Photocatalytic Synthesis of Hydrogen Peroxide by Rhenium Modified Metal–Organic Frameworks Incorporating Bianthracene Ligands

Boya Tang; David Brooks; Meng He; Yinlin Chen; Zhaozhao Hu; Xue Han; Jiangnan Li; Siyu Zhou; Jiarui Fan; Yukun Ye; Ivan da Silva; Cheng Li; Zi Wang; Lutong Shan; Bing Han; Weiyao Li; Daniil Polyukhov; Bing An; Catherine Dejoie; Martin Wilding; Shaojun Xu; Meredydd Kippax-Jones; Zhaodong Zhu; Yujie Ma; Floriana Tuna; Eric J.L. McInnes; Sarah J. Day; Stephen P. Thompson; Mark D. Frogley; Louise S. Natrajan; Martin Schröder; Sihai Yang

doi:10.1021/jacs.5c00603

Photocatalytic Synthesis of Hydrogen Peroxide by Rhenium Modified Metal–Organic Frameworks Incorporating Bianthracene Ligands

Boya Tang, David Brooks, Meng He, Yinlin Chen, Zhaozhao Hu, Xue Han, Jiangnan Li, Siyu Zhou, Jiarui Fan, Yukun Ye, Ivan da Silva, Cheng Li, Zi Wang, Lutong Shan, Bing Han, Weiyao Li, Daniil Polyukhov, Bing An, Catherine Dejoie, Martin WildingShaojun Xu, Meredydd Kippax-Jones, Zhaodong Zhu, Yujie Ma, Floriana Tuna, Eric J.L. McInnes, Sarah J. Day, Stephen P. Thompson, Mark D. Frogley, Louise S. Natrajan, Martin Schröder, Sihai Yang

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Abstract

Photocatalytic synthesis of hydrogen peroxide (H₂O₂) from oxygen (O₂) is a challenging process. Metal–organic framework (MOF) materials are emerging photocatalysts with potential tunable light absorption properties. Herein, we report a rhenium (Re) modified Zr-based MOF, Re10-MFM-67, in which active Re sites are incorporated into MFM-67 by partial replacement of 9,9′-bianthracene-10,10′-dicarboxylic acid (H₂L¹) with a [(H₂L²)Re^I(CO)₃Cl] (H₂L² = 2,2′-bipyridine-5,5′-dicarboxylic acid) moiety. Re10-MFM-67 (10 refers to the molar percentage content of Re complex within the material) exhibits broadband light absorption with an exceptional rate of formation of H₂O₂ from O₂ of 8.50 mmol g_cat^–1 h^–1 and a record turnover frequency (TOF) of 28.7 h^–1 under visible light irradiation (λ > 400 nm). Synchrotron powder X-ray diffraction (SPXRD) and neutron powder diffraction (NPD) confirm the structure of Re10-MFM-67, and together with extended X-ray absorption fine structure (EXAFS) analysis establish the coordination environment and binding of the [Re^I(CO)₃Cl] moiety within the framework structure. In situ electron paramagnetic resonance (EPR) spectroscopy suggests that photocatalytic H₂O₂ generation on Re10-MFM-67 occurs via a two-step oxygen reduction reaction (ORR) pathway with the superoxide anion formed as an intermediate. This study promotes the design of MOF-based photocatalysts with conjugated ligands for efficient photosynthesis.

Original language	English
Pages (from-to)	24326-24335
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	147
Issue number	28
DOIs	https://doi.org/10.1021/jacs.5c00603
State	Published - Jul 16 2025

Funding

We thank the EPSRC (EP/I011870, EP/V056409), the University of Manchester, National Science Foundation of China (22475022), and BNLMS for funding, and the EPSRC for funding of the EPSRC National EPR Facility at Manchester (EP/W014521/1, EP/X034623/1). This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No 742401, NANOCHEM). We thank European Synchrotron Radiation Facility (ESRF) and Diamond Light Source for access to the Beamlines ID22 and B22/I11, respectively. We acknowledge the U.K. catalysis Hub Block Allocation Group (BAG) Programme Mode Application for provision of beamtime at B18 for collection of the data presented in this work and the initial discussion of the data. The U.K. Catalysis Hub is kindly thanked for resources and support provided via our membership of the U.K. Catalysis Hub Consortium and funded by EPSRC grants: EP/R026939/1, EP/R026815/1, EP/R026645/1, EP/R027129/1 and EP/M013219/1 (biocatalysis). A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. B.T., M.H., J.L., L.S., and Y.M. thank the China Scholarship Council (CSC) for funding.

