合理设计具有空间分离催化位点的中空立方体顺序材料作为高效的全解水光催化剂

doi:10.1016/S1872-2067(20)63706-8

摘要/Abstract

摘要：

通过精细的纳米结构和化学组成控制, 开发高效的全解水纳米光催化剂是一项具有挑战性的任务. 此外, 在光催化水氧化的半反应过程中, 抑制纳米材料严重光腐蚀也是一项艰巨的任务, 需要有效地提高纳米材料光生空穴转移的动力学. 为此, 本文通过可控的化学反应, 设计制备了具有空间催化活性位点分布的Co-MnO₂@CdS/CoS中空立方体顺序材料, 并用作可见光催化全解水催化剂. 采用MOFs作为自模板, 经过连续的阴离子交换和阳离子交换反应, 将Co掺杂的氧化助催化剂(纳米片Co-MnO₂)和还原助催化剂(纳米粒子CoS)同时整合到中空的立方体CdS纳米材料中, 使得超薄的二维纳米片Co-MnO₂与立方体的内部界面均匀接触, 能够有效地提高空穴的转移效率. 同时, CoS纳米粒子均匀分散在CdS纳米材料的壁上, 能够有效地转移光生电子, 从而提高光生电子-空穴对的分离效率. 实验测试表明, Co-MnO₂@CdS/CoS中空立方体顺序材料可以为表面氧化-还原反应提供丰富的反应活性位点, 同时有助于提高CdS纳米材料光生电子-空穴对的分离和迁移效率. 特别是分散在CdS中空立方体壁面上的CoS纳米颗粒被确定为加速氢气生成的还原型助催化剂, 能够促进水中氢离子生成氢气; 而附着在CdS中空立方体内壁上的Co-MnO₂纳米片被确定为促进氧演化动力学的氧化型助催化剂, 能够促进水生成氧气. 因此, 在本实验中, 得益于理想的纳米结构和化学组成方面的优势, Co-MnO₂@CdS/CoS纳米立方体显示了高效的光催化全解水性能: 在没有贵金属作为助催化剂存在时, 它显示了很好的整体光催化水分解效率(735.4 (H₂)和361.1 (O₂) μmol h^-1 g^-1), 超过了大多数文献报道的CdS基催化剂光解水效率. 此外, 以420 nm单波长光为入射光, 进行了量子效率(AQE)测试, 最优的Co-MnO₂@CdS/CoS纳米材料的表观AQE达1.32%. 本文合成的顺序材料为构筑具有活性位点空间分布的高效全解水催化剂提供了新的思路.

关键词: 顺序材料, 空心立方体, 整体水裂解, 阴离子/阳离子交换, 空间分离位点

Abstract:

The development of metal sulfide catalysts with remarkable activity toward efficient overall photocatalytic water splitting remains challenging owing to the dominant charge recombination and deficient catalytic active sites. Moreover, in the process of water oxidation catalysis, the inhibition of severe photocorrosion is an immense task, requiring effective photogenic hole-transfer kinetics. Herein, stratified Co-MnO₂@CdS/CoS hollow cubes with spatially separated catalytic sites were rationally designed and fabricated as highly efficient controllable catalysts for photocatalytic overall water splitting. The unique self-templated method, including a continuous anion/cation-exchange reaction, integrates a Co-doped oxidation co-catalyst (Co-MnO₂) and a reduction co-catalyst (CoS) on the nanocubes with uniform interface contact and ultrathin two-dimensional (2D) nanometer sheets. We demonstrate that the stratified Co-MnO₂@CdS/CoS hollow cubes can provide an abundance of active sites for surface redox reactions and contribute to the separation and migration of the photoionization charge carriers. In particular, CoS nanoparticles dispersed on the walls of CdS hollow cubes were identified as reduction co-catalysts accelerating hydrogen generation, while Co-MnO₂ nanosheets attached to the inner walls of the CdS hollow cube were oxidation co-catalysts, promoting oxygen evolution dynamics. Benefiting from the desirable structural and compositional advantages, optimized stratification of Co-MnO₂@CdS/CoS nanocubes provided a catalytic system devoid of precious metals, which exhibited a remarkable overall photocatalytic water-splitting rate (735.4 (H₂) and 361.1 (O₂) μmol h^-1 g^-1), being among the highest values reported thus far for CdS-based catalysts. Moreover, an apparent quantum efficiency (AQE) of 1.32% was achieved for hydrogen evolution at 420 nm. This study emphasizes the importance of rational design on the structure and composition of photocatalysts for overall water splitting.

