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A novel porous sintered Ni metal as the matrix for supporting MoS 2 /Ni 3 S 2 hierarchical nanorods is successfully prepared by powder metallurgy and hydrothermal sulfurization. The porous sintered Ni-metal matrix supported with the MoS 2 /Ni 3 S 2 displays more advantages over Ni foam, including enhanced catalytic activity and stability, as well as the sufficient mechanical properties, which can be beneficial for the industrial service. [Display omitted] • The porous Ni metal substrate is fabricated via powder metallurgy. • The catalyst of MoS 2 /Ni 3 S 2 with hierarchical structures is confirmed. • The catalytic activity, conductivity and stability for HER are improved. • The self-supporting electrode exhibits sufficient mechanical properties. • NiO controlled by the annealing temperature determines the morphology. For the self-supporting catalysts of Hydrogen evolution reaction (HER), the rational design and fabrication of substrate with porous structure and sufficient mechanical strength are critical to promoting the industrial HER application. In this work, a novel porous sintered Ni metal as the matrix for supporting catalysts was successfully prepared by powder metallurgy, and a self-supporting electrode for HER was fabricated via a simple sulfurization process on this sintered Ni metal matrix. For instance, MoS 2 /Ni 3 S 2 nanorods (NRs) were vertically grown on the as-sintered porous Ni matrix, and the morphology of the sintered Ni matrix significantly affected the growth of MoS 2 /Ni 3 S 2 NRs. The NRs@Sintered Ni electrode shows a low overpotential of η10 = 56 mV and Tafel slope of 82 mV dec−1. Compared with NRs@Ni foam, the NRs@Sintered Ni exhibits superior stability, where no exfoliation and cracks are observed on the surface of the electrode after 5000 CV cycles. Ultra-high stability and long-term durability are obtained over 100 h even at high potentials of 200 and 300 mV. Moreover, the tensile strength of the as-obtained electrode based on the sintered Ni manifests nearly 260 times higher than that of NRs@Ni foam, evidencing an excellent mechanical property. This work provides an idea for the preparation of self-supporting metal-based catalytic electrodes in large-scale hydrogen production. [ABSTRACT FROM AUTHOR]

The review summarizes the typical synthetic strategies, morphologies, catalytic performances, mechanisms, application conditions and scope of various metallic matrices, such as Au, Mo, Ni, and Ti, for supporting TMCs catalysts. The development directions and outlook of self-supporting TMCs@Metal electrodes for large-scale preparation and catalytic water splitting in industrial applications are discussed in detail. [Display omitted] • The self-supporting catalytic electrodes for water splitting are studied. • The electrodes classified according to different substrates are summarized. • The loaded TMC materials and preparation strategies are discussed in detail. • The prospects of TMCs@Metal electrodes for industrial applications are suggested. Transition metal chalcogenides (TMCs) are the fascinating replacement of noble catalysts in catalytic water splitting due to their unique physical and chemical properties and low cost. However, their industrial application is substantially restricted by their poor conductivity. Decorating TMCs on metal substrates to fabricate self-supporting electrodes could be an efficient strategy for solving this problem. In this review, typical synthetic strategies for self-supporting TMCs on metal substrates are introduced in detail, while all types of metallic matrices, such as Au, Mo, Ni, Ti, Cu, etc., for supporting TMC catalysts are comprehensively summarized. By comparing the matrix types, types of loaded TMC materials, preparation strategies, application conditions, and scope, we attempt to establish rules of various metals as substrates, which may provide suggestions for material design. Finally, we briefly discuss the development directions of self-supporting TMCs@Metal electrodes for large-scale preparation and catalytic water splitting in industrial applications. [ABSTRACT FROM AUTHOR]

Based on the synergy between MoP and N-doped carbon, MoP nanoparticles encapsulated in N-doped carbon hollow spheres were synthesized using inorganic-organic hybrids as precursors, which shows an excellent stability and activity with an overpotential 96 mV at 10 mA cm−2 and a small Tafel slope of 53 mV dec−1 in alkaline solution. [Display omitted] • A template-free approach was developed to fabricate MoP@NC hollow microsphere. • Inorganic-organic hybrids were used as precursors. • Remarkable electrocatalytic hydrogen evolution performance could be achieved. • The synergy between MoP and the pyridinic N could optimize the electronic structure. Encapsulating transition metal phosphides into nitrogen-doped carbon (NC) materials is an effective strategy to enhance the electrocatalytic performance. Herein, we develop a novel template-free approach to rationally fabricate molybdenum phosphide (MoP) nanoparticles encapsulated in N-doped carbon (MoP@NC) hollow microspheres for alkaline hydrogen evolution reaction (HER) by employing inorganic-organic hybrids as precursors, in which phosphorus source of the MoP@NC derives from tetra (hydroxymethyl) phosphorus chloride for the first time. The optimized MoP@NC sample shows a low overpotential of 96 mV at 10 mA cm−2, a small Tafel slope of 53 mV dec−1, and excellent stability. The enhanced HER performance is mainly attributed to the integrated effects of a distinctive hollow structure, high pyridinic N-doping level, and the extremely intimate synergy between MoP and NC. Theoretical calculations indicate that the active sites of the catalyst are mainly located at Mo atoms adjacent to the pyridinic N-doped carbon layer (pyridinic-N-MoP); the synergistic interaction between MoP and pyridinic N (rather than pyrrolic or graphitic N) atoms can lower the d band center of Mo, weaken the Mo-H ads bond and thereby enhance HER performance. In addition, the pyridinic N atoms at the interactive sites play a key role in adsorbing H 2 O and preventing the adsorption of OH*, resulting in accelerating the water splitting. This work provides a new method to rationally synthesize high-efficient and stable MoP-based hollow sphere electrocatalysts for alkaline HER through designing inorganic-organic hybrid precursors. [ABSTRACT FROM AUTHOR]