Surface-Immobilized Rhodium Complex in Vertically Aligned Mesoporous Silica Films for Direct Electroreduction of Diluted CO 2
Abstract
Performing direct CO2 reduction reaction (CO2RR) from flue gas streams containing low-concentrated CO2 (4 – 25% v/v) represents an opportunity to obtain added value products while reducing anthropogenic emissions. The heterogenization of molecular complexes offers a pathway to scale up CO2RR systems, especially under CO2 diluted conditions where reactant is mass transport limited and competitive hydrogen evolution reaction (HER) might be boosted. In this work, a formate-selective rhodium complex ([Rh(bpy’)(Cp*)Cl]Cl, where bpy’ = 4-(2-propyn-1-yloxymethyl)-4’-methyl-2,2’-bipyridine and Cp* = pentamethylcyclopentadienyl, is immobilized at high loading within tridimensional (3D) vertically-aligned mesoporous silica films (VAMSF) electrochemically grown on glassy carbon electrodes. The resulting modified 3D-electrodes allow direct CO2RR under both pure and diluted (10% v/v) CO2 streams remaining selective for formate production in both organic and aqueous media and minimizing the contribution of HER from the support. In acetonitrile/1%H2O, faradaic efficiencies (FE) for formate production of 66% in 100% CO2 and 47% in 10% CO2 were achieved, while in KHCO3 (pH= 6.8), FE of 47% and 43% were reached under pure and diluted CO2 streams, respectively. Finally, in a more acidic aqueous solution (pH= 3.8) FE of 59% was achieved under pure CO2. The electrodes work without pre-activation or auxiliary overlayers, and show recyclability and stability over multiple electrolysis cycles, indicating no structural degradation under operation conditions. To our knowledge, this is the first formate-selective heterogenized molecular complex, tested under a diluted CO2 gas stream. These results point VAMSF as an attractive platform to bring molecular CO2RR catalysis closer to realistic applications.
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BibTeX
@article{seguraramirez2026surfaceimmobilized,
title = {{Surface-Immobilized Rhodium Complex in Vertically Aligned Mesoporous Silica Films for Direct Electroreduction of Diluted CO 2}},
author = {Yutzil Segura-Ramirez and Neus Vilà and Alain Walcarius and Marc Fontecave and Carlos Sánchez-Sánchez and Maria Gómez-Mingot},
journal = {Journal of the American Chemical Society},
year = {2026},
month = jun,
doi = {10.1021/jacs.5c22009},
url = {https://hal.science/hal-05762344v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Surface-Immobilized Rhodium Complex in Vertically Aligned Mesoporous Silica Films for Direct Electroreduction of Diluted CO 2
AU - Yutzil Segura-Ramirez
AU - Neus Vilà
AU - Alain Walcarius
AU - Marc Fontecave
AU - Carlos Sánchez-Sánchez
AU - Maria Gómez-Mingot
PY - 2026
DA - 2026/06/22
JO - Journal of the American Chemical Society
DO - 10.1021/jacs.5c22009
UR - https://hal.science/hal-05762344v1
AB - Performing direct CO2 reduction reaction (CO2RR) from flue gas streams containing low-concentrated CO2 (4 – 25% v/v) represents an opportunity to obtain added value products while reducing anthropogenic emissions. The heterogenization of molecular complexes offers a pathway to scale up CO2RR systems, especially under CO2 diluted conditions where reactant is mass transport limited and competitive hydrogen evolution reaction (HER) might be boosted. In this work, a formate-selective rhodium complex ([Rh(bpy’)(Cp*)Cl]Cl, where bpy’ = 4-(2-propyn-1-yloxymethyl)-4’-methyl-2,2’-bipyridine and Cp* = pentamethylcyclopentadienyl, is immobilized at high loading within tridimensional (3D) vertically-aligned mesoporous silica films (VAMSF) electrochemically grown on glassy carbon electrodes. The resulting modified 3D-electrodes allow direct CO2RR under both pure and diluted (10% v/v) CO2 streams remaining selective for formate production in both organic and aqueous media and minimizing the contribution of HER from the support. In acetonitrile/1%H2O, faradaic efficiencies (FE) for formate production of 66% in 100% CO2 and 47% in 10% CO2 were achieved, while in KHCO3 (pH= 6.8), FE of 47% and 43% were reached under pure and diluted CO2 streams, respectively. Finally, in a more acidic aqueous solution (pH= 3.8) FE of 59% was achieved under pure CO2. The electrodes work without pre-activation or auxiliary overlayers, and show recyclability and stability over multiple electrolysis cycles, indicating no structural degradation under operation conditions. To our knowledge, this is the first formate-selective heterogenized molecular complex, tested under a diluted CO2 gas stream. These results point VAMSF as an attractive platform to bring molecular CO2RR catalysis closer to realistic applications.
SN - 0002-7863
SN - 1520-5126
ER -