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Title: Photoelectrochemical alcohol oxidation by mixed-linker metal–organic frameworks

Abstract

Metal–organic frameworks (MOFs) provide a suitable platform for stable and efficient heterogeneous photoelectrochemical oxidation catalysis due to their highly ordered structure, large surface area, and synthetic tunability. Herein, a mixed-linker MOF comprising of a photosensitizer [Ru(dcbpy)(bpy)2]2+ (bpy = 2,2'-bipyridine, dcbpy = 5,5'-dicarboxy-2,2'-bipyridine) and catalyst [Ru(tpy)(dcbpy)Cl]+ (tpy = 2,2':6',2''-terpyridine) that were incorporated into the UiO-67 framework and grown as thin films on a TiO2-coated, fluorine-doped tin oxide (FTO) electrode (RuB-RuTB-UiO-67/TiO2/FTO). When used as an electrode for the photoelectrochemical oxidation of benzyl alcohol, the mixed-linker MOF film showed a faradaic efficiency of 34%, corresponding to a 3-fold increase in efficiency relative to the RuB-UiO-67/TiO2/FTO control. Furthermore, this increase in catalytic efficiency is ascribed to the activation of RuTB moieties via oxidation by photogenerated RuIIIB. Transient absorption spectroscopy revealed the delayed appearance of RuIIITB* or RuIIITB formation, occurring with a lifetime of 21 ns, due to energy and/or electron transfer. The recovery kinetics of the charge separated state was increased (283 μs) in comparison to single-component control experiments (105 μs for RuB-UiO-67/TiO2/FTO and 7 μs for RuTB-UiO-67/TiO2/FTO) indicating a cooperative effect that could be exploited in chromophore/catalyst MOF motifs.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Publication Date:
Research Org.:
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1833041
Alternate Identifier(s):
OSTI ID: 1690284; OSTI ID: 1890488
Grant/Contract Number:  
SC0012446; SC0012445
Resource Type:
Accepted Manuscript
Journal Name:
Faraday Discussions
Additional Journal Information:
Journal Volume: 225; Journal ID: ISSN 1359-6640
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lin, Shaoyang, Cairnie, Daniel R., Davis, Dylan, Chakraborty, Arnab, Cai, Meng, and Morris, Amanda J. Photoelectrochemical alcohol oxidation by mixed-linker metal–organic frameworks. United States: N. p., 2020. Web. doi:10.1039/d0fd00021c.
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Lin, Shaoyang, Cairnie, Daniel R., Davis, Dylan, Chakraborty, Arnab, Cai, Meng, & Morris, Amanda J. Photoelectrochemical alcohol oxidation by mixed-linker metal–organic frameworks. United States. https://doi.org/10.1039/d0fd00021c
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Lin, Shaoyang, Cairnie, Daniel R., Davis, Dylan, Chakraborty, Arnab, Cai, Meng, and Morris, Amanda J. Fri . "Photoelectrochemical alcohol oxidation by mixed-linker metal–organic frameworks". United States. https://doi.org/10.1039/d0fd00021c. https://www.osti.gov/servlets/purl/1833041.
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@article{osti_1833041,
title = {Photoelectrochemical alcohol oxidation by mixed-linker metal–organic frameworks},
author = {Lin, Shaoyang and Cairnie, Daniel R. and Davis, Dylan and Chakraborty, Arnab and Cai, Meng and Morris, Amanda J.},
abstractNote = {Metal–organic frameworks (MOFs) provide a suitable platform for stable and efficient heterogeneous photoelectrochemical oxidation catalysis due to their highly ordered structure, large surface area, and synthetic tunability. Herein, a mixed-linker MOF comprising of a photosensitizer [Ru(dcbpy)(bpy)2]2+ (bpy = 2,2'-bipyridine, dcbpy = 5,5'-dicarboxy-2,2'-bipyridine) and catalyst [Ru(tpy)(dcbpy)Cl]+ (tpy = 2,2':6',2''-terpyridine) that were incorporated into the UiO-67 framework and grown as thin films on a TiO2-coated, fluorine-doped tin oxide (FTO) electrode (RuB-RuTB-UiO-67/TiO2/FTO). When used as an electrode for the photoelectrochemical oxidation of benzyl alcohol, the mixed-linker MOF film showed a faradaic efficiency of 34%, corresponding to a 3-fold increase in efficiency relative to the RuB-UiO-67/TiO2/FTO control. Furthermore, this increase in catalytic efficiency is ascribed to the activation of RuTB moieties via oxidation by photogenerated RuIIIB. Transient absorption spectroscopy revealed the delayed appearance of RuIIITB* or RuIIITB formation, occurring with a lifetime of 21 ns, due to energy and/or electron transfer. The recovery kinetics of the charge separated state was increased (283 μs) in comparison to single-component control experiments (105 μs for RuB-UiO-67/TiO2/FTO and 7 μs for RuTB-UiO-67/TiO2/FTO) indicating a cooperative effect that could be exploited in chromophore/catalyst MOF motifs.},
doi = {10.1039/d0fd00021c},
journal = {Faraday Discussions},
number = ,
volume = 225,
place = {United States},
year = {Fri Mar 20 00:00:00 EDT 2020},
month = {Fri Mar 20 00:00:00 EDT 2020}
}
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https://doi.org/10.1039/d0fd00021c
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