Pushing the heterometal doping limit while preserving long-lived charge separation in a Ti-based MOF photocatalyst

Long, Conor L.; Zhang, Xiaoyi; Lockard, Jenny V.

doi:10.1063/5.0174664

Pushing the heterometal doping limit while preserving long-lived charge separation in a Ti-based MOF photocatalyst

Journal Article · Thu Nov 16 00:00:00 EST 2023 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0174664· OSTI ID:2569660

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Rutgers University, Newark, NJ (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)

Here, this study explores the nature, dynamics, and reactivity of the photo-induced charge separated excited state in a Fe³⁺-doped titanium-based metal organic framework (MOF), xFeMIL125-NH₂, as a function of iron concentration. The MOF is synthesized with doping levels x = 0.5, 1 and 2 Fe node sites per octameric Ti-oxo cluster and characterized by powder x-ray diffraction, UV-vis diffuse reflectance, atomic absorption, and steady state Fe K-edge X-ray absorption spectroscopy. For each doping level, time-resolved X-ray transient absorption spectroscopy studies confirm the electron trap site role of the Fe sites in the excited state. Time scan data reveal multiexponential decay kinetics for the charge recombination processes which extend into the microsecond range for all three concentrations. A series of dye photodegradation studies, based on the oxidative decomposition of Rhodamine B, demonstrates the reactivity of the charge separated excited state and the photocatalytic capacity of these MOF materials compared to traditional heterometal-doped semiconductor photocatalysts.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2569660

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 19 Vol. 159; ISSN 1089-7690; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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