Citation: Longjian Li, Ping Zhang, Yongchong Yu, Reyila Tuerhong, Xiaoping Su, Lijuan Han, Enzhou Liu, Jizhou Jiang. Electron trap-induced charge accumulation and surface reaction kinetics synergistically enhance overall nitrogen photofixation[J]. Chinese Chemical Letters, ;2025, 36(8): 111118. doi: 10.1016/j.cclet.2025.111118 shu

Electron trap-induced charge accumulation and surface reaction kinetics synergistically enhance overall nitrogen photofixation

Longjian Li ^a ,
Ping Zhang ^{a, *,} ,
Yongchong Yu ^a ,
Reyila Tuerhong ^a ,
Xiaoping Su ^a ,
Lijuan Han ^b ,
Enzhou Liu ^c ,
Jizhou Jiang ^{d, *,}

a.
Key Laboratory of Environment-Friendly Composite Materials of the State Ethnic Affairs Commission, Gansu Province Engineering Research Center for Biomass Functional Composite Materials, Key Laboratory for the Utilization of Environment Friendly Composite Materials and Biomass in Universities of Gansu Province, Gansu Province Research Center for Basic Sciences of Surface and Interface Chemistry, College of Chemical Engineering, Northwest Minzu University, Lanzhou 730030, China
b.
Gansu Natural Energy Research Institute, Gansu Academy of Science, Lanzhou 730046, China
c.
School of Chemical Engineering, Xi'an Key Laboratory of Special Energy Materials, Northwest University, Xi'an 710069, China
d.
School of Materials Science and Engineering, Key Laboratory of Green Chemical Engineering Process of Ministry of Education, Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education, Wuhan Institute of Technology, Wuhan 430205, China

zhangping@xbmu.edu.cn

027wit@163.com

Received Date: 13 December 2024
Revised Date: 17 March 2025
Accepted Date: 19 March 2025
Available Online: 20 March 2025

Figures(8)

Available online Further oxidation of NH₃ produced via photocatalytic N₂ fixation represents a promising strategy to enhance the economic value of N₂ fixation. This work employs first-principles density functional theory (DFT) calculations to demonstrate that incorporating Co into NiO improves both N₂ adsorption and activation as well as M-N electron exchange intensity. Guided by these predictions, a novel Co single-atom photocatalyst supported by nanoconfined NiO@C nanosheets was synthesized using a direct metal atomization method, achieving high HNO₃ production (60.54%). NH₄⁺ and NO₃⁻ production rates during N₂ photofixation reached 67.97 µmol g_cat⁻¹ h⁻¹ and 104.28 µmol g_cat⁻¹ h⁻¹, respectively. The overall N₂ → NH₃ → HNO₃ photofixation pathway was validated through in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ¹⁵N isotopic labeling. Mechanistic studies reveal that Co single-atom introduction serves as an electron trap, enhancing photogenerated electron accumulation with a five-fold increase in carrier density compared to NiO@C, as observed via in-situ X-ray photoelectron spectroscopy (XPS). This synergistic effect between electron traps and N₂ adsorption/activation sites at Co single-atom centers supports rapid N₂ reduction kinetics. Additionally, nanoconfined ink-bottle pores in the carbon layer impede NH₃ desorption, further boosting NO₃⁻ production. This work offers a comprehensive approach to optimizing N₂ photofixation through electron regulation and surface reaction kinetics.
- N₂ photofixation,
- Co single-atom,
- Nanoconfined NiO@C,
- Electron trap,
- NO₃⁻ production
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