揭示非对称电荷提取机理

doi:10.1016/S1872-2067(26)65156-X

催化学报 ›› 2026, Vol. 90: 298-308.DOI: 10.1016/S1872-2067(26)65156-X

揭示非对称电荷提取机理

李访^a^,^b, 关晨^a, 余治晗^a, 向全军^a^,^*()

^a 电子科技大学电子科学与工程学院, 电子薄膜与集成器件国家重点实验室, 四川成都 610054
^b 南通大学微电子与集成电路学院, 江苏省半导体开发与集成电路设计封装及测试重点实验室, 江苏南通 226019

收稿日期:2026-01-23 接受日期:2026-03-06 出版日期:2026-11-18 发布日期:2026-09-09
通讯作者: *电子信箱: xiangqj@uestc.edu.cn (向全军).
基金资助:
国家自然科学基金(22479020);国家自然科学基金(W2512051);国家自然科学基金(22272019);四川省科技计划(2026NSFSC0079)

Revealing the mechanism of asymmetric charge carrier extraction

Fang Li^a^,^b, Chen Guan^a, Zhihan Yu^a, Quanjun Xiang^a^,^*()

^a State a State Key Laboratory of Electronic Thin Film and Integrated Devices, School of Electronic Science and Engineering, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan, China
^b Jiangsu Key Laboratory of Semi. Dev. & IC Design, Package and Test, School of Microelectronics and Integrated Circuits, Nantong University, Nantong 226019, Jiangsu, China

Received:2026-01-23 Accepted:2026-03-06 Online:2026-11-18 Published:2026-09-09
Contact: *E-mail:xiangqj@uestc.edu.cn(Q. Xiang).
Supported by:
National Natural Science Foundation of China(22479020);National Natural Science Foundation of China(W2512051);National Natural Science Foundation of China(22272019);Sichuan Science and Technology Program(2026NSFSC0079)

摘要/Abstract

摘要：

半导体光催化技术因无需外部能量输入即可实现能量转换, 被视为应对能源与环境危机的理想解决方案之一. 然而, 严重的载流子复合现象导致其性能难以大幅提升. 尽管先进表征技术揭示了载流子激发与复合过程的微观机制, 但如何解决载流子寿命与催化反应所需时间尺度之间不匹配这一问题, 仍面临重大挑战. 非对称电荷提取策略为解决该问题提供了新思路. 目前该机制在催化领域的研究仍较为匮乏, 探究非对称电荷提取机制对光催化载流子动力学调控及性能提升具有重要意义.

载流子动力学调控与半导体材料特性及器件结构密切相关. 非对称载流子提取可有效延长载流子寿命, 实现时空分离, 但其内在机制仍不明确. 本文制备了集光吸收与存储、电荷存储与转换功能于一体的聚庚嗪亚胺(PHI)材料. 通过采用系列原位表征技术, 揭示了PHI电荷存储行为中的非对称电荷提取机制. 具体而言, 原位电子顺磁共振波谱和紫外-可见漫反射光谱表征证实了PHI中存在光诱导非对称电荷提取现象. 利用电子湮灭与定量空穴捕获技术证实了这种非对称提取可促进空穴载流子的释放. 通过O₂产量换算得出空穴数量, 多次重复实验证实了PHI的非对称电荷提取现象及暗态空穴催化活性具有良好的稳定性. H₂¹⁸O的同位素示踪实验表明, 空穴催化产生的O₂来源于水. 载流子衰减动力学测试显示, 非对称电荷提取将载流子衰减时间从50 ps延长至1000 ps, 长寿命载流子的寿命从5.06 ps增至768.38 ps, 改善了载流子的分离. 原位红外表征从结构变化的角度揭示了非对称电荷存储产生的原因, 即庚嗪单元被破坏与羰基基团形成是导致非对称电荷提取行为的关键因素. 反应前后的结构表征表明, 非对称电荷提取现象引起的结构变化是动态可逆的.

综上, 本文针对PHI材料的电荷存储特性, 通过一系列原位表征解析了电荷存储中的非对称电荷提取机制及其产生的原因, 为理解原子尺度电荷存储与释放动力学奠定了基础, 也为自充电器件的理性设计与优化提供了可行路径.

