Metal Organic Framework-Derived Transition Metal-Based Catalysts for Electrochemical Water splitting and Carbon Dioxide Reduction

Huang, Minghong

Metal Organic Framework-Derived Transition Metal-Based Catalysts for Electrochemical Water splitting and Carbon Dioxide Reduction

Huang, Minghong

Permalink

Publication Type:: Thesis
Issue Date:: 2023

Open Access

Copyright Clearance Process

Recently Added
In Progress
Open Access

This item is open access.

Adobe PDF

Download thesisAdobe PDF (13.69 MB)

View statistics

Full metadata record

Field	Value	Language
dc.contributor.author	Huang, Minghong
dc.date.accessioned	2023-10-16T04:13:36Z
dc.date.available	2023-10-16T04:13:36Z
dc.date.issued	2023
dc.identifier.uri	http://hdl.handle.net/10453/172697
dc.description	University of Technology Sydney. Faculty of Engineering and Information Technology.	en_US.UTF-8
dc.description.abstract	Developing renewable technologies that consume water or carbon dioxide (CO₂), utilize them as feedstocks and convert them into clean energy and value-added chemicals is meaningful but also challenging. Electrochemical water splitting and CO₂ reduction are promising routes to achieve these aspirations while closing the carbon cycle. The major challenge to realizing such electrochemical conversion is the performance-driven design and fabrication of efficient electrocatalysts. Recently, metal-organic framework (MOF)-derived transition metal (TM)-based layered double hydroxides (LDHs), carbides, and single-atom catalysts (SACs) have emerged as highly active electrocatalysts for oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and CO₂ reduction reaction (CO₂RR), respectively. However, despite the many achievements, developing TM-based catalysts with high activity and selectivity is an ongoing challenge. Hence, in this thesis, novel TM electrocatalysts have been obtained by developing effective control over morphology, composition, interface, and atomic structure. Morphology control and compositional engineering are first applied to synthesize zeolitic imidazolate framework (ZIF)-derived hollow CoFe-based LDH nanocages (h-CoFe-LDH NCs) and yolk-shell ZIF@CoFe-LDH nanocages (ys-ZIF@CoFe-LDH NCs) for OER and selective small organic molecule oxidation. The resultant h-CoFe-LDH NCs exhibited a commendable OER activity with a small overpotential of 278 mV at 50 mA cm⁻². Additionally, controlling the reconstruction degree enabled the formation of ys-ZIF@CoFe-LDH NCs with yolk-shell nanocage nanostructure, which have an appreciable electrocatalytic performance for the selective ethylene glycol oxidation reaction (EGOR) toward formate with a Faradaic efficiency (FE) up to 91%. Structural and interfacial engineering were then employed to construct molybdenum carbide decorated with iron nanoparticles (NPs) for water splitting. The MoC-Fe@NCNTs (N-doped carbon nanotubes) catalyst displayed fast kinetics and small overpotentials of 252 and 304 mV at 50 mA cm⁻² for the HER and OER, respectively. Theoretical calculations and experimental observation further prove that the incorporation of Fe NPs enables the creation of a heterointerface with MoC which promotes the OER activity of MoC, thereby endowing an outstanding bifunctional electrocatalytic performance. An atomic engineering strategy was further implemented to prepare a Fe-Se dual-metal SACs electrocatalyst for CO₂RR. Comprehensive analyses suggest that Se SA served as promoter for boosting the CO₂RR activity and selectivity. Consequently, a distinct synergistic effect was observed in the resultant FeSe-NC, which achieved an excellent CO₂RR performance. Overall, this thesis has realized the delicate design of MOF-derived TM-based catalysts for enhanced electrocatalytic water dissociation and CO₂ reduction, which will shed light on the further design of novel electrocatalysts for renewable energy conversion and other reactions.	en_US.UTF-8
dc.format	Thesis (PhD)
dc.language.iso	en_US	en_US.UTF-8
dc.relation	https://opus.lib.uts.edu.au/bitstream/10453/172697/1/thesis.pdf
dc.rights	info:eu-repo/semantics/openAccess
dc.rights	The author owns the copyright in this thesis including all reproduction and reuse rights for the work. The work may not be altered without the permission of the copyright owner. Attribution is essential when quoting or paraphrasing from this thesis.
dc.rights	© 2023 Minghong Huang
dc.rights	au.edu.uts.lib/cph
dc.title	Metal Organic Framework-Derived Transition Metal-Based Catalysts for Electrochemical Water splitting and Carbon Dioxide Reduction	en_US.UTF-8
dc.type	Thesis
utslib.copyright.status	open_access	*

Abstract:

Developing renewable technologies that consume water or carbon dioxide (CO₂), utilize them as feedstocks and convert them into clean energy and value-added chemicals is meaningful but also challenging. Electrochemical water splitting and CO₂ reduction are promising routes to achieve these aspirations while closing the carbon cycle. The major challenge to realizing such electrochemical conversion is the performance-driven design and fabrication of efficient electrocatalysts. Recently, metal-organic framework (MOF)-derived transition metal (TM)-based layered double hydroxides (LDHs), carbides, and single-atom catalysts (SACs) have emerged as highly active electrocatalysts for oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and CO₂ reduction reaction (CO₂RR), respectively. However, despite the many achievements, developing TM-based catalysts with high activity and selectivity is an ongoing challenge. Hence, in this thesis, novel TM electrocatalysts have been obtained by developing effective control over morphology, composition, interface, and atomic structure. Morphology control and compositional engineering are first applied to synthesize zeolitic imidazolate framework (ZIF)-derived hollow CoFe-based LDH nanocages (h-CoFe-LDH NCs) and yolk-shell ZIF@CoFe-LDH nanocages (ys-ZIF@CoFe-LDH NCs) for OER and selective small organic molecule oxidation. The resultant h-CoFe-LDH NCs exhibited a commendable OER activity with a small overpotential of 278 mV at 50 mA cm⁻². Additionally, controlling the reconstruction degree enabled the formation of ys-ZIF@CoFe-LDH NCs with yolk-shell nanocage nanostructure, which have an appreciable electrocatalytic performance for the selective ethylene glycol oxidation reaction (EGOR) toward formate with a Faradaic efficiency (FE) up to 91%. Structural and interfacial engineering were then employed to construct molybdenum carbide decorated with iron nanoparticles (NPs) for water splitting. The MoC-Fe@NCNTs (N-doped carbon nanotubes) catalyst displayed fast kinetics and small overpotentials of 252 and 304 mV at 50 mA cm⁻² for the HER and OER, respectively. Theoretical calculations and experimental observation further prove that the incorporation of Fe NPs enables the creation of a heterointerface with MoC which promotes the OER activity of MoC, thereby endowing an outstanding bifunctional electrocatalytic performance. An atomic engineering strategy was further implemented to prepare a Fe-Se dual-metal SACs electrocatalyst for CO₂RR. Comprehensive analyses suggest that Se SA served as promoter for boosting the CO₂RR activity and selectivity. Consequently, a distinct synergistic effect was observed in the resultant FeSe-NC, which achieved an excellent CO₂RR performance. Overall, this thesis has realized the delicate design of MOF-derived TM-based catalysts for enhanced electrocatalytic water dissociation and CO₂ reduction, which will shed light on the further design of novel electrocatalysts for renewable energy conversion and other reactions.

Please use this identifier to cite or link to this item:

http://hdl.handle.net/10453/172697