结晶氮化碳纳米阵列上双活性位点的构建及其协同光催化合成过氧化氢性能研究

doi:10.1016/S1872-2067(26)65229-1

催化学报 ›› 2027, Vol. 92: 157-169.DOI: 10.1016/S1872-2067(26)65229-1

结晶氮化碳纳米阵列上双活性位点的构建及其协同光催化合成过氧化氢性能研究

李佳琦^a, 宋豪杰^a, 高宇鑫^a, 张新明^a, 李静楠^a, 王思雨^b,*, 谷慧泉^a,*, 罗梾钰^b,*, 蒋保江^a,*

^a黑龙江大学功能无机材料化学教育部重点实验室, 黑龙江哈尔滨 150080;
^b深圳大学微纳光电子学研究院, 教育部二维材料光电科技国际联合实验室, 广东深圳 518060

收稿日期:2026-02-27 接受日期:2026-04-17 出版日期:2027-01-18 发布日期:2026-10-30
通讯作者: *电子信箱: ghq@hlju.edu.cn (谷慧泉), jbj@hlju.edu.cn (蒋保江), wangsiyu@szu.edu.cn (王思雨), luoly@szu.edu.cn (罗梾钰).
基金资助:
国家自然科学基金(U24A20550, 52273264); 黑龙江省自然科学基金(ZD2024B001); 黑龙江省自然科学基金(PL2024B011); 黑龙江省黑龙江大学基本科研业务费(2025-KYYWF-ZR0382); 中国博士后科学基金(2025M780997).

Decoupled active centers on crystalline carbon nitride nanoarrays for synergistic photocatalytic hydrogen peroxide synthesis

Jiaqi Li^a, Haojie Song^a, YuXin Gao^a, Xinming Zhang^a, Jingnan Li^a, Siyu Wang^b,*, Huiquan Gu^a,*, Laiyu Luo^b,*, Baojiang Jiang^a,*

^aKey Laboratory of Functional Inorganic Materials Chemistry, Ministry of Education of the People's Republic of China, Heilongjiang University, Harbin 150080, Heilongjiang, China;
^bInternational Collaborative Laboratory of 2D Materials for Optoelectronics Science and Technology of Ministry of Education, Institute of Microscale Optoelectronics, Shenzhen University, Shenzhen 518060, Guangdong, China

Received:2026-02-27 Accepted:2026-04-17 Online:2027-01-18 Published:2026-10-30
Contact: *E-mail: ghq@hlju.edu.cn (H. Gu), jbj@hlju.edu.cn (B. Jiang), wangsiyu@szu.edu.cn (S. Wang), luoly@szu.edu.cn (L. Luo).
Supported by:
National Natural Science Foundation of China (U24A20550, 52273264), the Key Project of the Heilongjiang Provincial Natural Science Foundation (ZD2024B001), the Natural Science Foundation of Heilongjiang Province (PL2024B011), the Basic Research Fund of Heilongjiang University in Heilongjiang Province (2025-KYYWF-ZR0382), and the China Postdoctoral Science Foundation (2025M780997).

