Graphene Quantum Dots Supported on Fe-based Metal-Organic Frameworks for Efficient Photocatalytic CO2 Reduction※

doi:10.6023/A21100455

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (1): 22-28.DOI: 10.6023/A21100455 Previous Articles Next Articles

Special Issue: 中国科学院青年创新促进会合辑

Article

石墨烯量子点/铁基金属-有机骨架复合材料高效光催化二氧化碳还原^※

王旭生^b^,^c^,^g, 杨胥^a^,^b, 陈春辉^b^,^d, 李红芳^a^,^b, 黄远标^a^,^b^,^f^,^*(), 曹荣^a^,^b^,^e^,^f

^a福州大学石油化工学院福州 350108
^b中国科学院福建物质结构研究所结构化学国家重点实验室福州 350002
^c浙江理工大学材料科学与工程学院杭州 310018
^d中国科学技术大学化学系合肥 230026
^e中国福建光电信息科学与技术创新实验室(闽都创新实验室) 福州 350108
^f中国科学院大学北京 100049
^g暨南大学化学与材料学院广州 510632

投稿日期:2021-10-13 发布日期:2021-11-29
通讯作者: 黄远标
作者简介:
^※ 庆祝中国科学院青年创新促进会十年华诞.
基金资助:
项目受国家重点基础研发计划项目(2018YFA0208600); 项目受国家重点基础研发计划项目(2018YFA0704502); 国家自然科学基金(21671188); 国家自然科学基金(21871263); 国家自然科学基金(22071245); 国家自然科学基金(22033008); 国家自然科学基金(22171265); 国家自然科学基金(22001094); 中国科学院青年创新促进会优秀会员项目(Y201850); 中国福建光电信息科学与技术创新实验室(闽都创新实验室)项目(2021ZZ103); 广东省基础与应用基础研究基金(2020A1515110003)

Graphene Quantum Dots Supported on Fe-based Metal-Organic Frameworks for Efficient Photocatalytic CO₂ Reduction^※

Xusheng Wang^b^,^c^,^g, Xu Yang^a^,^b, Chunhui Chen^b^,^d, Hongfang Li^a^,^b, Yuanbiao Huang^a^,^b^,^f(), Rong Cao^a^,^b^,^e^,^f

^aCollege of Chemical Engineering, Fuzhou University, Fuzhou 350108
^bState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002
^cSchool of Materials Science and Engineering, Zhejiang Sci-Tech University, Hangzhou 310018
^dDepartment of Chemistry, University of Science and Technology of China, Hefei 230026
^eFujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fuzhou 350108
^fUniversity of Chinese Academy of Sciences, Beijing 100049
^gCollege of Chemistry and Materials Science, Jinan University, Guangzhou 510632

Received:2021-10-13 Published:2021-11-29
Contact: Yuanbiao Huang
About author:
^※ Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
National Key Research and Development Program of China(2018YFA0208600); National Key Research and Development Program of China(2018YFA0704502); National Natural Science Foundation of China(21671188); National Natural Science Foundation of China(21871263); National Natural Science Foundation of China(22071245); National Natural Science Foundation of China(22033008); National Natural Science Foundation of China(22171265); National Natural Science Foundation of China(22001094); Youth Innovation Promotion Association, CAS(Y201850); Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ103); Guangdong Basic and Applied Basic Research Foundation(2020A1515110003)

