非补偿性Cu/N共掺杂协同石墨烯增强TiO2光催化双通道制H2O2

doi:10.1016/S1872-2067(25)64799-1

催化学报 ›› 2025, Vol. 78: 252-264.DOI: 10.1016/S1872-2067(25)64799-1

非补偿性Cu/N共掺杂协同石墨烯增强TiO₂光催化双通道制H₂O₂

申倩倩^a^,^b^,^*(), 董晨龙^a^,^b, 冯世龙^a^,^b, 张雪丽^a^,^b, 李秋蓉^a^,^b, 薛晋波^a^,^b^,^*()

^a太原理工大学, 新材料界面科学与工程教育部重点实验室, 山西太原 030024
^b太原理工大学材料科学与工程学院, 山西太原 030024

收稿日期:2025-05-19 接受日期:2025-06-24 出版日期:2025-11-18 发布日期:2025-10-14
通讯作者: *电子信箱: shenqianqian@tyut.edu.cn (申倩倩), xuejinbo@tyut.edu.cn (薛晋波).
基金资助:
国家自然科学基金(52472300);国家自然科学基金(62004137);山西省自然科学基金(20210302123102);中央引导地方科技发展资金(YDZJSX20231A020);山西浙大新材料与化工研究院项目(2022SX-TD002);山西省回国留学人员科技项目(2020-050);运城市科技计划项目(YCKJ-2023056)

The synergistic effect of non-compensated Cu/N co-doping and graphene enhances the dual-channel generation of H₂O₂ over TiO₂ photocatalysts

Qianqian Shen^a^,^b^,^*(), Chenlong Dong^a^,^b, Shilong Feng^a^,^b, Xueli Zhang^a^,^b, Qiurong Li^a^,^b, Jinbo Xue^a^,^b^,^*()

^aKey Laboratory of Interface Science and Engineering in Advanced Materials, Ministry of Education, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^bCollege of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2025-05-19 Accepted:2025-06-24 Online:2025-11-18 Published:2025-10-14
Contact: *E-mail: shenqianqian@tyut.edu.cn (Q. Shen), xuejinbo@tyut.edu.cn (J. Xue).
Supported by:
National Natural Science Foundation of China(52472300);National Natural Science Foundation of China(62004137);Natural Science Foundation of Shanxi Province(20210302123102);Central Leading Science and Technology Development Foundation of Shanxi Province(YDZJSX20231A020);Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2022SX-TD002);Shanxi Scholarship Council of China(2020-050);Science and Technology Program of Yuncheng City(YCKJ-2023056)

摘要/Abstract

摘要：

过氧化氢(H₂O₂)是世界上最重要的100种化学品之一, 自1818年由Thenard首次合成以来, 已受到越来越多的关注, 并被广泛应用于有机合成、污水处理、医疗消毒和漂白等领域. 近年来, 以水(H₂O)和氧气(O₂)为原料、以太阳光为能源的光催化合成H₂O₂路线, 因其绿色、经济、安全和可持续发展等优点而备受关注. 光催化生产H₂O₂可通过水氧化反应(WOR)、氧还原反应(ORR)或双通道途径实现. 双通道途径整合了ORR和WOR反应的优势, 无需牺牲剂即可将O₂和H₂O转化为H₂O₂, 从而实现更高的原子利用率和能量转换效率, 从而提高H₂O₂的生产效率. 由此可见, 双通道途径是光催化生产H₂O₂的理想途径.

