Publisher: American Chemical Society (ACS)

Issue:

License: [{"start"=>{"date-parts"=>[[2025, 7, 1]], "date-time"=>"2025-07-01T00:00:00Z", "timestamp"=>1751328000000}, "content-version"=>"stm-asf", "delay-in-days"=>0, "URL"=>"https://doi.org/10.15223/policy-029"}, {"start"=>{"date-parts"=>[[2025, 7, 1]], "date-time"=>"2025-07-01T00:00:00Z", "timestamp"=>1751328000000}, "content-version"=>"stm-asf", "delay-in-days"=>0, "URL"=>"https://doi.org/10.15223/policy-037"}, {"start"=>{"date-parts"=>[[2025, 7, 1]], "date-time"=>"2025-07-01T00:00:00Z", "timestamp"=>1751328000000}, "content-version"=>"stm-asf", "delay-in-days"=>0, "URL"=>"https://doi.org/10.15223/policy-045"}]

Publication date(s): 2025/07/01 (online)

Pages:

Volume: Issue:

Journal: Journal of the American Chemical Society

Link: [{"URL"=>"https://pubs.acs.org/doi/pdf/10.1021/jacs.5c00603", "content-type"=>"application/pdf", "content-version"=>"vor", "intended-application"=>"unspecified"}, {"URL"=>"https://pubs.acs.org/doi/pdf/10.1021/jacs.5c00603", "content-type"=>"unspecified", "content-version"=>"vor", "intended-application"=>"similarity-checking"}]

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.