Yi Ding, Lu Fei, Zhang Fengchu, Liu Shoujie, Zhou Bo, Gao Denglei, Wang Xi, Yao Jiannian
Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
Department of Physics, School of Science, Beijing Jiaotong University, Beijing, 100044, China.
Angew Chem Int Ed Engl. 2020 Sep 7;59(37):15855-15859. doi: 10.1002/anie.202004510. Epub 2020 May 14.
Single-atom catalysts have attracted much attention. Reported herein is that regulating charge transfer of lattice oxygen atoms in serial single-atom-doped titania enables tunable hydrogen evolution reaction (HER) activity. First-principles calculations disclose that the activity of lattice oxygen for the HER can be regularly promoted by substituting its nearest metal atom, and doping-induced charge transfer plays an essential role. Besides, the realm of the charge transfer of the active site can be enlarged to the second nearest atom by creating oxygen vacancies, resulting in further optimization for the HER. Various single-atom-doped titania nanosheets were fabricated to validate the proposed model. Taking advantage of the localized charge transfer to the lattice atom is demonstrated to be feasible for realizing precise regulation of the electronic structures and thus catalytic activity of the nanosheets.
单原子催化剂已引起广泛关注。本文报道，通过调控一系列单原子掺杂二氧化钛中晶格氧原子的电荷转移，可实现可调的析氢反应（HER）活性。第一性原理计算表明，通过取代其最近邻金属原子，晶格氧对HER的活性可得到规律性提升，且掺杂诱导的电荷转移起着至关重要的作用。此外，通过制造氧空位，活性位点的电荷转移范围可扩大到次近邻原子，从而进一步优化HER。制备了各种单原子掺杂的二氧化钛纳米片以验证所提出的模型。利用向晶格原子的局部电荷转移被证明对于实现电子结构的精确调控以及纳米片的催化活性是可行的。
