Citation: Jin Li, Xin Chen, Aling Chen, Zhi-Qiang Wang, Dengsong Zhang. Theoretical insight into the active sites for chlorobenzene oxidation: From phosphate to M₃ clusters[J]. Chinese Chemical Letters, ;2025, 36(8): 110527. doi: 10.1016/j.cclet.2024.110527 shu

Theoretical insight into the active sites for chlorobenzene oxidation: From phosphate to M₃ clusters

Jin Li ^a ,
Xin Chen ^a ,
Aling Chen ^{a, *,} ,
Zhi-Qiang Wang ^{b, *,} ,
Dengsong Zhang ^{a, *,}

a.
International Joint Laboratory of Catalytic Chemistry, State Key Laboratory of Advanced Special Steel, Innovation Institute of Carbon Neutrality, Department of Chemistry, College of Sciences, Shanghai University, Shanghai 200444, China
b.
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

chenalingshuo@shu.edu.cn

zhiqiangwang@ecust.edu.cn

dszhang@shu.edu.cn

Received Date: 3 April 2024
Revised Date: 21 August 2024
Accepted Date: 3 October 2024
Available Online: 5 October 2024

Figures(6)

Chlorobenzene is a model molecule for researching harmful chlorinated volatile organic compounds. Designing the chemical adsorption site for complex molecules such as chlorobenzene is challenging without a large dataset and reasonable descriptors. Here, the adsorption of chlorobenzene on a phosphorylated CeO₂ catalyst was analyzed using density functional theory calculations. Three different surface phosphate (H_xPO₄) models were constructed and used to adsorb chlorobenzene. An orbital interaction with fully occupied antibonding is found in one of three physical adsorptions. Based on this, the surface sites of a tri-cluster (M₃) located at the CeO₂ surface have been suggested to activate chlorobenzene. Three different clusters have been tested, namely Fe₃, Ru₃, and B₃. All these clusters can activate and twist chlorobenzene by donating electrons. Fe₃ and Ru₃ form bonds with weak covalent and strong ionic characters, while B₃ forms strong covalent bonds between boron and carbon. This work not only predicts a class of sites for chlorobenzene activation that may prevent polychlorinated by-products but also gives a template for catalyst rational design according to fundamental catalytic theory.
- Catalysts rational design,
- Chlorobenzene,
- Activation,
- Tri-cluster,
- Density functional theory
1. [1]
  V.V. Welborn, L. Ruiz Pestana, T. Head-Gordon, Nat. Catal. 1 (2018) 649–655. doi: 10.1038/s41929-018-0109-2
2. [2]
  Y. Zhao, J. Meijer, D.I. Walker, et al. Environ. Sci. Technol. 58 (2024) 258–268. doi: 10.1021/acs.est.3c07588
3. [3]
  Y. Gu, S. Shao, W. Sun, et al., J. Catal. 380 (2019) 375–386.
4. [4]
  B. Sun, Q. Li, G. Su, et al., Environ. Sci. Technol. 56 (2022) 16292–16302. doi: 10.1021/acs.est.2c05981
5. [5]
  A. Trovarelli, J. Llorca, ACS Catal. 7 (2017) 4716–4735. doi: 10.1021/acscatal.7b01246
6. [6]
  X. Dai, X. Wang, Y. Long, et al., Environ. Sci. Technol. 53 (2019) 12697–12705. doi: 10.1021/acs.est.9b05088
7. [7]
  X. Zhu, X. Yuan, Z. Song, Y. Peng, J. Li, Appl. Catal. B 342 (2024) 123364.
8. [8]
  L. Chen, Y. Shen, Q. Wang, et al., J. Hazard. Mater. 427 (2022) 128148.
9. [9]
  Y. Su, K. Cao, Y. Lu, et al., Environ. Sci. Technol. 58 (2024) 1369–1377. doi: 10.1021/acs.est.3c06878
10. [10]
  G. Li, K. Shen, L. Wang, et al., Appl. Catal. B 286 (2021) 119865.
11. [11]
  E. Hückel, Z. Phys. 70 (1931) 204–286.
12. [12]
  E. Hückel, Z. Phys. 72 (1931) 310–337.
13. [13]
  E. Hückel, Z. Phys. 76 (1932) 628–648.
14. [14]
  T.M. Buscagan, D.C. Rees, Joule, 3 (2019) 2662–2678.
15. [15]
