基于锌锗二元氧化物的光热协同分解CO2研究

doi:10.6023/A20060230

摘要/Abstract

本工作为非Ti基光热协同材料研究，使用溶液沉淀法制备了ZnO/Zn₂GeO₄复合材料（Z/ZGO）应用于光热协同分解CO₂.使用透射电子显微镜（TEM）、X射线衍射技术（XRD）、紫外可见漫反射光谱（UV-Vis DRS）、X射线光电子能谱（XPS）等表征手段对材料的形貌、光响应以及氧空位对反应的影响进行研究.锌锗二元氧化物复合材料综合两种半导体的优势，形成异质结，扩展了材料光谱响应范围，提高了材料氧空位形成能力，使得CO产率提高至单纯ZnO样品的5.55倍，并具有较好的循环稳定性.对扩展光热协同催化材料体系，进一步深化光热协同反应机理以及提升反应产率具有一定的前瞻和指导作用.

关键词: CO₂分解, 氧空位, 光热协同反应, 异质结, Zn基氧化物

Using solar energy to split CO₂ can realize the conversion and storage of solar energy at the same time, and alleviate the carbon emissions caused by the transitional use of fossil energy. Solar energy based photo-thermochemical reaction is a promising method for the CO₂ splitting. To further study the photo-thermochemical reaction mechanism and explore the non-titanium-based catalytic materials, the ZnO/Zn₂GeO₄ composite material (Z/ZGO) was prepared by solution precipitation method and used for photo-thermochemical CO₂ splitting. Composite semiconductor combined the advantages of the two components which made CO production reach 5.55 times that of pure ZnO. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) were used to illustrate the crystal structure and chemical composition of the samples. The XRD pattern found that the samples crystallized well, and no obvious crystal form changes occurred after the reaction. Using SEM to observe the samples before and after the reaction, the particle size did not increase significantly and no obvious sintering phenomenon was found, which indicated that the material has good reaction stability. Photoluminescence (PL), UV-visible diffuse reflectance spectra (UV-visible DRS) and Mott-Schottky plots were used to evaluate the material's light absorption characteristics and energy band position. The band gap of ZnO and Zn₂GeO₄ samples were 3.27 eV and 4.56 eV, respectively, and the heterojunction was formed in the Z/ZGO sample. The presence of ZnO extended the spectral response range of Zn₂GeO₄, and due to the migration of photogenerated electron-hole pairs (EHPs) to ZnO, the recombination of EHPs was reduced. XPS analyses were also used to investigate change of oxygen vacancies during the reaction. The O 1s XPS spectra of the samples in the three cases (Case A:before light irradiation, Case B:after light irradiation and Case C:after reaction) were analyzed and found that the signal of the oxygen near the vacancies increased after light irradiation and decreased after reaction, which may indicate that oxygen vacancies were formed after light irradiation then consumed by CO₂ in the reaction. The Zn₂GeO₄ sample showed the largest increase in oxygen vacancies signal after light irradiation, indicating that Zn₂GeO₄ had a strong ability to form oxygen vacancies. Zn₂GeO₄ improves the capacity of oxygen vacancies formation in the sample, and further improved the yield of photo-thermochemical CO₂ splitting reaction. As a result, Z/ZGO combined the advantages of ZnO in light response and Zn₂GeO₄ in oxygen vacancies formation and improved the CO₂ splitting yield. This research has a positive effect on expanding the photo-thermochemical material system and further deepening the photo-thermochemical reaction mechanism.

Key words: CO₂ splitting, oxygen vacancy, photo-thermochemical reaction, heterojunction, Zn-based oxide

引用此文

张旭寒, 邓博文, 范海东, 黄文辉, 张彦威. 基于锌锗二元氧化物的光热协同分解CO₂研究[J]. 化学学报, 2020, 78(10): 1120-1126.

