双内建电场驱动的D-A COFs/ZnIn2S4 S型异质结加速电荷分离实现纯水中高效光合成H2O2

doi:10.1016/j.actphy.2025.100177

摘要/Abstract

摘要：

构建双内建电场(IEF)驱动的S型异质结为光催化H₂O₂生产中的高效电荷分离与利用提供了一种极具前景的策略。本文报道了一种基于供体-受体共价有机框架(D-A COFs) TpAQ (由三醛基间苯三酚(Tp)和2, 6-二氨基蒽醌(AQ)合成)与ZnIn₂S₄ (ZIS)构筑的双IEF驱动的S型异质结，其中双内建电场分别源自异质结界面和D-A COFs中的D-A界面。值得注意的是，通过同时利用氧还原反应和水氧化反应路径，优化后的TpAQ/ZIS-10在纯水中的可见光驱动产H₂O₂速率达到2362 μmol g⁻¹ h⁻¹，显著高于单一组分TpAQ和ZIS。此外，实验结果与理论计算共同表明，TpAQ/ZIS异质结中双IEF的协同效应显著促进了载流子的传输与分离。本研究为构建具有双IEF的高效S型异质结提供了宝贵见解。

关键词: 双内建电场, S型异质结, D-A COFs, TpAQ/ZIS, 光催化产H₂O₂

Abstract:

The construction of dual built-in electric field (IEF)-driven S-scheme heterojunctions presents a promising strategy to accelerate efficient charge separation and improve charge utilization in photocatalytic H₂O₂ production. Herein, we report, the construction of a heterojunction based on donor-acceptor covalent organic frameworks (D-A COFs) TpAQ (synthesized from two monomers: 1, 3, 5-triformylphloroglucinol (Tp) and 2, 6-diaminoanthraquinone (AQ)) and ZnIn₂S₄ (ZIS), realizing a dual IEF-driven S-scheme heterojunction—one from the heterojunction interface and another from D-A interface within D-A COFs. In particular, the optimized TpAQ/ZIS-10 exhibits a significantly higher visible-light driven photocatalytic H₂O₂ production rate of 2362 μmol g⁻¹ h⁻¹ in pure water than TpAQ and ZIS by utilizing both the oxygen reduction reaction and water oxidation reaction pathways. Furthermore, the experimental results and theoretical calculations revealed that the synergistic effect of dual IEF in TpAQ/ZIS heterojunction significantly facilitates efficient charge carrier transfer and separation. This work provides valuable insight for constructing highly efficient S-scheme heterojunctions with dual IEF.

Key words: Dual built-in electric field, S-scheme heterojunction, D-A COFs, TpAQ/ZIS, Photocatalytic H₂O₂ production

郭杰, 薛丽君, 宋发辉, 李程鹏, 陈卓, 温丽丽. 双内建电场驱动的D-A COFs/ZnIn₂S₄ S型异质结加速电荷分离实现纯水中高效光合成H₂O₂[J]. 物理化学学报, 2026, 42(4), 100177. doi: 10.1016/j.actphy.2025.100177

Jie Guo, Lijun Xue, Fahui Song, Chengpeng Li, Zhuo Chen, Lili Wen. Dual built-in electric field-driven S-scheme heterojunction of D-A COFs/ZnIn₂S₄ for accelerated charge separation toward high-efficiency H₂O₂ photosynthesis in pure water[J]. Acta Phys. -Chim. Sin. 2026, 42(4), 100177. doi: 10.1016/j.actphy.2025.100177

