In-situ preparation of TiO2/N-doped graphene hollow sphere photocatalyst with enhanced photocatalytic CO2 reduction performance

doi:10.1016/S1872-2067(21)63805-6

Chinese Journal of Catalysis ›› 2021, Vol. 42 ›› Issue (10): 1648-1658.DOI: 10.1016/S1872-2067(21)63805-6

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In-situ preparation of TiO₂/N-doped graphene hollow sphere photocatalyst with enhanced photocatalytic CO₂ reduction performance

Libo Wang^a^,^b, Bicheng Zhu^c, Bei Cheng^a, Jianjun Zhang^a, Liuyang Zhang^a, Jiaguo Yu^a^,^b^,^d()

^aState Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, Hubei, China
^bFoshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Xianhu Hydrogen Valley, Foshan 528200, China
^cLaboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430074, Hubei, China
^dSchool of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China

Received:2021-02-06 Accepted:2021-03-16 Online:2021-10-18 Published:2021-06-20
Contact: Jiaguo Yu
About author:Jiaguo Yu received his BS and MS in chemistry from Central China Normal University and Xi’an Jiaotong University, respectively; his PhD in Materials Science from Wuhan University of Technology (WUT). In 2000, he became a Professor at WUT. His research interests include semiconductor photocatalysis, photocatalytic hydrogen production, CO2 reduction, dye-sensitized and perovskite Solar cells, indoor air purification and adsorption, supercapacitor, electrocatalysis and so on. He is Thomson Reuters "Hottest Researcher" of 2012. His name is also in the lists of 2014−2020 Highly Cited Researchers from Clarivate Analytics (Thomson Reuters) in Materials Science, Chemistry and Engineering. He is Foreign Member of Academia Europaea (The Academy of Europe) (2020), Foreign Fellow of the European Academy of Sciences (2020) and Fellow of the Royal Society of Chemistry (2015). He was appointed as the Associate Editor of Chin. J. Catal. in 2020.
Supported by:
National Natural Science Foundation of China(21905219);National Natural Science Foundation of China(51872220);National Natural Science Foundation of China(51932007);National Natural Science Foundation of China(51961135303);National Natural Science Foundation of China(21871217);National Natural Science Foundation of China(U1905215);National Natural Science Foundation of China(U1705251);Fundamental Research Funds for the Central Universities(WUT: 2019IVB050);Innovative Research Funds of Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory(XHD2020-001)

Abstract

Abstract:

Photocatalytic CO₂ conversion efficiency is hampered by the rapid recombination of photogenerated charge carriers. It is effective to suppress the recombination by constructing cocatalysts on photocatalysts with high-quality interfacial contact. Herein, we develop a novel strategy to in-situ grow ultrathin N-doped graphene (NG) layer on TiO₂ hollow spheres (HS) with large area and intimate interfacial contact via a chemical vapor deposition (CVD). The optimized TiO₂/NG HS nanocomposite achieves total CO₂ conversion rates (the sum yield of CO, CH₃OH and CH₄) of 18.11 μmol g^-1 h^-1, which is about 4.6 times higher than blank TiO₂ HS. Experimental results demonstrate that intimate interfacial contact and abundant pyridinic N sites can effectively facilitate photogenerated charge carrier separation and transport, realizing enhanced photocatalytic CO₂ reduction performance. In addition, this work provides an effective strategy for in-situ construction of graphene-based photocatalysts for highly efficient photocatalytic CO₂ conversion.

Key words: Ultrathin N-doped graphene layer, Chemical vapor deposition, Intimate interfacial contact, Photocatalytic CO₂ reduction, Pyridinic N site

Libo Wang, Bicheng Zhu, Bei Cheng, Jianjun Zhang, Liuyang Zhang, Jiaguo Yu. In-situ preparation of TiO₂/N-doped graphene hollow sphere photocatalyst with enhanced photocatalytic CO₂ reduction performance[J]. Chinese Journal of Catalysis, 2021, 42(10): 1648-1658.