本研究针对TiO₂光催化合成H₂O₂过程中存在的光吸收范围窄、载流子复合率高以及反应效率低等关键科学问题, 创新性地设计了一种石墨烯修饰的非补偿Cu/N共掺杂TiO₂ (Cu-N-TiO₂/rGO)光催化剂. 该催化剂通过独特的双通道反应途径, 实现了在温和条件下高效合成H₂O₂的目标. 在催化剂设计方面, 本研究采用了共掺杂策略, 将Cu²⁺和N³⁻共同掺入TiO₂晶格. 通过系统的表征和理论计算发现, Cu/N共掺杂的协同作用实现了对TiO₂导带和价带位置的精确调控, 使其带隙从原始TiO₂的3.25 eV显著降至2.88 eV, 在满足氧化还原电位要求的同时, 大幅度提高了对太阳光的转化效率. 此外, Cu掺杂通过促进氧空位的形成, 减少了光生电荷重组中心Ti³⁺的形成; 非补偿性的N掺杂有效地增加了Cu²⁺在TiO₂晶格中的溶解度, 增强了羟基自由基中间产物的吸附, 为后续生成H₂O₂创造了条件. 在催化剂结构优化方面, 引入了石墨烯作为电子传输介质. 石墨烯与Cu-N-TiO₂形成了紧密的界面接触, 构建了高效的电子传输通道. 该独特的结构设计实现了氧化还原反应位点的空间分离: 光生电子通过石墨烯快速传输至ORR活性位点, 而空穴则保留在WOR活性位点. 飞秒瞬态吸收光谱测试表明, Cu-N-TiO₂/rGO的载流子寿命达到179.9 ps, 是原始TiO₂ (32.1 ps)的5.6倍, 这为双通道反应的高效进行提供了动力学保障. 通过原位漫反射傅立叶变换红外光谱和密度泛函理论计算, 深入揭示了双通道反应机制. 研究表明, 该催化剂通过两条平行途径生成H₂O₂: ORR途径(贡献率为65.2%)遵循O₂ → •O₂⁻ → H₂O₂的两步单电子还原过程; WOR途径(贡献率为34.8%)则通过H₂O → •OH → H₂O₂的路径实现. 优化后的Cu-N-TiO₂/rGO在模拟太阳光下的H₂O₂产率达到1266.7 µmol·L⁻¹, 是原始TiO₂的25.2倍.

综上, 本文提出的非补偿共掺杂策略和双通道反应机制为光催化合成H₂O₂提供了新思路. 未来, 通过进一步优化掺杂元素组合和界面工程, 有望实现更高的太阳能转化效率. 本工作不仅解决了能带结构调控与载流子分离效率的关键难题, 还为设计高效的光催化剂提供了理论指导.

关键词: 光催化合成H₂O₂, 双通道, 能带结构调控, Cu/N共掺杂

Abstract:

Modulating the electronic structure of a photocatalyst and constructing spatially separated redox sites are key strategies for achieving the photocatalytic dual-channel generation of H₂O₂. In this study, a graphene-modified non-compensated Cu/N-co-doped titanium dioxide (Cu-N-TiO₂/rGO) photocatalyst was designed for the efficient synthesis of H₂O₂ via a dual-channel pathway. Precise modulation of the TiO₂ conduction band position was achieved through the synergistic coupling of Cu 3d orbitals hybridized with Ti 3d orbitals and hybridization of N 2p orbitals with O 2p orbitals. This approach significantly improved the utilization of sunlight while satisfying the redox potential requirements. Cu doping not only promoted the formation of oxygen vacancies but also reduced the formation of Ti³⁺ ions, the photogenerated charge recombination centers. The non-compensated doping of N effectively increased the solubility of Cu²⁺ ions in the titanium dioxide lattice, enhanced the adsorption of hydroxyl radical intermediates, and created conditions for the subsequent hydroxyl radical combinations promoting the generation of H₂O₂. In addition, the introduction of highly conductive graphene improved the interfacial carrier separation efficiency while realizing the spatial separation of redox sites, creating conditions for dual-channel reactions. The experimental results showed that the H₂O₂ yield of Cu-N-TiO₂/rGO under simulated sunlight reached 1266.7 µmol/L, which was 25.2 times higher than that of pristine TiO₂. This study elucidated the synergistic mechanism of the energy band structure modulation and interfacial optimization, which provided a new idea for the design of dual-channel H₂O₂ production photocatalysts.

Key words: Photocatalytic production of H₂O₂, Dual channel, Modulation of energy band structure, Cu/N co-doping

申倩倩, 董晨龙, 冯世龙, 张雪丽, 李秋蓉, 薛晋波. 非补偿性Cu/N共掺杂协同石墨烯增强TiO₂光催化双通道制H₂O₂[J]. 催化学报, 2025, 78: 252-264.

