源于功函数差异的界面内建电场调控载流子定向分离的作用机制研究

doi:10.1016/S1872-2067(20)63649-X

催化学报 ›› 2021, Vol. 42 ›› Issue (4): 583-594.DOI: 10.1016/S1872-2067(20)63649-X

源于功函数差异的界面内建电场调控载流子定向分离的作用机制研究

薛超^a, 安华^b, 邵国胜^a, 杨贵东^b^,^*()

^a郑州大学材料科学与工程学院, 国家低碳环保材料智能设计国际联合研究中心, 河南郑州450001
^b西安交通大学化学工程与技术学院, 西安交通大学-牛津大学催化国际联合实验室, 陕西西安710049

收稿日期:2020-04-29 接受日期:2020-05-26 出版日期:2021-04-18 发布日期:2021-01-22
通讯作者: 杨贵东
基金资助:
国家自然科学基金(U1862105);河南省重点研发与推广专项(科技攻关)(202102210053);中国博士后科学基金(2019M662515);王宽诚教育基金.

Accelerating directional charge separation via built-in interfacial electric fields originating from work-function differences

Chao Xue^a, Hua An^b, Guosheng Shao^a, Guidong Yang^b^,^*()

^aState Centre for International Cooperation on Designer Low-carbon and Environmental Materials (CDLCEM), School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
^bXJTU-Oxford International Joint Laboratory for Catalysis, School of Chemical Engineering and Technology, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, China

Received:2020-04-29 Accepted:2020-05-26 Online:2021-04-18 Published:2021-01-22
Contact: Guidong Yang
About author:^*Tel/Fax: +86-29-82668658; E-mail: guidongyang@xjtu.edu.cn
Supported by:
National Natural Science Foundation of China(U1862105);Key R&D and Promotion Special Project (Science and Technology Research) of Henan Province(202102210053);China Postdoctoral Science Foundation(2019M662515);K. C. Wong Education Foundation, Hong Kong, China

摘要/Abstract

摘要：

近年来, 由有机污染物和重金属引起的水污染对人类健康、生态系统和社会可持续发展构成了严重威胁. 而光催化技术以其高效、低成本、节能、无二次污染等优点成为解决日益严重的环境污染问题的一个极具吸引力的策略. 众所周知, 宽光谱吸收、高效载流子分离和快速的表面反应动力学是高性能光催化剂所必备的基本条件. 而多孔TiO₂空心球具有以下结构优势: (1)成本低、无毒、氧化还原电位适中、物理化学性质稳定; (2)中空结构有利于入射光多重散射, 而且大表面积可以暴露更多的活性位点; (3)多孔结构有利于传质过程. 但是, 窄光谱吸收和低的光生载流子分离效率严重阻碍了空心结构TiO₂的实际应用. 因此, 通过耦合窄带隙半导体构建异质结光催化剂可以有效提高光吸收和促进光生电荷的分离. 窄带隙(E_g = 2.18-2.44 eV)半导体材料SnS₂具有无毒、化学性质稳定、低成本和宽谱响应等诸多优点. 若将超薄SnS₂纳米片锚定生长在多孔TiO₂空心球表面, 将对异质结的光催化性能产生显著的影响. 一方面, 分级结构的空心球具有高可见光捕获率; 另一方面, 超薄SnS₂纳米片具有更短的载流子扩散距离, 从而有效地抑制光生载流子在催化剂体相内部复合. 然而, 由于其能带结构的限制, 二元TiO₂/SnS₂复合材料很容易形成嵌入式I型异质结, 在很大程度上降低了光催化氧化还原能力. 此外, 在光催化剂表面聚集的光生电子和空穴容易发生随机性复合. 因此, 迫切需要通过引入界面驱动力来调节表面载流子的分离和转移. 众多研究表明, 通过化学功能化可以实现对还原氧化石墨烯(rGO)的能带结构、功函数、电导率、亲水性和光学性质的调控. 功能化的rGO可以作为优良的空穴提取材料, 在rGO两侧分别耦合不同能级结构的半导体光催化材料, 通过异质界面能级和功函数差异带来的界面内建电场, 精确调控光生载流子在界面间的空间分离和定向迁移.
基于上述分析, 本文通过改进的“硅保护煅烧”方法合成了分级多孔SnS₂/rGO/TiO₂空心球异质结光催化剂. 分级多孔空心球的结构优势不仅增强其光捕获能力, 而且为光氧化还原反应提供了丰富的活性位点. 特别是, 在TiO₂和SnS₂纳米薄片之间嵌入的rGO中间层可以作为空穴注入层. 由不同功函数导致的界面内建电场可以精确地调控光生空穴从SnS₂纳米薄片的价带向rGO空穴注入层定向迁移, 显著延长了光生载流子的寿命. 在可见光照射下, 负载2 wt% rGO的分级多孔SnS₂/rGO/TiO₂空心球异质结光催化剂对罗丹明B染料的降解率可达97.3%, 对Cr(VI)的还原效率可达97.09%. 此外, 经过六个周期的循环实验, 该异质结催化降解罗丹明B和还原Cr(VI)的效率没有明显降低, 表现出较好的光催化稳定性.

