How interfacial electron-donating defects influence the structure and charge of gold nanoparticles on TiO₂ support

Xia, Guang-Jie1,2,3; Fu, Yu1,2; Cao, Wei1,2; Li, Jun4; Wang, Yang-Gang1,2

2024-05-01

10.1007/s12274-024-6625-2

NANO RESEARCH   影响因子和分区

1998-0124

1998-0000

The reduction degree of TiO2 support is critical to the performances of metal catalysts. In many previous theoretical calculations, only the bridge oxygen vacancy (O-v) was considered as the electron-donating defect on reduced rutile TiO2 (r-TiO2-x) supports. However, titanium adatoms (Ti-ad.), oxidized titanium islands (Tiad.On), and acid hydroxyls (ObrH) also exist at the metal/support interface. By conducting density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations, we compared r-TiO2-x surfaces with O-v, Ti-ad., Tiad.On, and ObrH sites loaded with Au nanoparticles (NPs). The results showed the Au NPs were oxygen-phobic but titanium-philic, resulting in wetting of O-v and Ti-ad. but short contact with Tiad.On and ObrH. The Bader charges of Au NPs (Q(M)) showed a good linear relationship with the ideal number of donating electrons (N-e) from the defective sites (Q(M) = -KeNe + Q(M,S)), demonstrating the intrinsic electron allocation at the interface. The O-v, Ti-ad., and Tiad.On exhibited similar slopes (K-e), relatively steeper than that of ObrH. That means in the scope of Au NP charge state, the Ti-ad. and Tiad.On have a close electron-donating ability with O-v, but the ObrH donates relatively fewer electrons. This linear relationship can be extended approximately to other metals. The higher the metal work function, the steeper the K-e for easier electron donation from defective sites. The stronger the metal oxygen affinity, the more positive the intercept (Q(M,S)). That explains the easy generation of metallic or negative Pt and Au NPs on r-TiO2-x, but hard for Cu and Zn in experiment. That provides theoretical guidance for regulating the charge of metal NPs over TiO2-x supports.

metal-support interaction titanium oxide oxygen vacancy surface hydroxyl titanium adatom

SCI ; EI

英语

第一 ; 通讯

National Key Research and Development Program of China[2022YFA1503102] ; National Natural Science Foundation of China["22022504","22003022","22203041"] ; Guangdong Basic and Applied Basic Research Foundation, China[2021A1515110406] ; Guangdong "Pearl River" Talent Plan[2019QN01L353] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry ; Science & Technology - Other Topics ; Materials Science ; Physics

Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary ; Physics, Applied

WOS:001227230300001

TSINGHUA UNIV PRESS

20242116110285

Catalysts ; Density functional theory ; Electrons ; Gold nanoparticles ; Metal nanoparticles ; Molecular dynamics ; Oxide minerals ; Oxygen ; Oxygen vacancies ; TiO2 nanoparticles ; Titanium dioxide ; Wetting

Minerals:482.2 ; Nanotechnology:761 ; Physical Chemistry:801.4 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2 ; Probability Theory:922.1 ; Mechanics:931.1 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4 ; Crystalline Solids:933.1

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China
3.Great Bay Univ, Sch Phys Sci, Dongguan 523000, Peoples R China
4.Tsinghua Univ, Dept Chem, Beijing 100084, Peoples R China

Xia, Guang-Jie,Fu, Yu,Cao, Wei,et al. How interfacial electron-donating defects influence the structure and charge of gold nanoparticles on TiO₂ support[J]. NANO RESEARCH,2024,17:5965-5974.

Xia, Guang-Jie,Fu, Yu,Cao, Wei,Li, Jun,&Wang, Yang-Gang.(2024).How interfacial electron-donating defects influence the structure and charge of gold nanoparticles on TiO₂ support.NANO RESEARCH,17,5965-5974.

Xia, Guang-Jie,et al."How interfacial electron-donating defects influence the structure and charge of gold nanoparticles on TiO₂ support".NANO RESEARCH 17(2024):5965-5974.