关键词: 非对称电荷提取机理, 电荷存储, 载流子动力学调控, 空穴释放, 聚庚嗪亚胺

Abstract:

Carrier dynamics modulation is closely tied to the properties of semiconductor materials and device architecture. Asymmetric charge carrier extraction effectively prolongs the carrier lifetime, enabling spatiotemporal separation; however, the underlying mechanism remains elusive. In this study, we elucidate the mechanism of asymmetric charge extraction during charge storage through a series of in-situ characterizations, using poly(heptazine imide) (PHI) as a model material. By employing electron annihilation and quantitative hole capture techniques, we demonstrate that this asymmetric extraction enhances the release of hole species. Carrier decay kinetics show that asymmetric charge extraction extends the carrier decay time from 50 to 1000 ps, with the lifetime of long-lived carriers increasing from 5.06 to 768.38 ps. Analysis of the photoinduced structural changes indicates that the degradation of the heptazine unit and the formation of carbonyl groups are responsible for the observed asymmetric charge extraction behavior. This work offers insights into the mechanisms governing asymmetric charge extraction and highlights its potential for application in self-charging devices.

Key words: Asymmetric charge extraction mechanism, Charge storage, Carrier dynamics modulation, Hole release, Poly(heptazine imide)

李访, 关晨, 余治晗, 向全军. 揭示非对称电荷提取机理[J]. 催化学报, 2026, 90: 298-308.

Fang Li, Chen Guan, Zhihan Yu, Quanjun Xiang. Revealing the mechanism of asymmetric charge carrier extraction[J]. Chinese Journal of Catalysis, 2026, 90: 298-308.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65156-X

https://www.cjcatal.com/CN/Y2026/V90/I11/298

图/表 5

Fig. 1. Origin and dynamic tracking of charge transfer. (a) DRS spectra of excited state (blue-green radical) and original state of PHI slurried with TEOA. The excited state of PHI sample was obtained by nitrogen purging for 5 min and Xenon lamp illumination for 10 min. (b) In-situ EPR spectroscopy of PHI dispersed in methanol solution under nitrogen purge. (c) Hole generation performance of PHI, PHI-S, and PHI-KLi samples in the light and dark-states (hole quantification is converted from O2 yield). Unless otherwise specified in the performance tests, methanol sacrificial agents were added. (d) Dark-state hole-generating activity of PHI without hole scavenger or catalyst. (e) Dark-state hole-generating activity of PHI under light-only and heat-only conditions. Here heat-only conditions are defined as three-necked flasks containing the samples being heated under a water bath at 80 °C for 1 h. (f) Apparent color change of PHI during charge storage and release. (g) Hole generation performance of PHI in light and dark-states under different hole scavenger conditions. Here, dark-state hole yields were obtained after heating for 1 h at 80 °C. (h) Cycling experiments on the release of holes from PHI. (i) Isotope tracking experiment labeled with H218O during O2 evolution among PHI.

Fig. 2. Mechanism verification of charge storage induced hole catalysis. (a) Hole release activity of the PHI sample before and after the addition of electron scavenger under light and dark conditions. (b) Schematic of hole transfer path in the presence of electron scavenger. When no electron scavenger is added, the electrons captured by free radicals are slowly released in the dark-state and the oxidized hole scavenger is reduced, inducing hole release. After adding electron scavenger, the released electrons are quenched by AgNO3, inhibiting the hole release process. Hole species capture experiment (c) and quantification (d) of hole concentration.

Fig. 3. Asymmetric carrier extraction kinetics. (a) Femtosecond transient absorption spectrum of PHI in its original state. The sample is dispersed in an acetonitrile solution. (b,c) Femtosecond transient absorption spectrum of PHI in its excited state. The sample is dispersed in a methanol solution and purged with nitrogen for 15 min prior to testing. (d) Decay kinetics of PHI in the original and excited states. (e) Kinetic decay plot of PHI in the original-state at 480.4 nm. Kinetic decay plot of PHI in the excited-state at 418 nm (f) and at 591.9 nm (g). (h) Mechanism of asymmetric charge carrier extraction.

Fig. 4. Structural analysis of the causes of asymmetric charge extraction. (a) TEM image of PHI. The crystal growth of PHI is shown in the lower right of the figure. (b) HRTEM image of PHI. (c) Crystal structure of PHI. (d) XRD patterns of PHI, PHI-S, and PHI-KLi. (e) FTIR spectra of PHI, PHI-S, and PHI-KLi. (f) In-situ DRIFTS of the structural changes of the PHI sample under illumination in a nitrogen and water vapor atmosphere.

