Theoretical Insights into Methane Activation on Transition-Metal Single-Atom Catalysts Supported on the CeO₂(111) Surface

Author(s)

Moraes, PedroIvo Ivo R. ; Bittencourt, Albert F. B. ; Andriani, Karla F. F. ; Da Silva, Juarez L. F.

• Document type: Journal article
• Source: Journal of Physical Chemistry C; v. N/A, p. 10-pg., 2023-08-11.

Abstract

Converting methane into high-value-added chemicals iscrucial foraddressing the energy transition, where novel processes and catalystsare required to improve the selective activation of methane. In thisstudy, we combined density functional theory within the Hubbard correctioncalculations and the unity bond index-quadratic exponential potentialmodel to investigate methane activation on TM/CeO2(111)systems, where TM represents single-adatoms of Fe, Co, Ni, Cu, Zn,Ru, Rh, Pd, Ag, Ir, Pt, and Au. Our results indicate that the moststable TM adatoms on CeO2(111) are those that donate moreelectrons to the surface, thereby reducing the Ce cations from Ce4+ to Ce3+. The first methane dehydrogenation becomesmore thermodynamically favored as the TM period increases; that is,the magnitude of both reaction and dissociation energies increases.In contrast, the C-H activation energy barriers, in general,decrease along with the TM period, which is related to the large magnitudeof the CH3 adsorption energy. Thus, our findings offervaluable insights into the exploration of ceria-supported transition-metalsingle-atom catalysts for methane activation. (AU)

• FAPESP's process: 18/21401-7 - Multi-User Equipment approved in grant 2017/11631-2: cluster computational de alto desempenho - ENIAC
• Grantee: Juarez Lopes Ferreira da Silva
• Support Opportunities: Multi-user Equipment Program
• FAPESP's process: 22/12778-5 - Computational material science applied to the screening of materials
• Grantee: Albert Frederico Barbosa Bittencourt
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 17/11631-2 - CINE: computational materials design based on atomistic simulations, meso-scale, multi-physics, and artificial intelligence for energy applications
• Grantee: Juarez Lopes Ferreira da Silva
• Support Opportunities: Research Grants - Research Centers in Engineering Program
• FAPESP's process: 17/11937-4 - A sustainable path to methane conversion by advanced electrochemical technologies
• Grantee: Fabio Coral Fonseca
• Support Opportunities: Research Grants - Research Centers in Engineering Program