Qianqian Shen, Chenlong Dong, Shilong Feng, Xueli Zhang, Qiurong Li, Jinbo Xue. The synergistic effect of non-compensated Cu/N co-doping and graphene enhances the dual-channel generation of H₂O₂ over TiO₂ photocatalysts[J]. Chinese Journal of Catalysis, 2025, 78: 252-264.

×
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(25)64799-1

https://www.cjcatal.com/CN/Y2025/V78/I11/252

图/表 7

Fig. 1. SEM images of TiO2 (a), Cu-N-TiO2 (b), and Cu-N-TiO2/rGO (c). TEM images of TiO2 (d) and Cu-N-TiO2/rGO (e). (f) HRTEM image of Cu-N-TiO2/rGO. (g-k) EDS maps of Cu-N-TiO2. (l) XRD patterns of TiO2, N-TiO2, Cu-TiO2, Cu-N-TiO2, and Cu-N-TiO2/rGO. (m) Magnified XRD peaks of the (101) surface.

Fig. 2. High-resolution XPS profiles of Ti 2p (a), O 1s (b), Cu 2p (c), and N 1s (d). (e) Schematic representation of the Cu2+ and N3? co-doped TiO2. (f) XRD patterns of the catalysts with different copper doping amounts. Enlarged XRD patterns (g) and copper doping concentrations (h) of Cu-TiO2 and Cu-N-TiO2.

Fig. 3. (a) UV-vis diffuse reflectance absorption spectra of TiO2, N-TiO2, Cu-TiO2, Cu-N-TiO2, and Cu-N-TiO2/rGO. The corresponding optical bandgaps (b), Mott-Schottky curves (c), and energy band structure diagrams (d).

Fig. 4. SPV spectra (a), PL spectra (b), transient photocurrent responses (c), EIS profiles (d), TRPL spectra (e), and photogenerated carrier lifetimes (f) of TiO2, N-TiO2, Cu-TiO2, Cu-N-TiO2, and Cu-N-TiO2/rGO.

Fig. 5. Contour plots showing the evolution of the femtosecond transient absorption spectra of TiO2 (a), Cu-N-TiO2 (b), and Cu-N-TiO2/rGO (c). Femtosecond transient absorption spectra of TiO2 (d), Cu-N-TiO2 (e), and Cu-N-TiO2/rGO (f). Kinetic decay curves of TiO2 obtained at 665 nm (g) and Cu-N-TiO2 (h) and Cu-N-TiO2/rGO (i) recorded at 625 nm.

Fig. 6. (a) H2O2 yields of TiO2, N-TiO2, Cu-TiO2, Cu-N-TiO2, and Cu-N-TiO2/rGO. (b) Comparative studies of the photocatalytic production of H2O2 under different reaction conditions. (c) Performances of Cu-N-TiO2/rGO and other photocatalysts. (d) Results of the Cu-N-TiO2/rGO cycling stability tests. (e) In-situ DRIFT spectra of Cu-N-TiO2/rGO obtained at different irradiation times during the photocatalytic production of H2O2. (f) Local magnification of the in-situ DRIFT spectra. (g,h) Free energy diagrams constructed for the H2O2 generation through the ORR and WOR pathways.

Fig. 7. Mechanistic diagram of the photocatalytic production of H2O2 over Cu-N-TiO2/rGO.