  Z.Q. Huang, L.P. Liu, S. Qi, et al., ACS Catal. 8 (2018) 546–554. doi: 10.1021/acscatal.7b02732
16. [16]
  Z. Song, Y. Peng, X. Zhao, et al., ACS Catal. 12 (2022) 11505–11517. doi: 10.1021/acscatal.2c03782
17. [17]
  Y. Wang, Z. Liu, Y. Wei, et al., J. Mater. Chem. A 12 (2024) 2949–2958. doi: 10.1039/d3ta06969a
18. [18]
  P. Shu, X. Qi, Q. Peng, et al., Mol. Catal. 539 (2023) 113036.
19. [19]
  M. Chen, J. Xu, D. Zhao, et al., Angew. Chem. Int. Ed. 61 (2022) e202205672.
20. [20]
  P.V. Gaikwad, J. Bang, J. Phys. Chem. C 127 (2023) 2581–2588. doi: 10.1021/acs.jpcc.2c07178
21. [21]
  Y. Wu, Z. Liu, T. Lu, et al., Inorg. Chem. 62 (2023) 19986–19996. doi: 10.1021/acs.inorgchem.3c02675
22. [22]
  P. Zhang, P. Wang, A. Chen, et al., Environ. Sci. Technol. 55 (2021) 11970–11978. doi: 10.1021/acs.est.1c02882
23. [23]
  B. Silvi, A. Savin, Nature 371 (1994) 683–686.
24. [24]
  J. Lichtenberger, M.D. Amiridis, J. Catal. 223 (2004) 296–308.
25. [25]
  D.M. Newns, Phys. Rev. 178 (1969) 1123–1135.
1. [1]
  Yuxiang Zhang , Jia Zhao , Sen Lin . Nitrogen doping retrofits the coordination environment of copper single-atom catalysts for deep CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(11): 100415-100415. doi: 10.1016/j.cjsc.2024.100415
2. [2]
  Wei Chen , Pieter Cnudde . A minireview to ketene chemistry in zeolite catalysis. Chinese Journal of Structural Chemistry, 2024, 43(11): 100412-100412. doi: 10.1016/j.cjsc.2024.100412
3. [3]
  Xu Huang , Kai-Yin Wu , Chao Su , Lei Yang , Bei-Bei Xiao . Metal-organic framework Cu-BTC for overall water splitting: A density functional theory study. Chinese Chemical Letters, 2025, 36(4): 109720-. doi: 10.1016/j.cclet.2024.109720
4. [4]
  Zixuan Guo , Xiaoshuai Han , Chunmei Zhang , Shuijian He , Kunming Liu , Jiapeng Hu , Weisen Yang , Shaoju Jian , Shaohua Jiang , Gaigai Duan . Activation of biomass-derived porous carbon for supercapacitors: A review. Chinese Chemical Letters, 2024, 35(7): 109007-. doi: 10.1016/j.cclet.2023.109007
5. [5]
  Lingling Su , Qunyan Wu , Congzhi Wang , Jianhui Lan , Weiqun Shi . Theoretical design of polyazole based ligands for the separation of Am(Ⅲ)/Eu(Ⅲ). Chinese Chemical Letters, 2024, 35(8): 109402-. doi: 10.1016/j.cclet.2023.109402
6. [6]
  Yahui Li , Quanchen Feng , Krisztina László , Ying Wang . High-throughput screening of high C/N-ratio homonuclear dual-atom catalysts for electrochemical reduction of nitrate to ammonia. Chinese Chemical Letters, 2026, 37(3): 111536-. doi: 10.1016/j.cclet.2025.111536
7. [7]
  Jiajun Wang , Guolin Yi , Shengling Guo , Jianing Wang , Shujuan Li , Ke Xu , Weiyi Wang , Shulai Lei . Computational design of bimetallic TM₂@g-C₉N₄ electrocatalysts for enhanced CO reduction toward C₂ products. Chinese Chemical Letters, 2024, 35(7): 109050-. doi: 10.1016/j.cclet.2023.109050
8. [8]
  Hao Chen , Haiyuan Liao , Qi Zhou , Yang Liu , Guojun Liu , Yuan Yao . Electronegativity-oriented coordination regulation of main-group metal single-atom catalysts for oxygen reduction to H₂O₂: A combined study of first-principles and machine learning. Chinese Chemical Letters, 2026, 37(3): 110711-. doi: 10.1016/j.cclet.2024.110711
9. [9]
  Mimi Wu , Shoufeng Tang , Zhibin Wang , Qingrui Zhang , Deling Yuan . Molybdenum carbide activated calcium sulfite for antibiotic decontamination at near-neutral pH: Dissolved oxygen promoted bisulfite adsorption for singlet oxygen generation. Chinese Chemical Letters, 2025, 36(8): 110613-. doi: 10.1016/j.cclet.2024.110613
10. [10]