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Abstract

Photocatalytic reduction of CO₂ to valuable chemicals is an essential but still remains challenging. Metal-organic frameworks (MOFs) featuring high special surface area, large CO₂ adsorption uptakes, adjustable structures and function, have become a kind of promising porous materials for photocatalytic CO₂ reduction. However, MOFs often suffer from problems like short light harvesting range, rapid recombination of photogenerated carriers, resulting in lower activity. Here, graphene quantum dots (GQD) were supported on the Fe-based nano-sized MOFs, NH₂-MIL-88B(Fe), via electrostatic self-assembly strategy. GQDs were prepared by electrolysis of graphite rod in pure water firstly, and then centrifuged to remove the large species. Transmission electron microscope (TEM) reveals that ultrafine GQDs with 3 nm were obtained. Atomic force microscope (AFM) further demonstrates that the thickness of GQDs is around 0.34—1.5 nm (1—4 stacked layers). The MOFs, NH₂-MIL-88B(Fe), were synthesized with traditional solvothermal method, with a nano spindle shape of 250 nm×40 nm. The amino groups on MOFs provide strong electrostatic force with the carboxylic groups on GQDs, making the composite very stable and efficient electron transfer. High resolution transmission electron microscope (TEM) reveals that the nano MOFs were surrounded by tiny GQDs firmly. The bandgap of composite was determined by solid ultraviolet visible diffuse reflectance spectroscopy (UV-Vis DRS) and Mott-Schottky measurement, which indicate that it is thermodynamically appropriate for photocatalytic CO₂ reduction. Photocurrent experiments further demonstrate the composite is beneficial for the photogenerated electron-hole separation. Thus, the resulting GQD/NH₂-MIL-88B(Fe) composite showed much enhanced CO production rate (4 times) compared with the parent NH₂-MIL-88B(Fe), reaching 590 μmol/g under 10 h visible light irradiation with triethanolamine (TEOA) as sacrificial agent. The hugely improved photoreduction activity benefits from both the high CO₂ adsorption of MOFs and the enhanced separation of photogenerated electrons and holes. This work provides an avenue for preparation of MOFs based materials with high CO₂ photoreduction activity.

Key words: metal-organic frameworks, photocatalysis, CO₂ reduction, electrostatic self-assembly, graphene quantum dots

Cite this article

Xusheng Wang, Xu Yang, Chunhui Chen, Hongfang Li, Yuanbiao Huang, Rong Cao. Graphene Quantum Dots Supported on Fe-based Metal-Organic Frameworks for Efficient Photocatalytic CO₂ Reduction^※[J]. Acta Chimica Sinica, 2022, 80(1): 22-28.

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Fig. & Tab. 4

Figure 1. (a) The photograph of water (left) and GQD dispersion (right) under sunlight; (b) the photograph of water (left) and GQD dispersion (right) under UV light (365 nm); (c) the wavelength dependent PL of GQD dispersion; (d) Raman spectra of GQD and oxidized graphite (λex=633 nm); (e) IR spectra of GQD powder; (f) C1s XPS spectra of GQD; (g) O1s XPS spectra of GQD

Figure 2. (a) The TEM image of GQD (scale bar 50 nm), (b) TEM images of GQD (scale bar 10 nm, the inset in b is the HRTEM image of GQD); (c) the AFM image of GQD; (d) the height of selected GQDs in figure (c)

Figure 3. (a~c) The SEM images of NH2-MIL-88B(Fe) with scale bar of 1 μm, 100 nm, 100 nm, respectively; (d~f) the TEM images of GQD/NH2-MIL-88B(Fe) with scale bar of 100 nm, 100 nm, 20 nm, respectively. The inset in (f) is the HRTEM of GQD on NH2-MIL-88B(Fe)

Figure 4. (a) The PXRD of NH2-MIL-88B(Fe); (b) the solid UV-Vis DRS of GQD/NH2-MIL-88B(Fe) and NH2-MIL-88B(Fe); (c) the Tauc plot of NH2-MIL-88B(Fe); (d) the Mott-Schottky plots of NH2-MIL-88B(Fe); (e) the photocurrents of GQD/NH2-MIL-88B(Fe) and NH2-MIL-88B(Fe); (f) photocatalytic performance of GQD/NH2-MIL-88B(Fe) and NH2-MIL-88B(Fe)

