Molecular Dye-Sensitized Photocatalysis with Metal-Organic Framework and Metal Oxide Colloids for Fuel Production
Colloidal dye-sensitized photocatalysis is a promising route toward efficient solar fuel production by merging properties of catalysis, support, light absorption, and electron mediation in one. Metal-organic frameworks (MOFs) are host materials with modular building principles allowing scaffold prop...
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MDPI AG
2021-07-01
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Online Access: | https://www.mdpi.com/1996-1073/14/14/4260 |
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author | Philip M. Stanley Julien Warnan |
author_facet | Philip M. Stanley Julien Warnan |
author_sort | Philip M. Stanley |
collection | DOAJ |
description | Colloidal dye-sensitized photocatalysis is a promising route toward efficient solar fuel production by merging properties of catalysis, support, light absorption, and electron mediation in one. Metal-organic frameworks (MOFs) are host materials with modular building principles allowing scaffold property tailoring. Herein, we combine these two fields and compare porous Zr-based MOFs UiO-66-NH<sub>2</sub>(Zr) and UiO-66(Zr) to monoclinic ZrO<sub>2</sub> as model colloid hosts with co-immobilized molecular carbon dioxide reduction photocatalyst <i>fac</i>-ReBr(CO)<sub>3</sub>(4,4′-dcbpy) (dcbpy = dicarboxy-2,2′-bipyridine) and photosensitizer Ru(bpy)<sub>2</sub>(5,5′-dcbpy)Cl<sub>2</sub> (bpy = 2,2′-bipyridine). These host-guest systems demonstrate selective CO<sub>2</sub>-to-CO reduction in acetonitrile in presence of an electron donor under visible light irradiation, with turnover numbers (TONs) increasing from ZrO<sub>2</sub>, to UiO-66, and to UiO-66-NH<sub>2</sub> in turn. This is attributed to MOF hosts facilitating electron hopping and enhanced CO<sub>2</sub> uptake due to their innate porosity. Both of these phenomena are pronounced for UiO-66-NH<sub>2</sub>(Zr), yielding TONs of 450 which are 2.5 times higher than under MOF-free homogeneous conditions, highlighting synergistic effects between supramolecular photosystem components in dye-sensitized MOFs. |
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id | doaj.art-3e321323388f4fdaacf341b4be528359 |
institution | Directory Open Access Journal |
issn | 1996-1073 |
language | English |
last_indexed | 2024-03-10T09:40:01Z |
publishDate | 2021-07-01 |
publisher | MDPI AG |
record_format | Article |
series | Energies |
spelling | doaj.art-3e321323388f4fdaacf341b4be5283592023-11-22T03:42:43ZengMDPI AGEnergies1996-10732021-07-011414426010.3390/en14144260Molecular Dye-Sensitized Photocatalysis with Metal-Organic Framework and Metal Oxide Colloids for Fuel ProductionPhilip M. Stanley0Julien Warnan1Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, Technical University of Munich, 85748 Garching, GermanyChair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, Technical University of Munich, 85748 Garching, GermanyColloidal dye-sensitized photocatalysis is a promising route toward efficient solar fuel production by merging properties of catalysis, support, light absorption, and electron mediation in one. Metal-organic frameworks (MOFs) are host materials with modular building principles allowing scaffold property tailoring. Herein, we combine these two fields and compare porous Zr-based MOFs UiO-66-NH<sub>2</sub>(Zr) and UiO-66(Zr) to monoclinic ZrO<sub>2</sub> as model colloid hosts with co-immobilized molecular carbon dioxide reduction photocatalyst <i>fac</i>-ReBr(CO)<sub>3</sub>(4,4′-dcbpy) (dcbpy = dicarboxy-2,2′-bipyridine) and photosensitizer Ru(bpy)<sub>2</sub>(5,5′-dcbpy)Cl<sub>2</sub> (bpy = 2,2′-bipyridine). These host-guest systems demonstrate selective CO<sub>2</sub>-to-CO reduction in acetonitrile in presence of an electron donor under visible light irradiation, with turnover numbers (TONs) increasing from ZrO<sub>2</sub>, to UiO-66, and to UiO-66-NH<sub>2</sub> in turn. This is attributed to MOF hosts facilitating electron hopping and enhanced CO<sub>2</sub> uptake due to their innate porosity. Both of these phenomena are pronounced for UiO-66-NH<sub>2</sub>(Zr), yielding TONs of 450 which are 2.5 times higher than under MOF-free homogeneous conditions, highlighting synergistic effects between supramolecular photosystem components in dye-sensitized MOFs.https://www.mdpi.com/1996-1073/14/14/4260dye-sensitizedmetal-organic frameworksmetal oxideshost-guest photosystemsmolecular catalysisfuel production |
spellingShingle | Philip M. Stanley Julien Warnan Molecular Dye-Sensitized Photocatalysis with Metal-Organic Framework and Metal Oxide Colloids for Fuel Production Energies dye-sensitized metal-organic frameworks metal oxides host-guest photosystems molecular catalysis fuel production |
title | Molecular Dye-Sensitized Photocatalysis with Metal-Organic Framework and Metal Oxide Colloids for Fuel Production |
title_full | Molecular Dye-Sensitized Photocatalysis with Metal-Organic Framework and Metal Oxide Colloids for Fuel Production |
title_fullStr | Molecular Dye-Sensitized Photocatalysis with Metal-Organic Framework and Metal Oxide Colloids for Fuel Production |
title_full_unstemmed | Molecular Dye-Sensitized Photocatalysis with Metal-Organic Framework and Metal Oxide Colloids for Fuel Production |
title_short | Molecular Dye-Sensitized Photocatalysis with Metal-Organic Framework and Metal Oxide Colloids for Fuel Production |
title_sort | molecular dye sensitized photocatalysis with metal organic framework and metal oxide colloids for fuel production |
topic | dye-sensitized metal-organic frameworks metal oxides host-guest photosystems molecular catalysis fuel production |
url | https://www.mdpi.com/1996-1073/14/14/4260 |
work_keys_str_mv | AT philipmstanley moleculardyesensitizedphotocatalysiswithmetalorganicframeworkandmetaloxidecolloidsforfuelproduction AT julienwarnan moleculardyesensitizedphotocatalysiswithmetalorganicframeworkandmetaloxidecolloidsforfuelproduction |