关键词: SnS₂/rGO/TiO₂, 空心球, 光催化剂, 空穴注入层, Cr(VI)还原

Abstract:

In this work, a hierarchical porous SnS₂/rGO/TiO₂ hollow sphere heterojunction that allows highly-efficient light utilization and shortening distance of charge transformation is rationally designed and synthesized. More importantly, an rGO interlayer is successfully embedded between the TiO₂hollow sphere shells and outermost SnS₂ nanosheets. This interlayer functions as a bridge to connect the two light-harvesting semiconductors and acts as a hole injection layer in the tandem heterojunction. The induced built-in electric fields on both sides of the interface precisely regulate the spatial separation and directional migration of the photo-generated holes from the light-harvesting semiconductor to the rGO hole injection interlayer. These synergistic effects greatly prolong the lifetime of the photo-induced charge carriers. The optimized tandem heterojunction with a 2 wt% rGO loading demonstrate enhanced visible-light-driven photocatalytic activity for Rhodamine B (RhB) dye degradation (removal rate: 97.3%) and Cr(VI) reduction (removal rate: 97.09%). This work reveals a new strategy for the rational design and assembly of hollow-structured photocatalytic materials with spatially separated reduction and oxidation surfaces to achieve excellent photocatalytic performance.

Key words: SnS₂/rGO/TiO₂, Hollow sphere, Photocatalyst, Hole injection layer, Cr(VI) reduction

薛超, 安华, 邵国胜, 杨贵东. 源于功函数差异的界面内建电场调控载流子定向分离的作用机制研究[J]. 催化学报, 2021, 42(4): 583-594.

Chao Xue, Hua An, Guosheng Shao, Guidong Yang. Accelerating directional charge separation via built-in interfacial electric fields originating from work-function differences[J]. Chinese Journal of Catalysis, 2021, 42(4): 583-594.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63649-X

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图/表 8

Scheme 1. Schematic illustration of the synthetic procedure of the hierarchical porous SnS2/rGO/TiO2 hollow spheres.

Fig. 1. SEM (a), TEM (b), and HRTEM (c) images of TiO2 hollow spheres; SEM (d), TEM (e), and HRTEM (f) images (inset of (e) is the corresponding SAED pattern) of GO/TiO2 composite (TG-4; 2 wt% GO loading).

Fig. 2. SnS2/rGO/TiO2 composite with 2 wt% GO loading (TGS-4 composite): (a,d) SEM and (b,c) TEM images. EDS elemental mapping images of a selected area: (e) Ti, (f) O, (g) C, (h) Sn, and (i) S. (j) Corresponding SAED pattern and (k) HRTEM image.

