Mn-based COF for electrochemical CO2 reduction to CO and formate

Changwei Liu^a, Geyla caridad dubed bandomo^a, Julio lloret-fillol^a^,^b

^aInstitute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Tarragona 43007, Spain

^bCatalan Institution for Research and Advanced Studies (ICREA), Passeig Lluïs Companys, 23, 08010, Barcelona, Spain

Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS23 & Sustainable Technology Forum València (STECH23) (MATSUS23)

#e-FuelSyn - Electrocatalysis for the Production of Fuels and Chemicals

VALÈNCIA, Spain, 2023 March 6th - 10th

Organizers: Carla Casadevall Serrano and Julio Lloret Fillol

Poster, Changwei Liu, 306
Publication date: 22nd December 2022

Excessive consumption of fossil fuels causes severe environmental problems and diminishing fossil fuels poses a threat to energy reservation. Therefore, newer techniques to use clean energy are urgent, and converting waste formed by consuming fossil fuels, mainly CO₂ into useful chemicals is in high demand. In this work, Mn^Itricarbonyl-based 2D covalent organic framework (COF_bpyMn) is employed as a mechanically constrained heterogeneous electrocatalyst deposited on carbon paper for the reduction of CO₂ in water. It is shown that the product selectivity can be shifted to CO and HCOOH using appropriate additives in the water. We observed HCOOH formation at a Faradic efficiency (FE) of 95% at a current density of 8 mA/cm² in an H-cell and FE of 90% at a current density of 25 mA/cm² in a flow cell in 1 M NaHCO₃containing pentamethyldiethylentriamine (PMDETA). Interestingly, when we swapped PMDETA with 2-tert-butyltetramethylguanidine (TBG), the product selectivity shifts to CO with FE of 98% at a current density of 2 mA/cm²in a H/cell. Furthermore, we systematically explored the mechanistic pathway through spectro-electrochemical studies.

References:

[1] Geyla C. Dubed Bandomo, Suvendu Sekhar Mondal, Federico Franco, Alberto Bucci, Vlad Martin-Diaconescu, Manuel A. Ortuño, Phebe H. van Langevelde, Alexandr Shafir, Núria López, and Julio Lloret-Fillol*. Mechanically Constrained Catalytic Mn(CO)3Br Single Sites in a Two-Dimensional Covalent Organic Framework for CO2 Electroreduction in H2O. ACS Catal. 2021, 11, 12, 7210–7222

[2] Monica R. Madsen Monica R. Madsen Carbon Dioxide Activation Center (CADIAC), Interdisciplinary Nanoscience Center, Department of Chemistry, Aarhus University, Gustav Wieds Vej 14, 8000 Aarhus C, Denmark More by Monica R. Madsen , Magnus H. Rønne, Marvin Heuschen, Dusanka Golo, Mårten S. G. Ahlquist, Troels Skrydstrup, Steen U. Pedersen, and Kim Daasbjerg*. Promoting Selective Generation of Formic Acid from CO2 Using Mn(bpy)(CO)3Br as Electrocatalyst and Triethylamine/Isopropanol as Additives. J. Am. Chem. Soc. 2021, 143, 48, 20491–20500

[3] Francesca Marocco Stuardi,Arianna Tiozzo, Laura Rotundo, Julien Leclaire,Roberto Gobetto, and Carlo Nervi. Efficient Electrochemical Reduction of CO2 to Formate in Methanol Solutions by Mn-Functionalized Electrodes in the Presence of Amines*. Chem. Eur. J. 2022, 28

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