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The Discovery of Novel Materials for the Electrocatalytic Reduction of Carbon Dioxide


Torelli, Daniel Anthony (2018) The Discovery of Novel Materials for the Electrocatalytic Reduction of Carbon Dioxide. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/RBD5-B141.


The removal of atmospheric carbon dioxide is likely the only route to mitigating the effects of decades of increased fossil fuel combustion. Artificial photosynthesis presents one method for removal and conversion of problematic carbon dioxide into chemically useful products. By coupling electrochemical CO2 reduction (CO2R) to a renewable energy source atmospheric CO2 could be converted back into a fuel such as ethanol, or a commodity chemical such as ethylene. These products could then be consumed for energy or used to generate plastics effectively removing CO2 from the atmosphere. Significant advances in current electrocatalysts are needed in order for large scale CO2R to become a reality. Most known catalysts are only capable of transferring 2 electrons with needed protons to CO2 producing either carbon monoxide or formic acid. Copper is the only known metal capable of reducing CO2 to hydrocarbons at appreciable rates and low overpotentials. This work aims to find new materials that produce similar hydrocarbons, but at lower overpotentials with higher rates and greater selectivity than current copper catalysts. By implementing a cyclic process referred to as the Catalyst Discovery Cycle (CDC) iterations between predications, catalyst testing, and active site characterization allow for the rational design and discovery of new and improved catalysts. This methodology led to the discovery of nickel-gallium bimetallics as low overpotential catalysts for CO2R to methane, ethylene, and ethane. In addition, theoretical and experimental observations have determined a proposed active site and side reactions detrimental to their activity.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:CO2 reduction, carbon dioxide, electrocatalysis, electrochemistry, electrochemical CO2 reduction, nickel-gallium, catalyst discovery cycle
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Minor Option:Materials Science
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Lewis, Nathan Saul
Thesis Committee:
  • Gray, Harry B. (chair)
  • Okumura, Mitchio
  • Goddard, William A., III
  • Lewis, Nathan Saul
Defense Date:16 April 2018
Record Number:CaltechTHESIS:05292018-142628914
Persistent URL:
Related URLs:
URLURL TypeDescription Temperature Solution-Phase Deposition of SnS Thin Films adapted for Ch. 2: Nickel–Gallium-Catalyzed Electrochemical Reduction of CO2 to Highly Reduced Products at Low Overpotentials reconstruction of pure-Cu single-crystal electrodes under CO-reduction potentials in alkaline solutions: A study by seriatim ECSTM-DEMS Study in Acidic and Alkaline Media of the Effects of pH and Crystallinity on the Hydrogen-Evolution Reaction on MoS2 and MoSe2 adapted for Ch. 4: Machine-Learning Methods Enable Exhaustive Searches for Active Bimetallic Facets and Reveal Active Site Motifs for CO2 Reduction
Torelli, Daniel Anthony0000-0002-6222-817X
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10962
Deposited By: Daniel Torelli
Deposited On:04 Jun 2018 21:16
Last Modified:08 Nov 2023 18:46

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