基于银−碳键的新型金属有机框架用于高效光催化合成过氧化氢★

doi:10.6023/A25110383

化学学报 ›› 2026, Vol. 84 ›› Issue (5): 626-630.DOI: 10.6023/A25110383 上一篇下一篇

研究论文

基于银−碳键的新型金属有机框架用于高效光催化合成过氧化氢^★

陈慧滢^a, 黄宁宇^b^,^*(), 廖培钦^a^,^*()

^a 中山大学化学学院广州 510275
^b 南洋理工大学材料科学与工程学院新加坡 639798

投稿日期:2025-11-26 发布日期:2026-01-04
通讯作者: 黄宁宇, 廖培钦
作者简介:
★ “框架材料化学”专辑.
基金资助:
国家重点研发计划(2024YFF0506100); 国家自然科学基金(22090061); 国家自然科学基金(22488101); 国家自然科学基金(22371304); 广东省科技创新战略专项资金(STKJ2023078); 中山大学中央高校基本科研业务费(24lgzy006); 以及广州市科技计划项目(SL2023A04J01767)

A Novel Silver-Carbon Bond-Engineered Metal-Organic Framework toward Efficient Artificial Photosynthesis of Hydrogen Peroxide^★

Huiying Chen^a, Ningyu Huang^b^,^*(), Peiqin Liao^a^,^*()

^a College of Chemistry, Sun Yat-sen University, Guangzhou 510275, China
^b School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore

Received:2025-11-26 Published:2026-01-04
Contact: Ningyu Huang, Peiqin Liao
About author:
★ For the VSI “Chemistry of Framework Materials”.
Supported by:
National Key R&D Program of China(2024YFF0506100); National Natural Science Foundation of China(22090061); National Natural Science Foundation of China(22488101); National Natural Science Foundation of China(22371304); Special Fund Project for Science and Technology Innovation Strategy of Guangdong Province(STKJ2023078); Fundamental Research Funds for the Central Universities, Sun Yat-Sen University(24lgzy006); Guangzhou Science and Technology Program(SL2023A04J01767)

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1. Supporting information-A25110383.pdf(857KB)

摘要/Abstract

开发高效稳定的光催化剂用于太阳能驱动过氧化氢(H₂O₂)合成是当前绿色化学研究的重要方向. 基于金属−碳键(M—C)配位策略, 成功设计并合成了一例新型银基金属有机框架(MOF)光催化剂Ag-TEPT (TEPT=2,4,6-三(4-乙炔基苯基)-1,3,5-三嗪). 在模拟太阳光照下, 该催化剂在不加任何牺牲剂的水-氧气体系中展现出优异的H₂O₂合成性能, 产率可达2880 μmol•g⁻¹•h⁻¹; 即使在空气氛围中仍能维持2024 μmol•g⁻¹•h⁻¹的高活性. 进一步的机理研究表明, H₂O₂的生成遵循两电子氧还原反应(ORR)与四电子水氧化反应(WOR)协同的双路径反应机制. 光致发光光谱和光电化学测试证实, 催化剂中活性位点与银−碳配位键协同调控, 不仅优化了催化剂的能带结构, 还显著促进了光生电子-空穴对的有效分离, 从而显著提升了光催化合成过氧化氢的活性.

关键词: 银−碳键, 金属有机框架, 光合成H₂O₂, 氧还原反应, 水氧化反应

The development of highly efficient and stable photocatalysts for solar-driven hydrogen peroxide (H₂O₂) production represents a pivotal direction in green chemistry research. Herein, we report the successful synthesis of a novel silver-based metal-organic framework (MOF) photocatalyst, Ag-TEPT (where TEPT=2,4,6-tris(4-ethynylphenyl)- 1,3,5-triazine), which was constructed via a metal-carbon (M—C) bond coordination strategy to bridge Ag(I) clusters with triazine-based linkers. Under simulated sunlight irradiation, Ag-TEPT exhibited an outstanding H₂O₂ production rate of 2880 μmol•g⁻¹•h⁻¹ in a pure water-oxygen system without any sacrificial agents, a performance that significantly surpasses most reported photocatalysts. Impressively, it maintained a high production rate of 2024 μmol•g⁻¹•h⁻¹ even in ambient air. Furthermore, Ag-TEPT demonstrated remarkable photocatalytic stability with negligible activity loss over three consecutive reaction cycles. Post-catalytic characterization confirmed its unvaried crystal structure, morphology, and surface chemical states, attesting to its potential as a high-performance and durable photocatalyst. Mechanistic studies revealed a dual-pathway reaction mechanism, wherein H₂O₂ generation proceeds via simultaneous 2e⁻ oxygen reduction reaction (ORR) and 4e⁻ water oxidation reaction (WOR) processes. Notably, the O₂ produced from the 4e⁻ WOR serves as an internal feedstock for the 2e⁻ ORR, mitigating the dependency on exogenous O₂ and thereby enhancing the overall catalytic efficiency. In addition, the band structure of AgC-MOF, constructed from Tauc plot fitting and Mott-Schottky measurements, provided thermodynamic validation that Ag-TEPT is suitable for the photocatalytic reduction of O₂ to H₂O₂ and the oxidation of H₂O to O₂, but not for the direct oxidation of H₂O to H₂O₂. Photoluminescence spectroscopy and photoelectrochemical measurements confirmed the exceptional photogenerated charge separation efficiency of AgC-MOF, a benefit derived from the superior electron transport capability of the Ag-alkynyl bonds, which led to markedly improved photocatalytic reaction kinetics. In particular, Ag-TEPT showed a substantially higher photocurrent density, attributable to the excellent photosensitivity of the triazine units within the TEPT linker.

