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Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO(2) reduction

Sunlight-driven CO(2) reduction to renewable fuels is a promising strategy towards a closed carbon cycle in a circular economy. For that purpose, colloidal quantum dots (QDs) have emerged as a versatile light absorber platform that offers many possibilities for surface modification strategies. Consi...

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Autores principales: Sahm, Constantin D., Ciotti, Anna, Mates-Torres, Eric, Badiani, Vivek, Sokołowski, Kamil, Neri, Gaia, Cowan, Alexander J., García-Melchor, Max, Reisner, Erwin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9132019/
https://www.ncbi.nlm.nih.gov/pubmed/35685808
http://dx.doi.org/10.1039/d2sc00890d
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author Sahm, Constantin D.
Ciotti, Anna
Mates-Torres, Eric
Badiani, Vivek
Sokołowski, Kamil
Neri, Gaia
Cowan, Alexander J.
García-Melchor, Max
Reisner, Erwin
author_facet Sahm, Constantin D.
Ciotti, Anna
Mates-Torres, Eric
Badiani, Vivek
Sokołowski, Kamil
Neri, Gaia
Cowan, Alexander J.
García-Melchor, Max
Reisner, Erwin
author_sort Sahm, Constantin D.
collection PubMed
description Sunlight-driven CO(2) reduction to renewable fuels is a promising strategy towards a closed carbon cycle in a circular economy. For that purpose, colloidal quantum dots (QDs) have emerged as a versatile light absorber platform that offers many possibilities for surface modification strategies. Considerable attention has been focused on tailoring the local chemical environment of the catalytic site for CO(2) reduction with chemical functionalities ranging from amino acids to amines, imidazolium, pyridines, and others. Here we show that dithiols, a class of organic compounds previously unexplored in the context of CO(2) reduction, can enhance photocatalytic CO(2) reduction on ZnSe QDs. A short dithiol (1,2-ethanedithiol) activates the QD surface for CO(2) reduction accompanied by a suppression of the competing H(2) evolution reaction. In contrast, in the presence of an immobilized Ni(cyclam) co-catalyst, a longer dithiol (1,6-hexanedithiol) accelerates CO(2) reduction. (1)H-NMR spectroscopy studies of the dithiol-QD surface interactions reveal a strong affinity of the dithiols for the QD surface accompanied by a solvation sphere governed by hydrophobic interactions. Control experiments with a series of dithiol analogues (monothiol, mercaptoalcohol) render the hydrophobic chemical environment unlikely as the sole contribution of the enhancement of CO(2) reduction. Density functional theory (DFT) calculations provide a framework to rationalize the observed dithiol length dependent activity through the analysis of the non-covalent interactions between the dangling thiol moiety and the CO(2) reduction intermediates at the catalytic site. This work therefore introduces dithiol capping ligands as a straightforward means to enhance CO(2) reduction catalysis on both bare and co-catalyst modified QDs by engineering the particle's chemical environment.
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spelling pubmed-91320192022-06-08 Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO(2) reduction Sahm, Constantin D. Ciotti, Anna Mates-Torres, Eric Badiani, Vivek Sokołowski, Kamil Neri, Gaia Cowan, Alexander J. García-Melchor, Max Reisner, Erwin Chem Sci Chemistry Sunlight-driven CO(2) reduction to renewable fuels is a promising strategy towards a closed carbon cycle in a circular economy. For that purpose, colloidal quantum dots (QDs) have emerged as a versatile light absorber platform that offers many possibilities for surface modification strategies. Considerable attention has been focused on tailoring the local chemical environment of the catalytic site for CO(2) reduction with chemical functionalities ranging from amino acids to amines, imidazolium, pyridines, and others. Here we show that dithiols, a class of organic compounds previously unexplored in the context of CO(2) reduction, can enhance photocatalytic CO(2) reduction on ZnSe QDs. A short dithiol (1,2-ethanedithiol) activates the QD surface for CO(2) reduction accompanied by a suppression of the competing H(2) evolution reaction. In contrast, in the presence of an immobilized Ni(cyclam) co-catalyst, a longer dithiol (1,6-hexanedithiol) accelerates CO(2) reduction. (1)H-NMR spectroscopy studies of the dithiol-QD surface interactions reveal a strong affinity of the dithiols for the QD surface accompanied by a solvation sphere governed by hydrophobic interactions. Control experiments with a series of dithiol analogues (monothiol, mercaptoalcohol) render the hydrophobic chemical environment unlikely as the sole contribution of the enhancement of CO(2) reduction. Density functional theory (DFT) calculations provide a framework to rationalize the observed dithiol length dependent activity through the analysis of the non-covalent interactions between the dangling thiol moiety and the CO(2) reduction intermediates at the catalytic site. This work therefore introduces dithiol capping ligands as a straightforward means to enhance CO(2) reduction catalysis on both bare and co-catalyst modified QDs by engineering the particle's chemical environment. The Royal Society of Chemistry 2022-04-11 /pmc/articles/PMC9132019/ /pubmed/35685808 http://dx.doi.org/10.1039/d2sc00890d Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Sahm, Constantin D.
Ciotti, Anna
Mates-Torres, Eric
Badiani, Vivek
Sokołowski, Kamil
Neri, Gaia
Cowan, Alexander J.
García-Melchor, Max
Reisner, Erwin
Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO(2) reduction
title Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO(2) reduction
title_full Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO(2) reduction
title_fullStr Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO(2) reduction
title_full_unstemmed Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO(2) reduction
title_short Tuning the local chemical environment of ZnSe quantum dots with dithiols towards photocatalytic CO(2) reduction
title_sort tuning the local chemical environment of znse quantum dots with dithiols towards photocatalytic co(2) reduction
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9132019/
https://www.ncbi.nlm.nih.gov/pubmed/35685808
http://dx.doi.org/10.1039/d2sc00890d
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