References 45

[1]	Meng, D. L.; Zhang, M. D.; Si, D. H.; Mao, M. J.; Hou, Y.; Huang, Y. B.; Cao, R. Angew. Chem., Int. Ed. 2021, 60, 25485. doi: 10.1002/anie.v60.48
[2]	Yi, J. D.; Si, D. H.; Xie, R.; Yin, Q.; Zhang, M. D.; Wu, Q.; Chai, G. L.; Huang, Y. B.; Cao, R. Angew. Chem., Int. Ed. 2021, 60, 17108. doi: 10.1002/anie.v60.31
[3]	Yi, J. D.; Xie, R.; Xie, Z. L.; Chai, G. L.; Liu, T. F.; Chen, R. P.; Huang, Y. B.; Cao, R. Angew. Chem., Int. Ed. 2020, 59, 23641. doi: 10.1002/anie.v59.52
[4]	Zou, Y. H.; Huang, Y. B.; Si, D. H.; Yin, Q.; Wu, Q. J.; Weng, Z.; Cao, R. Angew. Chem., Int. Ed. 2021, 60, 20915. doi: 10.1002/anie.v60.38
[5]	Diercks, C. S.; Liu, Y.; Cordova, K. E.; Yaghi, O. M. Nat. Mater. 2018, 17, 301. doi: 10.1038/s41563-018-0033-5
[6]	Zhang, W.; Mohamed, A. R.; Ong, W. J. Angew. Chem., Int. Ed. 2020, 59, 22894. doi: 10.1002/anie.v59.51
[7]	Wang, X. S.; Li, L.; Li, D.; Ye, J. Solar RRL 2020, 4, 1900547. doi: 10.1002/solr.v4.8
[8]	Hu, J.; Chen, D.; Mo, Z.; Li, N.; Xu, Q.; Li, H.; He, J.; Xu, H.; Lu, J. Angew. Chem., Int. Ed. 2019, 58, 2073. doi: 10.1002/anie.v58.7
[9]	Yu, H.; Li, J.; Zhang, Y.; Yang, S.; Han, K.; Dong, F.; Ma, T.; Huang, H. Angew. Chem., Int. Ed. 2019, 58, 3880. doi: 10.1002/anie.v58.12
[10]	Hong, D.; Kawanishi, T.; Tsukakoshi, Y.; Kotani, H.; Ishizuka, T.; Kojima, T. J. Am. Chem. Soc. 2019, 141, 20309. doi: 10.1021/jacs.9b10597
[11]	Yu, H.; Haviv, E.; Neumann, R. Angew. Chem., Int. Ed. 2020, 59, 6219. doi: 10.1002/anie.v59.15
[12]	Liang, J.; Wu, Q.; Huang, Y. B.; Cao, R. EnergyChem 2021, 3, 100064. doi: 10.1016/j.enchem.2021.100064
[13]	Wang, X.-S.; Liang, J.; Li, L.; Lin, Z.-J.; Bag, P. P.; Gao, S.-Y.; Huang, Y.-B.; Cao, R. Inorg. Chem. 2016, 55, 2641. doi: 10.1021/acs.inorgchem.6b00019
[14]	Wang, X.-S.; Chen, C.-H.; Ichihara, F.; Oshikiri, M.; Liang, J.; Li, L.; Li, Y.; Song, H.; Wang, S.; Zhang, T.; Huang, Y.-B.; Cao, R.; Ye, J. Appl. Catal. B: Environ. 2019, 253, 323. doi: 10.1016/j.apcatb.2019.04.074
[15]	He, C.; Liang, J.; Zou, Y.-H.; Yi, J.-D.; Huang, Y.-B.; Cao, R. Natl. Sci. Rev. 2021, DOI:10.1093/nsr/nwab157.
[16]	Xiong, W.; Li, H.; You, H.; Cao, M.; Cao, R. Natl. Sci. Rev. 2020, 7, 609. doi: 10.1093/nsr/nwz166