参考文献

[1]	K. Y. Zhang, Y. F. Li, S. D. Yuan, L. H. Zhang, Q. Wang, Acta Phys.-Chim. Sin., 2023, 39, 2212010.
[2]	W. Yu, C. Hu, L. Bai, N. Tian, Y. Zhang, H. Huang, Nano Energy, 2022, 104, 107906.
[3]	J. Chen, Q. Ma, X. Zheng, Y. Fang, J. Wang, S. Dong, Nat. Commun., 2022, 13, 2808.
[4]	Y. Guo, X. Tong, N. Yang, Nano-Micro Lett., 2023, 15, 77.
[5]	Y. Wu, Y. Yang, M. Gu, C. Bie, H. Tan, B. Cheng, J. Xu, Chin. J. Catal., 2023, 53, 123-133.
[6]	Y. Sun, L. Han, P. Strasser, Chem. Soc. Rev., 2020, 49, 6605-6631.
[7]	Q. Wu, Y. Liu, J. Cao, Y. Sun, F. Liao, Y. Liu, H. Huang, M. Shao, Z. Kang, J. Mater. Chem. A, 2020, 8, 11773-11780.
[8]	X. Wang, Y. Shao, J. Pan, D. Jiang, Y. Cong, S.-W. Lv, Chem. Eng. J., 2024, 490, 151923.
[9]	Y. Xie, Q. Zhang, H. Sun, Z. Teng, C. Su, Acta Phys.-Chim. Sin., 2023, 2301001.
[10]	P. Garcia-Munoz, L. Valenzuela, D. Wegstein, T. Schanz, G. E. Lopez, A. M. Ruppert, H. Remita, J. Z. Bloh, N. Keller, Top. Curr. Chem., 2023, 381, 15.
[11]	X. Zeng, Y. Liu, X. Hu, X. Zhang, Green Chem., 2021, 23, 1466-1494.
[12]	Z. Chen, D. Yao, C. Chu, S. Mao, Chem. Eng. J., 2023, 451, 138489.
[13]	A. Chen, Z. Jiang, J. Tang, G. Yu, Prog. Chem., 2024, 36, 357-366.
[14]	S. Huang, X. Yang, L. Zhou, J. Lei, L. Wang, Y. Liu, J. Zhang, Res. Chem. Intermed., 2024, 50, 2917-2969.
[15]	X. Fang, X. Huang, Q. Hu, B. Li, C. Hu, B. Ma, Y. Ding, Chem. Commun., 2024, 60, 5354-5368.
[16]	S. Zhou, H. Hu, H. Hu, Q. Jiang, H. Xie, C. Li, S. Gao, Y. Kong, Y. Hu, Sci. China Mater., 2023, 66, 1837-1846.
[17]	L. Wang, J. Zhang, Y. Zhang, H. Yu, Y. Qu, J. Yu, Small, 2022, 18, 2104561.
[18]	Z. Wang, P. Qin, Y. Jiang, X. Feng, P. Yang, F. Huang, J. Inorg. Mater., 2024, 39, 383-389.
[19]	H. Hou, X. Zeng, X. Zhang, Angew. Chem. Int. Ed., 2020, 59, 17356-17376.
[20]	V. Thi Quyen, K. Jitae, P. Thi Huong, L. Thi Thu Ha, D. My Thanh, N. Minh Viet, P. Quang Thang, Sol. Energy, 2021, 218, 150-156.
[21]	W. Zhu, X. Qiu, V. Iancu, X.-Q. Chen, H. Pan, W. Wang, N. M. Dimitrijevic, T. Rajh, H. M. Meyer, M. P. Paranthaman, G. M. Stocks, H. H. Weitering, B. Gu, G. Eres, Z. Zhang, Phys. Rev. Lett., 2009, 103, 226401.
[22]	J. Qin, J. Lin, T. Chen, D. Liu, J. Xie, B. Guo, L. Wang, Y. Chai, B. Dong, J. Energy Chem., 2019, 39, 182-187.
[23]	Y. Yang, B. Zhu, L. Wang, B. Cheng, L. Zhang, J. Yu, Appl. Catal. B, 2022, 317, 121788.
[24]	Z. Yousaf, S. Sajjad, S. Ahmed Khan Leghari, M. Mehboob, A. Kanwal, B. Uzair, J. Solid State Chem., 2020, 291, 121606.
[25]	H. Z. Zhang, J. J. Liu, Y. Zhang, B. Cheng, B. C. Zhu, L. X. Wang, J. Mater. Sci. Technol., 2023, 166, 241-249.