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Tang, B., Brooks, D., He, M., Chen, Y., Hu, Z., Han, X., Li, J., Zhou, S., Fan, J., Ye, Y., da Silva, I., Li, C., Wang, Z., Shan, L., Han, B., Li, W., Polyukhov, D., An, B., Dejoie, C., ... Yang, S. (2025). Photocatalytic Synthesis of Hydrogen Peroxide by Rhenium Modified Metal–Organic Frameworks Incorporating Bianthracene Ligands. Journal of the American Chemical Society, 147(28), 24326-24335. https://doi.org/10.1021/jacs.5c00603

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title = "Photocatalytic Synthesis of Hydrogen Peroxide by Rhenium Modified Metal–Organic Frameworks Incorporating Bianthracene Ligands",

abstract = "Photocatalytic synthesis of hydrogen peroxide (H2O2) from oxygen (O2) is a challenging process. Metal–organic framework (MOF) materials are emerging photocatalysts with potential tunable light absorption properties. Herein, we report a rhenium (Re) modified Zr-based MOF, Re10-MFM-67, in which active Re sites are incorporated into MFM-67 by partial replacement of 9,9′-bianthracene-10,10′-dicarboxylic acid (H2L1) with a [(H2L2)ReI(CO)3Cl] (H2L2 = 2,2′-bipyridine-5,5′-dicarboxylic acid) moiety. Re10-MFM-67 (10 refers to the molar percentage content of Re complex within the material) exhibits broadband light absorption with an exceptional rate of formation of H2O2 from O2 of 8.50 mmol gcat–1 h–1 and a record turnover frequency (TOF) of 28.7 h–1 under visible light irradiation (λ > 400 nm). Synchrotron powder X-ray diffraction (SPXRD) and neutron powder diffraction (NPD) confirm the structure of Re10-MFM-67, and together with extended X-ray absorption fine structure (EXAFS) analysis establish the coordination environment and binding of the [ReI(CO)3Cl] moiety within the framework structure. In situ electron paramagnetic resonance (EPR) spectroscopy suggests that photocatalytic H2O2 generation on Re10-MFM-67 occurs via a two-step oxygen reduction reaction (ORR) pathway with the superoxide anion formed as an intermediate. This study promotes the design of MOF-based photocatalysts with conjugated ligands for efficient photosynthesis.",

author = "Boya Tang and David Brooks and Meng He and Yinlin Chen and Zhaozhao Hu and Xue Han and Jiangnan Li and Siyu Zhou and Jiarui Fan and Yukun Ye and \{da Silva\}, Ivan and Cheng Li and Zi Wang and Lutong Shan and Bing Han and Weiyao Li and Daniil Polyukhov and Bing An and Catherine Dejoie and Martin Wilding and Shaojun Xu and Meredydd Kippax-Jones and Zhaodong Zhu and Yujie Ma and Floriana Tuna and McInnes, \{Eric J.L.\} and Day, \{Sarah J.\} and Thompson, \{Stephen P.\} and Frogley, \{Mark D.\} and Natrajan, \{Louise S.\} and Martin Schr{\"o}der and Sihai Yang",

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year = "2025",

month = jul,

day = "16",

doi = "10.1021/jacs.5c00603",

language = "English",

volume = "147",

pages = "24326--24335",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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Tang, B, Brooks, D, He, M, Chen, Y, Hu, Z, Han, X, Li, J, Zhou, S, Fan, J, Ye, Y, da Silva, I, Li, C, Wang, Z, Shan, L, Han, B, Li, W, Polyukhov, D, An, B, Dejoie, C, Wilding, M, Xu, S, Kippax-Jones, M, Zhu, Z, Ma, Y, Tuna, F, McInnes, EJL, Day, SJ, Thompson, SP, Frogley, MD, Natrajan, LS, Schröder, M & Yang, S 2025, 'Photocatalytic Synthesis of Hydrogen Peroxide by Rhenium Modified Metal–Organic Frameworks Incorporating Bianthracene Ligands', Journal of the American Chemical Society, vol. 147, no. 28, pp. 24326-24335. https://doi.org/10.1021/jacs.5c00603

TY - JOUR

T1 - Photocatalytic Synthesis of Hydrogen Peroxide by Rhenium Modified Metal–Organic Frameworks Incorporating Bianthracene Ligands

AU - Tang, Boya

AU - Brooks, David

AU - He, Meng

AU - Chen, Yinlin

AU - Hu, Zhaozhao

AU - Han, Xue

AU - Li, Jiangnan

AU - Zhou, Siyu

AU - Fan, Jiarui

AU - Ye, Yukun

AU - da Silva, Ivan

AU - Li, Cheng

AU - Wang, Zi

AU - Shan, Lutong

AU - Han, Bing

AU - Li, Weiyao

AU - Polyukhov, Daniil

AU - An, Bing

AU - Dejoie, Catherine

AU - Wilding, Martin

AU - Xu, Shaojun

AU - Kippax-Jones, Meredydd

AU - Zhu, Zhaodong

AU - Ma, Yujie

AU - Tuna, Floriana

AU - McInnes, Eric J.L.

