Citation: Du Yuting, Gao Denglei, Zhang Na, Yi Ding, Wang Xi. Regulation of the d-Orbitals of Platinum through Low-Entropy Alloying^#[J]. Chemistry, ;2020, 83(7): 652-658. shu

Regulation of the d-Orbitals of Platinum through Low-Entropy Alloying^#

Department of Physics, School of Science, Beijing Jiaotong University, Beijing, 100044

Corresponding author: Wang Xi, xiwang@bjtu.edu.cn
Received Date: 1 February 2020
Accepted Date: 28 March 2020

Fund Project: 中央高校基本科研基金项目 2018JBZ107化学与精细化工广东省实验室项目 1932004中国科学技术部"国际科技合作重点项目" 2018YFE0124600中央高校基本科研基金项目 2018JBZ107中央高校基本科研基金项目(2018JBZ107, 2019RC035)、国家自然科学基金项目(91961125, 21905019)、中国科学技术部"国际科技合作重点项目"(2018YFE0124600)、化学与精细化工广东省实验室项目(1932004)和北京交通大学"卓越百人"人才基金项目资助国家自然科学基金项目 91961125国家自然科学基金项目 21905019

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It has been reported that precisely regulating the electronic structures of the active site is one of the most effective means to realize precise catalysis, which often includes lattice strain and charge transfer, etc. In doping systems, some new theories, such as the Atom-Realm (AR) effect, have been used to explain the changes in physical and chemical properties of the substrates caused by the geometry and electronic structures of the active heteroatom sites. Based on the low-entropy alloy and using the first-principles calculations, we report a new strategy for achieving precise catalysis through regulating the orbitals and spin of the active sites, i.e. doping Fe atoms in Pt to change its d-orbitals for the regulation of catalytic performance. We established both the models of pure Pt and Pt-Fe alloy and calculated the O₂ adsorption energy on different active sites. We found that doping Fe atoms in pure Pt can weaken the binding of O₂-Pt without affecting the O₂ dissociation. Based on the projected density of states (PDOS) analysis, the hybridization of Fe-3d and Pt-5d states leads to the shift of atomic orbitals as well as the spin polarization of Pt metal. Therefore, part of the electronic states of Pt move above the Fermi level and overlap with O₂-π^*, making the hybridization of O₂-π^* and Pt-5d states in Pt-Fe alloy much stronger than that in pure Pt. The regulation of d-orbitals results in the improvement of the catalytic activity of O₂ on the surface of Pt-Fe alloy. Our study predicts that the orbital catalysis and spin catalysis will provide an effective method for precise catalysis as well as high-efficient catalysts design.
- Low-entropy Pt-Fe alloy,
- Density functional theory,
- d-Orbitals regulation,
- Catalysis
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Regulation of the d-Orbitals of Platinum through Low-Entropy Alloying#

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通讯作者: 陈斌, bchen63@163.com

Regulation of the d-Orbitals of Platinum through Low-Entropy Alloying^#