双表面活性剂导向组装构筑供体调控D-A纳米光催化剂用于高效光催化产氢

doi:10.1016/S1872-2067(26)65169-8

催化学报 ›› 2026, Vol. 89: 269-278.DOI: 10.1016/S1872-2067(26)65169-8

双表面活性剂导向组装构筑供体调控D-A纳米光催化剂用于高效光催化产氢

谢嘉慧^a, 葛璐瑶^a, 郑丕浪^a, 柯媛贞^a^,^*(), 杨启华^a^,^*(), 李小波^a^,^b^,^*()

^a浙江师范大学化学与材料科学学院,先进催化材料教育部重点实验室, 固体表面反应化学浙江省重点实验室,浙江金华 321004
^b中国科学技术大学,精准智能化学全国重点实验室,安徽合肥 230026

收稿日期:2025-11-23 接受日期:2026-03-22 出版日期:2026-10-18 发布日期:2026-09-01
通讯作者: *电子信箱: Yuanzhen.Ke@zjnu.edu.cn (柯媛贞),
qhyang@zjnu.cn (杨启华),
Xiaoboli@ustc.edu.cn (李小波).
基金资助:
国家自然科学基金(22372151);浙江省领军型创新创业团队引进计划(2022R01007)

Donor-engineered D-A nanophotocatalyst with dual surfactants-directed assembly for efficient photocatalytic hydrogen evolution

Jiahui Xie^a, Luyao Ge^a, Pilang Zheng^a, Yuanzhen Ke^a^,^*(), Qihua Yang^a^,^*(), Xiaobo Li^a^,^b^,^*()

^aKey Laboratory of the Ministry of Education for Advanced Catalysis Materials, Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Zhejiang Normal University, Jinhua 321004, Zhejiang, China
^bState Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2025-11-23 Accepted:2026-03-22 Online:2026-10-18 Published:2026-09-01
Contact: *E-mail: Yuanzhen.Ke@zjnu.edu.cn (Y. Ke),qhyang@zjnu.cn (Q. Yang),Xiaoboli@ustc.edu.cn (X. Li).
Supported by:
National Natural Science Foundation of China(22372151);Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(2022R01007)

摘要/Abstract

摘要：

有机半导体材料因其结构可调、能带易控等优点, 在光催化水分解制氢领域具有广阔应用前景. 然而, 有机半导体中较强的激子效应导致光生电子-空穴对难以有效解离和迁移, 严重制约了其光催化析氢效率. 如何促进激子解离、提升电荷分离效率, 是有机光催化领域亟待解决的关键科学问题. 供体-受体(D-A)分子工程可通过调控分子内建电场来降低激子结合能, 而表面活性剂导向组装则有助于优化材料形貌与界面性质. 基于此, 本文提出一种协同策略, 将供体工程与双表面活性剂诱导的纳米组装相结合, 旨在系统提升有机D-A分子的光催化析氢性能.

本文首先以4-([1,1′-联苯]-4-基)-2,6-双(4-氰基苯基)吡啶-3,5-二甲腈为基本的D-A骨架(CNP), 通过系统改变供体单元的取代基, 合成了一系列结构相似的D-A分子. 理论计算结果表明, 含甲氧基供体的CNP501分子具有最优的分子内电荷转移特性. 光催化性能测试结果显示, 其产氢速率比未修饰的CNP提高了26倍, 证实供体工程可有效调控分子内建电场, 促进激子解离. 在最优分子CNP501的基础上, 进一步采用双表面活性剂(DDBAB和SDBS)诱导的自组装方法, 构建了CNP501/DDBAB/SDBS纳米光催化剂. 与纯水体系相比, 双表面活性剂协同组装实现了更优的形貌控制与界面调控. 所制备的纳米光催化剂在365 nm光照下的产氢速率高达1093 mmol g^‒1 h^‒1, 表观量子产率达到77.2%, 相比纯水组装的CNP501活性提升了12倍. 对比实验结果表明, 双表面活性剂体系在亲水性、稳定性和电荷分离效率方面均显著优于纯水体系. 该催化剂的卓越性能源于两种效应的协同调控: (1)供体工程通过调控分子内建电场促进了激子解离; (2)表面活性剂介导的形貌控制优化了亲水性, 降低了界面电荷转移电阻, 并抑制了载流子复合. 值得注意的是, 双表面活性剂调控能够实现可调的多重光散射, 这是单表面活性剂体系所不具备的特性.