Fig. 3. XRD patterns (a) and Raman spectra (b) of the as-prepared samples obtained using an excitation wavelength of 633 nm; XPS survey spectrum (c) and high-resolution XPS spectra of the C 1s (d), O 1s (e), Ti 2p (f), S 2p (g), and Sn 3d (h) core levels of the different samples.

Fig. 4. Plots of RhB degradation (a) and Cr(VI) reduction (c); Cycling experiment results for the degradation of RhB (b) and reduction of Cr(VI) (d) over the TGS-4 composite; Plots of RhB degradation (e) and Cr(VI) reduction (f) over the TGS-4 composite in the presence of different scavengers. (CRhB = 20 mg L-1; CK2Cr2O7 = 100 mg·L-1).

Fig. 5. N2 adsorption-desorption isotherms of TiO2 (a) and the TGS-4 composite (b); (c) UV-vis DRS spectra; (d) PL spectra excited at 325 nm; Transient photocurrent responses (e) and Nyquist plots (f) for the as-synthesized samples. The insets in (a) and (b) are the corresponding pore-size distribution curves.

Fig. 6. (a-d) UPS spectra of the different samples; Mott-Schottky plots of TiO2 (e) and SnS2 (f) in 2 moL L-1 Na2SO4 electrolytes.

Fig. 7. Schematic of the energy level alignment and corresponding charge transfer process in the TS-2 (a) and TGS-4 (b) composites during the photoredox reactions.

