Identification of electronic descriptors for catalytic activity of transition-metal and non-metal doped MoS2

Xie, Zijuan1,2,3; Huang, Xiang1,2; Zhang, Zhe1,2; Xu, Hu1,2,4,5

2021-06-01

10.1039/d1cp01458g

PHYSICAL CHEMISTRY CHEMICAL PHYSICS   影响因子和分区

1463-9076

1463-9084

While the d-band theory offers successful electronic descriptors for catalytic activity of transition metals, transition metal compounds still need substantial theoretical input for the identification of reactivity descriptors for fast screening of earth-abundant catalysts. We study transition metal (TM) and non-metal doped MoS2, a promising substitute for noble metals as catalysts for multiple reactions, to clarify how doping modifies the reactivity by regulating the electronic structure of the host. We find that doping can significantly change the density of states (DOS) at band edges and the position of the Fermi level, which renders the S p-band center epsilon(p) a good descriptor for H adsorption on both TM and non-metal doped MoS2. Dopants to the left of the host elements in the periodic table that have fewer electrons pin the Fermi level into the valence band, and those to the right that have more electrons pin the Fermi level into the conduction band, resulting in separated linear relationships between H binding energy and S p-band center. Moreover, by a close examination of the electronic structure of late TM doped systems, we identify the position of the late TM dopant induced DOS peak near the conduction band minimum (CBM), epsilon(TM), as a refined descriptor which shows a linear relationship for H as well as C, N, O adsorption. Finally, we generalize our descriptor to MoSe2 and MoTe2 to include all three anions in transition metal dichalcogenides (TMDs) and show a universal scaling relationship between the H binding energy and anion p-band center. Together we further enhance our understanding on identifying electronic descriptors for TM compounds.

SCI ; EI

英语

第一 ; 通讯

National Natural Science Foundation of China[11974160] ; Guangdong Natural Science Funds for Distinguished Young Scholars[2017B030306008] ; Guangdong Provincial Key Laboratory of Computational Science and Material Design[2019B030301001] ; Guangdong-Hong Kong-Macao Joint Laboratory[2019B121205001]

Chemistry ; Physics

Chemistry, Physical ; Physics, Atomic, Molecular & Chemical

WOS:000671840200001

ROYAL SOC CHEMISTRY

20213110695369

Binding energy ; Catalyst activity ; Complexation ; Conduction bands ; Electronic structure ; Fermi level ; Layered semiconductors ; Molybdenum compounds ; Negative ions ; Precious metal compounds

Metallurgy and Metallography:531 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Atomic and Molecular Physics:931.3 ; High Energy Physics:932.1

CHEMISTRY

Web of Science

1.Southern Univ Sci & Technol, Dept Phys, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Inst Quantum Sci & Engn, Shenzhen 518055, Peoples R China
3.Southeast Univ, Dept Phys, Nanjing 210096, Peoples R China
4.Southern Univ Sci & Technol, Guangdong Prov Key Lab Computat Sci & Mat Design, Shenzhen 518055, Peoples R China
5.Southern Univ Sci & Technol, Guangdong Hong Kong Macao Joint Lab Photon Therma, Shenzhen 518055, Peoples R China

Xie, Zijuan,Huang, Xiang,Zhang, Zhe,et al. Identification of electronic descriptors for catalytic activity of transition-metal and non-metal doped MoS2[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2021,23:15101-15106.

Xie, Zijuan,Huang, Xiang,Zhang, Zhe,&Xu, Hu.(2021).Identification of electronic descriptors for catalytic activity of transition-metal and non-metal doped MoS2.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,23,15101-15106.

Xie, Zijuan,et al."Identification of electronic descriptors for catalytic activity of transition-metal and non-metal doped MoS2".PHYSICAL CHEMISTRY CHEMICAL PHYSICS 23(2021):15101-15106.