[17]	Li, X.; Yan, B.; Huang, W.; Fu, L.; Sun, X.; Lv, A. Acta Chim. Sinica 2021, 79, 459. (in Chinese) doi: 10.6023/A20100494
	( 李旭飞, 闫保有, 黄维秋, 浮历沛, 孙宪航, 吕爱华, 化学学报 2021, 79, 459.)
[18]	Wu, Q.; Zhang, C.; Sun, K.; Jiang, H.-L. Acta Chim. Sinica 2020, 78, 688. (in Chinese) doi: 10.6023/A20050141
	( 吴浅耶, 张晨曦, 孙康, 江海龙, 化学学报 2020, 78, 688.)
[19]	Lin, Z.-J.; Cao, R. Acta Chim. Sinica 2020, 78, 1309. doi: 10.6023/A20080359
	( 林祖金, 曹荣, 化学学报 2020, 78, 1309)
[20]	Zhang, X.; Li, X.; Xiong, W.; Li, H.; Cao, R. Acta Chim. Sinica 2021, 79, 180. (in Chinese) doi: 10.6023/A20090445
	( 张晓萌, 李希雅, 熊晚枫, 李红芳, 曹荣, 化学学报 2021, 79, 180.)
[21]	Pan, Y.; Qian, Y.; Zheng, X.; Chu, S. Q.; Yang, Y.; Ding, C.; Wang, X.; Yu, S. H.; Jiang, H. L. Natl. Sci. Rev. 2021, 8, nwaa224.
[22]	Wang, H.-N.; Zou, Y.-H.; Sun, H.-X.; Chen, Y.; Li, S.-L.; Lan, Y.-Q. Coord. Chem. Rev. 2021, 438, 213906. doi: 10.1016/j.ccr.2021.213906
[23]	Huang, Q.; Liu, J.; Feng, L.; Wang, Q.; Guan, W.; Dong, L. Z.; Zhang, L.; Yan, L. K.; Lan, Y. Q.; Zhou, H. C. Natl. Sci. Rev. 2020, 7, 53. doi: 10.1093/nsr/nwz096
[24]	Fu, Y.; Sun, D.; Chen, Y.; Huang, R.; Ding, Z.; Fu, X.; Li, Z. Angew. Chem., Int. Ed. 2012, 51, 3364. doi: 10.1002/anie.v51.14
[25]	Wang, D.; Huang, R.; Liu, W.; Sun, D.; Li, Z. ACS Catal. 2014, 4, 4254. doi: 10.1021/cs501169t
[26]	Xu, H. Q.; Hu, J.; Wang, D.; Li, Z.; Zhang, Q.; Luo, Y.; Yu, S. H.; Jiang, H. L. J. Am. Chem. Soc. 2015, 137, 13440. doi: 10.1021/jacs.5b08773
[27]	Zhang, H.; Wei, J.; Dong, J.; Liu, G.; Shi, L.; An, P.; Zhao, G.; Kong, J.; Wang, X.; Meng, X.; Zhang, J.; Ye, J. Angew. Chem., Int. Ed. 2016, 55, 14310. doi: 10.1002/anie.v55.46
[28]	Chen, E. X.; Qiu, M.; Zhang, Y. F.; Zhu, Y. S.; Liu, L. Y.; Sun, Y. Y.; Bu, X.; Zhang, J.; Lin, Q. Adv. Mater. 2018, 30, 1704388. doi: 10.1002/adma.v30.2
[29]	Dong, L. Z.; Zhang, L.; Liu, J.; Huang, Q.; Lu, M.; Ji, W. X.; Lan, Y. Q. Angew. Chem., Int. Ed. 2020, 59, 2659. doi: 10.1002/anie.v59.7
[30]	Chen, Q.; Kuang, Q.; Xie, Z. Acta Chim. Sinica 2021, 79, 10. (in Chinese) doi: 10.6023/A20080384
	( 陈钱, 匡勤, 谢兆雄, 化学学报 2021, 79, 10.)
[31]	Zhao, H.; Wang, X.; Feng, J.; Chen, Y.; Yang, X.; Gao, S.; Cao, R. Catal. Sci. Technol. 2018, 8, 1288. doi: 10.1039/C7CY02286G