AU - Day, Sarah J.

AU - Thompson, Stephen P.

AU - Frogley, Mark D.

AU - Natrajan, Louise S.

AU - Schröder, Martin

AU - Yang, Sihai

PY - 2025/7/16

Y1 - 2025/7/16

N2 - Photocatalytic synthesis of hydrogen peroxide (H2O2) from oxygen (O2) is a challenging process. Metal–organic framework (MOF) materials are emerging photocatalysts with potential tunable light absorption properties. Herein, we report a rhenium (Re) modified Zr-based MOF, Re10-MFM-67, in which active Re sites are incorporated into MFM-67 by partial replacement of 9,9′-bianthracene-10,10′-dicarboxylic acid (H2L1) with a [(H2L2)ReI(CO)3Cl] (H2L2 = 2,2′-bipyridine-5,5′-dicarboxylic acid) moiety. Re10-MFM-67 (10 refers to the molar percentage content of Re complex within the material) exhibits broadband light absorption with an exceptional rate of formation of H2O2 from O2 of 8.50 mmol gcat–1 h–1 and a record turnover frequency (TOF) of 28.7 h–1 under visible light irradiation (λ > 400 nm). Synchrotron powder X-ray diffraction (SPXRD) and neutron powder diffraction (NPD) confirm the structure of Re10-MFM-67, and together with extended X-ray absorption fine structure (EXAFS) analysis establish the coordination environment and binding of the [ReI(CO)3Cl] moiety within the framework structure. In situ electron paramagnetic resonance (EPR) spectroscopy suggests that photocatalytic H2O2 generation on Re10-MFM-67 occurs via a two-step oxygen reduction reaction (ORR) pathway with the superoxide anion formed as an intermediate. This study promotes the design of MOF-based photocatalysts with conjugated ligands for efficient photosynthesis.

AB - Photocatalytic synthesis of hydrogen peroxide (H2O2) from oxygen (O2) is a challenging process. Metal–organic framework (MOF) materials are emerging photocatalysts with potential tunable light absorption properties. Herein, we report a rhenium (Re) modified Zr-based MOF, Re10-MFM-67, in which active Re sites are incorporated into MFM-67 by partial replacement of 9,9′-bianthracene-10,10′-dicarboxylic acid (H2L1) with a [(H2L2)ReI(CO)3Cl] (H2L2 = 2,2′-bipyridine-5,5′-dicarboxylic acid) moiety. Re10-MFM-67 (10 refers to the molar percentage content of Re complex within the material) exhibits broadband light absorption with an exceptional rate of formation of H2O2 from O2 of 8.50 mmol gcat–1 h–1 and a record turnover frequency (TOF) of 28.7 h–1 under visible light irradiation (λ > 400 nm). Synchrotron powder X-ray diffraction (SPXRD) and neutron powder diffraction (NPD) confirm the structure of Re10-MFM-67, and together with extended X-ray absorption fine structure (EXAFS) analysis establish the coordination environment and binding of the [ReI(CO)3Cl] moiety within the framework structure. In situ electron paramagnetic resonance (EPR) spectroscopy suggests that photocatalytic H2O2 generation on Re10-MFM-67 occurs via a two-step oxygen reduction reaction (ORR) pathway with the superoxide anion formed as an intermediate. This study promotes the design of MOF-based photocatalysts with conjugated ligands for efficient photosynthesis.

UR - https://www.scopus.com/pages/publications/105009595659

U2 - 10.1021/jacs.5c00603

DO - 10.1021/jacs.5c00603

M3 - Article

C2 - 40591580

AN - SCOPUS:105009595659

SN - 0002-7863

VL - 147

SP - 24326

EP - 24335

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 28

ER -

Photocatalytic Synthesis of Hydrogen Peroxide by Rhenium Modified Metal–Organic Frameworks Incorporating Bianthracene Ligands

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