综上, 本工作通过供体工程与双表面活性剂导向组装的协同策略, 有效突破了有机半导体中激子解离与电荷传输瓶颈, 实现了高效的光催化产氢性能. 该策略为有机D-A光催化剂的理性设计提供了新思路, 未来可进一步拓展至其他有机光功能材料体系, 推动高效有机光催化材料的实际应用.

关键词: D-A分子纳米光催化剂, 供体工程, 表面活性剂导向组装, 光催化析氢, 双表面活性剂

Abstract:

Organic semiconductors hold promise for photocatalytic hydrogen production, yet their performance is often limited by excitonic effects that hinder charge separation and transport. To overcome these challenges, we present a synergistic strategy combining donor-acceptor (D-A) molecular engineering with dual-surfactant-directed nanoassembly. A series of structurally analogous D-A molecules based on 4-([1,1′-biphenyl]-4-yl)-2,6-bis(4-cyanophenyl) pyridine-3,5-dicarbonitrile (CNP) were synthesized with systematic variation of donor-unit substituents. Among them, the methoxy-containing CNP, namely CNP501, exhibited a 26-fold higher hydrogen evolution rate than pristine CNP. Leveraging this, a dual-surfactant-induced self-assembly approach yielded the CNP501/DDBAB/SDBS nanophotocatalyst, which achieved an additional 12-fold enhancement in photoactivity, delivering a hydrogen production rate of 1093 mmol g^-1 h^-1 and an apparent quantum yield of 77.2% at 365 nm. The exceptional performance arises from two synergistic effects: (1) donor engineering, which modulates intrinsic molecular electric fields to promote exciton dissociation, and (2) surfactant-mediated morphological control, which optimizes hydrophilicity, minimizes interfacial charge-transfer resistance, and suppresses carrier recombination. Notably, dual-surfactant regulation uniquely enables multiple light scattering with tunable efficiency, a feature absent in single-surfactant systems.

Key words: Donor-acceptor molecular, nanophotocatalyst, Donor engineering, Surfactant-directed assembly, Photocatalytic hydrogen evolution, Dual surfactants

谢嘉慧, 葛璐瑶, 郑丕浪, 柯媛贞, 杨启华, 李小波. 双表面活性剂导向组装构筑供体调控D-A纳米光催化剂用于高效光催化产氢[J]. 催化学报, 2026, 89: 269-278.

Jiahui Xie, Luyao Ge, Pilang Zheng, Yuanzhen Ke, Qihua Yang, Xiaobo Li. Donor-engineered D-A nanophotocatalyst with dual surfactants-directed assembly for efficient photocatalytic hydrogen evolution[J]. Chinese Journal of Catalysis, 2026, 89: 269-278.

×
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(26)65169-8

https://www.cjcatal.com/CN/Y2026/V89/I10/269

图/表 4

Fig. 1. (a) Chemical structures of donor-acceptor molecules CNP14, CNP147, CNP505, CNP506, and CNP501. (b) Calculated electrostatic potential (ESP) surfaces and molecular dipole moments for CNP505, CNP14, CNP501. Color code: N = blue, C = gray, Cl = green, O = red, H = light gray. (c) Electron-hole distribution analysis for: CNP505, CNP14, CNP501. Color code: N = blue, C = gray, Cl = green, O = red, H = light gray. Blue regions: hole density; Green regions: electron density. (d) Fluorescence emission spectra of CNPs in THF (10 μmol L-1); λexc = 365 nm. (e) Fluorescence emission spectra of quasi-homogeneous photocatalysts prepared by UNP (0.125 mg CNP in 5 mL H2O); λexc = 365 nm. (f) HERs of UNP-prepared quasi-homogeneous photocatalysts. Conditions: 0.125 mg CNP in 5 mL H2O, 5 mmol L-1 AA, 3 wt% Pt; light source = AM 1.5G (58.5 mW cm-2). Error bars: mean ± SD (n = 3).

