Zhao Yufei, Zhang Jinqiang, Xie Yuhan, Sun Bing, Jiang Junjie, Jiang Wen-Jie, Xi Shibo, Yang Hui Ying, Yan Kang, Wang Shijian, Guo Xin, Li Peng, Han Zhaojun, Lu Xunyu, Liu Hao, Wang Guoxiu
Center for Clean Energy Technology, School of Mathematical and Physical Science, Faculty of Science, University of Technology Sydney, Sydney, New South Wales 2007, Australia.
Particles and Catalysis Research Laboratory, School of Chemical Engineering, The University of New South Wales Sydney, Sydney, New South Wales 2052, Australia.
Nano Lett. 2021 Jan 13;21(1):823-832. doi: 10.1021/acs.nanolett.0c04569. Epub 2021 Jan 5.
Identification of active sites for highly efficient catalysts at the atomic scale for water splitting is still a great challenge. Herein, we fabricate ultrathin nickel-incorporated cobalt phosphide porous nanosheets (Ni-CoP) featuring an atomic heterometallic site (NiCoP) via a boron-assisted method. The presence of boron induces a release-and-oxidation mechanism, resulting in the gradual exfoliation of hydroxide nanosheets. After a subsequent phosphorization process, the resultant Ni-CoP nanosheets are implanted with unsaturated atomic heterometallic NiCoP sites (with Co vacancies) for alkaline hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The optimized Ni-CoP exhibits a low overpotential of 88 and 290 mV at 10 mA cm for alkaline HER and OER, respectively. This can be attributed to reduced free energy barriers, owing to the direct influence of center Ni atoms to the adjacent Co/P atoms in NiCoP sites. These provide fundamental insights on the correlation between atomic structures and catalytic activity.
在原子尺度上识别用于高效水分解催化剂的活性位点仍然是一项巨大挑战。在此，我们通过硼辅助方法制备了具有原子异质金属位点（NiCoP）的超薄镍掺杂磷化钴多孔纳米片（Ni-CoP）。硼的存在引发了一种释放-氧化机制，导致氢氧化物纳米片逐渐剥离。经过随后的磷化过程，所得的Ni-CoP纳米片植入了用于碱性析氢反应（HER）和析氧反应（OER）的不饱和原子异质金属NiCoP位点（具有Co空位）。优化后的Ni-CoP在10 mA cm下碱性HER和OER的过电位分别低至88和290 mV。这可归因于自由能垒的降低，这是由于中心Ni原子对NiCoP位点中相邻Co/P原子的直接影响。这些为原子结构与催化活性之间的相关性提供了基本见解。
