Density functional theory and 3D-RISM-KH molecular theory of solvation studies of CO 2 reduction on Cu-, Cu 2 O-, Fe-, a
- PDF / 2,798,572 Bytes
- 10 Pages / 595.276 x 790.866 pts Page_size
- 81 Downloads / 137 Views
ORIGINAL PAPER
Density functional theory and 3D-RISM-KH molecular theory of solvation studies of CO2 reduction on Cu-, Cu2O-, Fe-, and Fe3O4-based nanocatalysts Andriy Kovalenko 1,2
&
Vladimir Neburchilov 3
Received: 20 May 2020 / Accepted: 31 August 2020 # Crown 2020
Abstract Using OpenMX quantum chemistry software for self-consistent field calculations of electronic structure with geometry optimization and 3D-RISM-KH molecular theory of solvation for 3D site distribution functions and solvation free energy, we modeled the reduction of CO2+H2 in ambient aqueous electrolyte solution of 1.0-M KH2PO4 into (i) formic acid HCOOH and (ii) CO H2O on the surfaces of Cu-, Fe-, Cu2O-, and Fe3O4-based nanocatalysts. It is applicable to its further reduction to hydrocarbons. The optimized geometries and free energies were obtained for the pathways of adsorption of the reactants from the solution, successive reduction on the surfaces of the nanocatalysts, and then release back to the solution bulk. Keywords CO2 reduction to HCOOH, CO . Cu, Cu2O, Fe, Fe3O4 nanocatalysts . KH2PO4 ambient aqueous solution . OpenMX quantum chemistry . 3D-RISM-KH molecular theory of solvation
Introduction Electrochemical reduction of CO2 (ECRCO2) to hydrocarbon fuels and chemicals is one of the promising clean technologies. However, this new generation technology has one critical technical gap in terms of the insufficient stability and selectivity of the existing electrodes [1–3]. The main challenge in the development of efficient catalysts for ECRCO2 is the significant list of factors effecting on their performance, including morphology, temperature, pressure, pH, type and concentration of electrolytes, type of solvent and membranes, electrolyte flow, and type of electrode (flat, porous, gas
* Andriy Kovalenko [email protected]; [email protected] 1
Nanotechnology Research Centre, National Research Council of Canada, 11421 Saskatchewan Drive, Edmonton, Alberta T6G 2M9, Canada
2
Department of Mechanical Engineering, University of Alberta, 10-203 Donadeo Innovation Centre for Engineering, 9211-116 Str., Edmonton, Alberta T6G 1H9, Canada
3
Institute for Fuel Cell Innovation, Energy, Mining & Environment, National Research Council of Canada, 4250 Wesbrook Mall, Vancouver, British Columbia V6T 1W5, Canada
diffusion) [3]. By today, only the two most efficient processes of ECRCO2 to carbon monoxide (CO) and formic acid (FA) with a Faradaic efficiency (FA) of more than 90% at current density > 100 mA/cm2 were developed [4]. The most developed catalysts for ECRCO2 to formic acid are Cu- and Cu2Obased catalysts. The first copper catalysts for ECRCO2 to methane and ethylene were developed by Hori, demonstrating beneficial performance in terms of the higher Faradaic efficiency compared with other catalysts [5]. Formic acid is another product of ECRCO2 on Cu coming out through the formation of the intermediate formate [6]. This mechanism differs from the mechanism of ECRCO2 to hydrocarbon fuels through the formation of the
Data Loading...