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2025.100177

https://www.whxb.pku.edu.cn/CN/Y2026/V42/I4/100177

图/表 12

图Scheme 1

图1

图2

图3

图4

图5

图6

图7

图8

图9

图10

图11

参考文献 72

1	X. Sun, J. Yang, X. Zeng, L. Guo, C. Bie, Z. Wang, K. Sun, A. K. Sahu, M. Tebyetekerwa, T. E. Rufford, X. Zhang. Angew. Chem. Int. Ed. 2024, 63, e202414417. doi: 10.1002/anie.202414417
2	Z. Chen, D. Yao, C. Chu, S. Mao. Chem. Eng. J. 2023, 451, 138489. doi: 10.1016/j.cej.2022.138489
3	K. Mase, M. Yoneda, Y. Yamada, S. Fukuzumi. Nat. Commun. 2016, 7, 11470. doi: 10.1038/ncomms11470
4	J. Liu, Y. Zou, B. Jin, K. Zhang, J. H. Park. ACS Energy Lett. 2019, 4, 3018. doi: 10.1021/acsenergylett.9b02199
5	X. Zeng, Y. Liu, X. Hu, X. Zhang. Green Chem. 2021, 23, 1466. doi: 10.1039/D0GC04236F
6	X. Fang, B. Li, J. Huang, C. Hu, X. Yang, P. Feng, X. Dong, J. Wu, Y. Li, Y. Ding. Energy Environ. Sci. 2025, 18, 6202. doi: 10.1039/D5EE00652J
7	J. M. Campos-Martin, G. Blanco-Brieva, J. L. G. Fierro. Angew. Chem. Int. Ed. 2006, 45, 6962. doi: 10.1002/anie.200503779
8	X. Zhang, J. Zhang, J. Miao, X. Wen, C. Chen, B. Zhou, M. Long. Chem. Eng. J. 2023, 466, 143085. doi: 10.1016/j.cej.2023.143085
9	M. Sayed, H. Li, C. Bie. Acta Phys. Chim. Sin. 2025, 41, 100117. doi: 10.1016/j.actphy.2025.100117
10	X. Fang, X. Huang, Q. Hu, B. Li, C. Hu, B. Ma, Y. Ding. Chem. Commun. 2024, 60, 5354. doi: 10.1039/D4CC01577K
11	X. Ma, S. Li, Y. Gao, N. Li, Y. Han, H. Pan, Y. Bian, J. Jiang. Adv. Funct. Mater. 2024, 34, 2409913. doi: 10.1002/adfm.202409913
12	H. Hou, X. Zeng, X. Zhang. Angew. Chem. Int. Ed. 2020, 59, 17356. doi: 10.1002/anie.201911609
13	Y. Ma, S. Wang, Y. Zhang, B. Cheng, L. Zhang. J. Materiomics 2025, 11, 100978. doi: 10.1016/j.jmat.2024.100978
14	Z. Xie, X. Chen, W. Wang, X. Ke, X. Zhang, S. Wang, X. Wu, J. C. Yu, X. Wang. Angew. Chem. Int. Ed. 2024, 63, e202410179. doi: 10.1002/anie.202410179
15	Z. Zhang, Q. Zhang, Y. Hou, J. Li, S. Zhu, H. Xia, H. Yue, X. Liu. Angew. Chem. Int. Ed. 2024, 63, e202411546. doi: 10.1002/anie.202411546
16	Y. Zhang, Y. Wang, Y. Liu, S. Zhang, Y. Zhao, J. Zhang. J. Materiomics 2025, 11, 100985. doi: 10.1016/j.jmat.2024.100985
17	J. Su, B. Liu, B. Lu, X. Sun, Y. Guo, W. Chi, Y. Yang, X. Chen, H. Zhao, Y. Wang, et al.. Appl. Catal. B: Environ. 2025, 371, 125263. doi: 10.1016/j.apcatb.2025.125263