Key words: silver-carbon bond, metal-organic frameworks, photocatalytic H₂O₂ production, oxygen reduction reaction, water oxidation reaction

引用此文

陈慧滢, 黄宁宇, 廖培钦. 基于银−碳键的新型金属有机框架用于高效光催化合成过氧化氢^★[J]. 化学学报, 2026, 84(5): 626-630.

Huiying Chen, Ningyu Huang, Peiqin Liao. A Novel Silver-Carbon Bond-Engineered Metal-Organic Framework toward Efficient Artificial Photosynthesis of Hydrogen Peroxide^★[J]. Acta Chimica Sinica, 2026, 84(5): 626-630.

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图/表 3

图1. Ag-TEPT和Ag-TEPB的制备路径与结构特征

Figure 1. Preparation routes and structures of Ag-TEPT and Ag-TEPB

图2. (a) AgC-MOF光催化生成H2O2的时间曲线; (b) Ag-TEPT在不同气体氛围中的光催化H2O2产率对比; 光催化前后Ag-TEPT的(c) PXRD谱图和(d) XPS谱图; (e) Ag-TEPT在不同活性物质捕获剂作用下的H2O2产率对比; (f) RDE测试得到的Koutecky-Levich图

Figure 2. (a) Time course of photocatalytic production of H2O2 for AgC-MOFs; (b) Comparison of photocatalytic H2O2 production rates by Ag-TEPT under different gas atmospheres; (c) PXRD patterns and (d) XPS spectra for Ag-TEPT before and after the photocatalytic reaction; (e) H2O2 production efficiency of Ag-TEPT under different active material capture agents; (f) Koutecky-Levich plots from RDE measurements

图3. (a) Ag-TEPT和Ag-TEPB的紫外-可见漫反射光谱; (b) Ag-TEPT的Mott-Schottky曲线图; (c)能带结构示意图; (d) Nyquist图; (e)光电流响应曲线; (f) Ag-TEPT和Ag-TEPB的PL光谱(激发波长500 nm)

Figure 3. (a) UV-Vis DRS of Ag-TEPT and Ag-TEPB; (b) Mott-Schottky plots of Ag-TEPT; (c) Energy level diagrams; (d) Nyquist plots; (e) Photocurrent response curves; (f) PL emission spectra of Ag-TEPT and Ag-TEPB under 500 nm excitation

