Citation: Shao-Hua LIU, Yi LI, Kai-Ning DING, Wen-Kai CHEN, Yong-Fan ZHANG, Wei LIN. Mechanism on Carbon Vacancies in Polymeric Carbon Nitride for CO₂ Photoreduction[J]. Chinese Journal of Structural Chemistry, ;2020, 39(12): 2068-2076. doi: 10.14102/j.cnki.0254–5861.2011–3005 shu

Mechanism on Carbon Vacancies in Polymeric Carbon Nitride for CO₂ Photoreduction

Shao-Hua LIU ^a ,
Yi LI ^{a, b} ,
Kai-Ning DING ^a ,
Wen-Kai CHEN ^{a, b} ,
Yong-Fan ZHANG ^{a, b} ,
Wei LIN ^{a, b,,}

a.
State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou 350108, China
b.
Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, Xiamen 361005, China

Corresponding author: Wei LIN, wlin@fzu.edu.cn
Received Date: 22 October 2020
Accepted Date: 17 November 2020

Fund Project: the National Natural Science Foundation of China 21973014the National Natural Science Foundation of China 21773030

Figures(7)

Defect engineering has being regarded as one of the effective ways to regulate chemical and electronic structure of semiconductors. Recently, our collaborative work has shown experimentally that carbon vacancy on polymeric carbon nitride (CV) can greatly improve the CO₂ to CO conversion with a 45-fold improvement over the polymeric carbon nitride (Angew. Chem. Int. Ed., 2019, 58, 1134). In order to clarify the detailed mechanism of promotion, we have systematically studied the electronic properties of CV and hydrogenated CV (CV_+H) as well as the effective CO₂ reduction reaction through density functional theory calculations. We found that it is the synergistic effect for the CO₂ reduction reaction in the CV systems, as the onset potentials of several CVs are much lower than that of the polymeric carbon nitride. In particular, the onset potentials of CV₁, CV₂, and CV_2+H are around 0.9~1.5 eV with a strong chemisorbed CO₂ on them. Combined with the analysis of the electronic properties, our results confirm that defect engineering increases the lifetime of photo-generated charges, improves photocatalytic activity, and promotes the CO₂ reduction reaction on the defected polymeric carbon nitrides.
- polymeric carbon nitride (PCN),
- carbon vacancy,
- reaction mechanism,
- CO₂ reduction,
- density functional theory (DFT)
1. [1]
  Jiao, X. C.; Zheng, K.; Liang, L.; Li, X. D.; Sun, Y. F.; Xie, Y. Fundamentals and challenges of ultrathin 2d photocatalysts in boosting CO₂ photoreduction. Chem. Soc. Rev. 2020, 49, 6592−6604. doi: 10.1039/D0CS00332H
2. [2]
  Li, X.; Yu, J. G.; Jaroniec, M.; Chen, X. B. Cocatalysts for selective photoreduction of CO₂ into solar fuels. Chem. Rev. 2019, 119, 3962−4179. doi: 10.1021/acs.chemrev.8b00400
3. [3]
  Jing, L. Q.; Zhou, W.; Tian, G. H.; Fu, H. G. Surface tuning for oxide-based nanomaterials as efficient photocatalysts. Chem. Soc. Rev. 2013, 42, 9509−49. doi: 10.1039/c3cs60176e
4. [4]
  Usubharatana, P.; McMartin, D.; Veawab, A.; Tontiwachwuthikul, P. Photocatalytic process for CO₂ emission reduction from industrial flue gas streams. Ind. Eng. Chem. Res. 2006, 45, 2558−2568. doi: 10.1021/ie0505763
5. [5]
  Nakamura, H. Recent organic pollution and its biosensing methods. Anal. Methods 2010, 2, 430−444. doi: 10.1039/b9ay00315k
6. [6]
  Kemp, K. C.; Seema, H.; Saleh, M.; Le, N. H.; Mahesh, K.; Chandra, V.; Kim, K. S. Environmental applications using graphene composites: water remediation and gas adsorption. Nanoscale 2013, 5, 3149−71. doi: 10.1039/c3nr33708a