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Figures/Tables 13

Fig. 1. (a) Schematic illustration of TiO2/NG HS preparation processes; (b,c) FESEM images of SiO2/TiO2 spheres and TiO2/NG HS; TEM (d) and its corresponding HRTEM (e) image of TiO2/NG HS; (f) HAADF image of TiO2/NG HS; (g-j) EDS mapping images of Ti, O, N and C elements.

Fig. 2. EPR spectra of samples.

Fig. 3. XRD patterns (a) and Raman spectra (b) of TiO2 and TiO2/NG HS.

Fig. 4. (a) XPS survey spectra of TiO2 and TiO2/NG HS; XPS spectra of O 1s (b) and Ti 2p (c) of TiO2 and TiO2/NG HS in darkness or in light; (d) XPS spectra of N 1s of TiO2/NG HS in the dark or in light.

Fig. 5. Nitrogen physisorption isotherms and pore-size distribution curves (inset) (a) and CO2 adsorption isotherms (b) of samples.

Fig. 6. The Ead of CO2 on pyridinic N atom (a), graphitic N atom (b) and graphitic C atom (c) in NG, as well as graphitic C atom (d) in graphene, respectively.

Fig. 7. (a) UV-vis DRS spectra of different samples; (b) Tauc plots of TiO2 and TiO2/NG.

Fig. 8. Infrared thermograms of TiO2 (a) and TiO2/NG HS (b).

Fig. 9. (a) PCR activities of samples; (b) PCR stability of TiO2/NG HS.

Table 1 Physical properties of samples.

Sample	Pore volume (cm³ g^-1)	Average pore size (nm)	A_BET(m² g^-1)
TiO₂	0.24	14	77
TiO₂/NG	0.22	12	79
TiO₂/G	0.27	13	77

Fig. 10. In-situ DRIFT spectra of TiO2/NG HS. (a) Without flowing CO2/H2O gas in darkness; (b-d) with flowing CO2/H2O gas for 20-60 min in darkness; (e-g) with flowing CO2/H2O gas for 20-60 min with irradiation.

Fig. 11. PL spectra (a), time-resolved PL spectra (b), EIS spectra (c) and photocurrent density curves (d) of TiO2 and TiO2/NG HS.

Fig. 12. (a) CPD spectra of samples; (b-d) diagram of PCR reaction mechanism over TiO2/NG HS. Ef(dark): Ef in the dark; Ef(light): Ef under light irradiation; Evac: vacuum energy. (b) Before contact, (c) after contact, and (d) under light irradiation.