Key words: Stratified material, Hollow cubes, Overall water splitting, Anion/cation exchange, Spatially separated site

李义磊, 王晓静, 郝影娟, 赵君, 刘英, 穆惠英, 李发堂. 合理设计具有空间分离催化位点的中空立方体顺序材料作为高效的全解水光催化剂[J]. 催化学报, 2021, 42(6): 1040-1050.

Yi-Lei Li, Xiao-Jing Wang, Ying-Juan Hao, Jun Zhao, Ying Liu, Hui-Ying Mu, Fa-Tang Li. Rational design of stratified material with spatially separated catalytic sites as an efficient overall water-splitting photocatalyst[J]. Chinese Journal of Catalysis, 2021, 42(6): 1040-1050.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63706-8

https://www.cjcatal.com/CN/Y2021/V42/I6/1040

图/表 7

Fig. 1. Schematic illustration of hierarchical Co-MnO2@CdS/CoS hollow cube synthesis.

Fig. 2. SEM images of ZIF-67 (a), ZIF-67@CoS (b), Co-MnO2@CoS (c), and Co-MnO2@CdS/CoS (d) samples; TEM images of ZIF-67 (e), ZIF-67@CoS (f), Co-MnO2@CoS (g), and Co-MnO2@CdS/CoS (h); (i) Amplified TEM of Co-MnO2@CdS/CoS; (j,k) HRTEM images of Co-MnO2@CdS/CoS; (l) Scanning TEM (STEM) image of Co-MnO2@CdS/ CoS and its corresponding elemental mapping images.

Fig. 3. XPS spectra of Co-MnO2@CdS/CoS heterostructures. (a) survey spectrum; high-resolution XPS spectra of Cd 3d (b), Co 2p (c), S 2p (d), Mn 2p (e), and O 1s (f).

Fig. 4. Steady-state PL spectra (a), TRPL spectra (b), and transient photocurrent spectra (c) of CdS, CdS/CoS, Co-MnO2@CdS and Co-MnO2@CdS/CoS.

Fig. 5. (a) Time-yield plots of Co-MnO2@CdS/CoS-3 and CdS; (b) Photocatalytic H2 and O2 evolution activities of CdS and Co-MnO2@CdS/CoS-3; (c) Photocatalytic H2 and O2 evolution activities of distinct response time samples; (d) Photocatalytic H2 and O2 evolution activities of various constituent samples.

Fig. 6. (a) Cycling of photocatalytic water splitting over Co-MnO2@CdS/CoS-3; (b) Experimental study of the reverse reaction of Co-MnO2@CdS/CoS-3.

Fig. 7. Schematic illustration of the Co-MnO2@CdS/CoS hollow cube structures for overall photocatalytic water splitting.

