Li Qingqing, Zhang Botao, Sun Chang, Sun Xiaolei, Li Zhenxing, Du Yaping, Liu Jin-Cheng, Luo Feng
Nankai University, Tianjin Key Laboratory of Rare-earth Materials and Applications, School of Materials Science and Engineering, Centre of Rare Earth and Inorganic Functional Materials, Tianjin, 300350, P. R. China.
State Key Laboratory of Heavy Oil Processing, College of New Energy and Materials, China University of Petroleum (Beijing), Beijing, 102249, P. R. China.
Small. 2024 Aug;20(32):e2400662. doi: 10.1002/smll.202400662. Epub 2024 Mar 27.
Developing high-performance electrocatalysts for alkaline hydrogen evolution reaction (HER) is crucial for producing green hydrogen, yet it remains challenging due to the sluggish kinetics in alkaline environments. Pt is located near the peak of HER volcano plot, owing to its exceptional performance in hydrogen adsorption and desorption, and Rh plays an important role in HO dissociation. Lanthanides (Ln) are commonly used to modulate the electronic structure of materials and further influence the adsorption/desorption of reactants, intermediates, and products, and noble metal-Ln alloys are recognized as effective platforms where Ln elements regulate the catalytic properties of noble metals. Here PtRhTm alloy is synthesized using the sodium vapor reduction method. This alloy demonstrates superior catalytic activity, being 4.4 and 6.6 times more effective than Pt/C and Rh/C, respectively. Density Functional Theory (DFT) calculations reveal that the upshift of d-band center and the charge transfer induced by alloying promote adsorption and dissociation of HO, making PtRhTm alloy more favorable for the alkaline HER reaction, both kinetically and thermodynamically.
开发用于碱性析氢反应（HER）的高性能电催化剂对于绿色制氢至关重要，但由于碱性环境中动力学缓慢，这仍然具有挑战性。Pt位于HER火山图的峰值附近，因其在氢吸附和解吸方面具有卓越性能，而Rh在HO解离中起重要作用。镧系元素（Ln）通常用于调节材料的电子结构，并进一步影响反应物、中间体和产物的吸附/解吸，贵金属-Ln合金被认为是Ln元素调节贵金属催化性能的有效平台。在此，采用钠蒸汽还原法合成了PtRhTm合金。该合金表现出优异的催化活性，分别比Pt/C和Rh/C有效4.4倍和6.6倍。密度泛函理论（DFT）计算表明，合金化引起的d带中心上移和电荷转移促进了HO的吸附和解离，使得PtRhTm合金在动力学和热力学上都更有利于碱性HER反应。
