CO2 Electroreduction on Carbon-Based Electrodes Functionalized with Molecular Organometallic Complexes—A Mini Review

Heterogeneous electrochemical CO2 reduction has potential advantages with respect to the homogeneous counterpart due to the easier recovery of products and catalysts, the relatively small amounts of catalyst necessary for efficient electrolysis, the longer lifetime of the catalysts, and the elimination of solubility problems. Unfortunately, several disadvantages are also present, including the difficulty of designing the optimized and best-performing catalysts by the appropriate choice of the ligands as well as a larger heterogeneity in the nature of the catalytic site that introduces differences in the mechanistic pathway and in electrogenerated products. The advantages of homogeneous and heterogeneous systems can be preserved by anchoring intact organometallic molecules on the electrode surface with the aim of increasing the dispersion of active components at a molecular level and facilitating the electron transfer to the electrocatalyst. Electrode functionalization can be obtained by non-covalent or covalent interactions and by direct electropolymerization on the electrode surface. A critical overview covering the very recent literature on CO2 electroreduction by intact organometallic complexes attached to the electrode is summarized herein, and particular attention is given to their catalytic performances. We hope this mini review can provide new insights into the development of more efficient CO2 electrocatalysts for real-life applications

Synthesis and Electrochemical Studies of Rhenium(I) and Molybdenum(0) Complexes as Electrocatalysts for Reduction of Carbon Dioxide

The photochemical and electrochemical conversion of CO2 to higher-energy products has been a focus of research as a path to renewable fuels. This thermodynamically unfavorable process can be improved by employing transition-metal coordination compounds which, in the form of molecular or supramolecular organometallic catalysts, are capable of mediating CO2 reduction. Among them, we focused on Rhenium and Molybdenum. However, whereas a wide number of Rhenium(I) carbonyl-diimine complexes showed to be photo/redox active, and has already been successfully tested for the electrocatalytic CO2 reduction, to our knowledge, there are no reports about the use of tetracarbonyl polypyridyl molybdenum(0) complexes as electrocatalysts for the reduction of CO2. In this perspective, some [Mo(CO)4(L)] (L= 2,2’-bipyridine (bpy); 1,10-phenantroline (phen) and similar derivatives) were synthesized and tested for electrochemical reduction of carbon dioxide. Moreover, a series of novel Re(I)-carbonyl diimine complexes has been synthesized and tested for the same purpose. The latter class of compounds is characterized by new polypyridyl ligands, derived from PNI-phen (N-(1,10-phenantroline)-4-(1-piperidinyl)naphthalene-1,8-dicarboximide), which revealed to be able to provide a 3000-fold excited state lifetime enhancement in a Re(I) charge-transfer complex [1]. The electrochemical behavior of both the classes of compounds was compared with the activity of Re(CO)3Cl(bipy) [2]. Quite surprisingly, CV measurements (in MeCN and acetone), performed under both inert and CO2 atmosphere at room temperature, revealed that [Mo(CO)4(2,2’-bipyridyl)] shows redox activity as electrocatalyst for CO2 reduction, although the overpotential at which the process occurs is rather negative (about -1.9 V vs SCE). The catalytic activity was also confirmed by controlled-potential electrolysis at -1.80 V, coupled with gas chromatography (GC)