Yan Qiang-Qiang, Wu Dao-Xiong, Chu Sheng-Qi, Chen Zhi-Qin, Lin Yue, Chen Ming-Xi, Zhang Jing, Wu Xiao-Jun, Liang Hai-Wei
Hefei National Laboratory for Physical Sciences at the Microscale, School of Chemistry and Materials Sciences, University of Science and Technology of China, 230026, Hefei, China.
Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, 100049, Beijing, China.
Nat Commun. 2019 Oct 31;10(1):4977. doi: 10.1038/s41467-019-12851-w.
Metal-support interaction is of great significance for catalysis as it can induce charge transfer between metal and support, tame electronic structure of supported metals, impact adsorption energy of reaction intermediates, and eventually change the catalytic performance. Here, we report the metal size-dependent charge transfer reversal, that is, electrons transfer from platinum single atoms to sulfur-doped carbons and the carbon supports conversely donate electrons to Pt when their size is expanded to ~1.5 nm cluster. The electron-enriched Pt nanoclusters are far more active than electron-deficient Pt single atoms for catalyzing hydrogen evolution reaction, exhibiting only 11 mV overpotential at 10 mA cm and a high mass activity of 26.1 A mg at 20 mV, which is 38 times greater than that of commercial Pt/C. Our work manifests that the manipulation of metal size-dependent charge transfer between metal and support opens new avenues for developing high-active catalysts.
金属-载体相互作用对催化具有重要意义，因为它可诱导金属与载体之间的电荷转移，调控负载金属的电子结构，影响反应中间体的吸附能，并最终改变催化性能。在此，我们报道了金属尺寸依赖性的电荷转移反转现象，即电子从铂单原子转移至硫掺杂碳，而当碳载体尺寸扩展至约1.5纳米团簇时，碳载体则相反地向铂提供电子。富含电子的铂纳米团簇在催化析氢反应方面远比缺电子的铂单原子活跃，在10毫安/平方厘米电流密度下过电位仅为11毫伏，在20毫伏时质量活性高达26.1安/毫克，是商业铂碳催化剂的38倍。我们的工作表明，操控金属与载体之间的尺寸依赖性电荷转移为开发高活性催化剂开辟了新途径。
