Water splitting by photocatalysis technique is regarded as an eco-friendly hydrogen production strategy. However, the poor photoresponsivity and automatic electron-hole recombination greatly restrict the HER performance of conventional semiconductor photocatalyst. Here, to utilize the stable electrochemical property of hexagonal phase boron nitride (h-BN) and improve its defect of wide bandgap (E_g ≈ 4.2 eV), reduced graphene oxide (rGO) was applied to construct three-dimensional (3D) porous h-BN/rGO hybrid accompanied by a carbon-doping strategy without template assistance, then a carbon-doped 3D porous h-BN/rGO (C-BNRG) hybrid with large BET surface area was successfully prepared. As the synergistic effect of h-BN/rGO heterointerface and carbon-doping, the improved photoresponsivity and electrochemical property were presented, and the resultant 3D porous C_0.4-BNRG hybrid presented not only greatly enhanced HER activity (157.63 μmol·g⁻¹·h⁻¹) but excellent durability in pH = 8.5, which was prominently higher than pristine h-BN (～36.7 times), C-BN (～12.1 times) and 3D porous BNRG hybrid (～7.0 times). This study offers a template-free approach to develop non-metallic based 3D porous hybrid for outstanding HER performance.

通过光催化技术分解水被认为是一种环保的制氢策略。然而，不良的光响应性和自动的电子-空穴复合极大地限制了常规半导体光催化剂的HER性能。在此，利用六方相氮化硼（h-BN）的稳定电化学性能并改善其宽带隙（E _g≈4.2 eV），使用还原氧化石墨烯（rGO）来构建三维（3D）多孔h-BN / rGO杂化体，并伴随无模板辅助的碳掺杂策略，然后进行碳掺杂的3D多孔h-BN /成功制备了具有大BET表面积的rGO（C-BNRG）杂种。由于h-BN / rGO异质界面和碳掺杂的协同作用，改善了光响应性和电化学性能，所得3D多孔C _0.4 -BNRG杂化物不仅大大提高了HER活性（157.63μmol·g ^-1 · h ^-1），但在pH = 8.5时具有出色的耐久性，显着高于原始h-BN（约36.7倍），C-BN（约12.1倍）和3D多孔BNRG杂种（约7.0倍）。这项研究提供了一种无模板的方法来开发基于非金属的3D多孔混合材料，以实现出色的HER性能。