参考文献 36

[1]	Yong, Z.-J.; Ma, T.-Y. Angew. Chem. Int. Ed. 2023, 62, e202308980. doi: 10.1002/anie.v62.49
[2]	Shi, X.-J.; Back, S.; Gill, T. M.; Siahrostami, S.; Zheng, X.-L. Chem 2021, 7, 38. doi: 10.1016/j.chempr.2020.09.013
[3]	Yi, Y.-H.; Wang, L.; Li, G.; Guo, H.-C. Catal. Sci. Technol. 2016, 6, 1593. doi: 10.1039/C5CY01567G
[4]	Yan, S.-R.; Liu, W.-H.; Duan, F.; Chen, M.-Q.; Dong, W.-F.; Lu, S.-L.; Du, M.-L. Acta Chim. Sinica 2025, 83, 685 (in Chinese). doi: 10.6023/A25030077
	(闫生荣, 刘文浩, 段芳, 陈明清, 东为富, 陆双龙, 杜明亮, 化学学报, 2025, 83, 685.) doi: 10.6023/A25030077
[5]	Ma, D.; Xu, M.; Ding, L.; Guo, J.-K.; Yang, Y.; Dou, W.; Li, H.; Chen, F.-J.; Tang, Y. Angew. Chem. Int. Ed. 2026, 65, e21029. doi: 10.1002/anie.v65.1
[6]	Zuo, Q.; Chu, B.-X.; Ye, X.-H.; Li, F.-Y.; Li, L.; Xu, Q. J. Am. Chem. Soc. 2025, 147, 34681. doi: 10.1021/jacs.5c09922
[7]	Zeng, X.-K.; Liu, Y.; Hu, X.-Y.; Zhang, X.-W. Green Chem. 2021, 23, 1466. doi: 10.1039/D0GC04236F
[8]	Wu, Q.-Y.; Zhang, C.-X.; Sun, K.; Jiang, H.-L. Acta Chim. Sinica 2020, 78, 688 (in Chinese). doi: 10.6023/A20050141
	(吴浅耶, 张晨曦, 孙康, 江海龙, 化学学报, 2020, 78, 688.) doi: 10.6023/A20050141
[9]	Wang, W.-J.; Chen, D.; Li, F.-Y.; Xiao, X.; Xu, Q. Chem 2024, 10, 86. doi: 10.1016/j.chempr.2023.09.009
[10]	Chen, X.; Xia, R. Q.; Deng, Q. M.; Li, Y. Q.; Chen, M. H.; Li, Y. G.; Cai, X. C.; Titov, A. A.; Filippov, O. A.; Shubina, E. S.; Wei, R. J.; Ning, G. H.; Li, D. Chin. J. Chem. 2025, 43, 2277. doi: 10.1002/cjoc.v43.18
[11]	Wang, Y. X.; Zheng, F.; Song, D. X.; Niu, B. Y.; Deng, L. Q.; Zhang, X. M. Chin. J. Chem. 2024, 42, 1093. doi: 10.1002/cjoc.v42.10
[12]	Liu, X.-G.; Shan, Y.-Y.; Zhang, S.-T.; Kong, Q.-Q.; Pang, H. Green Energy Environ. 2023, 8, 698. doi: 10.1016/j.gee.2022.03.005
[13]	Shiraishi, Y.; Kanazawa, S.; Sugano, Y.; Tsukamoto, D.; Sakamoto, H.; Ichikawa, S.; Hirai, T. ACS Catal. 2014, 4, 774. doi: 10.1021/cs401208c
[14]	Kondo, Y.; Kuwahara, Y.; Mori, K.; Yamashita, H. Chem 2022, 8, 2924. doi: 10.1016/j.chempr.2022.10.007
[15]	Moon, G.; Kim, W.; Bokare, A. D.; Sung, N.; Choi, W. Energy Environ. Sci. 2014, 7, 4023. doi: 10.1039/C4EE02757D
[16]	Sayed, M.; Yu, J.-G.; Liu, G.; Jaroniec, M. Chem. Rev. 2022, 122, 10484. doi: 10.1021/acs.chemrev.1c00473
[17]	Matsuoka, M.; Iino, K.; Chen, H. J.; Anpo, M. Res. Chem. Intermed. 2005, 31, 153. doi: 10.1163/1568567053146869
[18]	Chen, H. Y.; Huang, J. R.; Liu, J. C.; Huang, N. Y.; Chen, X. M.; Liao, P. Q. Angew. Chem. Int. Ed. 2024, 63, e202412553. doi: 10.1002/anie.v63.47
[19]	Tang, Y. Y.; Luo, X.; Xia, R. Q.; Luo, J.; Peng, S. K.; Liu, Z. N.; Gao, Q.; Xie, M.; Wei, R. J.; Ning, G. H.; Li, D. Angew. Chem. Int. Ed. 2024, 63, e202408186. doi: 10.1002/anie.v63.36
[20]	Xia, R. Q.; Liu, Z. N.; Tang, Y. Y.; Wu, T.; Luo, X.; Deng, Q. M.; Ning, G. H.; Li, D. Angew. Chem. Int. Ed. 2025, 64, e202514091. doi: 10.1002/anie.v64.43
