Gas-Phase Errors Affect DFT-Based Electrocatalysis Models of Oxygen Reduction to Hydrogen Peroxide

Author(s)

Almeida, Michell O. ; Kolb, Manuel J. ; Lanza, Marcos R., V ; Illas, Francesc ; Calle-Vallejo, Federico

• Document type: Journal article
• Source: CHEMELECTROCHEM; v. 9, n. 12, p. 7-pg., 2022-05-13.

Abstract

Electrochemical production of H2O2 is more benign and affordable than the conventional route, yet its adoption requires the discovery of robust, cost-effective catalysts. DFT-based models lead to conspicuous breakthroughs but had some known limitations, for instance the poor description of molecules with certain chemical bonds. Here, the errors in H2O2 and O-2 displayed by various GGAs, meta-GGAs and hybrids were assessed and semi empirically corrected. The errors in O-2 with respect to experiments were in the range of -0.95 to -0.22 eV, whereas those in H2O2 spanned from -0.53 to -0.04 eV. Thus, single and double O-O bonds were poorly described in general, and the errors were nearly twice as negative for double bonds. Furthermore, these errors introduced large deviations in the predictions of free energies for O-2 reduction to H2O2, and the equilibrium potentials and optimal adsorption energies of *OOH could either be sizably overestimated or underestimated. (AU)

• FAPESP's process: 20/03166-0 - Computational study of modified amorphous carbon structures with metal oxide nanoparticles for hydrogen peroxide electrogeneration
• Grantee: Michell de Oliveira Almeida
• Support Opportunities: Scholarships abroad - Research Internship - Post-doctor
• FAPESP's process: 17/10118-0 - Study and application of electrochemical technology for the analysis and degradation of endocrine interferents: materials, sensors, processes and scientific dissemination
• Grantee: Marcos Roberto de Vasconcelos Lanza
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 14/50945-4 - INCT 2014: National Institute for Alternative Technologies of Detection, Toxicological Evaluation and Removal of Micropollutants and Radioactivies
• Grantee: Maria Valnice Boldrin
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 18/19103-8 - Computational Study of Electrochemical Properties Related to the Degradation of Endocrine Disruptors
• Grantee: Michell de Oliveira Almeida
• Support Opportunities: Scholarships in Brazil - Post-Doctoral
• FAPESP's process: 16/19612-4 - Degradation of endocrine disruptors carbofuran, methylparaben and propylparaben via electrogenerated H2O2 and associated processes (electrogenerated H2O2/UV, electro-Fenton e photoelectro-Fenton)
• Grantee: Paulo Jorge Marques Cordeiro Junior
• Support Opportunities: Scholarships in Brazil - Doctorate (Direct)