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ZHIHAO CUI MASTER THESIS.pdf (1.31 MB)

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

Cui, Zhihao
http://rave.ohiolink.edu/etdc/view?acc_num=osu1618311775442498

Abstract Details

, Master of Science, Ohio State University, 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.
Anne Co (Advisor)
Yiying Wu (Committee Member)
Chemistry

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Citations

  • Cui, Z. (n.d.). Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold [Master's thesis, Ohio State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=osu1618311775442498

    APA Style (7th edition)

  • Cui, Zhihao. Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold. Ohio State University, Master's thesis. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=osu1618311775442498.

    MLA Style (8th edition)

  • Cui, Zhihao. "Experimental and DFT Computational Study of the Electroreduction of Acetaldehyde on Copper and Gold." Master's thesis, Ohio State University. Accessed MAY 07, 2024. http://rave.ohiolink.edu/etdc/view?acc_num=osu1618311775442498

    Chicago Manual of Style (17th edition)

osu1618311775442498
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This open access ETD is published by The Ohio State University and OhioLINK.