Doctoral Dissertations

Keywords and Phrases

Carbon dioxide reduction; Chalcogenides; Electrochemistry; Metal compelexes; Nanomaterials; Water Splitting

Abstract

"This research focused on the synthetic design of transition metal mixed anionic chalcogenide catalysts containing various ligand types around the central metal atom (chalcogen anion and chalcogen-based organic ligand) generating diverse crystal structure types applied for water splitting and carbon dioxide reduction reactions (CO2RR).

A series of catalysts were synthesized starting with isolated metal complexes (MEn) with a central metal core (M = Co, Ni, Cu, and Cr) through molecular clusters, to bulk nanostructured solids of similar M-E coordination. Bis(dichalcogenoimidodiphosphinato) were employed as ligands in the metal complexes, and anionic chalcogen (E = S, Se, and Te) in bulk solids and metal clusters. This modulates the electron distribution and energy band structure of the catalyst to optimize their performances in electrocatalytic reactions.

The electrochemical oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performances of cobalt bis(dichalcogenoimidodiphosphinato) complex, chromium molecular cluster, and nickel (telluro) selenide series were studied. Density functional theory was employed to corroborate evolutionary activity trends and to predict OER catalytic performance using a constructed volcano plot in metal chalcogenides.

The molecular chromium carbonyl cluster was studied for electrochemical carbon dioxide reduction reactions (CO2RR). The catalyst is based on 3d early transition metal that was stabilized by bridging μ-Se and CO π-back bonding, increasing the nucleophilic character of the active center. This was capable of transforming CO2 into value-added C2 products and was highly selective with high yield, towards ethanol and acetic acid production at -0.9 and -1.2 V vs RHE potential with high faradaic efficiency" -- Abstract, p. iv

Advisor(s)

Nath, Manashi

Committee Member(s)

Sotiriou-Leventis, Lia
Stavropoulos, Pericles
Choudhury, Amitava
Liang, Xinhua

Department(s)

Chemistry

Degree Name

Ph. D. in Chemistry

Publisher

Missouri University of Science and Technology

Publication Date

Summer 2024

Pagination

xv, 217 pages

Note about bibliography

Includes_bibliographical_references_(pages 66, 97, 158, 187 & 193-216)

Rights

©2024 Ibrahim Abdullahi , All Rights Reserved

Document Type

Dissertation - Open Access

File Type

text

Language

English

Thesis Number

T 12417

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