Fig. 2. (a) HERs of CNP501 synthesized by UNP under varied chemical environments, with molecular structures of DDBAB and SDBS surfactants. (b) HERs of CNP501 photocatalysts synthesized in aqueous solutions with different mass fractions of DDBAB. (c) HERs of CNP501 photocatalysts fabricated with varying DDBAB/SDBS mixing ratios. (d) HERs of CNP501/DDBAB/SDBS nanophotocatalysts with varying Pt co-catalyst loading. (e) HERs of CNP501/DDBAB/SDBS nanophotocatalysts at different ascorbic acid concentrations. (f) AQYs of CNP501/DDBAB/SDBS nanophotocatalysts measured at 365, 400, 420, and 450 nm, overlaid with the UV-vis absorption spectrum of the nanophotocatalyst. Conditions: 0.125 mg CNP501 in 15 ml aqueous solution containing 0.4 wt% surfactant (except b), 0.2 mol L-1 AA (except e, f), 6 wt% Pt (except d); light source: AM 1.5G (58.5 mW cm-2).

Fig. 3. Structural and interfacial characterization of nanophotocatalysts. SEM images of nanophotocatalysts prepared in pure water (a) and DDBAB/SDBS surfactant solution (b). (c) Cryo-TEM image of CNP501/DDBAB/SDBS. (d) Photographs of post-heated DDBAB/SDBS dual surfactants systems at varied mass ratios and their laser-irradiated counterparts. Surface properties of CNP501 nanophotocatalysts prepared in DDBAB/SDBS versus pure water: water contact angles on drop-cast films (e) and Zeta potential values (f).

Fig. 4. Charge transfer dynamics of CNP501 nanophotocatalysts modulated by surfactant assembly. (a) Transient photocurrent responses of CNP501/Water versus CNP501/DDBAB/SDBS nanophotocatalysts. (b) EIS of CNP501-based nanophotocatalysts synthesized in different media. Measurement conditions: Three-electrode system with Ag/AgCl reference electrode and Pt counter electrode. (c) PL spectra of CNP501/DDBAB/SDBS under four conditions: no additives, with Pt only, with AA only, with both Pt and AA; λexc = 295 nm. Pseudocolor 2D fs-TAS maps for CNP501/DDBAB/SDBS (d), CNP501/DDBAB/SDBS+Pt (e), and CNP501/DDBAB/SDBS+Pt+AA (f) samples. (g-i) Corresponding transient absorption spectra of the samples. (j-l) Transient absorption decay kinetics at 860 nm and biexponential fitting, from which the lifetimes of the slow (τ1) and fast (τ2) components are extracted. The Pt loading is 6 wt% relative to the catalyst mass, and the concentration of AA is 0.1 mol L?1; the group without additives only contains the catalyst solution with the same concentration.

