A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen

Re(pyNHC-PhCF3)(CO)3Br is a highly active photocatalyst for CO2 reduction. The PhCF3 derivative was previously empirically shown to be a robust catalyst. Here, the role of the PhCF3 group is probed computationally and the robust nature of this catalyst is analyzed with regard to the presence of wate...

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Main Authors:	Casey A. Carpenter, Phillip Brogdon, Louis E. McNamara, Gregory S. Tschumper, Nathan I. Hammer, Jared H. Delcamp
Format:	Article
Language:	English
Published:	MDPI AG 2018-01-01
Series:	Inorganics
Subjects:	CO2 reduction photocatalysis NHC-ligated complexes
Online Access:	http://www.mdpi.com/2304-6740/6/1/22

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spelling	doaj-3dfe058ce6884986b35e00c040653c782020-11-24T21:04:51ZengMDPI AGInorganics2304-67402018-01-01612210.3390/inorganics6010022inorganics6010022A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and OxygenCasey A. Carpenter0Phillip Brogdon1Louis E. McNamara2Gregory S. Tschumper3Nathan I. Hammer4Jared H. Delcamp5Department of Chemistry and Biochemistry, University of Mississippi, 322 Coulter Hall, University, MS 38677, USADepartment of Chemistry and Biochemistry, University of Mississippi, 322 Coulter Hall, University, MS 38677, USADepartment of Chemistry and Biochemistry, University of Mississippi, 322 Coulter Hall, University, MS 38677, USADepartment of Chemistry and Biochemistry, University of Mississippi, 322 Coulter Hall, University, MS 38677, USADepartment of Chemistry and Biochemistry, University of Mississippi, 322 Coulter Hall, University, MS 38677, USADepartment of Chemistry and Biochemistry, University of Mississippi, 322 Coulter Hall, University, MS 38677, USARe(pyNHC-PhCF3)(CO)3Br is a highly active photocatalyst for CO2 reduction. The PhCF3 derivative was previously empirically shown to be a robust catalyst. Here, the role of the PhCF3 group is probed computationally and the robust nature of this catalyst is analyzed with regard to the presence of water and oxygen introduced in controlled amounts during the photocatalytic reduction of CO2 to CO with visible light. This complex was found to work well from 0–1% water concentration reproducibly; however, trace amounts of water were required for benchmark Re(bpy)(CO)3Cl to give reproducible reactivity. When ambient air is added to the reaction mixture, the NHC complex was found to retain substantial performance (~50% of optimized reactivity) at up to 40% ambient atmosphere and 60% CO2 while the Re(bpy)(CO)3Cl complex was found to give a dramatically reduced CO2 reduction reactivity upon introduction of ambient atmosphere. Through the use of time-correlated single photon counting studies and prior electrochemical results, we reasoned that this enhanced catalyst resilience is due to a mechanistic difference between the NHC- and bpy-based catalysts. These results highlight an important feature of this NHC-ligated catalyst: substantially enhanced stability toward common reaction contaminates.http://www.mdpi.com/2304-6740/6/1/22CO2 reductionphotocatalysisNHC-ligated complexes
collection	DOAJ
language	English
format	Article
sources	DOAJ
author	Casey A. Carpenter Phillip Brogdon Louis E. McNamara Gregory S. Tschumper Nathan I. Hammer Jared H. Delcamp
spellingShingle	Casey A. Carpenter Phillip Brogdon Louis E. McNamara Gregory S. Tschumper Nathan I. Hammer Jared H. Delcamp A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen Inorganics CO2 reduction photocatalysis NHC-ligated complexes
author_facet	Casey A. Carpenter Phillip Brogdon Louis E. McNamara Gregory S. Tschumper Nathan I. Hammer Jared H. Delcamp
author_sort	Casey A. Carpenter
title	A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen
title_short	A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen
title_full	A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen
title_fullStr	A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen
title_full_unstemmed	A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen
title_sort	robust pyridyl-nhc-ligated rhenium photocatalyst for co2 reduction in the presence of water and oxygen
publisher	MDPI AG
series	Inorganics
issn	2304-6740
publishDate	2018-01-01
description	Re(pyNHC-PhCF3)(CO)3Br is a highly active photocatalyst for CO2 reduction. The PhCF3 derivative was previously empirically shown to be a robust catalyst. Here, the role of the PhCF3 group is probed computationally and the robust nature of this catalyst is analyzed with regard to the presence of water and oxygen introduced in controlled amounts during the photocatalytic reduction of CO2 to CO with visible light. This complex was found to work well from 0–1% water concentration reproducibly; however, trace amounts of water were required for benchmark Re(bpy)(CO)3Cl to give reproducible reactivity. When ambient air is added to the reaction mixture, the NHC complex was found to retain substantial performance (~50% of optimized reactivity) at up to 40% ambient atmosphere and 60% CO2 while the Re(bpy)(CO)3Cl complex was found to give a dramatically reduced CO2 reduction reactivity upon introduction of ambient atmosphere. Through the use of time-correlated single photon counting studies and prior electrochemical results, we reasoned that this enhanced catalyst resilience is due to a mechanistic difference between the NHC- and bpy-based catalysts. These results highlight an important feature of this NHC-ligated catalyst: substantially enhanced stability toward common reaction contaminates.
topic	CO2 reduction photocatalysis NHC-ligated complexes
url	http://www.mdpi.com/2304-6740/6/1/22
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A Robust Pyridyl-NHC-Ligated Rhenium Photocatalyst for CO2 Reduction in the Presence of Water and Oxygen

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