Single-atom modified graphene cocatalyst for enhanced photocatalytic CO2 reduction on halide perovskite

doi:10.1016/S1872-2067(24)60081-1

Abstract

Abstract:

Metal halide perovskite (MHP) has become one of the most promising materials for photocatalytic CO₂ reduction owing to the wide light absorption range, negative conduction band position and high reduction ability. However, photoreduction of CO₂ by MHP remains a challenge because of the slow charge separation and transfer. Herein, a cobalt single-atom modified nitrogen-doped graphene (Co-NG) cocatalyst is prepared for enhanced photocatalytic CO₂ reduction of bismuth-based MHP Cs₃Bi₂Br₉. The optimal Cs₃Bi₂Br₉/Co-NG composite exhibits the CO production rate of 123.16 μmol g^-1 h^-1, which is 17.3 times higher than that of Cs₃Bi₂Br₉. Moreover, the Cs₃Bi₂Br₉/Co-NG composite photocatalyst exhibits nearly 100% CO selectivity as well as impressive long-term stability. Charge carrier dynamic characterizations such as Kelvin probe force microscopy (KPFM), single-particle PL microscope and transient absorption (TA) spectroscopy demonstrate the vital role of Co-NG cocatalyst in accelerating the transfer and separation of photogenerated charges and improving photocatalytic performance. The reaction mechanism has been demonstrated by in situ diffuse reflectance infrared Fourier-transform spectroscopy measurement. In addition, in situ X-ray photoelectron spectroscopy test and theoretical calculation reveal the reaction reactive sites and reaction energy barriers, demonstrating that the introduction of Co-NG promotes the formation of *COOH intermediate, providing sufficient evidence for the highly selective generation of CO. This work provides an effective single-atom-based cocatalyst modification strategy for photocatalytic CO₂ reduction and is expected to shed light on other photocatalytic applications.

Key words: Bismuth-based perovskite, Photocatalysis, CO₂ reduction, Single-atom cocatalyst, Charge separation

Hui Fu, Jin Tian, Qianqian Zhang, Zhaoke Zheng, Hefeng Cheng, Yuanyuan Liu, Baibiao Huang, Peng Wang. Single-atom modified graphene cocatalyst for enhanced photocatalytic CO₂ reduction on halide perovskite[J]. Chinese Journal of Catalysis, 2024, 64: 143-151.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60081-1

https://www.cjcatal.com/EN/Y2024/V64/I9/143

Figures/Tables 6

Fig. 1. (a) Schematic illustration of the synthetic process of Co-NG. SEM (b), TEM (c) and STEM-HAADF (d,e) images of Co-NG. Co XANES K-edge spectra (f) and FT-EXAFS spectra (g) of Co-NG with respect to the reference samples.

Fig. 2. SEM (a) and HRTEM (b) images of Cs3Bi2Br9. SEM (c), HRTEM (d), STEM (e) and EDS elemental mapping (f) images of Cs3Bi2Br9/Co-NG.

Fig. 3. XRD patterns (a) and UV-vis absorption spectra (b) of Cs3Bi2Br9, Co-NG and Cs3Bi2Br9/Co-NG. XPS spectra of Cs 3d (c), Bi 4f (d) and Br 3d (e) of Cs3Bi2Br9 and Cs3Bi2Br9/Co-NG. (f) XPS spectra of Co 2p of Co-NG and Cs3Bi2Br9/Co-NG.

Fig. 4. (a) Photocatalytic CO2 reduction performance of Cs3Bi2Br9 and Co-NG under different reaction conditions (with or without light, catalyst and CO2 atmosphere). (b) CO production rate of Cs3Bi2Br9 and Cs3Bi2Br9/xCo-NG (x = 1, 3, 5 and 7). (c) Photocatalytic CO2 reduction performance of Cs3Bi2Br9/5Co-NG during 10 consecutive cycles of experiments. Each cycle is 4 h. (d) XRD patterns of Cs3Bi2Br9/5Co-NG before and after photocatalytic cycling measurements.

Fig. 5. Surface scan KPFM image (a), surface photovoltage mapping image (b) and surface potential curve (c) of Cs3Bi2Br9/Co-NG. Single-particle PL images of Cs3Bi2Br9 (d) and Cs3Bi2Br9/Co-NG (e). PL spectra (f) and TRPL spectra (g) of Cs3Bi2Br9 and Cs3Bi2Br9/Co-NG. TA spectra of Cs3Bi2Br9 (h) and Cs3Bi2Br9/Co-NG (i). (j) Transient photocurrent response curves of Cs3Bi2Br9 and Cs3Bi2Br9/Co-NG.