参考文献

[1]	E. Kabir, P. Kumar, S. Kumar, A. A. Adelodun, K.-H. Kim, Renew. Sustain. Energy Rev., 2018, 82, 894-900.
[2]	D. G. Nocera, Acc. Chem. Res., 2017, 50, 616-619.
[3]	A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
[4]	J. Schneider, M. Matsuoka, M. Takeuchi, J. Zhang, Y. Horiuchi, M. Anpo, D. W. Bahnemann, Chem. Rev., 2014, 114, 9919-9986.
[5]	J. Jiang, G. Wang, Y. Shao, J. Wang, S. Zhou, Y. Su, Chin. J. Catal., 2022, 43, 329-338.
[6]	Y. Chen, W. Zhong, F. Chen, P. Wang, J. Fan, H. Yu, J. Mater. Sci. Technol., 2022, 121, 19-27.
[7]	D. Su, J. Zhang, B. Frank, A. Thomas, X. Wang, J. Paraknowitsch, R. Schlögl, ChemSusChem, 2010, 3, 169-180.
[8]	R. S. Sprick, J.-X. Jiang, B. Bonillo, S. Ren, T. Ratvijitvech, P. Guiglion, M. A. Zwijnenburg, D. J. Adams, A. I. Cooper, J. Am. Chem. Soc., 2015, 137, 3265-3270.
[9]	H. Zhuzhang, X. Liang, J. Li, S. Xue, Y. Lin, B. Sa, S. Wang, G. Zhang, Z. Yu, X. Wang, Angew. Chem. Int. Ed., 2025, 64, e202421861.
[10]	J. Zhang, X. Liang, C. Zhang, L. Lin, W. Xing, Z. Yu, G. Zhang, X. Wang, Angew. Chem. Int. Ed., 2022, 61, e202210849.
[11]	W. Yu, J. Chen, T. Shang, L. Chen, L. Gu, T. Peng, Appl. Catal. B, 2017, 219, 693-704.
[12]	M. Yang, R. Lian, X. Zhang, C. Wang, J. Cheng, X. Wang, Nat. Commun., 2022, 13, 4900.
[13]	X. Chen, J. Wang, Y. Chai, Z. Zhang, Y. Zhu, Adv. Mater., 2021, 33, 2007479.
[14]	C. Zhang, C. Xie, Y. Gao, X. Tao, C. Ding, F. Fan, H.-L. Jiang, Angew. Chem. Int. Ed., 2022, 61, e202204108.
[15]	X. Fang, Q. Shang, Y. Wang, L. Jiao, T. Yao, Y. Li, Q. Zhang, Y. Luo, H.-L. Jiang, Adv. Mater., 2018, 30, 1705112.
[16]	X. Ma, L. Wang, Q. Zhang, H.-L. Jiang, Angew. Chem. Int. Ed., 2019, 58, 12175-12179.
[17]	G. Zhang, W. Ou, J. Wang, Y. Xu, D. Xu, T. Sun, S. Xiao, M. Wang, H. Li, W. Chen, C. Su, Appl. Catal. B, 2019, 245, 114-121.
[18]	L. Wang, Y. Wan, Y. Ding, S. Wu, Y. Zhang, X. Zhang, G. Zhang, Y. Xiong, X. Wu, J. Yang, H. Xu, Adv. Mater., 2017, 29, 1702428.
[19]	A. F. Saber, A. M. Elewa, H.-H. Chou, A. F. M. EL-Mahdy, Appl. Catal. B, 2022, 316, 121624.
[20]	W. Huang, Q. He, Y. Hu, Y. Li, Angew. Chem. Int. Ed., 2019, 58, 8676-8680.
[21]	S. Zhang, G. Cheng, L. Guo, N. Wang, B. Tan, S. Jin, Angew. Chem. Int. Ed., 2020, 59, 6007-6014.
[22]	N. Wang, G. Cheng, L. Guo, B. Tan, S. Jin, Adv. Funct. Mater., 2019, 29, 1904781.
[23]	Z. A. Lan, M. Wu, Z. Fang, Y. Zhang, X. Chen, G. Zhang, X. Wang, Angew. Chem. Int. Ed., 2022, 61, e202201482.
[24]	R. Chen, Y. Wang, Y. Ma, A. Mal, X.-Y. Gao, L. Gao, L. Qiao, X.-B. Li, L.-Z. Wu, C. Wang, Nat. Commun., 2021, 12, 1354.
[25]	Y. Qian, Y. Han, X. Zhang, G. Yang, G. Zhang, H.-L. Jiang, Nat. Commun., 2023, 14, 3083.
