Boosting the Efficiency and Selectivity of Electrocatalytic Reduction of CO 2 to C1 Products by Mn-Porphyrin via Axial Ligation

作者：Hemjot Kaur, Sanchit Sharma, Neetu Goel · 发表于：The Journal of Physical Chemistry C · 年份：2024 · DOI：10.1021/acs.jpcc.4c04330 · 被引用次数：4 · 研究领域：CO2 Reduction Techniques and Catalysts、Electrocatalysts for Energy Conversion、Carbon dioxide utilization in catalysis

The urgency to address climate change hinges on developing efficient, selective, low-cost, and durable catalysts for effective CO 2 reduction, enabling the conversion of greenhouse gases into valuable resources. This study evaluates the performance of manganese porphyrin (MnPr) and its tailored derivatives that are designed by its axial ligation with imidazole, carbene, and pyridine groups (MnPr-Im, MnPr-NHC, and MnPr-Py) for the electrocatalytic reduction of CO 2 into value-added chemicals. The energetics and mechanism of the CO 2 reduction reaction (CO 2 RR) have been explored using the density functional theory-based computational approach. The goal is to devise strategies that improve the CO 2 RR efficiency while minimizing the competing hydrogen evolution reaction (HER). The primary reduction product is HCOOH, and the minimum overpotential (η HCOOH ) values to lead to this product are 0.22, 0.45, 0.82, and 0.12 V on MnPr, MnPr-Im, MnPr-NHC, and MnPr-Py, respectively. In particular, electrocatalysis by MnPr-Py (η HCOOH = 0.12 V) surpasses the catalytic activity of the state-of-the-art metal surfaces Pt(111) (η = 0.46 V) and Cu(211) (η = 0.77 V). The in-depth analysis of energy profiles, scaling relationships, electrode potentials, and pH provides a rationalization of the excellent reactivity and selectivity of the designed catalysts for the CO 2 RR over the competing HER. The study provides conclusive evidence that axial ligation of MnPr provides a highly efficient electr...