Kan Dongxiao, Zhang Xilin, Fu Zhaoming, Zhang Yanxing, Zhao Yuling, Yang Zongxian
College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007, China.
Phys Chem Chem Phys. 2018 Apr 18;20(15):10302-10310. doi: 10.1039/c8cp00069g.
The adsorption and activation of O2 is regarded as the first critical step for the oxygen reduction reaction (ORR), and catalysts with a high performance toward O2 adsorption and activation would provide a theoretical foundation for further investigations. Here, we have studied the adsorption and electronic properties as well as the catalytic activities of group 9-11 single metal atoms deposited on NbC(001), denoted M/NbC(001). According to the location of the d-band centers and the frontier molecular orbital analysis, single metals of Co, Rh, Ir and Ni on NbC(001) exhibit higher activities than other metals (Pd, Pt, Cu, Ag and Au). The quite different catalytic activities of M/NbC(001) may be attributed to the differences in their electro-negativities and work-functions. Meanwhile, the reasonable stabilities of Co, Rh, Ir and Ni on NbC(001) were clarified by investigating the agglomeration resistance and oxidation resistance, and the results indicate that Co and Ni have poor oxidative stability, and Rh and Ir are antioxidants on NbC(001). Further research into the adsorption and activation of O2 confirmed the outstanding properties of Rh/NbC(001) and Ir/NbC(001), which may provide great opportunities to find alternative catalysts.
氧气的吸附和活化被视为氧还原反应(ORR)的首个关键步骤,对氧气吸附和活化具有高性能的催化剂将为进一步研究提供理论基础。在此,我们研究了沉积在NbC(001)上的第9-11族单金属原子(记为M/NbC(001))的吸附和电子性质以及催化活性。根据d带中心的位置和前沿分子轨道分析,NbC(001)上的Co、Rh、Ir和Ni单金属比其他金属(Pd、Pt、Cu、Ag和Au)表现出更高的活性。M/NbC(001)截然不同的催化活性可能归因于它们电负性和功函数的差异。同时,通过研究抗团聚性和抗氧化性阐明了Co、Rh、Ir和Ni在NbC(001)上合理的稳定性,结果表明Co和Ni具有较差的氧化稳定性,而Rh和Ir在NbC(001)上是抗氧化剂。对氧气吸附和活化的进一步研究证实了Rh/NbC(001)和Ir/NbC(001)的优异性能,这可能为寻找替代催化剂提供巨大机遇。