It is of prime importance to develop efficient nonprecious noble-metal-free water splitting bifunctional electrocatalysts for both H₂ and O₂ evolution reactions (HER and OER), which remains a grand challenge. However, the design of hollow nanostructured based on di- and tri-metal selenides, particularly non-spherical hollow nanostructures, is scarcely reported. Herein, for the first time, novel tri-metal selenides based on hollow Cu_0.4Ni_0.3Co_0.3Se₂ mesoporous nanosheet double shell were successfully designed on hollow N-doped carbon nanoboxes (Cu_0.4Ni_0.3Co_0.3Se₂@N-C n-box) and nanopipes (Cu_0.4Ni_0.3Co_0.3Se₂@N-C n-pipe). The hollow N-C n-box and N-C n- pipe skeletons were obtained from the related Fe₂O₃ nanocubes and nanorods templates that have prepared with completely different morphologies via only a minor change in synthesis step. Remarkably, benefiting from the special electronic structure engineering and unique hollow hierarchical design with high surface areas, open channels for effective gas releasing, fast electron/mass transport, the resulting advanced electrocatalysts provide outstanding OER activity as well as desirable HER performance in the alkaline medium. Moreover, an overall water splitting device is assembled using two symmetrical Cu_0.4Ni_0.3Co_0.3Se₂@N-C n-box electrodes as anode and cathode, which can deliver a current density of 10 mA cm⁻² at a cell voltage as low as 1.53 V. More significantly, in addition to extraordinary operational stability of the electrolyzer, it can achieve high current density of 100 mA cm⁻² with only cell voltage of 1.79 V, respectively, which are very useful for practical application. This work offers a rational strategy for the structure engineering of advanced hollow hybrid nanostructures as a nonprecious noble-metal-free water splitting bifunctional electrocatalyst, which can push forward the development of high efficient and low cost H₂ production.

对于H ₂和O ₂析出反应（HER和OER），开发有效的非贵金属无贵金属的水分解双功能电催化剂至关重要，这仍然是一个巨大的挑战。然而，很少报道基于二金属和三金属硒化物的中空纳米结构的设计，特别是非球形中空纳米结构的设计。在此，首次在中空N掺杂碳纳米盒（Cu _0.4 Ni _0.3 Co _0.3 Se _2）上成功设计了基于中空Cu _0.4 Ni _0.3 Co _0.3 Se ₂介孔纳米片双壳的新型三金属硒化物。@NC n-盒）和纳米管（Cu _0.4 Ni _0.3 Co _0.3 Se ₂ @NC n-管）。从相关的Fe ₂ O ₃获得空心NC n-box和NC n-pipe骨架。仅在合成步骤中进行了很小的更改即可制备出形态完全不同的纳米立方体和纳米棒模板。值得注意的是，得益于特殊的电子结构工程和具有高表面积的独特空心层级设计，有效释放气体的开放通道，快速的电子/质量传输，所得先进的电催化剂在碱性介质中具有出色的OER活性和理想的HER性能。 。此外，总的水分解设备使用两个对称的Cu组装_0.4镍_0.3钴_0.3硒₂ @NC正箱电极作为阳极和阴极，其可提供为10mA cm 2的电流密度^-2电池电压低至1.53 V时。更重要的是，除了电解器的出色运行稳定性外，它还可以仅以1.79 V的电池电压实现100 mA cm ^-2的高电流密度，这对于实际应用。这项工作为先进的中空杂化纳米结构作为一种无贵金属无水裂解双功能电催化剂的结构工程提供了合理的策略，可以推动高效，低成本H ₂生产的发展。