References

[1]	Z. Sun, N. Talreja, H. Tao, J. Texter, M. Muhler, J. Strunk, J. Chen, Angew. Chem. Int. Ed., 2018,57, 7610-7627.
[2]	Y. Xia, J. Yu, Chem, 2020,6, 1039-1040.
[3]	S. Das, J. Pérez-Ramírez, J. Gong, N. Dewangan, K. Hidajat, B. Gates, S. Kawi, Chem. Soc. Rev., 2020,49, 2937-3004.
[4]	T. Kong, Y. Jiang, Y. Xiong, Chem. Soc. Rev., 2020,49, 6579-6591.
[5]	H. Deng, F. Xu, B. Cheng, J. Yu, W. Ho, Nanoscale, 2020,12, 7206-7213.
[6]	Y. Xia, Z. Tian, T. Heil, A. Meng, B. Cheng, S. Cao, J. Yu, M. Antonietti, Joule, 2019,3, 2792-2805.
[7]	H. Wang, Y. Wang, L. Guo, X. Zhang, C. Ribeiro, T. He, Chin. J. Catal., 2020,41, 131-139.
[8]	Z. Wang, J. Fan, B. Cheng, J. Yu, J. Xu, Mater. Today Phys., 2020,15, 100279.
[9]	Z. Wang, J. Hong, S. Ng, W. Liu, J. Huang, P. Chen, W. Ong, Acta Phys.-Chim. Sin., 2021,37, 2011033.
[10]	Z. Pan, M. Liu, P. Niu, F. Guo, X. Fu, X. Wang, Acta Phys.-Chim. Sin., 2020,36, 1906014.
[11]	W. Zhou, J. Guo, S. Shen, J. Pan, J. Tang, L. Chen, C. Au, S. Yin, Acta Phys.-Chim. Sin., 2020,36, 1906048.
[12]	G. Chen, K. Chen, J. Fu, M. Liu, Rare Metals, 2020,39, 607-609.
[13]	X. Chen, Q. Wei, J. Hong, R. Xu, T. Zhou, Rare Metals, 2019,38, 413-419.
[14]	L. Cheng, D. Zhang, Y. Liao, J. Fan, Q. Xiang, Chin. J. Catal., 2021,42, 131-140.
[15]	V. Rodríguez-González, S. Obregón, O. Patrón-Soberano, C. Terashima, A. Fujishima, Appl. Catal. B, 2020,270, 118853.
[16]	F. Xu, K. Meng, B. Cheng, S. Wang, J. Xu, J. Yu, Nat. Commun., 2020,11, 4613.
[17]	S. Duan, S. Wu, L. Wang, H. She, J. Huang, Q. Wang, Acta Phys.-Chim. Sin., 2020,36, 1905086.
[18]	R. Wang, M. Shi, F. Xu, Y. Qiu, P. Zhang, K. Shen, Q. Zhao, J. Yu, Y. Zhang, Nat. Commun., 2020,11, 4465.
[19]	H. Tang, Y. Ren, S. Wei, G. Liu, X. Xu, Rare Metals, 2019,38, 453-458.
[20]	R. He, H. Liu, H. Liu, D. Xu, L. Zhang, J. Mater. Sci. Technol., 2020,52, 145-151.
[21]	D. Gao, R. Yuan, J. Fan, X. Hong, H. Yu, J. Mater. Sci. Technol., 2020,56, 122-132.
[22]	M. Xiao, Z. Wang, M. Lyu, B. Luo, S. Wang, G. Liu, H. Cheng, L. Wang, Adv. Mater., 2019,31, 1801369.
[23]	A. Meng, L. Zhang, B. Cheng, J. Yu, Adv. Mater., 2019,31, 1807660.
[24]	J. Li, X. Wu, S. Liu, Acta Phys.-Chim. Sin., 2021,37, 2009038.
[25]	Y. Liu, Z. Xiao, S. Cao, J. Li, L. Piao, Chin. J. Catal., 2020,41, 219-226.
[26]	J. Wang, B. Liu, K. Nakata, Chin. J. Catal., 2019,40, 403-412.
[27]	V. Nguyen, M. Baynosa, V. Nguyen, D. Tuma, Y. Lee, J. Shim, Appl. Surf. Sci., 2019,486, 37-51.
[28]	P. Kuang, M. Sayed, J. Fan, B. Cheng, J. Yu, Adv. Energy Mater., 2020,10, 1903802.
[29]	L. Hu, J. Yan, C. Wang, B. Chai, J. Li, Chin. J. Catal., 2019,40, 458-469.
[30]	G. Das, A. Bhatnagar, P. Yli-Pirilä, K. Tripathi, T. Kim, Chem. Commun., 2020,56, 6953-6956.