[26]	W. Zhao, L. Luo, M. Cong, X. Liu, Z. Zhang, M. Bahri, B. Li, J. Yang, M. Yu, L. Liu, Y. Xia, N. D. Browning, W.-H. Zhu, W. Zhang, A. I. Cooper, Nat. Commun., 2024, 15, 6482.
[27]	Y. Wang, A. Vogel, M. Sachs, R. S. Sprick, L. Wilbraham, S. J. A. Moniz, R. Godin, M. A. Zwijnenburg, J. R. Durrant, A. I. Cooper, J. Tang, Nat. Energy, 2019, 4, 746-760.
[28]	Y. Zhu, Z. Zhang, W. Si, Q. Sun, G. Cai, Y. Li, Y. Jia, X. Lu, W. Xu, S. Zhang, Y. Lin, J. Am. Chem. Soc., 2022, 144, 12747-12755.
[29]	Z. Zhang, Y. Zhu, X. Chen, H. Zhang, J. Wang, Adv. Mater., 2019, 31, 1806626.
[30]	Y. Zhang, C. Pan, G. Bian, J. Xu, Y. Dong, Y. Zhang, Y. Lou, W. Liu, Y. Zhu, Nat. Energy, 2023, 8, 361-371.
[31]	X. Yuan, C. Wang, L. Vallan, A. T. Bui, G. Jonusauskas, N. D. McClenaghan, C. Grazon, S. Lacomme, C. Brochon, H. Remita, G. Hadziioannou, E. Cloutet, Adv. Funct. Mater., 2023, 33, 2211730.
[32]	M. Yu, W. Zhang, Z. Guo, Y. Wu, W. Zhu, Angew. Chem. Int. Ed., 2021, 60, 15590-15597.
[33]	H. Yang, C. Li, T. Liu, T. Fellowes, S. Y. Chong, L. Catalano, M. Bahri, W. Zhang, Y. Xu, L. Liu, W. Zhao, A. M. Gardner, R. Clowes, N. D. Browning, X. Li, A. J. Cowan, A. I. Cooper, Nat. Nanotechnol., 2023, 18, 307-315.
[34]	X. Liu, M. Yu, K. Huang, H. Huang, H. Gu, C. Tian, J. Qi, Z. Guo, C. Lian, Y. Wu, W. Zhang, Adv. Mater., 2025, 37, 2413440.
[35]	J. Kosco, M. Bidwell, H. Cha, T. Martin, C. T. Howells, M. Sachs, D. H. Anjum, S. Gonzalez Lopez, L. Zou, A. Wadsworth, W. Zhang, L. Zhang, J. Tellam, R. Sougrat, F. Laquai, D. M. DeLongchamp, J. R. Durrant, I. McCulloch, Nat. Mater., 2020, 19, 559-565.
[36]	J. Kosco, S. Gonzalez-Carrero, C. T. Howells, T. Fei, Y. Dong, R. Sougrat, G. T. Harrison, Y. Firdaus, R. Sheelamanthula, B. Purushothaman, F. Moruzzi, W. Xu, L. Zhao, A. Basu, S. De Wolf, T. D. Anthopoulos, J. R. Durrant, I. McCulloch, Nat. Energy, 2022, 7, 340-351.
[37]	B. Cai, A. Brnovic, M. V. Pavliuk, L. Hammarström, L. Kloo, S. A. Barnett, H. Tian, Nat. Chem., 2026, 18, 723-730.
[38]	Z. Zhang, C. Xu, Q. Sun, Y. Zhu, W. Yan, G. Cai, Y. Li, W. Si, X. Lu, W. Xu, Y. Yang, Y. Lin, Angew. Chem. Int. Ed., 2024, 63, e202402343.
[39]	S. Hou, J. Li, Y. Wang, Y. Jiang, Z. Wang, T. Geng, J. Mol. Liq., 2023, 376, 121427.
[40]	S. Kumar Shah, G. Chakraborty, A. Bhattarai, R. De, J. Mol. Liq., 2022, 368, 120678.
[41]	I. M. Tucker, Curr. Opin. Colloid Interface Sci., 2024, 71, 101789.
[42]	X. Li, Y. Che, L. Chen, T. Liu, K. Wang, L. Liu, H. Yang, E. O. Pyzer-Knapp, A. I. Cooper, Nat. Chem., 2024, 16, 1286-1294.
[43]	W. Zhang, M. Yu, T. Liu, M. Cong, X. Liu, H. Yang, Y. Bai, Q. Zhu, S. Zhang, H. Gu, X. Wu, Z. Zhang, Y. Wu, H. Tian, X. Li, W.-H. Zhu, A. I. Cooper, Nat. Synth., 2024, 3, 595-605.
[44]	D. Wang, Z. Xiao, J. He, W. Xu, J. Wang, Langmuir, 2023, 39, 12649-12661.