  Qiqi Lv , Zhiwei Tian , Weijun Li , Gaigai Duan , Xiaoshuai Han , Chunmei Zhang , Shuijian He , Haimei Mao , Chunxin Ma , Shaohua Jiang . Porous carbon derived from biomass-based polymers: Innovative applications in supercapacitors. Chinese Chemical Letters, 2026, 37(5): 110860-. doi: 10.1016/j.cclet.2025.110860
11. [11]
  Yu-Hang Li , Shuai Gao , Lu Zhang , Hanchun Chen , Chong-Chen Wang , Haodong Ji . Insights on selective Pb adsorption via O 2p orbit in UiO-66 containing rich-zirconium vacancies. Chinese Chemical Letters, 2024, 35(8): 109894-. doi: 10.1016/j.cclet.2024.109894
12. [12]
  Xin-Tong Zhao , Jin-Zhi Guo , Wen-Liang Li , Jing-Ping Zhang , Xing-Long Wu . Two-dimensional conjugated coordination polymer monolayer as anode material for lithium-ion batteries: A DFT study. Chinese Chemical Letters, 2024, 35(6): 108715-. doi: 10.1016/j.cclet.2023.108715
13. [13]
  Fanjun Kong , Yixin Ge , Shi Tao , Zhengqiu Yuan , Chen Lu , Zhida Han , Lianghao Yu , Bin Qian . Engineering and understanding SnS_0.5Se_0.5@N/S/Se triple-doped carbon nanofibers for enhanced sodium-ion batteries. Chinese Chemical Letters, 2024, 35(4): 108552-. doi: 10.1016/j.cclet.2023.108552
14. [14]
  Weiping Xiao , Yuhang Chen , Qin Zhao , Danil Bukhvalov , Caiqin Wang , Xiaofei Yang . Constructing the synergistic active sites of nickel bicarbonate supported Pt hierarchical nanostructure for efficient hydrogen evolution reaction. Chinese Chemical Letters, 2024, 35(12): 110176-. doi: 10.1016/j.cclet.2024.110176
15. [15]
  Ze Zhang , Lei Yang , Jin-Ru Liu , Hao Hu , Jian-Li Mi , Chao Su , Bei-Bei Xiao , Zhi-Min Ao . Improved oxygen electrocatalysis at FeN₄ and CoN₄ sites via construction of axial coordination. Chinese Chemical Letters, 2025, 36(2): 110013-. doi: 10.1016/j.cclet.2024.110013
16. [16]
  Chaozheng He , Menghui Xi , Chenxu Zhao , Ran Wang , Ling Fu , Jinrong Huo . Highly N₂ dissociation catalyst: Ir(100) and Ir(110) surfaces. Chinese Chemical Letters, 2025, 36(3): 109671-. doi: 10.1016/j.cclet.2024.109671
17. [17]
  Mianfeng Li , Haozhi Wang , Zijun Yang , Zexiang Yin , Yuan Liu , Yingmei Bian , Yang Wang , Xuerong Zheng , Yida Deng . Synergistic enhancement of alkaline hydrogen evolution reaction by role of Ni-Fe LDH introducing frustrated Lewis pairs via vacancy-engineered. Chinese Chemical Letters, 2025, 36(3): 110199-. doi: 10.1016/j.cclet.2024.110199
18. [18]
  Teng Wang , Jiachun Cao , Juan Li , Didi Li , Zhimin Ao . A novel photocatalytic mechanism of volatile organic compounds degradation on BaTiO₃ under visible light: Photo-electrons transfer from photocatalyst to pollutant. Chinese Chemical Letters, 2025, 36(3): 110078-. doi: 10.1016/j.cclet.2024.110078
19. [19]
  Yubang Liu , Jiaxin Lin , Huayu Liang , Yinwu Li , Zhuofeng Ke . Computational insights into three-centre four-electron bridging hydride bond in boryl type PBP-M dihydride complexes^{✰ ✩}. Chinese Chemical Letters, 2025, 36(5): 110291-. doi: 10.1016/j.cclet.2024.110291
20. [20]
  Yanhui Lu , Chengang Pei , Wenqiang Li , Qing Liu , Huan Pang , Xu Yu . Tailoring active sites of cerium and nitrogen Co-doped rhenium disulfide for enhanced hydrogen evolution reaction. Chinese Chemical Letters, 2025, 36(12): 111646-. doi: 10.1016/j.cclet.2025.111646

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(979)
HTML views(81)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Theoretical insight into the active sites for chlorobenzene oxidation: From phosphate to M3 clusters

Metrics

通讯作者: 陈斌, bchen63@163.com

Theoretical insight into the active sites for chlorobenzene oxidation: From phosphate to M₃ clusters