Fig. 5. Further extensions of the asymmetric charge extraction phenomenon. Mott-Schottky curves (a) and photocurrent curves (b) of PHI samples in excited and original state. The voltage applied in the photocurrent test was 0.5 V. (c) Schematic of electro-chemical tests of the sample in excited and original state. Compared to the original state, the free electron density of the sample is higher in the excited state, and the sample exhibits a significant charge storage behavior in the excited state. (d) The Barder charge distribution between O1 and C3 in PHI-CO (PHI-CO was used to simulate the structure of the PHI sample in the excited state). The inset shows the structural unit of PHI-CO. (e) Differential charge density of PHI-CO. The isosurface level is 1.28 × 10-3 e/bohr3. (f) PDOS plots of PHI and PHI-CO.

参考文献

[1]	Y. Bian, K. Dai, Chin. J. Catal., 2025, 76, 1-5.
[2]	B. Weng, M. Zhang, Y. Lin, J. Yang, J. Lv, N. Han, J. Xie, H. Jia, B.-L. Su, M. Roeffaers, J. Hofkens, Y. Zhu, S. Wang, W. Choi, Y.-M. Zheng, Nat. Rev. Clean Technol., 2025, 1, 201-215.
[3]	K. Wang, T. Yang, G. Dawson, J. Zhang, C. Shao, K. Dai, Chem. Res. Chin. Univ., 2025, 41, 716-725.
[4]	R. I. Rodríguez, V. Corti, L. Rizzo, S. Visentini, M. Bortolus, A. Amati, M. Natali, G. Pelosi, P. Costa, L. Dell’Amico, Nat. Catal., 2024, 7, 1223-1231.
[5]	C. Guan, X. Yue, Q. Xiang, Adv. Mater., 2025, 37, 2501209.
[6]	D. Nagornîi, F. Raymenants, N. Kaplaneris, T. Noël, Nat. Commun., 2024, 15, 5246.
[7]	Z. Li, Z. Yu, C. Guan, K. Xu, Q. Xiang, J. Materiomics, 2025, 11, 100982.
[8]	S. Karmakar, S. Barman, F. A. Rahimi, D. Rambabu, S. Nath, T. K. Maji, Nat. Commun., 2023, 14, 4508.
[9]	C. Guan, X. Yue, Y. Liao, Q. Xiang, Angew. Chem. Int. Ed., 2025, 64, e202415538.
[10]	L. Cheng, X. Y. Yue, J. J. Fan, Q. J. Xiang, Adv. Mater., 2022, 34, 2200929.
[11]	Z. Zhang, Y. Xia, C. Shao, L. Sun, G. Dawson, K. Dai, J. Mater. Sci. Technol., 2026, 252, 1-33.
[12]	Z. Yu, D. Zhang, C. Ai, J. Zhang, Q. Xiang, Chin. J. Catal., 2024, 67, 71-81.
[13]	Y. Yang, J. Gu, J. L. Young, E. M. Miller, J. A. Turner, N. R. Neale, M. C. Beard, Science, 2015, 350, 1061-1065.
[14]	X. Y. Yue, J. J. Fan, Q. J. Xiang, Adv. Funct. Mater., 2022, 32, 2110258.
[15]	F. Li, X. Yue, Y. Liao, L. Qiao, K. Lv, Q. Xiang, Nat. Commun., 2023, 14, 3901.
[16]	F. Li, Z. Fang, Z. Xu, Q. Xiang, Energy Environ. Sci., 2024, 17, 497-509.
[17]	X. Deng, J. Zhang, K. Qi, G. Liang, F. Xu, J. Yu, Nat. Commun., 2024, 15, 4807.
[18]	S. Corby, R. R. Rao, L. Steier, J. R. Durrant, Nat. Rev. Mater., 2021, 6, 1136-1155.
[19]	T. Liu, W. Li, D. Z. Wang, T. Luo, M. Fei, D. Shin, M. M. Waegele, D. Wang, Angew. Chem. Int. Ed., 2023, 62, e202307909.
[20]	A. J. Cowan, J. R. Durrant, Chem. Soc. Rev., 2013, 42, 2281-2293.
[21]	B. Ren, G. Yuen, S. Deng, L. Jiang, D. Zhou, L. Gu, P. Xu, M. Zhang, Z. Fan, F. S. Y. Yueng, R. Chen, H.-S. Kwok, G. Li, Adv. Funct. Mater., 2019, 29, 1807894.
