 mV to drive large current densities of 100 and 500 mA cm-2, respectively, and a small Tafel slope of 63.9 mV dec-1, extremely superior to RuO2/NF and NiZn-LDH/NF-ns counterpart. Meanwhile, the electrolyzer assembled for overall water splitting by Ni(ii,iii)Zn-LDH/NF-nm yields the outstanding catalytic activity and stability. This work highlights a feasible strategy to design and develop high-efficiency water splitting electrocatalysts via engineering on composition and nanostructure.

Boosting the activity of Prussian-blue analogue as efficient electrocatalyst for water and urea oxidation.

The design and fabrication of intricate hollow architectures as cost-effective and dual-function electrocatalyst for water and urea electrolysis is of vital importance to the energy and environment issues. Herein, a facile solvothermal strategy for construction of Prussian-blue analogue (PBA) hollow cages with an open framework was developed. The as-obtained CoFe and NiFe hollow cages (CFHC and NFHC) can be directly utilized as electrocatalysts towards oxygen evolution reaction (OER) and urea oxidation reaction (UOR) with superior catalytic performance (lower electrolysis potential, faster reaction kinetics and long-term durability) compared to their parent solid precursors (CFC and NFC) and even the commercial noble metal-based catalyst. Impressively, to drive a current density of 10 mA cm-2 in alkaline solution, the CFHC catalyst required an overpotential of merely 330 mV, 21.99% lower than that of the solid CFC precursor (423 mV) at the same condition. Meanwhile, the NFHC catalyst could deliver a current density as high as 100 mA cm-2 for the urea oxidation electrolysis at a potential of only 1.40 V, 24.32% lower than that of the solid NFC precursor (1.85 V). This work provides a new platform to construct intricate hollow structures as promising nano-materials for the application in energy conversion and storage.

Enhanced Kinetics over VS4 Microspheres with Multidimensional Na+ Transfer Channels for High-Rate Na-Ion Battery Anodes.

Developing 3 D self-assembled nanoarchitectures with well-defined crystal structures is an effective strategy to enhance the electrochemical performances of electrode materials. (1 1 0)-oriented and bridged-nanoblocks self-assembled VS4 microspheres are controllably synthesized by a facile one-step hydrothermal method. The (1 1 0)-bridged structure sets up open pathways for Na+ diffusion among nanoblocks, and the (1 1 0)-oriented structure provides unobstructed pathways for Na+ diffusion in the nanoblocks, which collectively constructs multidimensional Na+ transfer channels in the VS4 microspheres, promoting the electrochemical kinetics. As an anode for Na-ion batteries (SIBs), this material exhibits pseudocapacitive Na+ storage and excellent rate capability, delivering high capacities of 339 and 270 mAh g-1 at rates of 0.1 and 2.0 A g-1 , respectively, with a capacity retention of 79 % in the voltage window of 0.5-3.0 V. In particular, the reversible capacity reaches 575 mAh g-1 after 300 cycles even at 1.0 A g-1 in the voltage window of 0.05-3.0 V, outperforming those of the ever-reported VS4 -based anode materials. This work presents an effective strategy to the exploration and design of high-performance anodes for SIBs.

Co,N-Codoped porous vanadium nitride nanoplates as superior bifunctional electrocatalysts for hydrogen evolution and oxygen reduction reactions.

Developing efficient and low-cost bifunctional electrocatalysts as candidates for Pt-based materials to satisfy commercial applications in the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) is still very challenging. Herein, we show that Co,N-codoped porous vanadium nitride (VCoN) nanoplates are successfully synthesized via a simple one-step pyrolysis protocol without the use of NH3 gas. We also demonstrate that the crystallization, surface chemical state and porosity of vanadium nitride are well modulated by inventively using Co dopants as structural inducers. The resulting VCoN material exhibits an excellent catalytic activity towards the HER in alkaline media, with an extremely low onset potential of -0.03 V, an overpotential of 179 mV at 10 mA cm-2, and a remarkable durability for over 100 h. Moreover, it shows a superior ORR performance, which compares favorably with commercial 20% Pt/C, exhibiting an onset potential of ∼1.02 V, a half-wave potential of ∼0.91 V and a weak potential shift (-5 mV) after 2000 cycles at 1600 rpm in 0.1 M KOH. Such excellent electrocatalytic performance primarily contributes to the unique structural features of the heteroatom N (pyrrolic and graphitic N) and Co codoping in favor of improving the electrical conductivity and the high porosity contributing to exposing numerous catalytic active sites.