Surface Brønsted-Lewis dual acid sites for high-efficiency dinitrogen photofixation in pure water

Chen，Cai1; Chen，Jiewei3; Wang，Zhiyuan2; Huang，Fei4; Yang，Jian2; Qu，Yunteng2; Liang，Kuang2; Ge，Xiao2; Wang，Yanggang3; Zhang，Hui1; Wu，Yuen2

2022-04-01

Brønsted-Lewis dual acid sites F and H atoms Photocatalytic nitrogen fixation Surface states Surface-modified TiO2

英语

Reduction of overstable dinitrogen (N) is hampered by kinetically complex and challenging multi-electron reactions. One grand challenge is to develop efficient and economical catalysts for photocatalytic nitrogen fixation (PNF) under ambient conditions. Herein, we report that the intrinsic Brønsted-Lewis dual acid sites (F-H-TiO) on the surface of F-modified TiO nanosheets can significantly lower the energy barrier generated by *NH (the rate-determining step) to efficiently produce NH. The surface Lewis acid (the ≡Ti–F groups) allows strong chemisorption and activation of molecule N, and the surface Brønsted acid (the vicinal hanging OH groups) can further improve N adsorption energy and provide in-situ protons to accelerate the photocatalytic proton-coupled electron transfer (pPCET) process. The synergy of Brønsted-Lewis dual acid sites provides significantly enhanced PNF performance, exhibiting NH production rate up to 308.6 μmol gh with the corresponding apparent quantum efficiency (AQE) of 0.35% at 400 nm. Therefore, it provides a promising and facile strategy to achieve high-efficiency PNF on excellent semiconductor substrates by modifying the TiO surface with light elements.

10.1016/j.jechem.2021.10.039

Journal of Energy Chemistry

67

824-830

2095-4956

EI

其他

2-s2.0-85121150445

Scopus

20215111332146

Ammonia ; Bromine compounds ; Magnetic semiconductors ; Nitrogen fixation ; Titanium dioxide

Magnetic Materials:708.4 ; Semiconducting Materials:712.1 ; Chemical Reactions:802.2 ; Inorganic Compounds:804.2

1.College of Chemistry and Chemical Engineering,Southwest Petroleum University,Chengdu,610500,China
2.School of Chemistry and Materials Science,iChEM (Collaborative Innovation Center of Chemistry for Energy Materials),Hefei National Laboratory for Physical Sciences at the Microscale,University of Science and Technology of China,Hefei,230026,China
3.Department of Chemistry,Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,518000,China
4.Shenyang National Laboratory for Materials Science,Institute of Metal Research,Chinese Academy of Sciences,Shenyang,110016,China

Chen，Cai,Chen，Jiewei,Wang，Zhiyuan,et al. Surface Brønsted-Lewis dual acid sites for high-efficiency dinitrogen photofixation in pure water. 2022-04-01.