Volume 64, Issue 28 e202505544

Research Article

Photoelectrocatalytic Activation of C─H Bond in Toluene by Titanium Dioxide-Supported Subnanometric PtO_x Clusters

Dr. Lan Luo

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

Tianjin Key Laboratory of Brine Chemical Engineering and Resource Eco-utilization, College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology, Tianjin, 300457 P.R. China

These authors contributed equally to this work.

Search for more papers by this author

Dr. Yu-Quan Zhu,

Dr. Yu-Quan Zhu

Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Huangshi, 435002 P.R. China

These authors contributed equally to this work.

Search for more papers by this author

Wangsong Chen,

Wangsong Chen

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

These authors contributed equally to this work.

Search for more papers by this author

Yucong Miao,

Yucong Miao

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

Search for more papers by this author

Shanshan Zhang,

Shanshan Zhang

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

Search for more papers by this author

Prof. Dr. Yusen Yang,

Prof. Dr. Yusen Yang

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

Quzhou Institute for Innovation in Resource Chemical Engineering, Quzhou, Zhejiang, 323000 P.R. China

Search for more papers by this author

Prof. Zhenhua Li,

Corresponding Author

Prof. Zhenhua Li

[email protected]

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

Quzhou Institute for Innovation in Resource Chemical Engineering, Quzhou, Zhejiang, 323000 P.R. China

E-mail: [email protected]; [email protected]

Search for more papers by this author

Prof. Mingfei Shao,

Corresponding Author

Prof. Mingfei Shao

[email protected]

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

Quzhou Institute for Innovation in Resource Chemical Engineering, Quzhou, Zhejiang, 323000 P.R. China

E-mail: [email protected]; [email protected]

Search for more papers by this author

Dr. Lan Luo,

Dr. Lan Luo

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

These authors contributed equally to this work.

Search for more papers by this author

Dr. Yu-Quan Zhu,

Dr. Yu-Quan Zhu

Hubei Key Laboratory of Pollutant Analysis & Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Huangshi, 435002 P.R. China

These authors contributed equally to this work.

Search for more papers by this author

Wangsong Chen,

Wangsong Chen

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

These authors contributed equally to this work.

Search for more papers by this author

Yucong Miao,

Yucong Miao

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

Search for more papers by this author

Shanshan Zhang,

Shanshan Zhang

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

Search for more papers by this author

Prof. Dr. Yusen Yang,

Prof. Dr. Yusen Yang

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

Quzhou Institute for Innovation in Resource Chemical Engineering, Quzhou, Zhejiang, 323000 P.R. China

Search for more papers by this author

Prof. Zhenhua Li,

Corresponding Author

Prof. Zhenhua Li

[email protected]

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

Quzhou Institute for Innovation in Resource Chemical Engineering, Quzhou, Zhejiang, 323000 P.R. China

E-mail: [email protected]; [email protected]

Search for more papers by this author

Prof. Mingfei Shao,

Corresponding Author

Prof. Mingfei Shao

[email protected]

State Key Laboratory of Chemical Resource Engineering, College of Chemistry, Beijing University of Chemical Technology, Beijing, 100029 P.R. China

Quzhou Institute for Innovation in Resource Chemical Engineering, Quzhou, Zhejiang, 323000 P.R. China

E-mail: [email protected]; [email protected]

Search for more papers by this author

First published: 04 May 2025

https://doi.org/10.1002/anie.202505544

Share a link

Email
Wechat
Bluesky

Graphical Abstract

Photoelectrocatalytic activation of C(sp³)─H bonds in hydrocarbon molecules to produce valuable oxygenates still suffers from the limited generation of reactive species and the weak adsorption of reactants. This study achieved the selective oxidation of toluene using a TiO₂ supported subnanometric PtO_x cluster (PtO_x/TiO₂) photoanode via an electrophilic OH*-mediated pathway. The modification of PtO_x cluster can facilitate toluene adsorption and OH* generation, leading to the high efficiency of toluene oxidation.

