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

J Am Chem Soc. 2025 Jul 1. doi: 10.1021/jacs.5c00603. Online ahead of print.

Authors

Boya Tang¹, David Brooks¹, Meng He¹, Yinlin Chen¹, Zhaozhao Hu², Xue Han³, Jiangnan Li², Siyu Zhou², Jiarui Fan², Yukun Ye², Ivan da Silva⁴, Cheng Li⁵, Zi Wang^{1

6}, Lutong Shan¹, Bing Han⁷, Weiyao Li¹, Daniil Polyukhov¹, Bing An¹, Catherine Dejoie⁸, Martin Wilding⁹, Shaojun Xu^{9

10}, Meredydd Kippax-Jones^{1

11}, Zhaodong Zhu¹, Yujie Ma¹, Floriana Tuna^{1

6}, Eric J L McInnes^{1

6}, Sarah J Day¹¹, Stephen P Thompson¹¹, Mark D Frogley¹¹, Louise S Natrajan¹, Martin Schröder¹, Sihai Yang^{1

2}

Affiliations

¹ Department of Chemistry, University of Manchester, Manchester M13 9PL, U.K.
² College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing 100871, China.
³ College of Chemistry, Beijing Normal University, Beijing 100875, China.
⁴ ISIS Facility, STFC Rutherford Appleton Laboratory, Chilton, Oxfordshire OX11 0QX, U.K.
⁵ Neutron Scattering Division, Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830, United States.
⁶ Photon Science Institute, University of Manchester, Manchester M13 9PL, U.K.
⁷ Department of Materials, University of Manchester, Manchester M13 9PL, U.K.
⁸ European Synchrotron Radiation Facility, 38000 Grenoble, France.
⁹ Catalysis Hub, Research Complex at Harwell, Rutherford Appleton Laboratory, Harwell OX11 0FA, U.K.
¹⁰ Department of Chemical Engineering, University of Manchester, Manchester M13 9PL, U.K.
¹¹ Diamond Light Source, Harwell Science and Innovation Campus, Harwell OX11 0DE, Oxfordshire, U.K.

PMID: 40591580
DOI: 10.1021/jacs.5c00603

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.