7. [7]
  Mao, J.; Li, K.; Peng, T. Y. Recent advances in the photocatalytic CO₂ reduction over semiconductors. Catal. Sci. Technol. 2013, 3, 2481−2498. doi: 10.1039/c3cy00345k
8. [8]
  Yamashitaa, H.; Fujii, Y.; Ichihashi, Y.; Zhang, S. G.; Ikeue, K.; Park, D. R.; Koyano, K.; Tatsumi, T.; Anpo, M. Selective formation of CH₃OH in the photocatalytic reduction of CO₂ with H₂O on titanium oxides highly dispersed within zeolites and mesoporous molecular sieves. Catal. Today 1998, 10, 221−227.
9. [9]
  White, J. L.; Baruch, M. F.; Pander III, J. E.; Hu, Y.; Fortmeyer, I. C.; Park, J. E.; Zhang, T.; Liao, K.; Gu, J.; Yan, Y.; Shaw, T. W.; Abelev, E.; Bocarsly, A. B. Light-driven heterogeneous reduction of carbon dioxide: photocatalysts and photoelectrodes. Chem. Rev. 2015, 115, 12888−12935. doi: 10.1021/acs.chemrev.5b00370
10. [10]
  Lei, F. C.; Sun, Y. F.; Liu, K. T.; Gao, S.; Liang, L.; Pan, B. C.; Xie, Y. Oxygen vacancies confined in ultrathin indium oxide porous sheets for promoted visible-light water splitting. J. Am. Chem. Soc. 2014, 136, 6826−9. doi: 10.1021/ja501866r
11. [11]
  Tan, H.; Zhao, Z.; Zhu, W. B.; Coker, E. N.; Li, B.; Zheng, M.; Yu, W.; Fan, H.; Sun, Z. Oxygen vacancy enhanced photocatalytic activity of pervoskite SrtiO₃. ACS Appl. Mater. Inter. 2014, 6, 19184−19190. doi: 10.1021/am5051907
12. [12]
  Huang, B.; Gillen, R.; Robertson, J. Study of CeO₂ and its native defects by density functional theory with repulsive potential. J. Phys. Chem. C 2014, 118, 24248−24256. doi: 10.1021/jp506625h
13. [13]
  Ling, Y. C.; Wang, G. M.; Reddy, J.; Wang, C. C.; Zhang, J. Z.; Li, Y. The influence of oxygen content on the thermal activation of hematite nanowires. Angew. Chem. Int. Ed. 2012, 124, 4150−4155. doi: 10.1002/ange.201107467
14. [14]
  Ye, S.; Wang, R.; Wu, M. Z.; Yuan, Y. P. A review on g-C₃N₄ for photocatalytic water splitting and CO₂ reduction. Appl. Surf. Sci. 2015, 358, 15−27. doi: 10.1016/j.apsusc.2015.08.173
15. [15]
  Lakhi, K. S.; Park, D. H.; Al-Bahily, K.; Cha, W.; Viswanathan, B.; Choy, J. H.; Vinu, A. Mesoporous carbon nitrides: synthesis, functionalization, and applications. Chem. Soc. Rev. 2017, 46, 72−101. doi: 10.1039/C6CS00532B
16. [16]
  Wang, Y. L.; Tian, Y.; Yan, L.; Su, Z. M. DFT study on sulfur-doped g-C₃N₄ nanosheets as a photocatalyst for CO₂ reduction reaction. J. Phys. Chem. C 2018, 122, 7712−7719. doi: 10.1021/acs.jpcc.8b00098
17. [17]
  Ling, C. Y.; Niu, X. H.; Li, Q.; Du, A. J.; Wang, J. L. Metal-free single atom catalyst for N₂ fixation driven by visible light. J. Am. Chem. Soc. 2018, 140, 14161−14168. doi: 10.1021/jacs.8b07472
18. [18]
  Li, Y. H.; Ho, W. K.; Lv, K. L.; Zhu, B. C.; Lee, S. C. Carbon vacancy-induced enhancement of the visible light-driven photocatalytic oxidation of NO over g-C₃N₄ nanosheets. Appl. Surf. Sci. 2018, 430, 380−389. doi: 10.1016/j.apsusc.2017.06.054
19. [19]
  Liao, G. F.; Gong, Y.; Zhang, L.; Gao, H. Y.; Yang, G. J. Y.; Fang, B. Z. Semiconductor polymeric graphitic carbon nitride photocatalysts: the "Holy Grail" for the photocatalytic hydrogen evolution reaction under visible light. Energy Environ. Sci. 2019, 12, 2080−2147. doi: 10.1039/C9EE00717B
20. [20]