Zhang Xuhan, Deng Bowen, Fan Haidong, Huang Wenhui, Zhang Yanwei. Photo-thermochemical CO₂ Splitting Based on Zinc-germanium Binary Oxide[J]. Acta Chimica Sinica, 2020, 78(10): 1120-1126.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

参考文献

[1] Shih, C. F.; Zhang, T.; Li, J. H.; Bai, C. L. Joule 2018, 2, 1925.
[2] Shahsavari, A.; Akbari, M. Renew. Sust. Energ. Rev. 2018, 90, 275.
[3] Fu, J. W.; Yu, J. G.; Jiang, C. J.; Cheng, B. Adv. Energy Mater. 2018, 8, 1701503.
[4] Yang, L.; Chen, Z. G.; Dargusch, M. S.; Zou, J. Adv. Energy Mater. 2018, 8, 1701797.
[5] Guo, L.; Yang, Z.; Marcus, K.; Li, Z.; Luo, B.; Zhou, L.; Wang, X.; Du, Y.; Yang, Y. Energy Environ. Sci. 2018, 11, 106.
[6] Yan, J. Y.; Wang, C. H.; Ma, H.; Li, Y. Y.; Liu, Y. C.; Suzuki, N.; Terashima, C.; Fujishima, A.; Zhang, X. T. Appl. Catal. B-Environ. 2020, 268, 118401.
[7] Wang, L.; Ma, T.; Dai, S.; Ren, T.; Chang, Z.; Dou, L.; Fu, M.; Li, X. Chem. Eng. J. 2020, 389, 124426.
[8] Sun, S.; An, Q.; Watanabe, M.; Cheng, J.; Kim, H. H.; Akbay, T.; Takagaki, A.; Ishihara, T. Appl. Catal. B-Environ. 2020, 271, 118931.
[9] Thompson, W. A.; Fernandez, E. S.; Maroto-Valer, M. M. ACS Sustain. Chem. Eng. 2020, 8, 4677.
[10] Carrillo, R. J.; Scheffe, J. R. Energy Fuels 2019, 33, 12871.
[11] Marxer, D.; Furler, P.; Takacs, M.; Steinfeld, A. Energy Environ. Sci. 2017, 10, 1142.
[12] Agrafiotis, C.; Roeb, M.; Sattler, C. Renew. Sust. Energ. Rev. 2015, 42, 254.
[13] Xu, C.; Hong, J.; Sui, P.; Zhu, M.; Zhang, Y.; Luo, J.-L. Cell Rep. Phys. Sci. 2020, 1, 100101.
[14] Qi, Y.; Song, L.; Ouyang, S.; Liang, X.; Ning, S.; Zhang, Q.; Ye, J. Adv. Mater. 2020, 32, 1903915.
[15] Feng, C.; Tang, L.; Deng, Y.; Wang, J.; Liu, Y.; Ouyang, X.; Chen, Z.; Yang, H.; Yu, J.; Wang, J. Appl. Catal. B-Environ. 2020, 276, 119167.
[16] Cai, Q.; Wang, F.; He, J. Z.; Dan, M.; Cao, Y. H.; Yu, S.; Zhou, Y. Appl. Surf. Sci. 2020, 517, 146198.
[17] Zhao, L.; Qi, Y.; Song, L.; Ning, S.; Ouyang, S.; Xu, H.; Ye, J. Angew. Chem. Int. Ed. 2019, 58, 7708.
[18] Zhang, Y.; Xu, C.; Chen, J.; Zhang, X.; Wang, Z.; Zhou, J.; Cen, K. Appl. Energy. 2015, 156, 223.
[19] Zhang, Y.; Chen, J.; Xu, C.; Zhou, K.; Wang, Z.; Zhou, J.; Cen, K. Int. J. Hydrog. Energy 2016, 41, 2215.
[20] Xu, C.; Zhang, Y.; Pan, F.; Huang, W.; Deng, B.; Liu, J.; Wang, Z.; Ni, M.; Cen, K. Nano Energy 2017, 41, 308.
[21] Bhatta, S.; Nagassou, D.; Trelles, J. P. Solar Energy 2017, 142, 253.
[22] Li, Y.; Peng, Y. K.; Hu, L.; Zheng, J.; Prabhakaran, D.; Wu, S.; Puchtler, T. J.; Li, M.; Wong, K. Y.; Taylor, R. A.; Tsang, S. C. E. Nat Commun 2019, 10, 4421.
[23] Bhosale, R. R. Int. J. Hydrog. Energy 2020, 45, 5760.
[24] Carrillo, R. J.; Scheffe, J. R. Solar Energy 2017, 156, 3.
[25] Ebadi, A.; Mozaffari, M. J. Nanostructures 2020, 10, 1.
[26] Pei, L.; Xu, Y.; Liu, J.; Wu, J.; Han, Y.; Zhang, X. J. Am. Ceram. Soc. 2019, 102, 6517.