Abstract

Selective oxidation of C(sp³)─H bonds via photoelectrocatalytic (PEC) strategy provides a promising approach to synthesize valuable oxygenates, but the efficiency of this process is still unsatisfactory due to the stable nature of hydrocarbon molecules. Herein, we report the PEC oxidation of toluene to benzaldehyde (BA) over a subnanometric PtO_x cluster-loaded TiO₂ (PtO_x/TiO₂) photoanode, achieving BA production rate of 1.75 µmol cm^‒2 h^‒1 with selectivity of 83.5% in aqueous medium, which is 4.4-fold higher than that of pristine TiO₂. The strategy is also effective for the selective oxidation of toluene derivatives. As a proof-of-concept, we fabricate a self-powered PEC tandem device with S-shaped flow channels for the oxidation of toluene, producing BA with a productivity of ∼170 µmol under light irradiation. Experimental studies combined with density functional theory (DFT) results demonstrate that the toluene oxidation over PtO_x/TiO₂ photoanode follow an electrophilic hydroxyl species (OH*)-mediated pathway, which can suppress the over-oxidation of BA. Moreover, we reveal that subnanometric PtO_x clusters promote toluene adsorption and OH* species generation, leading to the high efficiency of toluene oxidation. This work is expected to broaden the avenue toward the activation of C(sp³)─H bond under mild conditions in aqueous solution via a sustainable way.

Conflict of Interests

The authors declare no conflict of interest.

Open Research

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.

