Restricted Research - Award List, Note/Discussion Page
Fiscal Year: 2023
108 University of North Texas (141996)
Principal Investigator: Cundari,Thomas Richard
Total Amount of Contract, Award, or Gift (Annual before 2011): $ 300,000
Exceeds $250,000 (Is it flagged?): Yes
Start and End Dates: 6/1/23 - 5/31/26
Restricted Research: YES
Academic Discipline: Chemistry
Department, Center, School, or Institute: College of Science
Title of Contract, Award, or Gift: Collaborative Research: Sustainable Ammonia Produc
Name of Granting or Contracting Agency/Entity:
Robert A. Welch Foundation
CFDA:
Program Title: none
Note:
The proposed research targets electro- and photoelectrochemical nitrogen reduction by molecular catalysts, which has the potential to provide a sustainable route to ammonia manufacturing for fertilizers and energy storage, while minimizing reliance on the CO2-producing, energy-intensive Haber-Bosch process. Supported by key preliminary experimental and theoretical results, the guiding hypothesis of this fundamental study is that easily reducible metalloporphyrins bind N2 at metal sites, thus weakening the N≡N bond via p-backbonding under electro-reductive conditions, and leading to facile conversion of N2 to NH3 at ambient conditions and lower overpotentials. Two key fundamental and interrelated issues, viz N2-binding and splitting and nitride reduction through proton-coupled electron transfer reactions, will be probed. Electro- and photoelectrochemistry, surface science, and theoretical studies will explore the functionalities of cheaper, metal-macrocyclic catalysts toward nitrogen reduction, and focus on how the redox potentials and metal site d-orbital occupancy impact catalyst function for specific reactions over a range of pH values. Photochemical studies will also involve ultrafast spectroscopic probing of photon-adsorbate interactions. Surface science studies will elucidate reaction pathways using in-situ photoemission studies, synchrotron-based operando photoemission studies, and operando electrochemical AFM and FTIR studies. Theoretical efforts will include DFT calculations modified to incorporate potentials appropriate to the electrolyte/solid interface. Post-doctoral and graduate student education will focus on multidisciplinary training incorporating both theory and experiment, appropriate for ensuring future success in the scientific study of increasingly complex fundamental problems of societal impact.
Discussion: No discussion notes