[27] Wang, Y.; Zheng, M.; Zhao, H.; Qin, H.; Fan, W.; Zhao, X. Phys. Chem. Chem. Phys. 2020, 22, 10265.
[28] Zhang, H.; Chen, Y.; Zhu, X.; Zhou, H.; Yao, Y.; Li, X. Int. J. Energy Res. 2019, 43, 5013.
[29] Xu, C.; Huang, W.; Li, Z.; Deng, B.; Zhang, Y.; Ni, M.; Cen, K. ACS Catal. 2018, 8, 6582.
[30] Ghoussoub, M.; Xia, M. K.; Duchesne, P. N.; Segal, D.; Ozin, G. Energy Environ. Sci. 2019, 12, 1122.
[31] Huang, D.; Yan, X.; Yan, M.; Zeng, G.; Zhou, C.; Wan, J.; Cheng, M.; Xue, W. ACS Appl. Mater. Interfaces 2018, 10, 21035.
[32] Ong, W. J.; Tan, L. L.; Ng, Y. H.; Yong, S. T.; Chai, S. P. Chem. Rev. 2016, 116, 7159.
[33] Xu, C.; Lin, J.; Pan, F.; Deng, B.; Wang, Z.; Zhou, J.; Chen, Y.; Ma, J.; Gu, Z.; Zhang, Y. Acta Chim. Sinica 2017, 75, 699. (许辰宇, 林伽毅, 潘富强, 邓博文, 王智化, 周俊虎, 陈云, 马京程, 顾志恩, 张彦威, 化学学报, 2017, 75, 699.)
[34] Kumar, P.; Kumar, A.; Rizvi, M. A.; Moosvi, S. K.; Krishnan, V.; Duvenhage, M. M.; Roos, W. D.; Swart, H. C. Appl. Surf. Sci. 2020, 514, 145930.
[35] Tong, Z. K.; Fang, S.; Zheng, H.; Zhang, X. G. Acta Chim. Sinica 2016, 74, 185. (童震坤, 方姗, 郑浩, 张校刚, 化学学报, 2016, 74, 185.)
[36] Zhou, J.; Zhang, W.; Zhao, H.; Tian, J.; Zhu, Z.; Lin, N.; Qian, Y. ACS Appl. Mater. Interfaces 2019, 11, 22371.
[37] Zhang, F.; Li, Y.-H.; Qi, M.-Y.; Tang, Z.-R.; Xu, Y.-J. Appl. Catal. B-Environ. 2020, 268, 118380.
[38] Adhikari, S.; Kim, D.-H. Appl. Surf. Sci. 2020, 511, 145595.
[39] Docao, S.; Koirala, A. R.; Kim, M. G.; Hwang, I. C.; Song, M. K.; Yoon, K. B. Energy Environ. Sci. 2017, 10, 628.
[40] Long, X.; Gao, L.; Li, F.; Hu, Y.; Wei, S.; Wang, C.; Wang, T.; Jin, J.; Ma, J. Appl. Catal. B 2019, 257, 117813.
[41] Mandal, S.; Ananthakrishnan, R. Inorg. Chem. 2020, 59, 7681.
[42] Low, J. X.; Yu, J. G.; Jaroniec, M.; Wageh, S.; Al-Ghamdi, A. A. Adv. Mater. 2017, 29, 1601694.
[43] Mei, Q. F.; Zhang, F. Y.; Wang, N.; Lu, W. S.; Su, X. T.; Wang, W.; Wu, R. L. Chin. J. Inorg. Chem. 2019, 35, 1321. (梅邱峰, 张飞燕, 王宁, 鲁闻生, 宿新泰, 王伟, 武荣兰, 无机化学学报, 2019, 35, 1321.)
[44] Luo, X.; Ke, Y.; Yu, L.; Wang, Y.; Homewood, K. P.; Chen, X.; Gao, Y. Appl. Surf. Sci. 2020, 515, 145970.
[45] Du, S.-Q.; Yuan, Y.-F.; Tu, W.-X. Acta Phys.-Chim. Sin. 2013, 29, 2062. (杜书青, 袁宇峰, 涂伟霞, 物理化学学报, 2013, 29, 2062.)
[46] Zhang, X.; Zhang, L.; Deng, B.; Jin, J.; Xu, C.; Zhang, Y. Catal. Commun. 2020, 138, 105955.
[47] Tien, L.-C.; Yang, F.-M.; Huang, S.-C.; Fan, Z.-X.; Chen, R.-S. J. Appl. Phys. 2018, 124, 174503.
[48] Kim, D. Y.; Yoon, T.; Jang, Y. J.; Lee, J. H.; Na, Y.; Lee, B. J.; Lee, J. S.; Kim, K. S. J. Phys. Chem. C 2019, 123, 14573.
[49] Wang, B.; Wang, X.; Lu, L.; Zhou, C.; Xi, Z.; Wang, J.; Ke, X.-k.; Sheng, G.; Yan, S.; Zou, Z. ACS Catal. 2018, 8, 516.
[50] Liang, Y. C.; Lin, T. Y. Nanoscale Res. Lett. 2014, 9, 344.
[51] Xiao, F.-X. ACS Appl. Mater. Interfaces 2012, 4, 7052.