参考文献

[1]	R. Kuriki, T. Ichibha, K. Hongo, D. Lu, R. Maezono, H. Kageyama, O. Ishitani, K. Oka, K. Maeda, J. Am. Chem. Soc., 2018,140, 6648-6655.
[2]	Y. Xiao, G. Tian, W. Li, Y. Xie, B. Jiang, C. Tian, D. Zhao, H. Fu, J. Am. Chem. Soc., 2019,141, 2508-2515.
[3]	X. Tian, Y.-J. Sun, J.-Y. He, X.-J. Wang, J. Zhao, S.-Z. Qiao, F.-T. Li, J. Mater. Chem. A, 2019,7, 7628-7635.
[4]	J. Ran, J. Qu, H. Zhang, T. Wen, H. Wang, S. Chen, L. Song, X. Zhang, L. Jing, R. Zheng, S. Z. Qiao, Adv. Energy Mater., 2019,9, 1803402.
[5]	X. Chen, R. Shi, Q. Chen, Z. Zhang, W. Jiang, Y. Zhu, T. Zhang, Nano Energy, 2019,59, 644-650.
[6]	R. Gao, B. Cheng, J. Fan, J. Yu, W. Ho, Chin. J. Catal., 2021,42, 15-24.
[7]	Y. Jia, D. Zhao, M. Li, H. Han, C. Li, Chin. J. Catal., 2018,39, 421-430.
[8]	M. F. Kuehnel, C. E. Creissen, C. D. Sahm, D. Wielend, A. Schlosser, K. L. Orchard, E. Reisner, Angew. Chem. Int. Ed., 2019,58, 5059-5063.
[9]	Z. Zhang, Z. Zhao, Y. Hou, H. Wang, X. Li, G. He, M. Zhang, Angew. Chem. Int. Ed., 2019,58, 8862-8866.
[10]	J. Ran, W. Guo, H. Wang, B. Zhu, J. Yu, S. Z. Qiao, Adv. Mater., 2018,30, e1800128.
[11]	Y.-L. Li, Y. Liu, Y.-J. Hao, X.-J. Wang, R.-H. Liu, F.-T. Li, Mater. Design, 2020,187, 108379.
[12]	H. Yang, J. Yin, R. Cao, P. Sun, S. Zhang, X. Xu, Sci. Bull., 2019,64, 1510-1517.
[13]	R. Li, Chin. J. Catal., 2017,38, 5-12.
[14]	Z. Li, L. Zhang, Y. Liu, C. Shao, Y. Gao, F. Fan, J. Wang, J. Li, J. Yan, R. Li, C. Li, Angew. Chem. Int. Ed., 2020,59, 935-942.
[15]	Y. Zhao, C. Ding, J. Zhu, W. Qin, X. Tao, F. Fan, R. Li, C. Li, Angew. Chem. Int. Ed., 2020,59, 9653-9658.
[16]	W. Wei, Q. Tian, H. Sun, P. Liu, Y. Zheng, M. Fan, J. Zhuang, Appl. Catal. B, 2020,260, 118153.
[17]	L. Su, L. Luo, H. Song, Z. Wu, W. Tu, Z.-J. Wang, J. Ye, Chem. Eng. J., 2020,124346.
[18]	Y. Li, T. Jin, G. Ma, Y. Li, L. Fan, X. Li, Dalton Trans., 2019,48, 5649-5655.
[19]	X. Zhang, H. Liang, H. Li, Y. Xia, X. Zhu, L. Peng, W. Zhang, L. Liu, T. Zhao, C. Wang, Angew. Chem. Int. Ed., 2019,58, 3287-3293.
[20]	R. Li, Chin. J. Catal., 2018,39, 1180-1188.
[21]	S. Wang, Y. Wang, S. Q. Zang, X. W. Lou, Small Methods, 2019,4, 1900586.
[22]	J. Qi, X. Lai, J. Wang, H. Tang, H. Ren, Y. Yang, Q. Jin, L. Zhang, R. Yu, G. Ma, Z. Su, H. Zhao, D. Wang, Chem. Soc. Rev., 2015,44, 6749-6773.
[23]	X. Li, S. Guo, W. Li, X. Ren, J. Su, Q. Song, A. J. Sobrido, B. Wei, Nano Energy, 2019,57, 388-397.
[24]	D. Zheng, X.-N. Cao, X. Wang, Angew. Chem. Int. Ed., 2016,55, 11512-11516.
[25]	S. Wang, B. Y. Guan, X. W. D. Lou, J. Am. Chem. Soc., 2018,140, 5037-5040.
[26]	P. Zhang, S. Wang, B. Y. Guan, X. W. Lou, Energy Environ. Sci., 2019,12, 164-168.
[27]	J. Kong, Z. Rui, H. Ji, Ind. Eng. Chem. Res., 2017,56, 9999-10008.
[28]	P. Zhang, X. W. D. Lou, Adv. Mater., 2019,31, e1900281.
[29]	B. Qiu, Q. Zhu, M. Du, L. Fan, M. Xing, J. Zhang, Angew. Chem. Int. Ed., 2017,56, 2684-2688.
[30]	J. Chu, G. Sun, X. Han, X. Chen, J. Wang, W. Hu, I. Waluyo, A. Hunt, Y. Du, B. Song, P. Xu, Nanoscale, 2019,11, 15633-15640.
[31]	D. Wang, T. Hisatomi, T. Takata, C. Pan, M. Katayama, J. Kubota, K. Domen, Angew. Chem. Int. Ed., 2013,52, 11252-11256.
[32]	M. Xing, B. Qiu, M. Du, Q. Zhu, L. Wang, J. Zhang, Adv. Funct. Mater., 2017,27, 1702624.