  Gu, Z. Y.; Cui, Z. T.; Wang, Z. J.; Qin, K. S.; Asakura, Y.; Hasegawa, T.; Tsukuda, S.; Hongo, K.; Maezono, R.; Yin, S. Carbon vacancies and hydroxyls in graphitic carbon nitride: promoted photocatalytic NO removal activity and mechanism. Appl. Catal. B-Environ. 2020, 9, 119376−11.
21. [21]
  Wen, J. Q.; Xie, J.; Chen, X. B.; Li, X. A review on g-C₃N₄-based photocatalysts. Appl. Surf. Sci. 2017, 391, 72−123. doi: 10.1016/j.apsusc.2016.07.030
22. [22]
  Wang, Y. L.; Zhang, Y.; Li. B. Z.; Luo, K.; Shi, K. Y.; Zhang, L.; Li, Y.; Yu T. J.; Hu, W. T.; Xie C. L.; Wu, Y. J.; Su, L.; Dong, X.; Zhao, Z. S.; Yang, G. Q.; Restacked Melon as highly-efficient photocatalyst. Nano Energy 2020, 77, 105124−10. doi: 10.1016/j.nanoen.2020.105124
23. [23]
  Yang, P. J.; Zhuzhang, H. Y; Wang, R. R.; Lin, W.; Wang, X. C. Carbon vacancies in a melon polymeric matrix promote photocatalytic carbon dioxide conversion. Angew. Chem. Int. Ed. 2019, 58, 1134−1137. doi: 10.1002/anie.201810648
24. [24]
  Shen, M.; Zhang, L. X.; Wang, M.; Tian, J. J.; Jin, X. X.; Guo, L. M.; Wang, L. Z.; Shi, J. L. Carbon-vacancy modified graphitic carbon nitride: enhanced CO₂ photocatalytic reduction performance and mechanism probing. J. Mater. Chem. A 2019, 7, 1556−1563. doi: 10.1039/C8TA09302D
25. [25]
  Kresse. G.; Furthmuller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 1995, 54, 11169−11186.
26. [26]
  Kresse, G.; Furthmuller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comp. Mater. Sci. 1996, 6, 16−50.
27. [27]
  Blochl, P. E. A projector augmented-wave method. Phys. Rev. B 1994, 50, 17953−17979. doi: 10.1103/PhysRevB.50.17953
28. [28]
  Kresse, G. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 1998, 59, 1759−1775.
29. [29]
  Perdew, J.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865−3868. doi: 10.1103/PhysRevLett.77.3865
30. [30]
  Grimme, S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. J. Comput. Chem. 2006, 27, 1787−1799. doi: 10.1002/jcc.20495
31. [31]
  Kong, T. T.; Jiang, Y. W.; Xiong, Y. J. Photocatalytic CO₂ conversion: what can we learn from conventional CO_x hydrogenation? Chem. Soc. Rev. 2020, 49, 6579−6591. doi: 10.1039/C9CS00920E
32. [32]
  Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.; Lindqvist, L. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J. Phys. Chem. B 2004, 108, 17886−17892. doi: 10.1021/jp047349j
33. [33]
  Zhang, F. L.; Yi, J.; Peng, W.; Radjenovic, P. M.; Zhang, H.; Tian, Z. Q.; Li, J. F. Elucidating molecule-plasmon interactions in nanocavities with 2 nm spatial resolution and at the single-molecule level. Angew. Chem. Int. Ed. 2019, 58, 12133−12137. doi: 10.1002/anie.201906517
34. [34]
  Shi, H. N.; Long, S.; Hou, J. G.; Ye, L.; Sun, Y. W.; Ni, W. J.; Song, C. S.; Li, K. Y.; Gurzadyan, G. G.; Guo, X. W. Defects promote ultrafast charge separation in graphitic carbon nitride for enhanced visible-light-driven CO₂ reduction activity. Chem. Eur. J. 2019, 25, 5028−5035. doi: 10.1002/chem.201805923
35. [35]
  Xue, J. W.; Fujitsuka, M.; Majima, T. Shallow trap state-induced efficient electron transfer at the interface of heterojunction photocatalysts: the crucial role of vacancy defects. ACS Appl. Mater. Inter. 2019, 11, 40860−7. doi: 10.1021/acsami.9b14128
36. [36]
  Yang, P. J.; Wang, L.; ZhuZhang, H. Y.; Wang, R.; Titirici, M. M.; Wang, X. X. Photocarving nitrogen vacancies in a polymeric carbon nitride for metal-free oxygen synthesis. Appl. Catal. B-Environ. 2019, 256, 117794−8. doi: 10.1016/j.apcatb.2019.117794