基于锌锗二元氧化物的光热协同分解CO₂研究

Photo-thermochemical CO₂ Splitting Based on Zinc-germanium Binary Oxide

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

参考文献

相关文章 15

编辑推荐

相关统计

本文评价

[1]	张凯, 武晓君. 具有室温铁磁性的二维Janus钛硫属化物^★[J]. 化学学报, 2023, 81(9): 1142-1147.
[2]	刘嘉文, 林玮璜, 王惟嘉, 郭学益, 杨英. Cu_1.94S-SnS纳米异质结的合成及其光催化降解研究[J]. 化学学报, 2023, 81(7): 725-734.
[3]	郭瑞, 魏星, 曹末云, 张研, 杨云, 樊继斌, 刘剑, 田野, 赵泽坤, 段理. AlAs/InSe范德华异质结构的光学和可调谐电子特性[J]. 化学学报, 2022, 80(4): 526-534.
[4]	刘欢, 李京哲, 李平, 张广智, 张广智, 张豪, 邱灵芳, 齐晖, 多树旺. 2D/3D ZnIn₂S₄/TiO₂复合物的原位构筑及其提高的光催化性能[J]. 化学学报, 2021, 79(10): 1293-1301.
[5]	李宸, 陈凤华, 叶丽, 李伟, 于晗, 赵彤. B,N共掺杂的In₂O₃/TiO₂制备与光催化产氢性能研究[J]. 化学学报, 2020, 78(12): 1448-1454.
[6]	张宇, 王世兴, 杨蕊, 戴腾远, 张楠, 席聘贤, 严纯华. Co₉S₈/MoS₂异质结构的构筑及电催化析氢性能研究[J]. 化学学报, 2020, 78(12): 1455-1460.
[7]	刘茹雪, 何小燕, 牛力同, 吕柏霖, 余菲, 张哲, 杨志旺. 具有分级纳米结构的In₂S₃/CdIn₂S₄在可见光下催化苯甲胺的氧化偶联反应[J]. 化学学报, 2019, 77(7): 653-660.
[8]	张倩, 刘庆青, 张倩倩, 范霞, 翟锦. 简易制备高整流比的异质纳米通道[J]. 化学学报, 2018, 76(5): 400-407.
[9]	许辰宇, 林伽毅, 潘富强, 邓博文, 王智化, 周俊虎, 陈云, 马京程, 顾志恩, 张彦威. Ni离子替位掺杂TiO₂增强光热化学循环还原CO₂研究[J]. 化学学报, 2017, 75(7): 699-707.
[10]	赵秘, 李浩华, 沈小平. 电化学沉积法制备CeO₂@Ag@CdSe纳米管阵列及其光电化学性能研究[J]. 化学学报, 2016, 74(10): 825-832.
[11]	蔡钊, 邝允, 罗亮, 王利人, 孙晓明. Au-Ni异质结纳米晶的尺寸调控[J]. 化学学报, 2013, 71(9): 1265-1269.
[12]	田雷雷, 魏贤勇, 庄全超, 宗志敏, 孙世刚. 石墨烯包裹Cu₂₊₁O/Cu复合材料的制备及其储锂性能[J]. 化学学报, 2013, 71(9): 1270-1274.
[13]	谢云龙, 钟国, 杜高辉. 硫化锌与硫化锌/氧化锌异质结纳米线的化学气相沉积法制备与表征[J]. 化学学报, 2012, 70(10): 1221-1226.
[14]	杨志胜, 杨立功, 吴刚, 汪茫, 陈红征. 基于有机/无机杂化钙钛矿有序结构的异质结及其光伏性能的研究[J]. 化学学报, 2011, 69(06): 627-632.
[15]	阎建辉,刘强,关鲁雄,梁丰,顾豪杰. 载铂Sr(Zr_1－xY_x)O_3－δ-TiO₂异质结光催化剂模拟太阳光催化产氢[J]. 化学学报, 2008, 66(8): 879-884.