Fig. 6. (a,b) In situ DRIFTS measurement for CO2 reduction of Cs3Bi2Br9/Co-NG under dark and light irradiation. In-situ XPS spectra of Bi 4f (c), N 1s (d) and Co 2p (e) of Cs3Bi2Br9/Co-NG under dark and light conditions. (f) Gibbs free energy diagrams of intermediates generated during CO2-to-CO catalysis over Cs3Bi2Br9 and Cs3Bi2Br9/Co-NG. (g) The possible photocatalytic CO2 reduction mechanism in the Cs3Bi2Br9/Co-NG photocatalytic system.

References

[1]	S. Jin, Z. Hao, K. Zhang, Z. Yan, J. Chen, Angew. Chem. Int. Ed., 2021, 60, 20627-20648.
[2]	L. Zhang, Z. Zhao, J. Gong, Angew. Chem. Int. Ed., 2017, 56, 11326-11353.
[3]	L. Ran, Z. Li, B. Ran, J. Cao, Y. Zhao, T. Shao, Y. Song, M. K. H. Leung, L. Sun, J. Hou, J. Am. Chem. Soc., 2022, 144, 17097-17109.
[4]	D. Yang, X. Wang, Smartmat, 2022, 3, 54-67.
[5]	S. Das, J. Perez-Ramirez, J. Gong, N. Dewangan, K. Hidajat, B. C. Gates, S. Kawi, Chem. Soc. Rev., 2020, 49, 2937-3004.
[6]	K. Wong, J. Foo, T. Siang, W. Ong, Smartmat, 2024, 5, e1238.
[7]	C. Gao, Q. Meng, K. Zhao, H. Yin, D. Wang, J. Guo, S. Zhao, L. Chang, M. He, Q. Li, H. Zhao, X. Huang, Y. Gao, Z. Tang, Adv. Mater., 2016, 28, 6485-6490.
[8]	Y. Shen, C. Ren, L. Zheng, X. Xu, R. Long, W. Zhang, Y. Yang, Y. Zhang, Y. Yao, H. Chi, J. Wang, Q. Shen, Y. Xiong, Z. Zou, Y. Zhou, Nat. Commun. 2023, 14, 1117.
[9]	H. Huang, R. Shi, Z. Li, J. Zhao, C. Su, T. Zhang, Angew. Chem. Int. Ed., 2022, 61, e202200802.
[10]	G. Yin, X. Huang, T. Chen, W. Zhao, Q. Bi, J. Xu, Y. Han, F. Huang, ACS Catal., 2018, 8, 1009-1017.
[11]	T. Di, J. Zhang, B, Cheng, J. Yu, J. Xu, Sci. China Chem., 2018, 61, 344-350.
[12]	J. Jin, J. Yu, D. Guo, C. Cui, W. Ho, Small, 2015, 11, 5262-5271.
[13]	M. Zhou, S. Wang, P. Yang, C. Huang, X. Wang, ACS Catal., 2018, 8, 4928-4936.
[14]	C. Bie, B. Zhu, F. Xu, L. Zhang, J. Yu, Adv. Mater., 2019, 31, 1902868.
[15]	Z. Sun, H. Wang, Z. Wu, L. Wang, Catal. Today, 2018, 300, 160-172.
[16]	Y. Li, B. Li, D. Zhang, L. Cheng, Q. Xiang, ACS Nano, 2020, 14, 10552-10561.
[17]	M. Ou, W. Tu, S. Yin, W. Xing, S. Wu, H. Wang, S. Wan, Q. Zhong, R. Xu, Angew. Chem. Int. Ed., 2018, 57, 13570-13574.
[18]	H. Deng, X. Fei, Y. Yang, J. Fan, J. Yu, B. Cheng, L. Zhang, Chem. Eng. J., 2021, 409, 127377.
[19]	J. Nunez, V. A. de la Pena O'Shea, P. Jana, J. M. Coronado, D. P. Serrano, Catal. Today, 2013, 209, 21-27.
[20]	C. Kim, K. M. Cho, A. Al-Saggaf, I. Gereige, H. Jung, ACS Catal., 2018, 8, 4170-4177.
[21]	H. Fu, X. Liu, J. Fu, Y. Wu, Q. Zhang, Z. Wang, Y. Liu, Z. Zheng, H. Cheng, Y. Dai, B. Huang, P. Wang, ACS Catal., 2023, 13, 14716-14724.
[22]	X. Liu, Q. Zhang, S. Zhao, Z. Wang, Y. Liu, Z. Zheng, H. Cheng, Y. Dai, B. Huang, P. Wang, Adv. Mater., 2023, 35, 2208915.
[23]	Y. Jiang, J. Liao, H. Chen, H. Zhang, J. Li, X. Wang, D. Kuang, Chem. 2020, 6, 766-780.
