文献类型：期刊文献

英文题名：Single-atom catalysts based on TiN for the electrocatalytic hydrogen evolution reaction: a theoretical study

作者：He, Bingling[1,2,3];Shen, Jiansheng[1];Wang, Bin[1];Lu, Zhansheng[4];Ma, Dongwei[2,3]

第一作者：赫丙玲;He, Bingling

通讯作者：Ma, DW[1];Ma, DW[2]

机构：[1]Xinxiang Univ, Coll Phys & Elect Engn, Xinxiang 453003, Henan, Peoples R China;[2]Henan Univ, Key Lab Special Funct Mat, Minist Educ, Kaifeng 475004, Peoples R China;[3]Henan Univ, Sch Mat Sci & Engn, Kaifeng 475004, Peoples R China;[4]Henan Normal Univ, Coll Phys, Xinxiang 453007, Henan, Peoples R China

第一机构：新乡学院物理与电子工程学院

通讯机构：[1]corresponding author), Henan Univ, Key Lab Special Funct Mat, Minist Educ, Kaifeng 475004, Peoples R China;[2]corresponding author), Henan Univ, Sch Mat Sci & Engn, Kaifeng 475004, Peoples R China.

年份：2021

卷号：23

期号：29

起止页码：15685-15692

外文期刊名：PHYSICAL CHEMISTRY CHEMICAL PHYSICS

收录：;EI(收录号：20213210725454);Scopus(收录号：2-s2.0-85111743666);WOS:【SCI-EXPANDED(收录号:WOS:000672953800001)】；

基金：This work is supported by the Program for Science & Technology Innovation Talents in Universities of Henan Province (Grant No. 20HASTIT028), the Science and Technology Breakthrough Project of Henan Province (No. 202102210199 and 202102210001), and the National Natural Science Foundation of China (Grant No. U1904198).

语种：英文

外文关键词：Atoms - Catalyst activity - Costs - Electrocatalysis - Electrocatalysts - Free energy - Hydrogen evolution reaction - Hydrogen fuels - Sustainable development - Titanium - Titanium nitride

摘要：The electrocatalytic hydrogen evolution reaction (HER) for water splitting is crucial for the sustainable production of clean hydrogen fuel, while the high cost of Pt catalysts impedes its commercialization. Herein, we have performed a systematic theoretical study on the electrocatalytic HER over single-atom catalysts (SACs) based on low-cost TiN. Specifically, the TiN(100) surface with a Ti or N vacancy has been considered as the support. 20 transition-metal (TM) atoms and 3 nonmetallic atoms are embedded into the Ti or N vacancy, accordingly denoted as M@Tiv or M@Nv. All the single atoms can be stabilized by the surface vacancies, controlled by the adjustable chemical potential. Interestingly, for TM-embedded TiN(100), the hydrogen binding is much stronger over M@Nv than M@Tiv, which can be attributed to the more localized d states of the TM atoms anchored by the N vacancies, indicating a strong coordination effect. Among 43 catalysts, 10 (Ni, Zn, Nb, Mo, Rh@Tiv, and Au, Pd, W, Mo, B@Nv) were predicted to have high HER catalytic activity with near-zero hydrogen adsorption free energy. For the further gaseous hydrogen evolution, Zn@Tiv can adopt both Tafel (with an energy barrier of 0.68 eV) and Heyrovsky mechanisms, while the others may prefer the Heyrovsky mechanism. This work provides a promising strategy to realize cost-efficient electrocatalysts for the HER, and highlights the important role of the local coordination environment for SACs.