18	C. Shu, X. Yang, L. Liu, X. Hu, R. Sun, X. Yang, A. I. Cooper, B. Tan, X. Wang. Angew. Chem. Int. Ed. 2024, 63, e202403926. doi: 10.1002/anie.202403926
19	R. Liu, Y. Chen, H. Yu, M. Položij, Y. Guo, T. C. Sum, T. Heine, D. Jiang. Nat. Catal. 2024, 7, 195. doi: 10.1038/s41929-023-01102-3
20	H. Ding, R. Shen, K. Huang, C. Huang, G. Liang, P. Zhang, X. Li. Adv. Funct. Mater. 2024, 34, 2400065. doi: 10.1002/adfm.202400065
21	T. Wang, B. Yang, Z. Zhou, Y. Wu, Z. Jin. Small 2025, 21, 2501128. doi: 10.1002/smll.202501128
22	Y. Zhou, P. Dong, J. Liu, B. Zhang, B. Zhang, X. Xi, J. Zhang. Adv. Funct. Mater. 2025, 35, 2500733. doi: 10.1002/adfm.202500733
23	Q. Li, X. Li, B. Zhang, B. Jiang. Adv. Funct. Mater. 2025, 35, 2506421. doi: 10.1002/adfm.202506421
24	Z. Hu, X. Hao, Y. Fan, Z. Jin. Chem. Eng. J. 2024, 481, 148455. doi: 10.1016/j.cej.2023.148455
25	W. Deng, X. Hao, J. Yang, Z. Jin. Appl. Catal. B: Environ. 2025, 360, 124551. doi: 10.1016/j.apcatb.2024.124551
26	S. Wang, L. Huang, L. Xue, Q. Kang, L. Wen, K. Lv. Appl. Catal. B: Environ. 2024, 358, 124366. doi: 10.1016/j.apcatb.2024.124366
27	Y. Liu, Y. Wu, Y. Liu, Y. Wang, X. Sun, P. Chen, S.-F. Yin. ACS Catal. 2024, 14, 7726. doi: 10.1021/acscatal.4c00924
28	C. Zhang, L. Lin, M. Zhou, Y. Wang, S. Xu, X. Chen, Z. Li. Chem. Eng. J. 2024, 495, 153563. doi: 10.1016/j.cej.2024.153563
29	S. Bao, Q. Tan, S. Wang, J. Guo, K. Lv, S. A. C. Carabineiro, L. Wen. Appl. Catal. B: Environ. 2023, 330, 122624. doi: 10.1016/j.apcatb.2023.122624
30	H. Fan, M. Hu, Y. Duan, L. Zuo, R. Yu, Z. Li, Q. Liu, B. Li, L. Wang. Chem. Sci. 2025, 16, 2316. doi: 10.1039/D4SC07077A
31	Y. Zhao, Y. Zhang, H. Tan, C. Ai, J. Zhang. J. Materiomics 2025, 11, 100970. doi: 10.1016/j.jmat.2024.100970
32	C. Cui, X. Xu, X. Zhao, N. Xi, M. Li, X. Wang, Y. Sang, X. Yu, H. Liu, J. Wang. Nano Energy 2024, 126, 109632. doi: 10.1016/j.nanoen.2024.109632
33	J. Yang, X. Hao, J. Jing, Y. Hao, Z. Jin. Acta Phys. Chim. Sin. 2025, 41, 100131. doi: 10.1016/j.actphy.2025.100131
34	Z. Chen, J. Guo, F. Song, S. Wang, S. A. C. Carabineiro, S. Ouyang, L. Wen. ACS Catal. 2025, 15, 8284. doi: 10.1021/acscatal.5c01163
35	F. Liu, P. Zhou, Y. Hou, H. Tan, Y. Liang, J. Liang, Q. Zhang, S. Guo, M. Tong, J. Ni. Nat. Commun. 2023, 14, 4344. doi: 10.1038/s41467-023-40007-4