[22]	I. Mora-Sero, L. Bertoluzzi, V. Gonzalez-Pedro, S. Gimenez, F. Fabregat-Santiago, K. W. Kemp, E. H. Sargent, J. Bisquert, Nat. Commun., 2013, 4, 2272.
[23]	S. Bae, T. Moehl, E. Service, M. Kim, P. Adams, Z. Wang, Y. Choi, J. Ryu, S. D. Tilley, Nat. Commun., 2024, 15, 9439.
[24]	M. Brändlin, B. Pfund, O. S. Wenger, Nat. Chem., 2025, 17, 1777-1784.
[25]	H. Schlomberg, J. Kröger, G. Savasci, M. W. Terban, S. Bette, I. Moudrakovski, V. Duppel, F. Podjaski, R. Siegel, J. Senker, R. E. Dinnebier, C. Ochsenfeld, B. V. Lotsch, Chem. Mater., 2019, 31, 7478-7486.
[26]	W. Yang, R. Godin, H. Kasap, B. Moss, Y. Dong, S. A. J. Hillman, L. Steier, E. Reisner, J. R. Durrant, J. Am. Chem. Soc., 2019, 141, 11219-11229.
[27]	S. Yang, X. Deng, P. Chen, T. Zhao, F. Liu, C. Deng, S.-F. Yin, Appl. Catal. B, 2022, 311, 121370.
[28]	J. Zhang, X. Liang, C. Zhang, L. Lin, W. Xing, Z. Yu, G. Zhang, X. Wang, Angew. Chem. Int. Ed., 2022, 61, e202210849.
[29]	A. Rogolino, I. F. Silva, N. V. Tarakina, M. A. R. da Silva, G. F. S. R. Rocha, M. Antonietti, I. F. Teixeira, ACS Appl. Mater. Interfaces, 2022, 14, 49820-49829.
[30]	M. Hattori, M. Nakamichi, A. Yamaguchi, C. Miyazaki, G. Seo, R. Ohnuki, S. Yoshioka, K. Kanai, Chem. Mater., 2023, 35, 1283-1294.
[31]	B. Kurpil, K. Otte, A. Mishchenko, P. Lamagni, W. Lipiński, N. Lock, M. Antonietti, A. Savateev, Nat. Commun., 2019, 10, 945.
[32]	A. Gouder, L. Yao, Y. Wang, F. Podjaski, K. S. Rabinovich, A. Jiménez-Solano, B. V. Lotsch, Adv. Energy Mater., 2023, 13, 2300245.
[33]	A. Galushchinskiy, Y. Zou, J. Odutola, P. Nikačević, J.-W. Shi, N. Tkachenko, N. López, P. Farràs, O. Savateev, Angew. Chem. Int. Ed., 2023, 62, e202301815.
[34]	V. W.-H. Lau, B. V. Lotsch, Adv. Energy Mater., 2022, 12, 2101078.
[35]	A. Savateev, Y. Markushyna, C. M. Schüßlbauer, T. Ullrich, D. M. Guldi, M. Antonietti, Angew. Chem. Int. Ed., 2021, 60, 7436-7443.
[36]	Y. Markushyna, P. Lamagni, C. Teutloff, J. Catalano, N. Lock, G. Zhang, M. Antonietti, A. Savateev, J. Mater. Chem. A, 2019, 7, 24771-24775.
[37]	A. Savateev, M. Antonietti, ChemCatChem, 2019, 11, 6166-6176.
[38]	J. Kröger, A. Jiménez-Solano, G. Savasci, V. W. H. Lau, V. Duppel, I. Moudrakovski, K. Küster, T. Scholz, A. Gouder, M.-L. Schreiber, F. Podjaski, C. Ochsenfeld, B. V. Lotsch, Adv. Funct. Mater., 2021, 31, 2102468.
[39]	A. Savateev, B. Kurpil, A. Mishchenko, G. Zhang, M. Antonietti, Chem. Sci., 2018, 9, 3584-3591.
[40]	J. Kröger, F. Podjaski, G. Savasci, I. Moudrakovski, A. Jiménez-Solano, M. W. Terban, S. Bette, V. Duppel, M. Joos, A. Senocrate, R. Dinnebier, C. Ochsenfeld, B. V. Lotsch, Adv. Mater., 2022, 34, 2107061.
[41]	A. Rogolino, O. Savateev, Adv. Funct. Mater., 2023, 33, 2305028.
[42]	M. Isobe, M. Hattori, C. Miyazaki, T. Izumi, R. Ohnuki, S. Yoshioka, K. Kanai, Chem. Mater., 2025, 37, 7484-7491.
[43]	G. Seo, R. Hayakawa, Y. Wakayama, R. Ohnuki, S. Yoshioka, K. Kanai, Phys. Chem. Chem. Phys., 2024, 26, 20585-20597.
