| Photoelectrocatalytic reduction of CO2 catalyzed by TiO2/TiN nanotube heterojunction: Nitrogen assisted active hydrogen mechanism | |
Wei, Yan1; Duan, Ruizhi2,3; Zhang, QL(张巧兰)1,2 ; Cao, Youzhi1; Wang, Jinyuan1; Wang, Bing1; Wan, Wenrui1; Liu, Chunyan1; Chen, Jiazang4; Gao, H(高红)1,2; Jing, HW(景欢旺)1,2,3 | |
| 2023-04-01 | |
| Source Publication | Chinese Journal of Catalysis
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| Volume | 47Pages:243-253 |
| Abstract | To address the over-emission of CO2, the construction of new heterojunction materials is a promising approach for the photoelectrocatalytic (PEC) conversion of CO2 into valuable chemicals. Herein, a series of heterojunctions of TiO2/TiN nanotube arrays were designed and fabricated by anodic oxidation of titanium plates, followed by in situ partial oxidation to form heterojunctions. The surface of the heterojunction with nitrogen instead of oxygen contained more active Ti3+ species, and the oxygen vacancies were able to harvest solar light and showed excellent performance in the PEC reduction of CO2. As a porous material, the TiO2/TiN nanotube supports good adsorption of CO2 as well as a confined space favoring C–C coupling. Operando Fourier transform infrared (FTIR) analysis revealed that the active species *COOH? and *CHO were the major intermediates. Density functional theory (DFT) calculations revealed that the highly active hydrogen atoms could attach to the surface of the heterojunction to form Ti–H species with Ti3+, and the existence of nitrogen atoms could promote the migration of lattice oxygen to form new oxygen vacancies, which is conducive to the adsorption and coupling of CO2 and intermediates. The vibration frequency of Ti–H predicted by DFT calculations matches well with the operando FTIR observations. The PEC cell of Pd/R-TiO2/TiN-30|SCE|BiVO4 efficiently produced carbon-based chemicals at a rate of 115.9 μmol L−1 h−1 cm−2 with high selectivity for C2 products. The total efficiency of the PEC cell approached 6.0%, exceeding that of the plant cell by 0.4%. Isotopic labeling experiments of 13CO2 and H218O verified the elemental source and inferred the reaction pathway via highly active hydrogen. © 2023 Dalian Institute of Chemical Physics, the Chinese Academy of Sciences |
| Keyword | Anodic oxidation Atoms Carbon nitride Density functional theory Fourier transform infrared spectroscopy Heterojunctions Hydrogen Nanotubes Nitrogen Porous materials Solar light Titanium dioxide Titanium nitride % reductions Active hydrogens CO 2 reduction Density-functional theory calculations Fourier transform infrared Operando Operando fourier transform infrared Photo-electrocatalysis Photoelectrocatalysis Photoelectrocatalytic |
| Publisher | Science Press |
| DOI | 10.1016/S1872-2067(23)64395-5 |
| Indexed By | EI |
| Language | 英语 |
| EI Accession Number | 20231513871862 |
| EI Keywords | Carbon dioxide |
| EI Classification Number | 539.2.1 Protection Methods ; 657.1 Solar Energy and Phenomena ; 714.2 Semiconductor Devices and Integrated Circuits ; 761 Nanotechnology ; 801 Chemistry ; 804 Chemical Products Generally ; 804.2 Inorganic Compounds ; 922.1 Probability Theory ; 931.3 Atomic and Molecular Physics ; 931.4 Quantum Theory ; Quantum Mechanics ; 933.1 Crystalline Solids ; 951 Materials Science |
| Original Document Type | Journal article (JA) |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | https://ir.lzu.edu.cn/handle/262010/500491 |
| Collection | 化学化工学院 |
| Corresponding Author | Gao, Hong |
| Affiliation | 1.State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Gansu, Lanzhou; 730000, China; 2.Key Laboratory of Advanced Catalysis, Gansu Province, State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Gansu, Lanzhou; 730000, China; 3.State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian National Laboratory for Clean Energy, Liaoning, Dalian; 116023, China; 4.State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Shanxi, Taiyuan; 030001, China |
| First Author Affilication | College of Chemistry and Chemical Engineering |
| Corresponding Author Affilication | College of Chemistry and Chemical Engineering |
| Recommended Citation GB/T 7714 | Wei, Yan,Duan, Ruizhi,Zhang, Qiaolan,et al. Photoelectrocatalytic reduction of CO2 catalyzed by TiO2/TiN nanotube heterojunction: Nitrogen assisted active hydrogen mechanism[J]. Chinese Journal of Catalysis,2023,47:243-253. |
| APA | Wei, Yan.,Duan, Ruizhi.,Zhang, Qiaolan.,Cao, Youzhi.,Wang, Jinyuan.,...&Jing, Huanwang.(2023).Photoelectrocatalytic reduction of CO2 catalyzed by TiO2/TiN nanotube heterojunction: Nitrogen assisted active hydrogen mechanism.Chinese Journal of Catalysis,47,243-253. |
| MLA | Wei, Yan,et al."Photoelectrocatalytic reduction of CO2 catalyzed by TiO2/TiN nanotube heterojunction: Nitrogen assisted active hydrogen mechanism".Chinese Journal of Catalysis 47(2023):243-253. |
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