36	Y. Hou, P. Zhou, F. Liu, Y. Lu, H. Tan, Z. Li, M. Tong, J. Ni. Angew. Chem. Int. Ed. 2024, 63, e202318562. doi: 10.1002/anie.202318562
37	S. Gu, S. Wu, L. Cao, M. Li, N. Qin, J. Zhu, Z. Wang, Y. Li, Z. Li, J. Chen, Z. Lu. J. Am. Chem. Soc. 2019, 141, 9623. doi: 10.1021/jacs.9b03467
38	Z. A. Lan, Y. Fang, Y. Zhang, X. Wang. Angew. Chem. Int. Ed. 2018, 57, 470. doi: 10.1002/anie.201711155
39	C. R. DeBlase, K. E. Silberstein, T.-T. Truong, H. D. Abruña, W. R. Dichtel. J. Am. Chem. Soc. 2013, 135, 16821. doi: 10.1021/ja409421d
40	K. Xiong, F. Zhang, Y. Wang, B. Zeng, X. Lang. J. Colloid Interface Sci. 2023, 643, 340. doi: 10.1016/j.jcis.2023.04.017
41	C. Li, X. Du, S. Jiang, Y. Liu, Z. Niu, Z. Liu, S. Yi, X. Yue. Adv. Sci. 2022, 9, 2201773. doi: 10.1002/advs.202201773
42	P. Dong, T. Cheng, J. Zhang, J. Jiang, L. Zhang, X. Xi, J. Zhang. ACS Appl. Energy Mater. 2023, 6, 1103. doi: 10.1021/acsaem.2c03806
43	L. Wang, B. Cheng, L. Zhang, J. Yu. Small 2021, 17, 2103447. doi: 10.1002/smll.202103447
44	H. Chen, S. Gao, G. Huang, Q. Chen, Y. Gao, J. Bi. Appl. Catal. B: Environ. 2024, 343, 123545. doi: 10.1016/j.apcatb.2023.123545
45	J. Qiu, K. Meng, Y. Zhang, B. Cheng, J. Zhang, L. Wang, J. Yu. Adv. Mater. 2024, 36, 2400288. doi: 10.1002/adma.202400288
46	Y. Yang, X. Zhou, M. Gu, B. Cheng, Z. Wu, J. Zhang. Acta Phys. Chim. Sin. 2025, 41, 100064. doi: 10.1016/j.actphy.2025.100064
47	H. Cheng, J. Cheng, L. Wang, H. Xu. Chem. Mater. 2022, 34, 4259. doi: 10.1021/acs.chemmater.2c00936
48	Z. Yong, T. Ma. Angew. Chem. Int. Ed. 2023, 62, e202308980. doi: 10.1002/anie.202308980
49	Y. Luo, C. Liu, J. Liu, X. Liu, Y. Zhou, X. Ou, B. Weng, J. Jiang, B. Han. Chem. Eng. J. 2024, 481, 148494. doi: 10.1016/j.cej.2023.148494
50	X. Zhang, S. Cheng, C. Chen, X. Wen, J. Miao, B. Zhou, M. Long, L. Zhang. Nat. Commun. 2024, 15, 2649. doi: 10.1038/s41467-024-47023-y
51	J. Li, C. Wu, J. Li, B. Dong, L. Zhao, S. Wang. Chin. J. Catal. 2022, 43, 339. doi: 10.1016/S1872-2067(21)63875-5
52	L. Zhuo, S. Dong, Y. T. Sham, J. Zhang, X. Xu, K. C. K. Ho, M. Pan, Q. Chen, G. Huang, J. Bi. npj Clean Water 2025, 8, 5. doi: 10.1038/s41545-025-00437-7
53	Y. Yang, Q. Guo, Q. Li, L. Guo, H. Chu, L. Liao, X. Wang, Z. Li, W. Zhou. Adv. Funct. Mater. 2024, 34, 2400612. doi: 10.1002/adfm.202400612
54	Y. He, J. Zhao, Y.-T. Sham, S. Gao, M. Pan, Q. Chen, G. Huang, P. K. Wong, J. Bi. ACS Sustainable Chem. Eng. 2023, 11, 17552. doi: 10.1021/acssuschemeng.3c06421