摘要/Abstract

摘要： 过氧化氢(H₂O₂)不仅是一种环境友好的氧化剂, 还是一种有前景的高能量密度液体燃料, 在工业和环境应用领域具有巨大潜力. 预计到2027年, 全球对H₂O₂的需求将达到570万吨. 然而, 传统的蒽醌法不仅依赖化石燃料, 还会产生大量污染, 使其在可持续性上面临挑战. 在此背景下, 以水和氧气为原料, 利用太阳能驱动的光催化生产H₂O₂已成为一种前景广阔的绿色合成路线. 该路线的关键在于水氧化反应(WOR)和氧还原反应(ORR)之间的协同过程, 这是因为WOR产生的质子(H⁺)是ORR途径所必需的反应物. 然而, 当前光催化制备H₂O₂的整体效率, 正受到ORR动力学不足以及WOR供应H⁺缓慢的双重制约.
本文报道了一种具有空间分离双活性中心的光催化剂, 将铟单原子(In SAs)和氰基共同锚定于结晶氮化碳纳米阵列上, 利用不对称电子密度分布, 协同驱动ORR与WOR反应.该设计有效克服了传统石墨相氮化碳因轨道重叠所导致的载流子分离效率低下的瓶颈. 研究表明, In 5p轨道与C/N 2p轨道之间的杂化有效提升了载流子迁移率, 而双活性位点的构建有效延长光生载流子的寿命, 从而增强了光催化反应效率. 其核心机制在于氰基作为吸电子基团, 既作为高效的电子陷阱, 又充当两电子ORR的活性位点; 而In SAs作为高度局域化的空穴富集中心, 能有效降低水氧化的动力学势垒, 从而提高水氧化供应H⁺的能力. 双活性位点的构建不仅有效提高了ORR和WOR各自的反应效率, 还有效促进WOR产物在氧还原位点上进行高效转化, 从而消除了两个半反应之间的动力学不匹配问题. 得益于这一设计, 催化剂的H₂O₂产率高达475 μmol g^–1 h^–1, 约为原始石墨相氮化碳的17倍. 通过X-射线吸收谱、X-射线光电子能谱、固体核磁共振和高分辨电子显微镜等测试对催化剂的结构进行解析, 证明了In SAs和氰基双活性中心的成功构建. 结合飞秒瞬态吸收光谱, 密度泛函理论计算, 原位漫反射红外傅里叶变换光谱以及同位素标记等机理研究, 进一步揭示了质子耦合电子转移机制以及反应中间体的演化过程.
综上, 本工作成功构建了一种结晶氮化碳纳米阵列, 其具有空间分离的ORR和WOR双活性中心. 该结构不仅可以提升电子-空穴分离效率, 还能高效耦合ORR和WOR. 这些发现不仅阐明了催化剂活性增强的原因, 还为其他光催化剂的理性设计提供了新策略, 即精确构建空间分离的双活性位点以有效驱动协同的光催化反应.

关键词: 催化位点, 结晶氮化碳, 过氧化氢, 光催化, 单原子催化剂

Abstract: Photocatalytic hydrogen peroxide (H₂O₂) synthesis from water and oxygen represents a sustainable pathway for solar energy conversion. However, its efficiency is limited by rapid charge recombination, sluggish water oxidation kinetics, and insufficient proton supply. Herein, we report a photocatalyst featuring spatially separated redox centers, constructed by co-anchoring indium single atoms (In SAs) and cyano groups on highly crystalline carbon nitride nanoarrays. Structural and in situ spectroscopic analyses reveal that cyano groups act as efficient oxygen reduction reaction (ORR) sites. Concurrently, the In SAs act as water oxidation reaction (WOR) centers, which activate water molecules and supply protons for the ORR pathway. The optimized catalyst achieves a remarkable H₂O₂ production rate of 475 μmol g^–1 h^–1 under visible light, a 17-fold improvement over pristine carbon nitride. Theoretical calculations attribute this performance to an induced orbital distribution asymmetry, which facilitates directional carrier migration to respective active sites and concurrently lowers the energy barrier for the critical OOH* intermediate formation. This work establishes a dual-site design strategy to synergistically advance WOR and ORR, offering a promising route for efficient solar-driven H₂O₂ production.

Key words: Catalytic sites, Crystalline carbon nitride, Hydrogen peroxide, Photocatalysis, Single-atom catalyst

李佳琦, 宋豪杰, 高宇鑫, 张新明, 李静楠, 王思雨, 谷慧泉, 罗梾钰, 蒋保江. 结晶氮化碳纳米阵列上双活性位点的构建及其协同光催化合成过氧化氢性能研究[J]. 催化学报, 2027, 92: 157-169.

Jiaqi Li, Haojie Song, YuXin Gao, Xinming Zhang, Jingnan Li, Siyu Wang, Huiquan Gu, Laiyu Luo, Baojiang Jiang. Decoupled active centers on crystalline carbon nitride nanoarrays for synergistic photocatalytic hydrogen peroxide synthesis[J]. Chinese Journal of Catalysis, 2027, 92: 157-169.

