Reducing kinetic energy barriers and developing accessible active sites are critical to deliver high hydrogen evolution reaction(HER)efficiency.In this paper,we synthesized defect-modulated and heteroatom(boron)-funct...Reducing kinetic energy barriers and developing accessible active sites are critical to deliver high hydrogen evolution reaction(HER)efficiency.In this paper,we synthesized defect-modulated and heteroatom(boron)-functionalized three-dimensional(3D)bowl-shaped Ti_(3−x)C_(2)T_(y)MXene(B-TCT)nanocavities coupled with the vertical growth of MoSe_(2)nanoflakes.The B-TCT@MoSe_(2)nanohybrids catalyst delivers the overpotentials of 49.9,52.7,and 67.8 mV to reach a HER current density of 10 mA·cm^(−2)under acidic,alkaline,and neutral conditions,respectively.Such outstanding HER activity is predominantly attributed to the heteroatom functionalization,self-adapting Ti vacancy(VTi)defect modulation,and spatial configuration design in the 3D B-TCT nanocavity,which synergistically regulate the electronic structure,activate the basal plane/edge unsaturated sites,and reduce the reaction energy barrier.Experimental and theoretical calculations demonstrate that strong heterogeneous interfacial bonding interactions between B-TCT and MoSe_(2)can dramatically reduce the free energy of hydrogen adsorption and facilitate efficient interfacial charge migration,thus essentially improving the HER kinetics.We used this 3D porous nanohybrid system assembled by defectrich lamellar structures to elucidate the advantageous synergistic effects of multiple mechanisms among defect structure,heteroatom functionalization,and interfacial coupling,which provided important insights for the development of efficient hybridtype catalysts.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52072182 and 51872145)Natural Science Foundation of Jiangsu Province(No.BK20211278)+2 种基金the China Postdoctoral Science Foundation(Nos.2019M650120 and 2020M671554)the National Synergetic Innovation Center for Advanced Materials(SICAM)Postgraduate Research Practice Innovation Program of Jiangsu Province(No.KYCX22_0977).
文摘Reducing kinetic energy barriers and developing accessible active sites are critical to deliver high hydrogen evolution reaction(HER)efficiency.In this paper,we synthesized defect-modulated and heteroatom(boron)-functionalized three-dimensional(3D)bowl-shaped Ti_(3−x)C_(2)T_(y)MXene(B-TCT)nanocavities coupled with the vertical growth of MoSe_(2)nanoflakes.The B-TCT@MoSe_(2)nanohybrids catalyst delivers the overpotentials of 49.9,52.7,and 67.8 mV to reach a HER current density of 10 mA·cm^(−2)under acidic,alkaline,and neutral conditions,respectively.Such outstanding HER activity is predominantly attributed to the heteroatom functionalization,self-adapting Ti vacancy(VTi)defect modulation,and spatial configuration design in the 3D B-TCT nanocavity,which synergistically regulate the electronic structure,activate the basal plane/edge unsaturated sites,and reduce the reaction energy barrier.Experimental and theoretical calculations demonstrate that strong heterogeneous interfacial bonding interactions between B-TCT and MoSe_(2)can dramatically reduce the free energy of hydrogen adsorption and facilitate efficient interfacial charge migration,thus essentially improving the HER kinetics.We used this 3D porous nanohybrid system assembled by defectrich lamellar structures to elucidate the advantageous synergistic effects of multiple mechanisms among defect structure,heteroatom functionalization,and interfacial coupling,which provided important insights for the development of efficient hybridtype catalysts.