[31]	C. Bie, B. Zhu, F. Xu, L. Zhang, J. Yu, Adv. Mater., 2019,31, 1902868.
[32]	L. Lin, Y. Nie, S. Kavadiya, T. Soundappan, P. Biswas, Chem. Eng. J., 2017,316, 449-460.
[33]	T. Liu, L. Zhang, B. Cheng, X. Hu, J. Yu, Cell Rep. Phys. Sci., 2020,1, 100215.
[34]	C. Bie, H. Yu, B. Cheng, W. Ho, J. Fan, J. Yu, Adv. Mater., 2021,33, 2003521.
[35]	X. Cui, W. An, X. Liu, H. Wang, Y. Men, J. Wang, Nanoscale, 2018,10, 15262-15272.
[36]	S. Liu, H. Yang, X. Huang, L. Liu, W. Cai, J. Gao, X. Li, T. Zhang, Y. Huang, B. Liu, Adv. Funct. Mater., 2018,28, 1800499.
[37]	Y. Xia, B. Cheng, J. Fan, J. Yu, G. Liu, Sci. China Mater., 2020,63, 552-565.
[38]	B. Deng, Z. Liu, H. Peng, Adv. Mater., 2019,31, 1800996.
[39]	Y. Xue, B. Wu, L. Jiang, Y. Guo, L. Huang, J. Chen, J. Tan, D. Geng, B. Luo, W. Hu, J. Am. Chem. Soc., 2012,134, 11060-11063.
[40]	L. Wang, H. Tan, L. Zhang, B. Cheng, J. Yu, Chem. Eng. J., 2021,411, 128501.
[41]	L. Pei, Y. Yuan, W. Bai, T. Li, H. Zhu, Z. Ma, J. Zhong, S. Yan, Z. Zou, ACS Catal., 2020,10, 15083-15091.
[42]	W. Stöber, A. Fink, E. Bohn, J. Colloid Interface Sci., 1968,26, 62-69.
[43]	I. B. Johns, E. A. McElhill, J. Q. Smith. J. Chem. Eng. Data, 1962,7, 277-281.
[44]	M. H. Khan, M. Moradi, M. Dakhchoune, M. Rezaei, S. Huang, J. Zhao, K. V. Agrawal, Carbon, 2019,153, 458-466.
[45]	H. Liu, W. Li, D. Shen, D. Zhao, G. Wang, J. Am. Chem. Soc., 2015,137, 13161-13166.
[46]	A. C. Ferrari, D. M. Basko, Nat. Nanotechnol., 2013,8, 235-246.
[47]	J. Wang, G. Wang, B. Cheng, J. Yu, J. Fan, Chin. J. Catal., 2021,42, 56-68.
[48]	F. He, B. Zhu, B. Cheng, J. Yu, W. Ho, W. Macyk, Appl. Catal. B, 2020,272, 119006.
[49]	Z. Wang, Y. Chen, L. Zhang, B. Cheng, J. Yu, J. Fan, J. Mater. Sci. Technol., 2020,56, 143-150.
[50]	Y. Li, M. Zhou, B. Cheng, Y. Shao, J. Mater. Sci. Technol., 2020,56, 1-17.
[51]	W. Li, B. Herkt, M. Seredych, T. Bandosz, Appl. Catal. B, 2017,207, 195-206.
[52]	F. He, A. Meng, B. Cheng, W. Ho, J. Yu, Chin. J. Catal., 2020,41, 9-20.
[53]	J. Low, L. Zhang, B. Zhu, Z. Liu, J. Yu, ACS Sustainable Chem. Eng., 2018,6, 15653-15661.
[54]	C. Du, B. Yan, Z. Lin, G. Yang, Catal. Sci. Technol., 2019,9, 4066-4076.
[55]	T. He, L. Wang, F. Fabregat-Santiago, G. Liu, Y. Li, C. Wang, R. Guan, J. Mater. Chem. A, 2017,5, 6455-6464.
[56]	Z. He, Y. Han, S. Liu, W. Cui, Y. Qiao, T. He, Q. Wang, ChemElectroChem, 2020,7, 4390-4397.
[57]	X. Wang, X. Tian, Y. Sun, J. Zhu, F. Li, H. Mu, J. Zhao, Nanoscale, 2018,10, 12315-12321.
[58]	H. Xu, R. Xiao, J. Huang, Y. Jiang, C. Zhao, X. Yang, Chin. J. Catal., 2021,42, 107-114.

In-situ preparation of TiO₂/N-doped graphene hollow sphere photocatalyst with enhanced photocatalytic CO₂ reduction performance

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