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参考文献

[1] S. Yang, D. Si, L. Zou, M. Shi, Y. Huang, R. Cao,J. Am. Chem. Soc., 2025, 147, 30287-30295.
[2] Z. Liu, J. Zhou, S. Yuan, M. Zhang, M. Zhang, T. Lu,Adv. Funct. Mater. 2025, e23126.
[3] J. Lv, H. Chu, C. Shao, L. Sun, G. Dawson, K. Dai,Chin. J. Catal., 2025, 78, 75-99.
[4] T. Freese, J. T. Meijer, B. L. Feringa, S. B. Beil,Nat. Catal., 2023, 6, 553-558.
[5] Y. Shiraishi, S. Kanazawa, Y. Kofuji, H. Sakamoto, S. Ichikawa, S. Tanaka, T. Hirai,Angew. Chem. Int. Ed., 2014, 53, 13454-13459.
[6] Y. Bian, H. He, G. Dawson, J. Zhang, K. Dai,Sci. China Mater., 2024, 67, 514-523.
[7] A. Zadehnazari, F. Auras, A. Abbaspourrad,Adv. Funct. Mater., 2025, 35, 2503961.
[8] Z. Teng, Q. Zhang, H. Yang, K. Kato, W. Yang, Y.-R. Lu, S. Liu, C. Wang, A. Yamakata, C. Su, B. Liu, T. Ohno,Nat. Catal., 2021, 4, 374-384.
[9] K. Yang, L. Chen, K. Xiong, J. Yang, M. Adeli, S. Li, M. Wang, C. Cheng, C. Zhao,Adv. Funct. Mater., 2026, 36, e20900.
[10] Z. Zhang, Y. Xia, C. Shao, L. Sun, G. Dawson, K. Dai,J. Mater. Sci. Technol., 2026, 252, 1-33.
[11] Z. Liu, Y. Bian, G. Dawson, J. Zhu, K. Dai,Chin. Chem. Lett., 2025, 36, 111272.
[12] Z. Li, K. Tong, H. Dong, Y. Li, K. Wang, T. Ding, Y. Yun, Y. Zhou, M. Zhu,Angew. Chem. Int. Ed., 2025, 64, e202502390.
[13] K. Wang, T. Yang, G. Dawson, J. Zhang, C. Shao, K. Dai,Chem. Res. Chin. Univ., 2025, 41, 716-725.
[14] 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, 6202-6213.
[15] Y. Pan, X. J. Liu, W. Zhang, B. B. Shao, Z. F. Liu, Q. H. Liang, T. Wu, Q. Y. He, J. Huang, Z. Peng, Y. Liu, C. H. Zhao,Chem. Eng. J., 2022, 427, 132032.
[16] R. Chen, Y. Quan, W. Cai, Y. Ng, J. Huang, Y. Lai,Chin. J. Catal., 2026, 84, 250-260.
[17] H. He, Z. Wang, J. Zhang, S. Mamatkulov, O. Ruzimuradov, K. Dai, J. Low, Y. Li,Energy Environ. Sci., 2025, 18, 6191-6201.
[18] C. Ding, X. Lu, B. Tao, L. Yang, X. Xu, L. Tang, H. Chi, Y. Yang, D. M. Meira, L. Wang, X. Zhu, S. Li, Y. Zhou, Z. Zou,Adv. Funct. Mater., 2023, 33, 2302824.
[19] B. Li, N. Li, Z. Guo, C. Wang, Z. Zhu, X. Tang, G. Andrew Penyikie, X. Wang, P. Huo,Chem. Eng. J., 2024, 491, 152022.
[20] X. Zhang, P. Ma, C. Wang, L. Gan, X. Chen, P. Zhang, Y. Wang, H. Li, L. Wang, X. Zhou, K. Zheng,Energy Environ. Sci., 2022, 15, 830-842.
