Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold

Bibliographic Details
Main Author:	Cui, Zhihao
Language:	English
Published:	The Ohio State University / OhioLINK 2021
Subjects:	Chemistry
Online Access:	http://rave.ohiolink.edu/etdc/view?acc_num=osu1618311775442498

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spelling	ndltd-OhioLink-oai-etd.ohiolink.edu-osu16183117754424982021-10-08T05:09:08Z Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold Cui, Zhihao Chemistry Investigating the electrochemical reduction of aldehydes to alcohols provides insights into the mechanistic pathways of converting CO2 to alcohols electrochemically. In this work, both acetaldehyde and propionaldehyde were electrochemically reduced on a Cu catalyst to illustrate that it is a viable pathway to ethanol and 1-propanol, respectively, supporting the mechanistic route previously proposed in the literature. Also noteworthy is that the electroreduction of acetaldehyde to ethanol is selective on Cu and does not occur on catalyst such as Au. 13C and 1H NMR analysis on isotopically labeled acetaldehyde was utilized to trace the reduction process. DFT calculations using Vienna Ab-initio Simulation Package (VASP) are performed to support experimental observations. In this thesis, adsorption energy is derived from the DFT geometry optimization. Charge transfer upon adsorption is evaluated by using bader charge analysis implemented in VASP. Reaction free energies are calculated based on Computational Hydrogen Electrode (CHE) model where the solvent effect is simulated by using an implicit solvent model, VASPsol. These calculations indicate a higher energy reaction intermediate on Au(111) over Cu(100). Additionally, in an aqueous solution, acetaldehyde is at equilibrium with ethanediol, and propionaldehyde with propanediol. DFT calculations suggest that acetaldehyde, not ethanediol, is more likely to be reduced to ethanol. The dissociation of adsorbed ethanediol to acetaldehyde and water was also found to be favorable on both Cu and Au surfaces. In summary, the results from this study supports previously proposed mechanisms and provide a framework for testing other stable CO2 reaction intermediates to gain insights into the overall CO2 reaction pathway. 2021-10-07 English text The Ohio State University / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=osu1618311775442498 http://rave.ohiolink.edu/etdc/view?acc_num=osu1618311775442498 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws.
collection	NDLTD
language	English
sources	NDLTD
topic	Chemistry
spellingShingle	Chemistry Cui, Zhihao Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold
author	Cui, Zhihao
author_facet	Cui, Zhihao
author_sort	Cui, Zhihao
title	Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold
title_short	Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold
title_full	Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold
title_fullStr	Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold
title_full_unstemmed	Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold
title_sort	experimental and dft computational study of the electroreduction of acetaldehyde on copper and gold
publisher	The Ohio State University / OhioLINK
publishDate	2021
url	http://rave.ohiolink.edu/etdc/view?acc_num=osu1618311775442498
work_keys_str_mv	AT cuizhihao experimentalanddftcomputationalstudyoftheelectroreductionofacetaldehydeoncopperandgold
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Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold

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