[33]	Z. Ye, T. Li, G. Ma, Y. Dong, X. Zhou, Adv. Funct. Mater., 2017,27, 1704083.
[34]	J. Zhang, Z. Yu, Z. Gao, H. Ge, S. Zhao, C. Chen, S. Chen, X. Tong, M. Wang, Z. Zheng, Y. Qin, Angew. Chem. Int. Ed., 2017,56, 816-820.
[35]	B. Sun, W. Zhou, H. Li, L. Ren, P. Qiao, W. Li, H. Fu, Adv. Mater., 2018,30, 1804282.
[36]	J. Peng, J. Shen, X. Yu, H. Tang, Zulfiqar, Q. Liu, Chin. J. Catal., 2021,42, 87-96.
[37]	B. Li, Y. Zhang, D. Ma, Z. Xing, T. Ma, Z. Shi, X. Ji, S. Ma, Chem. Sci., 2016,7, 2138-2144.
[38]	D. Zhang, A. B. Wong, Y. Yu, S. Brittman, J. Sun, A. Fu, B. Beberwyck, A. P. Alivisatos, P. Yang, J. Am. Chem. Soc., 2014,136, 17430-17433.
[39]	Y. Zhou, W. Zhou, D. Hou, G. Li, J. Wan, C. Feng, Z. Tang, S. Chen, Small, 2016,12, 2768-2774.
[40]	C. Guan, X. Liu, W. Ren, X. Li, C. Cheng, J. Wang, Adv. Energy Mater., 2017,7, 1602391.
[41]	J. Chen, Z. Shen, S. Lv, K. Shen, R. Wu, X.-F. Jiang, T. Fan, J. Chen, Y. Li, J. Mater. Chem. A, 2018,6, 19631-19642.
[42]	X. Zhang, H. Liang, H. Li, Y. Xia, X. Zhu, L. Peng, W. Zhang, L. Liu, T. Zhao, C. Wang, Z. Zhao, C. T. Hung, M. M. Zagho, A. A. Elzatahry, W. Li, D. Zhao, Angew. Chem. Int. Ed. Engl., 2020,59, 3287-3293.
[43]	H. Hu, B. Y. Guan, X. W. Lou, Chem, 2016,1, 102-113.
[44]	Y. Yun, H. Sheng, K. Bao, L. Xu, Y. Zhang, D. Astruc, M. Zhu, J. Am. Chem. Soc., 2020,142, 4126-4130.
[45]	Y. Zhang, M. Wu, Y. H. Kwok, Y. Wang, W. Zhao, X. Zhao, H. Huang, D. Y. C. Leung, Appl. Catal. B, 2019,259, 118034.
[46]	Y. Zhao, J. Zhang, W. Wu, X. Guo, P. Xiong, H. Liu, G. Wang, Nano Energy, 2018,54, 129-137.
[47]	S. Wang, B. Zhu, M. Liu, L. Zhang, J. Yu, M. Zhou, Appl. Catal. B, 2019,243, 19-26.
[48]	H. Xu, J. Cao, C. Shan, B. Wang, P. Xi, W. Liu, Y. Tang, Angew. Chem. Int. Ed., 2018,57, 8654-8658.
[49]	M. Wang, M. Shen, L. Zhang, J. Tian, X. Jin, Y. Zhou, J. Shi, Carbon, 2017,120, 23-31.
[50]	L. Shang, B. Tong, H. Yu, G. I. N. Waterhouse, C. Zhou, Y. Zhao, M. Tahir, L.-Z. Wu, C.-H. Tung, T. Zhang, Adv. Energy Mater., 2016,6, 1501241.
[51]	J. Wen, X. Li, H. Li, S. Ma, K. He, Y. Xu, Y. Fang, W. Liu, Q. Gao, Appl. Surf. Sci., 2015,358, 204-212.
[52]	J. Zhang, S. Z. Qiao, L. Qi, J. Yu, Phys. Chem. Chem. Phys., 2013,15, 12088-12094.
[53]	R.-B. Wei, Z.-L. Huang, G.-H. Gu, Z. Wang, L. Zeng, Y. Chen, Z.-Q. Liu, Appl. Catal. B, 2018,231, 101-107.
[54]	G. R. Bamwenda, T. Uesigi, Y. Abe, K. Sayama, H. Arakawa, Appl. Catal. A, 2001,205, 117-128.
[55]	T. Takata, C. Pan, M. Nakabayashi, N. Shibata, K. Domen, J. Am. Chem. Soc., 2015,137, 9627-9634.
[56]	Z. Pan, G. Zhang, X. Wang, Angew. Chem. Int. Ed., 2019,58, 7102-7106.
[57]	K. Maeda, K. Teramura, D. Lu, N. Saito, Y. Inoue, K. Domen, Angew. Chem. Int. Ed., 2006,118, 7970-7973.
[58]	S. Samanta, S. Martha, K. Parida, ChemCatChem, 2014,6, 1453-1462.
[59]	R. Li, J. Liu, X. Zhang, Y. Wang, Y. Wang, C. Zhang, X. Zhang, C. Fan, Chem. Eng. J., 2018,339, 42-50.
[60]	J. Fu, C. Bie, B. Cheng, C. Jiang, J. Yu, ACS Sustain. Chem. Eng., 2018,6, 2767-2779.
[61]	R. Li, F. Zhang, D. Wang, J. Yang, M. Li, J. Zhu, X. Zhou, H. Han, C. Li, Nat. Commun., 2013,4, 1432.
[62]	X. Zhou, Y. Fang, X. Cai, S. Zhang, S. Yang, H. Wang, X. Zhong, Y. Fang, ACS Appl. Mater. Interfaces, 2020,12, 20579-20588.