Ab initio screening of Pt-based transition-metal nanoalloys using descriptors derived from the adsorption and activation of CO2

Author(s)

Mendes, Paulo C. D. ^[1] ; Verga, Lucas G. ^[1] ; Da Silva, Juarez L. F. ^[1]

Affiliation

^[1] Univ Sao Paulo, Sao Carlos Inst Chem, POB 780, BR-13560970 Sao Carlos, SP - Brazil

• Document type: Journal article
• Source: Physical Chemistry Chemical Physics; v. 23, n. 10, p. 6029-6041, MAR 14 2021.
• Web of Science Citations: 0

Abstract

In this study, we report an ab initio screening, based on density functional theory calculations, of Pt-based transition-metal nanoalloys using physicochemical descriptors derived from the adsorption and activation of CO2 on 55-atom nanoclusters, namely, PtnTM55-n, with n = 0, 13, 42, 55, TM = Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Os, Ir, Au. From the adsorption on the unary and binary nanoclusters, at the chemisorption regime (bent CO2), we identified a linear correlation between the interaction energy and charge transfer from the nanoclusters towards CO2 and the bent CO2 angle; moreover, the interaction energy is enhanced for larger values of the molecular charge and angle. The alloying of Cu-55, Ag-55, and Au-55 with Pt provides a path to change the CO2 adsorption from physisorption (linear, non-activated) to chemisorption (enhanced interaction energies, bent, activated), while the strong interaction energy of CO2 with Os-55, Ru-55, and Fe-55 can be decreased by alloying with Pt using different structural configurations, i.e., the trends are similar for core-shell and segregated structures. Thus, based on our results and analyses, we can select different combinations of PtnTM55-n nanoalloys to yield the desired interaction strength and magnitude of the charge transfer towards the activated anionic CO2, which can help in the design of nanocatalysts for CO2 activation or different chemical reactions in which charge transfer plays a crucial role. (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: 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: 19/05561-7 - A Multiscale Framework Applied to the Investigation of CO2 Reduction on Metallic Nanoparticles: The Role of Size and Adsorbate Coverage Effects
• Grantee: Lucas Garcia Verga
• Support Opportunities: Scholarships in Brazil - Post-Doctoral