[21]	Mohata, S.; Majumder, P.; Banerjee, R. Chem. Soc. Rev. 2025, 54, 6062. doi: 10.1039/D5CS00106D
[22]	Gong, Z.-H.; Gao, Y.; Li, J.; Cai, Z.-C.; Liu, N.-F.; Jiang, J.-Z. Angew. Chem. Int. Ed. 2025, 64, e202423205. doi: 10.1002/anie.v64.13
[23]	Liu, X.-Q.; Huang, R.-R.; Peng, L.-Y.; Yang, J.-L.; Yan, J.-B.; Zhai, B.-B.; Luo, Y.; Zhang, C.; Tan, S.-W.; Liu, X.-Y.; Ding, L.-P.; Fang, Y. Angew. Chem. Int. Ed. 2024, 64, e202414472. doi: 10.1002/anie.v64.2
[24]	Sun, R.-X.; Yang, X.-J.; Hu, X.-L.; Guo, Y.-T.; Zhang, Y.-Q.; Shu, C.; Yang, X.; Gao, H.; Wang, X.-Y.; Hussain, I.; Tan, B. Angew. Chem. Int. Ed. 2024, 64, e202416350. doi: 10.1002/anie.v64.4
[25]	Yang, H.-Y.; Chen, X.-K.; Mou, Y.-J.; Li, Q.; Liu, J.-J.; Sun, L.-J.; Zhai, S.-L.; Deng, W. Q.; Wu, H. Small 2024, 20, 2406737. doi: 10.1002/smll.v20.51
[26]	Chen, H.-Y.; Zhao, Z.-H.; Huang, N.-Y.; Huang, J.-R.; Liao, P.-Q. J. Am. Chem. Soc. 2025, 147, 38484. doi: 10.1021/jacs.5c11801
[27]	Jiang, L.; Lin, L.; Wang, Z.-H.; Ai, H.-Y.; Jia, J.-T.; Zhu, G.-S. J. Am. Chem. Soc. 2024, 146, 22930. doi: 10.1021/jacs.4c07945 pmid: 39115250
[28]	De Riggi, N.; Imberdis, A.; Nicolas, E.; Cantat, T. Organometallics 2024, 43, 2466. doi: 10.1021/acs.organomet.4c00023
[29]	Sun, Q.; Cai, L.-L.; Ma, H.-H.; Yuan, C.-X.; Xu, W. ACS Nano 2016, 10, 7023. doi: 10.1021/acsnano.6b03048
[30]	Qin, Y.-Y.; Wang, Y.; Lu, J.; Xu, L.-L.; Wong, W. Y. Angew. Chem. Int. Ed. 2024, 64, e202418269. doi: 10.1002/anie.v64.6
[31]	Jiang, L.; Jia, J.-T.; Ma, Y.-H.; Tian, Y.-Y.; Zou, X.-Q.; Zhu, G.-S. Chem 2024, 10, 557. doi: 10.1016/j.chempr.2023.09.022
[32]	Liu, J.; Chen, Q.-W.; Cai, K.; Li, J.; Li, Y.; Yang, X.; Zhang, Y.-J.; Wang, Y.-F.; Tang, H.; Zhao, D.-H.; Wu, K. Nat. Commun. 2019, 10, 2545. doi: 10.1038/s41467-019-10522-4
[33]	Le´tinois-Halbes, U.; Pale, P.; Berger, S. J. Org. Chem. 2005, 70, 9185. doi: 10.1021/jo0511546
[34]	Feng, Y.-L.; Wang, G.-R.; Chang, Y.; Cheng, Y.; Sun, B.-B.; Wang, L.-M.; Chen, C.-Y.; Zhang, H.-Y. Nano Lett. 2019, 19, 4478. doi: 10.1021/acs.nanolett.9b01293
[35]	Xu, L.; Xiao, Y.; Yu, Z. X.; Yang, Y.; Yan, C.; Huang, J. Q. Angew. Chem. Int. Ed. 2024, 63, e202406054. doi: 10.1002/anie.v63.41
[36]	Wang, C.; Wang, S.-J.; Kong, F.-G. Inorg. Chem. 2021, 60, 5034. doi: 10.1021/acs.inorgchem.1c00063

基于银−碳键的新型金属有机框架用于高效光催化合成过氧化氢^★

A Novel Silver-Carbon Bond-Engineered Metal-Organic Framework toward Efficient Artificial Photosynthesis of Hydrogen Peroxide^★

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基于银−碳键的新型金属有机框架用于高效光催化合成过氧化氢★

A Novel Silver-Carbon Bond-Engineered Metal-Organic Framework toward Efficient Artificial Photosynthesis of Hydrogen Peroxide★

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基于银−碳键的新型金属有机框架用于高效光催化合成过氧化氢^★

A Novel Silver-Carbon Bond-Engineered Metal-Organic Framework toward Efficient Artificial Photosynthesis of Hydrogen Peroxide^★