[44]	B. Wang, L. W. Le Fevre, A. Brookfield, E. J. L. McInnes, R. A. W. Dryfe, Angew. Chem. Int. Ed., 2021, 60, 21860-21867.
[45]	R. Pan, J. Yuan, X. Huang, Q. Liu, Y. Cui, B. Wu, Adv. Funct. Mater., 2026, 36, e13118.
[46]	D. Ke, T. Peng, L. Ma, P. Cai, P. Jiang, Appl. Catal. A, 2008, 350, 111-117.
[47]	J. Li, J. Barrio, Y. Fang, Y. Pan, M. Volokh, S. Mondal, J. Tzadikov, L. Abisdris, A. Tashakory, X. Wang, X. Zhang, M. Shalom, Energy Fuels, 2023, 37, 18145-18153.
[48]	A. Savateev, I. Ghosh, B. König, M. Antonietti, Angew. Chem. Int. Ed., 2018, 57, 15936-15947.
[49]	S. K. Sahoo, I. F. Teixeira, A. Naik, J. Heske, D. Cruz, M. Antonietti, A. Savateev, T. D. Kühne, J. Phys. Chem. C, 2021, 125, 13749-13758.
[50]	A. Savateev, N. V. Tarakina, V. Strauss, T. Hussain, K. ten Brummelhuis, J. M. Sánchez Vadillo, Y. Markushyna, S. Mazzanti, A. P. Tyutyunnik, R. Walczak, M. Oschatz, D. M. Guldi, A. Karton, M. Antonietti, Angew. Chem. Int. Ed., 2020, 59, 15061-15068.
[51]	M. Wang, Z. Zhang, Z. Chi, L.-L. Lou, H. Li, H. Yu, T. Ma, K. Yu, H. Wang, Adv. Funct. Mater., 2023, 33, 2211565.
[52]	M. Zhou, L. Zeng, R. Li, C. Yang, X. Qin, W. Ho, X. Wang, Appl. Catal. B, 2022, 317, 121719.
[53]	W. Wang, Z. Shu, J. Zhou, H. Tang, T. Li, D. Meng, ACS Appl. Mater. Interfaces, 2022, 14, 41131-41140.
[54]	L. Lin, H. Ou, Y. Zhang, X. Wang, ACS Catal., 2016, 6, 3921-3931.
[55]	L. Xing, Q. Yang, C. Zhu, Y. Bai, Y. Tang, M. Rueping, Y. Cai, Nat. Commun., 2023, 14, 1501.
[56]	Z. Pan, M. Zhao, H. Zhuzhang, G. Zhang, M. Anpo, X. Wang, ACS Catal., 2021, 11, 13463-13471.
[57]	Z. Yu, X. Yue, J. Fan, Q. Xiang, ACS Catal., 2022, 12, 6345-6358.
[58]	Z. Chen, A. Savateev, S. Pronkin, V. Papaefthimiou, C. Wolff, M. G. Willinger, E. Willinger, D. Neher, M. Antonietti, D. Dontsova, Adv. Mater., 2017, 29, 1700555.
[59]	G. Zhang, L. Lin, G. Li, Y. Zhang, A. Savateev, S. Zafeiratos, X. Wang, M. Antonietti, Angew. Chem. Int. Ed., 2018, 57, 9372-9376.
[60]	J. N. Burrow, R. A. Ciufo, L. A. Smith, Y. Wang, D. C. Calabro, G. Henkelman, C. B. Mullins, ACS Nano, 2022, 16, 5393-5403.
[61]	W. Wang, Z. Shu, Z. Liao, J. Zhou, D. Meng, T. Li, Z. Zhao, L. Xu, Chem. Eng. J., 2021, 424, 130332.
[62]	C. M. Pelicano, J. Li, M. Cabrero-Antonino, I. F. Silva, L. Peng, N. V. Tarakina, S. Navalón, H. García, M. Antonietti, J. Mater. Chem. A, 2023, 12, 475-482.
[63]	V. Matsouka, M. Konsolakis, R. M. Lambert, I. V. Yentekakis, Appl. Catal. B, 2008, 84, 715-722.
[64]	D. Lorito, C. Ruocco, V. Palma, A. Giroir-Fendler, F. C. Meunier, Appl. Catal. B, 2016, 197, 56-61.
[65]	Q. Deng, H. Li, W. Hu, W. Hou, Angew. Chem. Int. Ed., 2023, 62, e202314213.
[66]	X. Li, X. Chen, Y. Fang, W. Lin, Y. Hou, M. Anpo, X. Fu, X. Wang, Chem. Sci., 2022, 13, 7541-7551.

揭示非对称电荷提取机理

Revealing the mechanism of asymmetric charge carrier extraction

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