[21] Y. Ban, M. Zhang, J. He, C. Shao, Z. Wang, W. Zhao, K. Dai,Chin. Chem. Lett., 2026, 37, 112096.
[22] L.-L. Liu, F. Chen, J.-H. Wu, M.-K. Ke, C. Cui, J.-J. Chen, H.-Q. Yu,Appl. Catal. B, 2022, 302, 120845.
[23] P. Liu, T. Liang, Y. Li, Z. Zhang, Z. Li, J. Bian, L. Jing,Nat. Commun., 2024, 15, 9224.
[24] Y. Yao, T. Liang, Z. Li, Z. Wang, P. Wang, T. Dou, Z. Chen, Z. Li, J. Bian, L. Jing,Adv. Funct. Mater., 2026, 36, e15298.
[25] H. Ou, Y. Jin, B. Chong, J. Bao, S. Kou, H. Li, Y. Li, X. Yan, B. Lin, G. Yang,Adv. Mater., 2024, 36, 2404851.
[26] C. Chu, Q. Zhu, Z. Pan, S. Gupta, D. Huang, Y. Du, S. Weon, Y. Wu, C. Muhich, E. Stavitski, K. Domen, J.-H. Kim,Proc. Natl. Acad. Sci. U. S. A., 2020, 117, 6376-6382.
[27] J.-R. Huang, H.-Y. Chen, H.-L. Zhu, P.-Q. Liao, X.-M. Chen,J. Am. Chem. Soc., 2025, 147, 37167-37175.
[28] Y. Zhao, P. Zhang, Z. Yang, L. Li, J. Gao, S. Chen, T. Xie, C. Diao, S. Xi, B. Xiao, C. Hu, W. Choi,Nat. Commun., 2021, 12, 3701.
[29] C. X. Shi, R. L. Pan, J. L. Yuan, C. B. Liu,Adv. Funct. Mater., 2025, 35, 2500342.
[30] J. Hou, K. Wang, X. Zhang, Y. Wang, H. Su, C. Yang, X. Zhou, W. Liu, H. Hu, J. Wang, C. Li, P. Ma, R. Zhang, Z. Wei, Z. Sun, Q. Liu, K. Zheng,ACS Catal., 2024, 14, 10893-10903.
[31] G. Liu, Z. Tang, X. Gu, N. Li, H. Lv, Y. Huang, Y. Zeng, M. Yuan, Q. Meng, Y. Zhou, C. Wang,Appl. Catal. B, 2022, 317, 121752.
[32] L. Luo, S. Wang, L. Zhang, X. Xiao, B. Wu, M. Jaroniec, B. Jiang,Appl. Catal. B, 2024, 343, 123475.
[33] C. Xu, H. Liu, D. Wang, D. Li, Y. Zhang, X. Liu, J. Huang, S. Wu, D. Fan, H. Liu, H. Pan,Appl. Catal. B, 2023, 334, 122835.
[34] Y. Xu, C. Qiu, X. Fan, Y. Xiao, G. Zhang, K. Yu, H. Ju, X. Ling, Y. Zhu, C. Su,Appl. Catal. B, 2020, 268, 118457.
[35] J. Li, J. Huang, G. Zeng, C. Zhang, H. Yu, Q. Wan, K. Yi, W. Zhang, H. Pang, S. Liu, S. Li, W. He,Chem. Eng. J., 2023, 463, 142512.
[36] J. Luo, C. Fan, L. Tang, Y. Liu, Z. Gong, T. Wu, X. Zhen, C. Feng, H. Feng, L. Wang, L. Xu, M. Yan,Appl. Catal. B, 2022, 301, 120757.
[37] W. Cai, Y. Tanaka, X. Zhu, T. Ohno,Nano Res., 2024, 17, 7027-7038.
[38] H. Tan, P. Zhou, M. Liu, Q. Zhang, F. Liu, H. Guo, Y. Zhou, Y. Chen, L. Zeng, L. Gu, Z. Zheng, M. Tong, S. Guo,Nat. Synth, 2023, 2, 557-563.
