Li Zhenxing, Yu Chengcheng, Kang Yikun, Zhang Xin, Wen Yangyang, Wang Zhao-Kui, Ma Chang, Wang Cong, Wang Kaiwen, Qu Xianlin, He Miao, Zhang Ya-Wen, Song Weiyu
State Key Laboratory of Heavy Oil Processing, College of New Energy and Materials, Beijing Key Laboratory of Biogas Upgrading Utilization, China University of Petroleum (Beijing), Beijing 102249, China.
College of Science, China University of Petroleum (Beijing), Beijing 102249, China.
Natl Sci Rev. 2020 Aug 28;8(7):nwaa204. doi: 10.1093/nsr/nwaa204. eCollection 2021 Jul.
Hollow nanoparticles with large specific surface area and high atom utilization are promising catalysts for the hydrogen evolution reaction (HER). We describe herein the design and synthesis of a series of ultra-small hollow ternary alloy nanostructures using a simple one-pot strategy. The same technique was demonstrated for hollow PtNiCu nanoparticles, hollow PtCoCu nanoparticles and hollow CuNiCo nanoparticles. During synthesis, the displacement reaction and oxidative etching played important roles in the formation of hollow structures. Moreover, our hollow PtNiCu and PtCoCu nanoparticles were single crystalline, with an average diameter of 5 nm. Impressively, ultra-small hollow PtNiCu nanoparticles, containing only 10% Pt, exhibited greater electrocatalytic HER activity and stability than a commercial Pt/C catalyst. The overpotential of hollow PtNiCu nanoparticles at 10 mA cm was 28 mV versus reversible hydrogen electrode (RHE). The mass activity was 4.54 A mg at -70 mV versus RHE, which is 5.62-fold greater than that of a commercial Pt/C system (0.81 A mg ). Through analyses of bonding and antibonding orbital filling, density functional theory calculations demonstrated that the bonding strength of different metals to the hydrogen intermediate (H) was in the order of Pt > Co > Ni > Cu. The excellent HER performance of our hollow PtNiCu nanoparticles derives from moderately synergistic interactions between the three metals and H. This work demonstrates a new strategy for the design of low-cost and high-activity HER catalysts.
具有大比表面积和高原子利用率的中空纳米粒子是用于析氢反应（HER）的有前景的催化剂。我们在此描述了使用简单的一锅法策略设计和合成一系列超小中空三元合金纳米结构。该技术同样适用于中空PtNiCu纳米粒子、中空PtCoCu纳米粒子和中空CuNiCo纳米粒子。在合成过程中，置换反应和氧化蚀刻在中空结构的形成中起重要作用。此外，我们的中空PtNiCu和PtCoCu纳米粒子是单晶的，平均直径为5纳米。令人印象深刻的是，仅含10% Pt的超小中空PtNiCu纳米粒子表现出比商业Pt/C催化剂更高的电催化HER活性和稳定性。中空PtNiCu纳米粒子在10 mA cm时相对于可逆氢电极（RHE）的过电位为28 mV。在相对于RHE为 -70 mV时，质量活性为4.54 A mg，比商业Pt/C体系（0.81 A mg）高5.62倍。通过对成键和反键轨道填充的分析，密度泛函理论计算表明不同金属与氢中间体（H）的结合强度顺序为Pt > Co > Ni > Cu。我们的中空PtNiCu纳米粒子优异的HER性能源于三种金属与H之间适度的协同相互作用。这项工作展示了一种设计低成本、高活性HER催化剂的新策略。
