Long Haoyu, Zhang Xidong, Zhang Zhenyi, Zhang Jianjun, Yu Jiaguo, Yu Huogen
Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan, PR China.
Key Laboratory of New Energy and Rare Earth Resource Utilization of State Ethnic Affairs Commission, School of Physics and Materials Engineering, Dalian Minzu University, Dalian, PR China.
Nat Commun. 2025 Jan 22;16(1):946. doi: 10.1038/s41467-025-56306-x.
The H-evolution kinetics play a pivotal role in governing the photocatalytic hydrogen-evolution process. However, achieving precise regulation of the H-adsorption and H-desorption equilibrium (H/H) still remains a great challenge. Herein, we propose a fine-tuning d-p hybridization strategy to precisely optimize the H/H kinetics in a Ni-B modified CdS photocatalyst (Ni-B/CdS). X-ray absorption fine-structure spectroscopy and theoretical calculations reveal that increasing B-atom amount in the Ni-B cocatalyst gradually strengthens the d-p orbital interaction between Ni and B, resulting in a consecutive d-band broadening and controllable d-band center on Ni active sites. The above consecutive d-band optimization allows for precise modulation of the H/H dynamics in the Ni-B/CdS, ultimately demonstrating a remarkable H-evolution activity of 13.4 mmol g h (AQE = 56.1 %). The femtosecond transient absorption spectroscopy further confirms the rapid electron-transfer dynamics in the Ni-B/CdS photocatalyst. This work provides insights into the optimal design of prospective H-evolution catalysts.
氢析出动力学在光催化析氢过程中起着关键作用。然而，实现对氢吸附和氢脱附平衡（H/H）的精确调控仍然是一个巨大的挑战。在此，我们提出一种微调d-p杂化策略，以精确优化镍硼改性硫化镉光催化剂（Ni-B/CdS）中的H/H动力学。X射线吸收精细结构光谱和理论计算表明，在Ni-B助催化剂中增加硼原子量会逐渐增强Ni和B之间的d-p轨道相互作用，导致Ni活性位点上的d带连续展宽且d带中心可控。上述连续的d带优化使得能够精确调节Ni-B/CdS中的H/H动力学，最终展现出13.4 mmol g h的显著析氢活性（表观量子效率AQE = 56.1%）。飞秒瞬态吸收光谱进一步证实了Ni-B/CdS光催化剂中快速的电子转移动力学。这项工作为前瞻性析氢催化剂的优化设计提供了见解。