55	M. Gu, Y. Yang, L. Zhang, B. Zhu, G. Liang, J. Yu. Appl. Catal. B: Environ. 2023, 324, 122227. doi: 10.1016/j.apcatb.2022.122227
56	Z. Zhou, M. Sun, Y. Zhu, P. Li, Y. Zhang, M. Wang, Y. Shen. Appl. Catal. B: Environ. 2023, 334, 122862. doi: 10.1016/j.apcatb.2023.122862
57	L. Yang, G. Dong, D. L. Jacobs, Y. Wang, L. Zang, C. Wang. J. Catal. 2017, 352, 274. doi: 10.1016/j.jcat.2017.05.010
58	Y. Luo, B. Zhang, C. Liu, D. Xia, X. Ou, Y. Cai, Y. Zhou, J. Jiang, B. Han. Angew. Chem. Int. Ed. 2023, 62, e202305355. doi: 10.1002/anie.202305355
59	Y.-Y. Tang, X. Luo, R.-Q. Xia, J. Luo, S.-K. Peng, Z.-N. Liu, Q. Gao, M. Xie, R.-J. Wei, G.-H. Ning, et al.. Angew. Chem. Int. Ed. 2024, 63, e202408186. doi: 10.1002/anie.202408186
60	D. Chen, W. Chen, Y. Wu, L. Wang, X. Wu, H. Xu, L. Chen. Angew. Chem. Int. Ed. 2023, 62, e202217479. doi: 10.1002/anie.202217479
61	H. Zhang, J. Liu, Y. Zhang, B. Cheng, B. Zhu, L. Wang. J. Mater. Sci. Technol. 2023, 166, 241. doi: 10.1016/j.jmst.2023.05.030
62	C. Jiang, C. Yuan, K. Xu, X. Zhou, C. Bie. J. Mater. Sci. Technol. 2025, 231, 36. doi: 10.1016/j.jmst.2024.12.071
63	Y. Liu, M. Li, T. Liu, Z. Wu, L. Zhang. J. Mater. Sci. Technol. 2025, 233, 201. doi: 10.1016/j.jmst.2025.03.005
64	L. Wang, J. Zhao. J. Mater. Sci. Technol. 2026, 241, 18. doi: 10.1016/j.jmst.2025.04.009
65	K. Meng, J. Zhang, B. Zhu, C. Jiang, H. García, J. Yu. Adv. Mater. 2025, 37, 2505088. doi: 10.1002/adma.202505088
66	X. Wang, K. Qi, K. Xu. Chin. J. Catal. 2025, 70, 1. doi: 10.1016/S1872-2067(24)60246-9
67	Y. Wu, C. Cheng, K. Qi, B. Cheng, J. Zhang, J. Yu, L. Zhang. Acta Phys. Chim. Sin. 2024, 40, 2406027. doi: 10.3866/PKU.WHXB202406027
68	B. Liu, J. Zhang, H. Li, B. Cheng, C. Bie. Acta Phys. Chim. Sin. 2025, 41, 100121. doi: 10.1016/j.actphy.2025.100121
69	Y. Zhang, J. Qiu, B. Zhu, G. Sun, B. Cheng, L. Wang. Chin. J. Catal. 2024, 57, 143. doi: 10.1016/S1872-2067(23)64580-2
70	M. Gu, Y. Yang, B. Cheng, L. Zhang, P. Xiao, T. Chen. Chin. J. Catal. 2024, 59, 185. doi: 10.1016/S1872-2067(23)64610-8
71	L. Zhang, J. Zhang, J. Yu, H. García. Nat. Rev. Chem. 2025, 9, 328. doi: 10.1016/10.1038/s41570-025-00698-3
72	M. Sayed, K. Qi, X. Wu, L. Zhang, H. García, J. Yu. Chem. Soc. Rev. 2025, 54, 4874. doi: 10.1016/10.1039/D4CS01091D