[39] D. Chen, W. Chen, Y. Wu, L. Wang, X. Wu, H. Xu, L. Chen,Angew. Chem. Int. Ed., 2023, 62, e202217479.
[40] L. Y. Luo, Q. L. Wu, S. Y. Wang, H. J. Song, J. Q. Li, L. P. Zhang, Q. Zhang, Y. X. Fang, B. J. Jiang, X. C. Wang,Angew. Chem. Int. Ed., 2025, 64, e202507415.
[41] S. Li, J. Wang, X. Cai, S. Li, X. Liang, H. Ye, R. Xiong, C. Yang, W. Lin, Z. Yu, Y. Hou, X. Wang,Appl. Catal. B, 2026, 381, 125807.
[42] J. M. Wu, K. Y. Li, B. Zhou, R. Li, Y. Han, C. S. Song, X. W. Guo,Adv. Mater., 2026, 38, e19554.
[43] O. Fónagy, E. Szabó-B rdos, O. Horvath,J. Photochem. Photobiol. A, 2021, 407, 113057.
[44] C. B. Wu, Z. Y. Teng, C. Yang, F. S. Chen, H. B. Yang, L. Wang, H. X. Xu, B. Liu, G. F. Zheng, Q. Han,Adv. Mater., 2022, 34, 2110266.
[45] Q. Liu, H. Bi, R. Zhao, X. W. Yang, F. Y. Chen, Z. R. Shen,Angew. Chem. Int. Ed., 2025, 64, e202511687.
[46] Z. Liao, L. Jiang, Y. Yang, L. Wang, W. Yang, H. Hou,Chin. J. Catal., 2026, 83, 143-161.
[47] Y. Hou, P. Zhou, F. Liu, Y. Lu, H. Tan, Z. Li, M. Tong, J. Ni,Angew. Chem. Int. Ed., 2024, 63, e202318562.
[48] J. Mao, H. Li, Y. Xu, K. Zhang, Q. Wang, L. Yang, Z. Gu, Y. Bai, X. Lang, X. An, J. Qu,Appl. Catal. B, 2026, 381, 125862.
[49] W. Wang, Y. Tan, B. Li, J. Wang, X. Yu, L. Wang, X. Wang, X. Wang, L. Huang, Z. Sun, W.-M. Lau,J. Colloid Interface Sci., 2025, 686, 903-914.
[50] Y. Chen, Y. Guo, T. Wang, S. Ji, H. Shao, M. Lin, S. Seki, N. Yan, D. Jiang,Nat. Commun., 2025, 16, 6495.
[51] M. Xu, R. Wang, H. Fu, Y.Shi, L. Ling,Proc. Natl. Acad. Sci. U. S. A., 2024, 121, e2318787121.
[52] H. Tan, P. Zhou, M. Liu, Y. Gu, W. Chen, H. Guo, J. Zhang, K. Yin, Y. Zhou, C. Shang, Q. Zhang, L. Gu, N. Zhang, J. Ma, Z. Zheng, M. Luo, S. Guo,J. Am. Chem. Soc., 2024, 146, 31950-31960.
[53] 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.

结晶氮化碳纳米阵列上双活性位点的构建及其协同光催化合成过氧化氢性能研究

Decoupled active centers on crystalline carbon nitride nanoarrays for synergistic photocatalytic hydrogen peroxide synthesis

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[14]	王洋, 范存冯, 刘洋, 郑晓芹, 刘譞懿, 张凯, 寇佳慧, 黄亨明, 孙林兵. 基于限域空间内原位形成的碳层构筑铁单原子催化剂用于高效芬顿反应[J]. 催化学报, 2026, 88(9): 432-441.
[15]	Vladimir I. Kurganskii, Dmitry P. Lubov, Alexander G. Medvedev, 王瑞虎, Konstantin P. Bryliakov. 非血红素锰配合物催化的缺电子烯烃仿生不对称顺式羟基叠氮化反应[J]. 催化学报, 2026, 88(9): 468-477.