Heterogenous electrocatalysts based on transition metal sulfides (TMS) are being actively explored in renewable energy research because nanostructured forms support high intrinsic activities for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this review article, the authors describe how researchers are working to improve the This article is protected by copyright. All rights reserved. 2 performance of TMS-based materials by manipulating its internal and external nanoarchitectures. A general introduction to the water splitting reaction is initially provided to explain the most important parameters in accessing the catalytic performance of nanomaterials catalysts. Later, the general synthetic methods used to prepare TMS-based materials is explained in order to delve into the various strategies being used to achieve higher electrocatalytic performance in HER. Complementary strategies can be used to increase the OER performance of TMS, resulting in bifunctional water-splitting electrocatalysts for both HER and OER. Finally, the current challenges and future opportunities of TMS materials in the context of water splitting are summarized. The authors aim to provide insights gathered in the process of studying TMS, and describe valuable guidelines for engineering other kinds of nanomaterial catalysts for energy conversion and storage technologies.

Two-dimensional (2D) metals are an emerging class of nanostructures that have attracted enormous research interest due to their unusual electronic and thermal transport properties. Adding mesopores in the plane of ultrathin 2D metals is the next big step in manipulating these structures because increasing their surface area improves the utilization of the material and the availability of active sites. Here, we report a novel synthetic strategy to prepare an unprecedented type of 2D mesoporous metallic iridium (Ir) nanosheet. Mesoporous Ir nanosheets can be synthesized with close-packed assemblies of diblock copolymer (poly-(ethylene oxide)- b-polystyrene, PEO- b-PS) micelles aligned in the 2D plane of the nanosheets. This novel synthetic route opens a new dimension of control in the synthesis of 2D metals, enabling new kinds of mesoporous architectures with abundant catalytically active sites. Because of their unique structural features, the mesoporous metallic Ir nanosheets exhibit a high electrocatalytic activity toward the oxygen evolution reaction (OER) in acidic solution as compared to commercially available catalysts.

Herein, we present a facile metal–organic framework-engaged strategy to synthesize hollow Co3S4@MoS2 heterostructures as efficient bifunctional catalysts for both H2 and O2 generation. The well-known cobalt-based metal–organic zeolitic imidazolate frameworks (ZIF-67) are used not only as the morphological template but also as the cobalt precursor. During the two-step temperature-raising hydrothermal process, ZIF-67 polyhedrons are first transformed to hollow cobalt sulfide polyhedrons by sulfidation, and then molybdenum disulfide nanosheets further grow and deposit on the surface of hollow cobalt sulfide polyhedrons at the increased temperature. The crystalline hollow Co3S4@MoS2 heterostructures are finally obtained after subsequent thermal annealing under a N2 atmosphere. Due to the synergistic effects between the hydrogen evolution reaction active catalyst of MoS2 and the oxygen evolution reaction active catalyst of Co3S4, the obtained hollow Co3S4@MoS2 heterostructures exhibit outstanding bifunctional catalytic performances toward both hydrogen and oxygen evolution reactions in acidic and alkaline media.

Low efficiency, short lifetimes, and limited kinds of catalysts are still three fundamental shortcomings that have plagued electrochemical water splitting. Herein, we rationally synthesized a cost-effective Co 3 S 4 @MoS 2 hetero-structured catalyst that has proven to be a highly active and stable bifunctional catalyst for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in an alkaline environment. The heterostructure was obtained via a first hydrothermal approach to obtain hollow Co 3 S 4 nanoboxes based on the ionic exchange reaction between Fe(CN) 6 3of Co-Fe Prussian blue analogue (PBA) and S 2at 120 ºC, and the subsequent in-situ growth of MoS 2 nanosheets on the surface of Co 3 S 4 nanoboxes at an elevated temperature of 200 ºC. The synergistic effects between the active and stable HER catalyst of MoS 2 and the efficient OER catalyst of Co 3 S 4 , as well as the morphological superiority of hollow and core-shell structures, endow Co 3 S 4 @MoS 2 with remarkable electrocatalytic performance and robust durability toward overall water splitting. As a result, the designed non-noble electrocatalyst of Co 3 S 4 @MoS 2 exhibits a low overpotential of 280 mV for OER and 136 mV for HER at a current density of 10 mA•cm-2 in an alkaline solution. Meanwhile, a low cell voltage of 1.58 V is achieved by using the heterostructure as both anode and cathode catalysts. This work paves the way to the design and construction of other prominent electrocatalysts for overall water splitting.

Highly efficient earth‐abundant electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are of great importance for renewable energy conversion systems. Herein, hollow porous heterometallic phosphide nanocubes are developed as a highly active and robust catalyst for electrochemical water splitting via one‐step phosphidation of a NiCoFe Prussian blue analogue. Through modulation of the composition of metals in the precursors, the optimal NiCoFeP exhibiting increased electrical conductivity and abundant electrochemically active sites, leading to high electrocatalytic activities and outstanding kinetics for both HER and OER, is successfully obtained. NiCoFeP shows low overpotentials of 273 mV for OER and 131 mV for HER at a current density of 10 mA cm−2 and quite low Tafel slopes of 35 mV dec−1 for OER and 56 mV dec−1 for HER.

A simple method is developed to prepare Mo2C-embedded mesoporous N-doped carbon nanosheets which assemble into hollow spheres.

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Mesoporous metal sulfide hybrid (meso-MoS2/CoMo2S4) materials via a soft-templating approach using diblock copolymer polystyrene-block-poly­(acrylic acid) micelles are reported. The formation of the meso-MoS2/CoMo2S4 heterostructures is based on the sophisticated coassembly of dithiooxamide and metal precursors (i.e., Co2+, PMo12), which are subsequently annealed in nitrogen atmosphere to generate the mesoporous material. Decomposing the polymer leaves behind mesopores throughout the spherical MoS2/CoMo2S4 hybrid particles, generating numerous electrochemical active sites in a network of pores that enable faster charge transfer and mass/gas diffusion that enhance the electrocatalytic performance of MoS2/CoMo2S4. Doping the spherical meso-MoS2/CoMo2S4 heterostructures with iron improves the electronic properties of the hybrid meso-Fe-MoS2/CoMo2S4 material and consequently results in its superior electrochemical activities for both hydrogen evolution reaction and oxygen evolution reaction.