37. [37]
  Lu, S.; Li, C.; Li, H. H.; Zhao, Y. F.; Gong, Y. Y.; Niu, L. Y.; Liu, X. J.; Wang, T. The effects of nonmetal dopants on the electronic, optical and chemical performances of monolayer g-C₃N₄ by first-principles study. Appl. Surf. Sci. 2017, 392, 966−974. doi: 10.1016/j.apsusc.2016.09.136
38. [38]
  Azofra, L. M.; MacFarlane, D. R.; Sun, C. A DFT study of planar vs. corrugated graphene-like carbon nitride (g-C₃N₄) and its role in the catalytic performance of CO₂ conversion. Phys. Chem. Chem. Phys. 2016, 18, 18507−14. doi: 10.1039/C6CP02453J
39. [39]
  Esrafili, M. D.; Sharifi, F.; Dinparast, L. Catalytic hydrogenation of CO₂ over Pt- and Ni-doped graphene: a comparative DFT study. J. Mol. Graph. Model. 2017, 77, 143−152. doi: 10.1016/j.jmgm.2017.08.016
40. [40]
  Wu, H. Z.; Bandaru, S.; Huang, X. L.; Liu, J.; Li, L. L.; Wang, Z. Theoretical insight into the mechanism of photoreduction of CO₂ to CO by graphitic carbon nitride. Phys. Chem. Chem. Phys. 2019, 21, 1514−1520. doi: 10.1039/C8CP06956E
41. [41]
  Wang, X. C.; Maeda, K.; Thomas, A.; Takanabe, K.; Gang, X.; Carlsson, J. M.; Domen, K.; Antonietti, M. A metal-free polymeric photocatalyst for hydrogen production from water under visible light. Nat. Mater. 2009, 8, 76−80. doi: 10.1038/nmat2317
42. [42]
  Tong, Y. W.; Wei, C. G.; Li, Y.; Zhang, Y. F.; Lin, W. Unraveling the mechanisms of S-doped carbon nitride for photocatalytic oxygen reduction to H₂O₂. Phys. Chem. Chem. Phys. 2020, 22, 21099−21107. doi: 10.1039/D0CP03533E
1. [1]
  Ziruo Zhou , Wenyu Guo , Tingyu Yang , Dandan Zheng , Yuanxing Fang , Xiahui Lin , Yidong Hou , Guigang Zhang , Sibo Wang . Defect and nanostructure engineering of polymeric carbon nitride for visible-light-driven CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100245-100245. doi: 10.1016/j.cjsc.2024.100245
2. [2]
  Yaoyin Lou , Xiaoyang Jerry Huang , Kuang-Min Zhao , Mark J. Douthwaite , Tingting Fan , Fa Lu , Ouardia Akdim , Na Tian , Shigang Sun , Graham J. Hutchings . Stable core-shell Janus BiAg bimetallic catalyst for CO₂ electrolysis into formate. Chinese Chemical Letters, 2025, 36(3): 110300-. doi: 10.1016/j.cclet.2024.110300
3. [3]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
4. [4]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
5. [5]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-. doi: 10.3866/PKU.WHXB202408005
6. [6]
  Xianghai Song , Xiaoying Liu , Zhixiang Ren , Xiang Liu , Mei Wang , Yuanfeng Wu , Weiqiang Zhou , Zhi Zhu , Pengwei Huo . 氮掺杂显著提升BiOBr光催化还原CO₂性能研究. Acta Physico-Chimica Sinica, 2025, 41(6): 100055-. doi: 10.1016/j.actphy.2025.100055
7. [7]
  Runhua Chen , Qiong Wu , Jingchen Luo , Xiaolong Zu , Shan Zhu , Yongfu Sun . 缺陷态二维超薄材料用于光/电催化CO₂还原的基础与展望. Acta Physico-Chimica Sinica, 2025, 41(3): 2308052-. doi: 10.3866/PKU.WHXB202308052
8. [8]
  Fangfang WANG , Jiaqi CHEN , Weiyin SUN . CuBi@Cu-MOF composite catalysts for electrocatalytic CO₂ reduction to HCOOH. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 97-104. doi: 10.11862/CJIC.20240350
9. [9]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . 碳修饰的铜催化剂实现安培级电流电化学还原CO₂制C₂₊产物. Acta Physico-Chimica Sinica, 2025, 41(3): 2404012-. doi: 10.3866/PKU.WHXB202404012
10. [10]
