Urea synthesis by Plasmon-Assisted N2 and CO2 co-electrolysis onto heterojunctions decorated with silver nanoparticles

Author(s)

Faustino, Leandro A. ; de Angelis, Leonardo D. ; de Melo, Eduardo C. ; Farias, Giliandro ; dos Santos, Egon C. ; Miranda, Caetano R. ; Buzanich, Ana G. ; Torresi, Roberto M. ; de Oliveira, Paulo F. M. ; de Torresi, Susana I. Cordoba

• Document type: Journal article
• Source: CHEMICAL ENGINEERING JOURNAL; v. 513, p. 13-pg., 2025-04-28.

Abstract

The N2 + CO2 co-electrolysis to urea synthesis has become a promising alternative to the energy intensive traditional processes for urea production. However, there are still challenges in this approach, especially due to the competition with HER (Hydrogen Evolution Reaction) leading to low efficiency. Electrochemistry assisted by localized surface plasmon resonance (LSPR) using metal nanoparticles has been reported to enhance different electrochemical reactions. Here we report an electrochemical LSPR assisted urea synthesis using Ag nano-particles (NPs) supported on BiVO4/BiFeO3 catalyst mechanochemically synthesized. The electrochemical experiments were performed under dark and upon plasmon excitation at the LSPR region of Ag NPs. Our results demonstrated that exciting in the LSPR range, urea yield rate and Faradic efficiency were considerably improved with reduced overpotential, 19.2 mu mol h-1 g-1 and FE 24.4% at +0.1 V vs RHE compared to 9.6 mu mol h-1 g-1 and FE 9.4% at-0.2 V vs RHE under dark conditions. Further in situ FTIR-RAS experiments for mechanism investigation revealed the presence of N-H and C-N intermediates and the real effect of Ag plasmon excitation on HER and N2 + CO2 co-electrolysis. Theoretical calculations confirm the energy of the species involved in C-N coupling as well the role of the complex catalytic sites, which agrees with XAS measurements. (AU)

• FAPESP's process: 24/09385-7 - Exploring the plasmon-enhanced CO2 reduction reaction: An advanced in situ/operando X-ray study of Au-Cu2O electrocatalysts
• Grantee: Leonardo Domenico De Angelis
• Support Opportunities: Scholarships abroad - Research Internship - Doctorate (Direct)
• FAPESP's process: 22/15960-9 - First principles calculations applied to understand catalyst and solvent effects on the conversion of CO2 into C2+ products
• Grantee: Giliandro Farias
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 22/04604-7 - Plasmonic contributions to N2 and CO2 co-electrolysis
• Grantee: Leandro Augusto Faustino
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 20/14955-6 - Designing the next generation of advanced multicomponent materials through mechanochemical synthesis
• Grantee: Paulo Filho Marques de Oliveira
• Support Opportunities: Research Grants - Young Investigators Grants
• FAPESP's process: 13/07937-8 - Redoxome - Redox Processes in Biomedicine
• Grantee: Ohara Augusto
• Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC
• FAPESP's process: 20/15230-5 - Research Centre for Greenhouse Gas Innovation - RCG2I
• Grantee: Julio Romano Meneghini
• Support Opportunities: Research Grants - Research Centers in Engineering Program
• FAPESP's process: 21/08007-0 - Study of CO2 plasmon-assisted electroreduction over Cu2O-Au nanostructures towards C2 compounds synthesis
• Grantee: Leonardo Domenico De Angelis
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• FAPESP's process: 23/01223-5 - Mechanochemistry as a tool in the preparation of multimetallic nanomaterials
• Grantee: Ismael Pinheiro Lucas Xavier
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)
• FAPESP's process: 21/00675-4 - Tying up materials for electrochemical energy storage and catalysis
• Grantee: Roberto Manuel Torresi
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 24/13493-0 - Investigation of urea electrosynthesis assisted by localized surface plasmon resonance using labeled gases and in situ X- ray Absorption Spectroscopy
• Grantee: Leandro Augusto Faustino
• Support Opportunities: Scholarships abroad - Research Internship - Post-doctor