Engineering efficient bifunctional catalysts for hydrogen production is crucial for advancing hydrogenation technologies and reducing infrastructure costs. However, the inferior kinetics of water dissociation during the hydrogen evolution reaction (HER) and the sluggish OH− adsorption during oxygen evolution reaction (OER) under alkaline conditions greatly hinder their electrolytic efficiencies. Given this, we established Ni3S2-MoS2 heterojunctions with a tunable built-in electric field (BEF) by integrating nitrogen-doped carbon (NC) to enhance water splitting. Specifically, NC-coupled Ni3S2-MoS2 heterojunctions were synthesized by assembling chitosan, thiourea, and sodium molybdate onto nickel foam, followed by carbonization. The chitosan amount was adjusted to control the NC content, which in turn modulated the BEF of the Ni3S2-MoS2 heterojunctions. Profiting from the strong electronegativity, N element serves as an electron acceptor, and the BEF of Ni3S2-MoS2 is effectively manipulated by NC, facilitating fast electron transfer and targeted modulation of active sites. Consequently, the optimized NC-coupled Ni3S2-MoS2 heterojunction with the robust BEF exhibits competitive overpotentials of 75 and 146 mV at 10 mA·cm−2 for HER and OER, respectively. Relative to Ni3S2-MoS2, theoretical calculations confirm that the robust BEF of NC-coupled Ni3S2-MoS2 lowers the water dissociation energy by 0.62 eV and increases the OH− adsorption energy by 0.22 eV for HER and OER, respectively. Moreover, the robust BEF of NC-coupled Ni3S2-MoS2 contributes to reconstructing a highly active NiOOH phase. This pioneering study introduces a groundbreaking BEF architecture to effectively modulate the surface/interface charge states of electrocatalysts, opening new avenues for exploring robust homologous heterostructures in the future.
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NiTiCu-based shape memory alloys have been considered as ideal materials for solid-state refrigeration due to their superb cycling stability for elastocaloric effect. However, the embrittlement and deterioration caused by secondary phase and coarse grains restrict their applications, and it is still challenging since the geometric components are required. Here, bulk NiTiCuCo parts with excellent forming quality were fabricated by laser powder bed fusion (LPBF) technique. The as-fabricated alloy exhibits refined three-phases hierarchical microcomposite formed based on the rapid cooling mode of LPBF, composed of intricate dendritic Ti2Ni–NiTi composite and nano Ti2Cu embedded inside the NiTi-matrix. This configuration endows far superior elastocaloric stability compared to the as-cast counterpart. The low fatigue stems from the strong elastic coupling between the interphases with reversible martensite transformation, revealed by in-situ synchrotron high-energy x-ray diffraction. The fabrication of NiTiCuCo alloy via LPBF fills the bill of complex geometric structures for elastocaloric NiTiCu alloys. The understanding of interphase micro-coupling could provide the guide for designing LPBF fabricated shape memory-based composites, enabling their applications for special demands on other functionalities.
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