Supporting Information

References

1J. T. Grant, J. M. Venegas, W. P. McDermott, I. Hermans, Chem. Rev. 2018, 118, 2769–2815.
10.1021/acs.chemrev.7b00236
CAS PubMed Web of Science® Google Scholar
2M. Ravi, M. Ranocchiari, J. A. van Bokhoven, Angew. Chem. Int. Ed. 2017, 56, 16464–16483.
10.1002/anie.201702550
CAS PubMed Web of Science® Google Scholar
3M. Ravi, V. L. Sushkevich, A. J. Knorpp, M. A. Newton, D. Palagin, A. B. Pinar, M. Ranocchiari, J. A. van Bokhoven, Nat. Catal. 2019, 2, 485–494.
10.1038/s41929-019-0273-z
CAS Web of Science® Google Scholar
4J. Ge, M. Xue, Q. Sun, A. Auroux, J. Shen, J. Mol. Catal. A Chem. 2007, 278, 209–214.
10.1016/j.molcata.2007.09.005
CAS Web of Science® Google Scholar
5P. G. Lustemberg, R. M. Palomino, R. A. Gutiérrez, D. C. Grinter, M. Vorokhta, Z. Liu, P. J. Ramírez, V. Matolín, M. V. Ganduglia-Pirovano, S. D. Senanayake, J. A. Rodriguez, J. Am. Chem. Soc. 2018, 140, 7681–7687.
10.1021/jacs.8b03809
CAS PubMed Web of Science® Google Scholar
6L. Kesavan, R. Tiruvalam, M. H. A. Rahim, M. I. bin Saiman, D. I. Enache, R. L. Jenkins, N. Dimitratos, J. A. Lopez-Sanchez, S. H. Taylor, D. W. Knight, C. J. Kiely, G. J. Hutchings, Science 2011, 331, 195–199.
10.1126/science.1198458
CAS PubMed Web of Science® Google Scholar
7Z. Sun, G. Li, Y. Zhang, H.-O. Liu, X. Gao, Catal. Commun. 2015, 59, 92–96.
10.1016/j.catcom.2014.09.047
CAS Web of Science® Google Scholar
8X. Wu, Z. Deng, J. Yan, F. Zhang, Z. Zhang, Ind. Eng. Chem. Res. 2014, 53, 14601–14606.
10.1021/ie502686u
CAS Web of Science® Google Scholar
9Z. B. Zhenmin Xu, Acta Phys.-Chim. Sin. 2020, 36, 1907013.
10.3866/PKU.WHXB201907013
Web of Science® Google Scholar
10J. Tripathy, K. Lee, P. Schmuki, Angew. Chem. Int. Ed. 2014, 53, 12605–12608.
10.1002/anie.201406324
CAS PubMed Web of Science® Google Scholar
11K. Su, H. Liu, B. Zeng, Z. Zhang, N. Luo, Z. Huang, Z. Gao, F. Wang, ACS Catal. 2020, 10, 1324–1333.
10.1021/acscatal.9b04215
CAS Web of Science® Google Scholar
12B. Seo, W. H. Lee, Y. J. Sa, U. Lee, H.-S. Oh, H. Lee, Appl. Surf. Sci. 2020, 534, 147517.
10.1016/j.apsusc.2020.147517
CAS Web of Science® Google Scholar
13W. J. Zhuang, M. Kan, T. Meng, J. L. Zhang, Sci. China Chem. 2024, 67, 1904–1921.
10.1007/s11426-024-2041-9
CAS Web of Science® Google Scholar
14Y. C. Miao, M. F. Shao, Chinese J. Catal. 2022, 43, 595–610.
10.1016/S1872-2067(21)63923-2
CAS Web of Science® Google Scholar
15N. S. Lewis, Science 2016, 351, aad1920.
10.1126/science.aad1920
CAS PubMed Web of Science® Google Scholar
16T. Yao, X. An, H. Han, J. Q. Chen, C. Li, Adv. Energy Mater. 2018, 8, 1800210.
10.1002/aenm.201800210
Web of Science® Google Scholar
17L. Luo, Z.-J. Wang, X. Xiang, D. Yan, J. Ye, ACS Catal. 2020, 10, 4906–4913.
10.1021/acscatal.0c00660
CAS Web of Science® Google Scholar
18T.-G. Vo, C.-C. Kao, J.-L. Kuo, C.-C. Chiu, C.-Y. Chiang, Appl. Catal. B 2020, 278, 119303.
10.1016/j.apcatb.2020.119303
CAS Web of Science® Google Scholar
19R. Zhang, M. Shao, Z. Li, F. Ning, M. Wei, D. G. Evans, X. Duan, Chem. - Eur. J. 2017, 23, 8142–8147.
10.1002/chem.201701107
CAS PubMed Web of Science® Google Scholar
20L. Luo, W. Chen, S.-M. Xu, J. Yang, M. Li, H. Zhou, M. Xu, M. Shao, X. Kong, Z. Li, H. Duan, J. Am. Chem. Soc. 2022, 144, 7720–7730.
