Feng Yumei, Xie Yuhua, Yu Yingjie, Chen Yazhou, Liu Qingting, Bao Haifeng, Luo Fang, Pan Shuyuan, Yang Zehui
State Key Laboratory of New Textile Materials & Advanced Processing Technology, College of Materials Science and Engineering, Wuhan Textile University, Wuhan, 430200, China.
Faculty of Materials Science and Chemistry, China University of Geosciences Wuhan, 388 Lumo RD, Wuhan, 430074, China.
Angew Chem Int Ed Engl. 2025 Jan 2;64(1):e202413417. doi: 10.1002/anie.202413417. Epub 2024 Nov 6.
The substantial promotion of hydrogen evolution reaction (HER) catalytic performance relies on the breakup of the Sabatier principle, which can be achieved by the alternation of the support and electronic metal support interaction (EMSI) is noticed. Due to the utilization of tungsten disulfides as support for platinum (Pt@WS), surprisingly, Pt@WS demands only 31 mV overpotential to attain 10 mA cm in acidic HER test, corresponding to a 2.5-fold higher mass activity than benchmarked Pt/C. The pH dependent electrochemical measurements associated with H-TPD and in situ Raman spectroscopy indicate a hydrogen spillover involved HER mechanism is confirmed. The WS support triggers a higher hydrogen binding strength for Pt leading to the increment in hydrogen concentration at Pt sites proved by upshifted d band center as well as lower Gibbs free energy of hydrogen, favourable for hydrogen spillover. Besides, the WS shows a comparably lower effect on Gibbs free energy for different Pt layers (-0.50 eV layer) than carbon black (-0.88 eV layer) contributing to a better Pt utilization. Also, the theoretical calculation suggests the hydrogen spillover occurs on the 3 Pt layer in Pt@WS; moreover, the energy barrier is lowered with increment in hydrogen coverage on Pt. Therefore, the boosted HER activity attributes to the EMSI effect caused hydrogen spillover and enhancement in Pt utilization efficiency.
析氢反应（HER）催化性能的大幅提升依赖于对Sabatier原理的突破，通过载体的改变以及电子金属载体相互作用（EMSI）得以实现。令人惊讶的是，由于使用二硫化钨作为铂的载体（Pt@WS），在酸性HER测试中，Pt@WS仅需31 mV的过电位即可达到10 mA cm，其质量活性比基准Pt/C高2.5倍。与H-TPD和原位拉曼光谱相关的pH依赖性电化学测量结果证实了一种涉及氢溢流的HER机制。WS载体使Pt具有更高的氢结合强度，导致Pt位点处的氢浓度增加，这由d带中心上移以及更低的氢吉布斯自由能所证明，有利于氢溢流。此外，与炭黑（-0.88 eV/层）相比，WS对不同Pt层（-0.50 eV/层）的吉布斯自由能影响相对较低，这有助于更好地利用Pt。理论计算表明，氢溢流发生在Pt@WS的第3层Pt上；此外，随着Pt上氢覆盖率的增加，能垒降低。因此，HER活性的提高归因于EMSI效应导致的氢溢流和Pt利用效率的提高。