双表面活性剂导向组装构筑供体调控D-A纳米光催化剂用于高效光催化产氢

Donor-engineered D-A nanophotocatalyst with dual surfactants-directed assembly for efficient photocatalytic hydrogen evolution

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 4

参考文献

相关文章 15

编辑推荐

Metrics

[1]	马明宇, 刘棕阳, 袁阔, 刘哲源, 王嘉新, 林清清, 钟地长, 鲁统部. 自光敏金属配合物用于光催化析氢[J]. 催化学报, 2026, 86(7): 375-383.
[2]	李晗溪, 罗振东, 薛强, 支云飞, 杜骏, 周旭凯. 基于Povarov环化的共价有机框架孔道与电荷动力学调控及其光催化产氢增强[J]. 催化学报, 2026, 86(7): 363-374.
[3]	张宝龙, 孙彬, 刘兴朋, 刘文宇, 顾少楠, 周国伟. 缺陷工程促进TiO₂/Zn_0.5Cd_0.5S S型异质结电荷转移实现高效光催化析氢[J]. 催化学报, 2026, 84(5): 117-129.
[4]	张洪文, 蔡颖慧, 李秉岳, 山巍, 唐华. Cu单原子与CuO纳米团簇协同增强TiO₂光催化析氢性能[J]. 催化学报, 2026, 83(4): 162-171.
[5]	杨博霖, 靳菲, 靳治良. 非贵金属负载共价有机框架构建异质结高效光催化产氢[J]. 催化学报, 2026, 81(2): 172-184.
[6]	张瑞琪, 姚欣彤, 刘君昌, 陈智, 张大凤, 蒲锡鹏. 界面Cu‒S键和局域表面等离子体共振协同调控的Cu₃P@Cu/Mn_0.3Cd_0.7S S型异质结用于高效光催化析氢[J]. 催化学报, 2026, 89(10): 258-268.
[7]	张云超, 潘劲康, 倪响, 莫非奇, 徐远国, 董鹏玉. 有机/无机杂化FS-COF/WO₃ S型异质结电荷载流子动力学及其光催化析氢性能[J]. 催化学报, 2025, 74(7): 250-263.
[8]	鄢雨晴, 吴永辉, 汪军, 霍晋荣, 杨凯, 卢康强. S型Cd_0.8Zn_0.2S纳米线/CeO₂纳米立方体异质结用于高效光催化产氢[J]. 催化学报, 2025, 79(12): 231-239.
[9]	项祥林, 程蓓, 朱必成, 姜传佳, 梁桂杰. 高熵合金纳米晶体促进光催化析氢耦合肉桂醇选择性氧化[J]. 催化学报, 2025, 68(1): 326-335.
[10]	潘劲康, 张艾彩珺, 张莉华, 董鹏玉. 由质子化D-A型聚合物和MoS₂构建S型异质结实现高效光催化析氢[J]. 催化学报, 2024, 58(3): 180-193.
[11]	杨婷婷, 汪静, 王中辽, 张金锋, 代凯. 双聚合物Cd₃(C₃N₃S₃)₂/Zn₃(C₃N₃S₃)₂ S型异质结增强光催化产氢性能[J]. 催化学报, 2024, 58(3): 157-167.
[12]	王明, 李亚玲, 严登鑫, 胡慧, 宋玉洁, 苏晓芳, 孙佳敏, 肖松涛, 高艳安. 通过偶极极化调制乙烯键连接的共价有机框架以实现高效光催化析氢[J]. 催化学报, 2024, 65(10): 103-112.
[13]	李春雪, 卢豪, 丁桂祥, 马天翼, 刘诗咏, 张力, 廖光福. 界面配位键加速S型异质结电荷分离用于高效光催化析氢[J]. 催化学报, 2024, 65(10): 174-184.
[14]	孙利娟, 王伟康, 路平, 刘芹芹, 王乐乐, 唐华. 纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应[J]. 催化学报, 2023, 51(8): 90-100.
[15]	余治晗, 关晨, 岳晓阳, 向全军. 碳环渗入的结晶氮化碳S型同质结及其光催化析氢[J]. 催化学报, 2023, 50(7): 361-371.