10.1021/jacs.2c00465
CAS PubMed Web of Science® Google Scholar
21M. Kunitski, N. Eicke, P. Huber, J. Köhler, S. Zeller, J. Voigtsberger, N. Schlott, K. Henrichs, H. Sann, F. Trinter, L. P. H. Schmidt, A. Kalinin, M. S. Schöffler, T. Jahnke, M. Lein, R. Dörner, Nat. Commun. 2019, 10, 1.
10.1038/s41467-018-07882-8
CAS PubMed Web of Science® Google Scholar
22Y. Miao, Z. Li, Y. Song, K. Fan, J. Guo, R. Li, M. Shao, Appl. Catal. B 2023, 323, 122147.
10.1016/j.apcatb.2022.122147
CAS Web of Science® Google Scholar
23Y. Miao, Z. Li, L. Luo, W. Chen, L. Ma, K. Fan, Y. Song, Y. Hu, R. Li, M. Shao, Appl. Catal. B 2025, 361, 124588.
10.1016/j.apcatb.2024.124588
CAS Web of Science® Google Scholar
24L. Luo, Y. Liu, W. Chen, X. Xue, S.-M. Xu, M. Li, H. Zhou, L. Ma, M. Xu, X. Kong, M. Shao, Z. Li, H. Duan, Chem Catal 2023, 3, 100472.
10.1016/j.checat.2022.11.011
CAS Web of Science® Google Scholar
25F. Amano, A. Shintani, K. Tsurui, H. Mukohara, T. Ohno, S. Takenaka, ACS Energy Lett. 2019, 4, 502–507.
10.1021/acsenergylett.8b02436
CAS Web of Science® Google Scholar
26F. Amano, A. Shintani, T. Sakakura, Y. Takatsuji, T. Haruyama, Catal. Sci. Technol. 2023, 13, 4640–4645.
10.1039/D3CY00632H
CAS Web of Science® Google Scholar
27S. Nie, L. Wu, X. Wang, J. Am. Chem. Soc. 2023, 145, 23681–23690.
10.1021/jacs.3c07984
CAS PubMed Web of Science® Google Scholar
28Z. Li, L. Luo, M. Li, W. Chen, Y. Liu, J. Yang, S.-M. Xu, H. Zhou, L. Ma, M. Xu, X. Kong, H. Duan, Nat. Commun. 2021, 12, 6698.
10.1038/s41467-021-26997-z
CAS PubMed Web of Science® Google Scholar
29Y. Kadosh, E. Korin, A. Bettelheim, Sustain. Energy Fuels 2021, 5, 127–134.
10.1039/D0SE00984A
CAS Web of Science® Google Scholar
30S. Wu, X. Tan, J. Lei, H. Chen, L. Wang, J. Zhang, J. Am. Chem. Soc. 2019, 141, 6592–6600.
10.1021/jacs.8b13858
CAS PubMed Web of Science® Google Scholar
31Y. Miao, Z. Li, M. Shao, ChemCatChem 2024, 16, e202301321.
10.1002/cctc.202301321
CAS Web of Science® Google Scholar
32W. Zhang, H. Wang, J. Jiang, Z. Sui, Y. Zhu, D. Chen, X. Zhou, ACS Catal. 2020, 10, 12932–12942.
10.1021/acscatal.0c03286
CAS Web of Science® Google Scholar
33W. Li, D. He, G. Hu, X. Li, G. Banerjee, J. Li, S. H. Lee, Q. Dong, T. Gao, G. W. Brudvig, M. M. Waegele, D.-E. Jiang, D. Wang, ACS Cent. Sci. 2018, 4, 631–637.
10.1021/acscentsci.8b00130
CAS PubMed Web of Science® Google Scholar
34P. Mishra, P. Saravanan, G. Packirisamy, Int. J. Hydrogen Energy 2023, 48, 586–599.
10.1016/j.ijhydene.2022.09.277
CAS Web of Science® Google Scholar
35J. Yang, P. Chen, J. Dai, Y. Chen, L. Rong, D. Wang, Energy Convers. Manag. 2021, 247, 114767.
10.1016/j.enconman.2021.114767
CAS Web of Science® Google Scholar
36J. Ma, X. Tan, Q. Zhang, Y. Wang, J. Zhang, L. Wang, ACS Catal. 2021, 11, 3352–3360.
10.1021/acscatal.0c04943
CAS Web of Science® Google Scholar
37F. Ning, M. Shao, S. Xu, Y. Fu, R. Zhang, M. Wei, D. G. Evans, X. Duan, Energy Environ. Sci. 2016, 9, 2633–2643.
10.1039/C6EE01092J
CAS Web of Science® Google Scholar
38L. Luo, L. X. Li, L. Xu, Y. F. Yan, S. S. Zhang, H. Zhou, Z. H. Li, M. F. Shao, X. Duan, CCS Chem. 2025, 7, 266–278.
10.31635/ccschem.024.202403988
CAS Web of Science® Google Scholar