  Qiyan Wu , Qing Li . Topologically close-packed intermetallic alloy electrocatalysts for CO₂ reduction towards high value-added multi-carbon chemicals. Chinese Chemical Letters, 2025, 36(1): 110384-. doi: 10.1016/j.cclet.2024.110384
11. [11]
  Yue Pan , Wenping Si , Yahao Li , Haotian Tan , Ji Liang , Feng Hou . Promoting exciton dissociation by metal ion modification in polymeric carbon nitride for photocatalysis. Chinese Chemical Letters, 2024, 35(12): 109877-. doi: 10.1016/j.cclet.2024.109877
12. [12]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
13. [13]
  Hao Lv , Zhi Li , Peng Yin , Ping Wan , Mingshan Zhu . Recent progress on non-metallic carbon nitride for the photosynthesis of H₂O₂: Mechanism, modification and in-situ applications. Chinese Chemical Letters, 2025, 36(1): 110457-. doi: 10.1016/j.cclet.2024.110457
14. [14]
  Tianbo Jia , Lili Wang , Zhouhao Zhu , Baikang Zhu , Yingtang Zhou , Guoxing Zhu , Mingshan Zhu , Hengcong Tao . Modulating the degree of O vacancy defects to achieve selective control of electrochemical CO₂ reduction products. Chinese Chemical Letters, 2024, 35(5): 108692-. doi: 10.1016/j.cclet.2023.108692
15. [15]
  Yuan Dong , Mutian Ma , Zhenyang Jiao , Sheng Han , Likun Xiong , Zhao Deng , Yang Peng . Effect of electrolyte cation-mediated mechanism on electrocatalytic carbon dioxide reduction. Chinese Chemical Letters, 2024, 35(7): 109049-. doi: 10.1016/j.cclet.2023.109049
16. [16]
  Chenhao Zhang , Qian Zhang , Yezhou Hu , Hanyu Hu , Junhao Yang , Chang Yang , Ye Zhu , Zhengkai Tu , Deli Wang . N-doped carbon confined ternary Pt₂NiCo intermetallics for efficient oxygen reduction reaction. Chinese Chemical Letters, 2025, 36(3): 110429-. doi: 10.1016/j.cclet.2024.110429
17. [17]
  Yuhao Guo , Na Li , Tingjiang Yan . Tandem catalysis for photoreduction of CO2 into multi-carbon fuels on atomically thin dual-metal phosphochalcogenides. Chinese Journal of Structural Chemistry, 2024, 43(7): 100320-100320. doi: 10.1016/j.cjsc.2024.100320
18. [18]
  Lili Zhang , Hui Gao , Gong Zhang , Yuning Dong , Kai Huang , Zifan Pang , Tuo Wang , Chunlei Pei , Peng Zhang , Jinlong Gong . Cross-section design of the flow channels in membrane electrode assembly electrolyzer for CO₂ reduction reaction through numerical simulations. Chinese Chemical Letters, 2025, 36(1): 110204-. doi: 10.1016/j.cclet.2024.110204
19. [19]
  Xiuzheng Deng , Changhai Liu , Xiaotong Yan , Jingshan Fan , Qian Liang , Zhongyu Li . Carbon dots anchored NiAl-LDH@In₂O₃ hierarchical nanotubes for promoting selective CO₂ photoreduction into CH₄. Chinese Chemical Letters, 2024, 35(6): 108942-. doi: 10.1016/j.cclet.2023.108942
20. [20]
  Xingxing Jiang , Yuxin Zhao , Yan Kong , Jianju Sun , Shangzhao Feng , Xin Lu , Qi Hu , Hengpan Yang , Chuanxin He . Support effect and confinement effect of porous carbon loaded tin dioxide nanoparticles in high-performance CO₂ electroreduction towards formate. Chinese Chemical Letters, 2025, 36(1): 109555-. doi: 10.1016/j.cclet.2024.109555

Get Citation

PDF

XML

Metrics

PDF Downloads(8)
Abstract views(454)
HTML views(52)

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

Mechanism on Carbon Vacancies in Polymeric Carbon Nitride for CO2 Photoreduction

Metrics

通讯作者: 陈斌, bchen63@163.com

Mechanism on Carbon Vacancies in Polymeric Carbon Nitride for CO₂ Photoreduction