[1]	许凯强, 于佳, 夏伟, 张建军, 韩生. 范德华S型异质结赋予快速电荷转移助力光催化活性提升[J]. 物理化学学报, 2026, 42(7): 100211 - .
[2]	袁成成, 夏伟, 王骏, 朱潇锋, 张勇, 朱必成, 余家国. 双功能单原子修饰SnS₂/CdS S型光催化剂用于协同产氢与乳酸氧化的DFT研究[J]. 物理化学学报, 2026, 42(6): 100244 - .
[3]	孟奥运, 李振华, 熊国远, 李真, 张金锋. S型异质结Al₆Si₂O₁₃/BiOBr通过增强电荷转移效应实现高效稳定光催化降解三唑磷和敌敌畏农药[J]. 物理化学学报, 2026, 42(5): 100186 - .
[4]	邱艳平, 张佳桐, 李林萍, 高旸钦, 李宁, 戈磊. MOF衍生的g-C₃N₄/ZnIn₂S₄ S型异质结：界面工程增强光催化NO转化[J]. 物理化学学报, 2026, 42(4): 100175 - .
[5]	李振, 张素娟, 王中辽, 张金锋, 陈高礼, 陈士夫. S型CdS/MnO₂异质结的合理构建用于高附加值甲苯光热协同催化选择性氧化[J]. 物理化学学报, 2026, 42(4): 100179 - .
[6]	朱文君, 艾陈斌, 许凯强, 周亚太, 张锡东, 张勇. WO₃@TP无机@有机S型光催化剂用于促进产H₂O₂[J]. 物理化学学报, 2026, 42(3): 100184 - .
[7]	周玲, 李龙, 黄礼文, 吴艳. 通过间接两电子还原的HOF/BiVO₄ (010) S型光催化剂增强H₂O₂生产性能[J]. 物理化学学报, 2026, 42(3): 100172 - .
[8]	骆泽, 朱玉坤, 罗雅丹, 任广敏, 王永红, 唐华. S型异质结In₂O₃/ZnIn₂S₄光催化5-羟甲基糠醛选择性氧化耦合产氢[J]. 物理化学学报, 2026, 42(3): 100166 - .
[9]	樊凡, 修浩, 王宇婷, 崔永朋, 王雅君. NH₂-MIL-125/Na掺杂g-C₃N₄复合S型异质结的构建及其光催化产过氧化氢性能[J]. 物理化学学报, 2026, 42(2): 100143 - .
[10]	葛成艳, 胡佳伟, 刘星雨, 宋玉玺, 刘超, 邹志刚. 自集成黑色NiO团簇与ZnIn₂S₄微球实现S型电子转移机制下光热辅助制氢[J]. 物理化学学报, 2026, 42(1): 100154 - .
[11]	陈轼逸, 付家龙, 裘建平, 常国菊, 郝仕油. 废弃医用口罩衍生的碳量子点增强BiOBr/g-C₃N₄ S型异质结光催化降解聚对苯二甲酸乙二醇酯(PET)[J]. 物理化学学报, 2026, 42(1): 100135 - .
[12]	韦梦兰, 欧晓霞, 王艺濛, 张梦圆, 滕飞, 王凯旋. S型异质结g-C₃N₄/Bi₂WO₆高效降解左氧氟沙星：性能、机理及降解路径[J]. 物理化学学报, 2025, 41(9): 100105 - .
[13]	王文龙, 郝文韬, 何浪, 乔佳, 李宁, 陈朝秋, 覃勇. 碳量子点/TiO₂ S型异质结的能带和吸附工程促进光催化CO₂甲烷化[J]. 物理化学学报, 2025, 41(9): 100116 - .
[14]	蔡家杰, 程畅, 刘博文, 张建军, 姜传佳, 程蓓. CdS/DBTSO-BDTO S型异质结光催化制氢及其电荷转移动力学[J]. 物理化学学报, 2025, 41(8): 100084 - .
[15]	孟凡鹏, 赵飞, 林靖恺, 赵金生, 张华阳, 王少彬. 优化氮化碳纳米片/球形共轭聚合物S型异质结界面电场以促进析氢反应[J]. 物理化学学报, 2025, 41(8): 100095 - .

双内建电场驱动的D-A COFs/ZnIn₂S₄ S型异质结加速电荷分离实现纯水中高效光合成H₂O₂

Dual built-in electric field-driven S-scheme heterojunction of D-A COFs/ZnIn₂S₄ for accelerated charge separation toward high-efficiency H₂O₂ photosynthesis in pure water

RichHTML

PDF

赞

补充材料

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 72

相关文章 15

Metrics

推荐阅读 0