39H. Wang, C. Cao, D. Li, Y. Ge, R. Chen, R. Song, W. Gao, X. Wang, X. Deng, H. Zhang, B. Ye, Z. Li, C. Li, J. Am. Chem. Soc. 2023, 145, 16852–16861.
10.1021/jacs.3c05237
CAS PubMed Web of Science® Google Scholar
40Q. Wang, Y. Li, A. Serrano-Lotina, W. Han, R. Portela, R. Wang, M. A. Bañares, K. L. Yeung, J. Am. Chem. Soc. 2021, 143, 196–205.
10.1021/jacs.0c08640
CAS PubMed Web of Science® Google Scholar
41X. Shi, C. Dai, X. Wang, J. Hu, J. Zhang, L. Zheng, L. Mao, H. Zheng, M. Zhu, Nat. Commun. 2022, 13, 1287.
10.1038/s41467-022-28995-1
CAS PubMed Web of Science® Google Scholar
42Y. Zhao, P. V. Kumar, X. Tan, X. Lu, X. Zhu, J. Jiang, J. Pan, S. Xi, H. Y. Yang, Z. Ma, T. Wan, D. Chu, W. Jiang, S. C. Smith, R. Amal, Z. Han, X. Lu, Nat. Commun. 2022, 13, 2430.
10.1038/s41467-022-30155-4
CAS PubMed Web of Science® Google Scholar
43D. R. Dreyer, S. Park, C. W. Bielawski, R. S. Ruoff, Chem. Soc. Rev. 2010, 39, 228–240.
10.1039/B917103G
CAS PubMed Web of Science® Google Scholar
44A. Razzaq, C. A. Grimes, S.-I. In, Carbon 2016, 98, 537–544.
10.1016/j.carbon.2015.11.053
CAS Web of Science® Google Scholar
45F. Kang, Q. Wang, D. Du, L. Wu, D. W. F. Cheung, J. Luo, Angew. Chem. Int. Ed. 2025, 64, e202417648.
10.1002/anie.202417648
CAS PubMed Web of Science® Google Scholar
46Q. Wang, K. Wang, L. Zhang, H. Wang, W. Wang, Appl. Surf. Sci. 2019, 470, 832–839.
10.1016/j.apsusc.2018.11.197
CAS Web of Science® Google Scholar
47X. Cao, Z. Chen, R. Lin, W.-C. Cheong, S. Liu, J. Zhang, Q. Peng, C. Chen, T. Han, X. Tong, Y. Wang, R. Shen, W. Zhu, D. Wang, Y. Li, Nat. Catal. 2018, 1, 704–710.
10.1038/s41929-018-0128-z
CAS Web of Science® Google Scholar
48Y. Fan, W. Zhou, X. Qiu, H. Li, Y. Jiang, Z. Sun, D. Han, L. Niu, Z. Tang, Nat. Sustain. 2021, 4, 509–515.
10.1038/s41893-021-00682-x
Web of Science® Google Scholar
49X. Li, T. Wang, X. Tao, G. Qiu, C. Li, B. Li, J. Mater. Chem. A 2020, 8, 17657–17669.
10.1039/D0TA05733A
CAS Web of Science® Google Scholar
50L. Xu, Z. Huang, M. Yang, J. Wu, W. Chen, Y. Wu, Y. Pan, Y. Lu, Y. Zou, S. Wang, Angew. Chem. Int. Ed. 2022, 61, e202210123.
10.1002/anie.202210123
CAS PubMed Web of Science® Google Scholar
51J. Zhang, Y. Nosaka, J. Phys. Chem. C 2014, 118, 10824–10832.
10.1021/jp501214m
CAS Web of Science® Google Scholar
52Z. Xue, J. Yang, L. Ma, H. Li, L. Luo, K. Ji, Z. Li, X. Kong, M. Shao, L. Zheng, M. Xu, H. Duan, ACS Catal. 2024, 14, 249–261.
10.1021/acscatal.3c04484
CAS Web of Science® Google Scholar

Volume64, Issue28

July 7, 2025

e202505544

Photoelectrocatalytic Activation of C─H Bond in Toluene by Titanium Dioxide-Supported Subnanometric PtO_x Clusters

Graphical Abstract

Abstract

Conflict of Interests

Open Research

Data Availability Statement

Supporting Information

References

References

Information

About Wiley Online Library

Help & Support

Opportunities

Connect with Wiley

Photoelectrocatalytic Activation of C─H Bond in Toluene by Titanium Dioxide-Supported Subnanometric PtOx Clusters

Graphical Abstract

Abstract

Conflict of Interests

Open Research

Data Availability Statement

Supporting Information

References

References

Related

Information

Photoelectrocatalytic Activation of C─H Bond in Toluene by Titanium Dioxide-Supported Subnanometric PtO_x Clusters