参考文献

[1]	L. Yang, J. Huang, L. Shi, L. Cao, H. Liu, Y. Liu, Y. Li, H. Song, Y. Jie, J. Ye, Appl. Catal. B, 2018,221, 670-680.
[2]	L. Han Y.-L. Zhong, K. Lei, D. Mao, Y.-Z. Dong, G. Hong, Y.-T. Zhou, D. Fang, , J. Phys. Chem. C, 2019,123, 2398-2409.
[3]	M.-H. Wu, L. Li, Y.-C. Xue, G. Xu, L. Tang, N. Liu, W.-Y. Huang, Appl. Catal. B, 2018,228, 103-112.
[4]	D. Cao, H. An, X. Yan, Y. Zhao, G. Yang, H. Mei, Acta Phys.-Chim. Sin., 2020,36, 1901051.
[5]	X. Shi, Z. Lou, P. Zhang, M. Fujitsuka, T. Majima, ACS Appl. Mater. Interfaces, 2016,8, 31738-31745.
[6]	B. Sun, W. Zhou, H. Li, L. Ren, P. Qiao, W. Li, H. Fu, Adv. Mater., 2018,30, e1804282.
[7]	P. Zhang, X. W. D. Lou, Adv. Mater., 2019,31, e1900281.
[8]	M. Xiao, Z. Wang, M. Lyu, B. Luo, S. Wang, G. Liu, H. M. Cheng, L. Wang, Adv. Mater., 2018,e1801369.
[9]	Q. Sun, N. Wang, J. Yu, J. C. Yu, Adv. Mater., 2018,30, e1804368.
[10]	S. Wang, B. Y. Guan, X. Wang, X. W. D. Lou, J. Am. Chem. Soc., 2018,140, 15145-15148.
[11]	M. Xing, B. Qiu, M. Du, Q. Zhu, L. Wang, J. Zhang, Adv. Funct. Mater., 2017,27, 1702624.
[12]	L. Ling, L. Liu, Y. Feng, J. Zhu, Z. Bian, Chin. J. Catal., 2018,39, 639-645.
[13]	X. Chen, R. Shi, Q. Chen, Z. Zhang, W. Jiang, Y. Zhu, T. Zhang, Nano Energy, 2019,59, 644-650.
[14]	Y. Al Salka, L. I. Granone, W. Ramadan, A. Hakki, R. Dillert, D. W. Bahnemann, Appl. Catal. B, 2019,244, 1065-1095.
[15]	G. D. Gesesse, C. Li, E. Paineau, Y. Habibi, H. Remita, C. Colbeau-Justin, M. N. Ghazzal, Chem. Mater., 2019,31, 4851-4863.
[16]	J. Pan, Z. Guan, J. Yang, Q. Li, Chin. J. Catal., 2020,41, 200-208.
[17]	B. Srinivas, M. A. Pandit, K. Muralidharan, ACS Omega, 2019,4, 14970-14980.
[18]	X. Jiao, X. Li, X. Jin, Y. Sun, J. Xu, L. Liang, H. Ju, J. Zhu, Y. Pan, W. Yan, Y. Lin, Y. Xie, J. Am. Chem. Soc., 2017,139, 18044-18051.
[19]	G. Li, R. Su, J. Rao, J. Wu, P. Rudolf, G. R. Blake, R. A. Groot, F. Besenbacher, T. T. M. Palstra, J. Mater. Chem. A, 2016,4, 209-216.
[20]	Z. Xie, H. L. Tan, X. Wen, Y. Suzuki, A. Iwase, A. Kudo, R. Amal, J. Scott, Y. H. Ng, ACS Appl. Mater. Interfaces, 2019,11, 23125-23134.
[21]	E. Jokar, Z. Y. Huang, S. Narra, C.-Y. Wang, V. Kattoor, C.-C. Chung, E. W.-G. Diau, Adv. Energy Mater., 2018,8, 1701640.
[22]	J. Liu, Y. Xue, Y. Gao, D. Yu, M. Durstock, L. Dai, Adv. Mater., 2012,24, 2228-33.
[23]	S. Ye, C. Ding, R. Chen, F. Fan, P. Fu, H. Yin, X. Wang, Z. Wang, P. Du, C. Li, J. Am. Chem. Soc., 2018,140, 3250-3256.
[24]	L. Xu, W.-Q. Huang, L.-L. Wang, Z.-A. Tian, W. Hu, Y. Ma, X. Wang, A. Pan, G.-F. Huang, Chem. Mater., 2015,27, 1612-1621.
[25]	D. Yang, L. Zhou, W. Yu, J. Zhang, C. Li, Adv. Energy Mater., 2014,4, 1400591.
[26]	J. B. Joo, Q. Zhang, I. Lee, M. Dahl, F. Zaera, Y. Yin, Adv. Funct. Mater., 2012,22, 166-174.
[27]	D. Zhou, Z. Cai, X. Lei, W. Tian, Y. Bi, Y. Jia, N. Han, T. Gao, Q. Zhang, Y. Kuang, J. Pan, X. Sun, X. Duan, Adv. Energy Mater., 2018,8, 1701905.
[28]	C. Xue, H. Li, H. An, B. Yang, J. Wei, G. Yang, ACS Catal., 2018,8, 1532-1545.
[29]	C. Xue, X. Yan, H. An, H. Li, J. Wei, G. Yang, Appl. Catal. B, 2018,222, 157-166.