[24]	S. S. Bhosale, A. K. Kharade, E. Jokar, A. Fathi, S. Chang, E. W. Diau, J. Am. Chem. Soc., 2019, 141, 20434-20442.
[25]	Y. Xu, M. Yang, B. Chen, X. Wang, H. Chen, D. Kuang, C. Su, J. Am. Chem. Soc., 2017, 139, 5660-5663.
[26]	J. S. Martin, N. Dang, E. Raulerson, M. C. Beard, J. Hartenberger, Y. Yan, Angew. Chem. Int. Ed., 2022, 61, e202205572.
[27]	Y. Wang, H. Huang, Z. Zhang, C. Wang, Y. Yang, Q. Li, D. Xu, Appl. Catal. B, 2021, 282, 119570.
[28]	H. Fu, X. Liu, Y. Wu, Q. Zhang, Z. Wang, Z. Zheng, H. Cheng, Y. Liu, Y. Dai, B. Huang, P. Wang, Appl. Surf. Sci., 2023, 622, 156964.
[29]	Z. Cui, P. Wang, Y. Wu, X. Liu, G. Chen, P. Gao, Q. Zhang, Z. Wang, Z. Zheng, H. Cheng, Y. Liu, Y. Dai, B. Huang, Appl. Catal. B, 2022, 310, 121375.
[30]	Z. Liu, H. Yang, J. Wang, Y. Yuan, K. Hills-Kimball, T. Cai, P. Wang, A. Tang, O. Chen, Nano Lett., 2021, 21, 1620-1627.
[31]	D. Chen, H. Zhang, Y. Liu, J. Li, Energy Environ. Sci., 2013, 6, 1362-1387.
[32]	C. Han, R. Qi, R. Sun, K. Fan, B. Johannessen, D. Qi, S. Cao, J. Xu, Appl. Catal. B, 2023, 320, 121954.
[33]	H. Li, B. Zhu, B. Cheng, G. Luo, J. Xu, S. Cao, J. Mater. Sci. Technol., 2023, 161, 192-200.
[34]	Z. Tang, W. He, Y. Wang, Y. Wei, X. Yu, J. Xiong, X. Wang, X. Zhang, Z. Zhao, J. Liu, Appl. Catal. B, 2022, 311, 121371.
[35]	Y. Wu, P. Wang, X. Zhu, Q. Zhang, Z. Wang, Y. Liu, G. Zou, Y. Dai, M. Whangbo, B. Huang, Adv. Mater., 2018, 30, 1704342.
[36]	Q. Zhao, J. Sun, S. Li, C. Huang, W. Yao, W. Chen, T. Zeng, Q. Wu, Q. Xu, ACS Catal., 2018, 8, 11863-11874.
[37]	Y. Liu, X. Xu, S. Zheng, S. Lv, H. Li, Z. Si, X. Wu, R. Ran, D. Weng, F. Kang, Carbon, 2021, 183, 763-773.
[38]	X. Zhang, H. Liu, P. An, Y. Shi, J. Han, Z. Yang, C. Long, J. Guo, S. Zhao, K. Zhao, H. Yin, L. Zheng, B. Zhang, X. Liu, L. Zhang, G. Li, Z. Tang, Sci. Adv., 2020, 6, eaaz4824.
[39]	Y. Wu, Q. Wu, Q. Zhang, Z. Lou, K. Liu, Y. Ma, Z. Wang, Z. Zheng, H. Cheng, Y. Liu, Y. Dai, B. Huang, P. Wang, Energy Environ. Sci., 2022, 15, 1271-1281.
[40]	Y. Wang, X. Shang, J. Shen, Z. Zhang, D. Wang, J. Lin, J. C. S. Wu, X. Fu, X. Wang, C. Li, Nat. Commun., 2020, 11, 3043.
[41]	H. Zhang, Q. Hong, J. Li, F. Wang, X. Huang, S. Chen, W. Tu, D. Yu, R. Xu, T. Zhou, J. Zhang, Angew. Chem. Int. Ed., 2019, 58, 11752-11756.
[42]	Y. Liu, D. Shen, Q. Zhang, Y. Lin, F. Peng, Appl. Catal. B, 2021, 283, 119630.
[43]	P. Zhang, X. Zhan, L. Xu, X. Fu, T. Zheng, X. Yang, Q. Xu, D. Wang, D. Qi, T. Sun, J. Jiang, J. Mater. Chem. A, 2021, 9, 26286-26297.
[44]	B. Lei, W. Cui, P. Chen, L. Chen, J. Li, F. Dong, ACS Catal., 2022, 12, 9670-9678.
[45]	S. Karmakar, S. Barman, F. A. Rahimi, T. K. Maji, Energy Environ. Sci., 2021, 14, 2429-2440.
[46]	F. A. Rahimi, S. Dey, P. Verma, T. K. Maji, ACS Catal., 2023, 13, 5969-5978.

Single-atom modified graphene cocatalyst for enhanced photocatalytic CO₂ reduction on halide perovskite

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