[32]	Shi, L.; Wang, T.; Zhang, H.; Chang, K.; Ye, J. Adv. Funct. Mater. 2015, 25, 5360. doi: 10.1002/adfm.201502253
[33]	Wang, X.; Zhao, X.; Zhang, D.; Li, G.; Li, H. Appl. Catal. B: Environ. 2018, 228, 47. doi: 10.1016/j.apcatb.2018.01.066
[34]	Han, Z.; Fu, Y.; Zhang, Y.; Zhang, X.; Meng, X.; Zhou, Z.; Su, Z. Dalton Trans. 2021, 50, 3186. doi: 10.1039/D1DT00128K
[35]	Jiang, Z.; Xu, X.; Ma, Y.; Cho, H. S.; Ding, D.; Wang, C.; Wu, J.; Oleynikov, P.; Jia, M.; Cheng, J.; Zhou, Y.; Terasaki, O.; Peng, T.; Zan, L.; Deng, H. Nature 2020, 586, 549. doi: 10.1038/s41586-020-2738-2
[36]	Li, H.; Kang, Z.; Liu, Y.; Lee, S.-T. J. Mater. Chem. 2012, 22, 24230. doi: 10.1039/c2jm34690g
[37]	Lim, S. Y.; Shen, W.; Gao, Z. Chem. Soc. Rev. 2015, 44, 362. doi: 10.1039/C4CS00269E
[38]	Wang, J.; Cheng, C.; Huang, Y.; Zheng, B.; Yuan, H.; Bo, L.; Zheng, M.-W.; Yang, S.-Y.; Guo, Y.; Xiao, D. J. Mater. Chem. C 2014, 2, 5028. doi: 10.1039/C3TC32131B
[39]	Aguilera-Sigalat, J.; Bradshaw, D. Coord. Chem. Rev. 2016, 307, 267. doi: 10.1016/j.ccr.2015.08.004
[40]	Martindale, B. C.; Hutton, G. A.; Caputo, C. A.; Reisner, E. J. Am. Chem. Soc. 2015, 137, 6018. doi: 10.1021/jacs.5b01650
[41]	Dong, Y.; Han, Q.; Hu, Q.; Xu, C.; Dong, C.; Peng, Y.; Ding, Y.; Lan, Y. Appl. Catal. B: Environ. 2021, 293, 120214. doi: 10.1016/j.apcatb.2021.120214
[42]	Ming, H.; Ma, Z.; Liu, Y.; Pan, K.; Yu, H.; Wang, F.; Kang, Z. Dalton Trans. 2012, 41, 9526. doi: 10.1039/c2dt30985h
[43]	Liu, J.; Liu, Y.; Liu, N.; Han, Y.; Zhang, X.; Huang, H.; Lifshitz, Y.; Lee, S. T.; Zhong, J.; Kang, Z. Science 2015, 347, 970. doi: 10.1126/science.aaa3145
[44]	Bian, J.; Huang, C.; Wang, L.; Hung, T.; Daoud, W. A.; Zhang, R. ACS Appl. Mater. Inter. 2014, 6, 4883. doi: 10.1021/am4059183
[45]	Li, H.; He, X.; Kang, Z.; Huang, H.; Liu, Y.; Liu, J.; Lian, S.; Tsang, C. H.; Yang, X.; Lee, S. T. Angew. Chem., Int. Ed. 2010, 49, 4430. doi: 10.1002/anie.200906154

石墨烯量子点/铁基金属-有机骨架复合材料高效光催化二氧化碳还原^※

Graphene Quantum Dots Supported on Fe-based Metal-Organic Frameworks for Efficient Photocatalytic CO₂ Reduction^※

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石墨烯量子点/铁基金属-有机骨架复合材料高效光催化二氧化碳还原※