[30]	W. Lu, D. Wang, L. Guo, Y. Jia, M. Ye, J. Huang, Z. Li, Y. Peng, W. Yuan, X. Chen, Adv. Mater., 2015,27, 7986-7991.
[31]	M. Wang, L. Cai, Y. Wang, F. Zhou, K. Xu, X. Tao, Y. Chai, J. Am. Chem. Soc., 2017,139, 4144-4151.
[32]	X. Liu, D. Chao, D. Su, S. Liu, L. Chen, C. Chi, J. Lin, Z. X. Shen, J. Zhao, L. Mai, Y. Li, Nano Energy, 2017,37, 108-117.
[33]	Y. Lei, C. Yang, J. Hou, F. Wang, S. Min, X. Ma, Z. Jin, J. Xu, G. Lu, K.-W. Huang, Appl. Catal. B, 2017,216, 59-69.
[34]	T. Wu, L. Zou, D. Han, F. Li, Q. Zhang, L. Niu, Green Chem., 2014,16, 2142-2146.
[35]	Z. Xiong, Y. Luo, Y. Zhao, J. Zhang, C. Zheng, J. C. Wu, Phys. Chem. Chem. Phys., 2016,18, 13186-95.
[36]	Q. Lang, Y. Chen, T. Huang, L. Yang, S. Zhong, L. Wu, J. Chen, S. Bai, Appl. Catal. B, 2018,220, 182-190.
[37]	Z. Yue, A. Liu, C. Zhang, J. Huang, M. Zhu, Y. Du, P. Yang, Appl. Catal. B, 2017,201, 202-210.
[38]	C. Liu, Y. Fu, J. Zhao, H. Wang, H. Huang, Y. Liu, Y. Dou, M. Shao, Z. Kang, Chem. Eng. J., 2019,358, 134-142.
[39]	I. Shown, S. Samireddi, Y. C. Chang, R. Putikam, P. H. Chang, A. Sabbah, F. Y. Fu, W. F. Chen, C. I. Wu, T. Y. Yu, P. W. Chung, M. C. Lin, L. C. Chen, K. H. Chen, Nat. Commun., 2018,9, 169.
[40]	C. Xue, T. Zhang, S. Ding, J. Wei, G. Yang, ACS Appl. Mater. Interfaces, 2017,9, 16091-16102.
[41]	Y. Chao, P. Zhou, N. Li, J. Lai, Y. Yang, Y. Zhang, Y. Tang, W. Yang, Y. Du, D. Su, Y. Tan, S. Guo, Adv. Mater., 2019,31, e1807226.
[42]	W. Liu, L. Cao, W. Cheng, Y. Cao, X. Liu, W. Zhang, X. Mou, L. Jin, X. Zheng, W. Che, Q. Liu, T. Yao, S. Wei, Angew. Chem. Int. Ed., 2017,56, 9312-9317.
[43]	C. Zhu, C. Liu, Y. Zhou, Y. Fu, S. Guo, H. Li, S. Zhao, H. Huang, Y. Liu, Z. Kang, Appl. Catal. B, 2017,216, 114-121.
[44]	J. Liu, Y. Liu, N. Liu, Y. Han, X. Zhang, H. Huang, Y. Lifshitz, S.-T. Lee, J. Zhong, Z. Kang, Science, 2015,347, 970-974.
[45]	J. Barbe, M. L. Tietze, M. Neophytou, B. Murali, E. Alarousu, A. E. Labban, M. Abulikemu, W. Yue, O. F. Mohammed, I. McCulloch, A. Amassian, S. Del Gobbo, ACS Appl. Mater. Interfaces, 2017,9, 11828-11836.
[46]	Z. Jiang, W. Wan, H. Li, S. Yuan, H. Zhao, P. K. Wong, Adv. Mater., 2018,30, 1706108.
[47]	T. F. Yeh, C. Y. Teng, S. J. Chen, H. Teng, Adv. Mater., 2014,26, 3297-303.
[48]	L. Pan, S. Wang, J. Xie, L. Wang, X. Zhang, J.-J. Zou, Nano Energy, 2016,28, 296-303.
[49]	W. Zhen, X. Ning, B. Yang, Y. Wu, Z. Li, G. Lu, Appl. Catal. B, 2018,221, 243-257.
[50]	K. Chang, X. Hai, H. Pang, H. Zhang, L. Shi, G. Liu, H. Liu, G. Zhao, M. Li, J. Ye, Adv. Mater., 2016,28, 10033-10041.
[51]	C. Xue, X. Xu, G. Yang, S. Ding, RSC Adv., 2015,5, 102228-102237.
[52]	C. Xue, X. Yan, S. Ding, G. Yang, RSC Adv., 2016,6, 68653-68662.
[53]	J. Li, Y. Xie, Y. Zhong, Y. Hu, J. Mater. Chem. A, 2015,3, 5474-5481.
[54]	R. Liang, L. Shen, F. Jing, W. Wu, N. Qin, R. Lin, L. Wu, Appl. Catal. B, 2015,162, 245-251.

源于功函数差异的界面内建电场调控载流子定向分离的作用机制研究

Accelerating directional charge separation via built-in interfacial electric fields originating from work-function differences

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