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]
  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
3. [3]
  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
4. [4]
  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
5. [5]
  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
6. [6]
  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
7. [7]
  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
8. [8]
  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
9. [9]
  Jin Long , Xingqun Zheng , Bin Wang , Chenzhong Wu , Qingmei Wang , Lishan Peng . Improving the electrocatalytic performances of Pt-based catalysts for oxygen reduction reaction via strong interactions with single-CoN₄-rich carbon support. Chinese Chemical Letters, 2024, 35(5): 109354-. doi: 10.1016/j.cclet.2023.109354
10. [10]
  Peng Wang , Daijie Deng , Suqin Wu , Li Xu . Cobalt-based deep eutectic solvent modified nitrogen-doped carbon catalyst for boosting oxygen reduction reaction in zinc-air batteries. Chinese Journal of Structural Chemistry, 2024, 43(1): 100199-100199. doi: 10.1016/j.cjsc.2023.100199
11. [11]
  Zixuan Zhu , Xianjin Shi , Yongfang Rao , Yu Huang . Recent progress of MgO-based materials in CO₂ adsorption and conversion: Modification methods, reaction condition, and CO₂ hydrogenation. Chinese Chemical Letters, 2024, 35(5): 108954-. doi: 10.1016/j.cclet.2023.108954
12. [12]
  Zhenyu Hu , Zhenchun Yang , Shiqi Zeng , Kun Wang , Lina Li , Chun Hu , Yubao Zhao . Cationic surface polarization centers on ionic carbon nitride for efficient solar-driven H₂O₂ production and pollutant abatement. Chinese Chemical Letters, 2024, 35(10): 109526-. doi: 10.1016/j.cclet.2024.109526
13. [13]
  Yuhao Ma , Yufei Zhou , Mingchuan Yu , Cheng Fang , Shaoxia Yang , Junfeng Niu . Covalently bonded ternary photocatalyst comprising MoSe₂/black phosphorus nanosheet/graphitic carbon nitride for efficient moxifloxacin degradation. Chinese Chemical Letters, 2024, 35(9): 109453-. doi: 10.1016/j.cclet.2023.109453
14. [14]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029
15. [15]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
16. [16]
  Hang Meng , Bicheng Zhu , Ruolun Sun , Zixuan Liu , Shaowen Cao , Kan Zhang , Jiaguo Yu , Jingsan Xu . Dynamic photoluminescence switching of carbon nitride thin films for anticounterfeiting and encryption. Chinese Journal of Structural Chemistry, 2024, 43(10): 100410-100410. doi: 10.1016/j.cjsc.2024.100410
17. [17]
  Wenda WANG , Jinku MA , Yuzhu WEI , Shuaishuai MA . Waste biomass-derived carbon modified porous graphite carbon nitride heterojunction for efficient photodegradation of oxytetracycline in seawater. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 809-822. doi: 10.11862/CJIC.20230353
18. [18]
  Muhammad Humayun , Mohamed Bououdina , Abbas Khan , Sajjad Ali , Chundong Wang . Designing single atom catalysts for exceptional electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(1): 100193-100193. doi: 10.1016/j.cjsc.2023.100193
19. [19]
  Hong Dong , Feng-Ming Zhang . Covalent organic frameworks for artificial photosynthetic diluted CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(7): 100307-100307. doi: 10.1016/j.cjsc.2024.100307
20. [20]
  Uttam Pandurang Patil . Porous carbon catalysis in sustainable synthesis of functional heterocycles: An overview. Chinese Chemical Letters, 2024, 35(8): 109472-. doi: 10.1016/j.cclet.2023.109472

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(260)
HTML views(38)

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