[26]	J. Gao, Q. Shen, R. Guan, J. Xue, X. Liu, H. Jia, Q. Li, Y. Wu, J. CO₂ Util., 2020, 35, 205-215.
[27]	R. A. Vicente, I. T. Neckel, S. K. R. S. Sankaranarayanan, J. Solla-Gullon, P. S. Fernández, ACS Nano, 2021, 15, 6129-6146.
[28]	L. Jia, L.-M. Yang, W. Wang, S.-T. Huang, Z. Xu, Rare Metals, 2024, 43, 555-561.
[29]	X. Xin, T. Xu, L. Wang, C. Wang, Sci. Rep., 2016, 6, 23684.
[30]	H. Li, Z. Sun, C. Lei, W. Kang, L. Ma, Q. Shen, H. Jia, J. Xue, Y. Zhu, Small, 2024, 20, 2311041.
[31]	R. Jaiswal, J. Bharambe, N. Patel, A. Dashora, D. C. Kothari, A. Miotello, Appl. Catal. B, 2015, 168, 333-341.
[32]	P. Pongwan, K. Wetchakun, S. Phanichphant, N. Wetchakun, Res. Chem. Intermed., 2016, 42, 2815-2830.
[33]	G. Cao, N. A. Deskins, N. Yi, Appl. Catal. B, 2021, 285, 119748.
[34]	J. Gao, J. Xue, Q. Shen, T. Liu, X. Zhang, X. Liu, H. Jia, Q. Li, Y. Wu, Chem. Eng. J., 2022, 431, 133281.
[35]	Y. Qin, H. Li, J. Lu, F. Meng, C. Ma, Y. Yan, M. Meng, Chem. Eng. J., 2020, 384, 123275.
[36]	Y. Zhao, Y. Zhao, R. Shi, B. Wang, G. I. N. Waterhouse, L. Wu, C. Tung, T. Zhang, Adv. Mater., 2019, 31, 1806482.
[37]	T. Takata, K. Domen, J. Phys. Chem. C, 2009, 113, 19386-19388.
[38]	L. Ma, R. Guan, W. Kang, Z. Sun, H. Li, Q. Li, Q. Shen, C. Chen, X. Liu, H. Jia, J. Xue, J. Colloid Interface Sci., 2024, 660, 381-392.
[39]	Y.-J. Xia-Hou, X.-C. Li, E.-M. You, H.-P. He, J. Yi, J.-R. Zheng, H.-L. Wang, H.-X. Lin, Z.-Q. Tian, Nano Res., 2023, 16, 11326-11333.
[40]	A. Dashora, N. Patel, D. C. Kothari, B. L. Ahuja, A. Miotello, Sol. Energy Mater. Sol. Cells, 2014, 125, 120-126.
[41]	K. Gao, B. Wang, L. Tao, B. V. Cunning, Z. Zhang, S. Wang, R. S. Ruoff, L. Qu, Adv. Mater., 2019, 31, 1805121.
[42]	L. Wang, L. Wang, K. Zhao, D. Cheng, W. Yu, J. Li, J. Wang, F. Shi, Int. J. Hydrogen Energy, 2022, 47, 39047-39057.
[43]	H. Li, Q. Shen, H. Zhang, J. Gao, H. Jia, X. Liu, Q. Li, J. Xue, J. Adv. Ceram., 2022, 11, 1873-1888.
[44]	R. Chen, F. Fan, T. Dittrich, C. Li, Chem. Soc. Rev., 2018, 47, 8238-8262.
[45]	Z. Jiang, Q. Long, B. Cheng, R. He, L. Wang, J. Mater. Sci. Technol., 2023, 162, 1-10.
[46]	Y. Yang, Q. Guo, Q. Li, L. Guo, H. Chu, L. Liao, X. Wang, Z. Li, W. Zhou, Adv. Funct. Mater., 2024, 34, 2400612.
[47]	Y. An, C. Lin, C. Dong, R. Wang, J. Hao, J. Miao, X. Fan, Y. Min, K. Zhang, ACS Energy Lett., 2024, 9, 1415-1422.

非补偿性Cu/N共掺杂协同石墨烯增强TiO₂光催化双通道制H₂O₂

The synergistic effect of non-compensated Cu/N co-doping and graphene enhances the dual-channel generation of H₂O₂ over TiO₂ photocatalysts

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 7

参考文献

相关文章 1

编辑推荐

Metrics