Insights into the alloy-support synergistic effects for the CO2 hydrogenation towards methanol on oxide-supported Ni5Ga3 catalysts: An experimental and DFT study

Author(s)

Rasteiro, Leticia F. ^[1] ; De Sousa, Rafael A. ^[1] ; Vieira, Luiz H. ^{[1, 2]} ; Ocampo-Restrepo, Vivianne K. ^[1] ; Verga, Lucas G. ^[1] ; Assaf, Jose M. ^[2] ; Da Silva, Juarez L. F. ^[1] ; Assaf, Elisabete M. ^[1]

Affiliation

^[1] Univ Sao Paulo, Sao Carlos Inst Chem, Av Trabalhador Sao Carlense 400, BR-13560970 Sao Carlos, SP - Brazil

^[2] Univ Fed Sao Carlos, Chem Engn Dept, Rod W Luiz, Km 235, BR-13565905 Sao Carlos, SP - Brazil

• Document type: Journal article
• Source: APPLIED CATALYSIS B-ENVIRONMENTAL; v. 302, MAR 2022.
• Web of Science Citations: 0

Abstract

Supported Ni-Ga alloys have emerged as potential catalyst to mitigate CO2 emissions by its conversion into methanol at mild conditions, however, its performance depends on the optimization of the alloy-support effects, which is unclear up to now. Herein, we investigate the influence of alloy-support synergy in the catalytic performance of Ni5Ga3 supported on SiO2, CeO2, and ZrO2, by combining in-depth structural, chemical and spectroscopic characterization and density functional theory (DFT) calculations. In situ DRIFTS confirmed further hydrogenation of key reaction intermediates in Ni5Ga3/ZrO2 surface, while weak CO2 adsorption in Ni5Ga3/SiO2 avoided intermediate stabilization on the surface and, strong interaction with Ni5Ga3/CeO2 poisoned interface active sites. Additionally, the relative energies of reactants and key intermediates in the three distinct regions of the catalyst (support surface, alloy surface, and alloy-support interface), calculated through DFT, allowed us to propose a reaction mechanism for the most promising catalyst, Ni5Ga3/ZrO2. (AU)

• 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: 15/06246-7 - Biorefinery concept applied to biological wastewater treatment plants: environmental pollution control coupled with material and energy recovery
• Grantee: Marcelo Zaiat
• Support Opportunities: Research Projects - Thematic Grants
• 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
• 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: 18/12021-6 - Partial oxidation of methane to methanol catalyzed by single-atom noble metal (Rh, Pd or Pt) supported on doped mesoporous CeO2 (Ce1-xMxO2, M = Zr, Sn or La)
• Grantee: Luiz Henrique Vieira
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 14/50279-4 - Brasil Research Centre for Gas Innovation
• Grantee: Julio Romano Meneghini
• Support Opportunities: Research Grants - Research Centers in Engineering Program
• FAPESP's process: 17/22671-5 - Ga-Ni nanoparticles supported on porous silica for methanol synthesis from CO2 at low pressures
• Grantee: Letícia Fernanda Rasteiro
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 19/22260-0 - Sub-monolayer control of the growth of ZrO2 films over ordered mesoporous silica supports and interface tailoring of Ni-Ga catalysts by atomic layer deposition (ALD)
• Grantee: Letícia Fernanda Rasteiro
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate