Understanding the Interplay of the Brønsted Acidity of Catalyst Ancillary Groups and the Solution Components in Iron-porphyrin-Mediated Carbon Dioxide Reduction.

The rapid and efficient conversion of carbon dioxide (CO2) to carbon monoxide (CO) is an ongoing challenge. Catalysts based on iron-porphyrin cores have emerged as excellent electrochemical mediators of the two proton + two electron reduction of CO2 to CO, and many of the design features that promote function are known. Of those design features, the incorporation of Brønsted acids in the second coordination sphere of the iron ion has a significant impact on catalyst turnover kinetics. The Brønsted acids are often in the form of hydroxyphenyl groups. Herein, we explore how the acidity of an ancillary 2-hydroxyphenyl group affects the performance of CO2 reduction electrocatalysts. A series of meso-5,10,15,20-tetraaryl porphyrins were prepared where only the functional group at the 5-meso position has an ionizable proton. A series of cyclic voltammetry (CV) experiments reveal that the complex with -OMe positioned para to the ionizable -OH shows the largest CO2 reduction rate constants in acetonitrile solvent. This is the least acidic -OH of the compounds surveyed. The turnover frequency of the -OMe derivative can be further improved with the addition of 4-trifluoromethylphenol to the solution. In contrast, the iron-porphyrin complex with -CF3 positioned opposite the ionizable -OH shows the smallest CO2 reduction rate constants, and its turnover frequency is less enhanced with the addition of phenols to the reaction solutions. The origin of this effect is rationalized based on kinetic isotope effect experiments and density functional calculations. We conclude that catalysts with weaker internal acids coupled with stronger external acid additives provide superior CO2 reduction kinetics.

Further Understanding the Roles of Solvent, Brønsted Acids, and Hydrogen Bonding in Iron Porphyrin-Mediated Carbon Dioxide Reduction.

Improving our understanding of how molecules and materials mediate the electrochemical reduction of carbon dioxide (CO2) to upgraded products is of great interest as a means to address climate change. A leading class of molecules that can facilitate the electrochemical conversion of CO2 to carbon monoxide (CO) is iron porphyrins. These molecules can have high rate constants for CO2-to-CO conversion; they are robust, and they rely on abundant and inexpensive synthetic building blocks. Important foundational work has been conducted using chloroiron 5,10,15,20-tetraphenylporphyrin (FeTPPCl) in N,N-dimethylformamide (DMF) solvent. A related and recent report points out that the corresponding perchlorate complex, FeTPPClO4, can have superior function due to its solubility in other organic solvents. However, the importance of hydrogen bonding and solvent effects was not discussed. Herein, we present a detailed kinetic study of the triflate (CF3SO3-) complex of FeTPP in DMF and in MeCN using a range of phenol Brønsted acid additives. We also detected the formation of Fe(III)TPP-phenolate complexes using cyclic voltammetry experiments. Importantly, our new analysis of apparent rate constants with different added phenols allows for a modification to the established mechanistic model for CO2-to-CO conversion. Critically, our improved model accounts for hydrogen bonding and solvent effects by using simple hydrogen bond acidity and basicity descriptors. We use this augmented model to rationalize function in other reported porphyrin systems and to make predictions about operational conditions that can enhance the CO2 reduction chemistry.

Arrays of Microscale Linear Ridges with Self-Cleaning Functionality for the Oxygen Evolution Reaction.

Gas management during electrocatalytic water splitting is vital for improving the efficiency of clean hydrogen production. The accumulation of gas bubbles on electrode surfaces prevents electrolyte access and passivates the electrochemically active surface area. Electrode morphologies are sought to assist in the removal of gas from surfaces to achieve higher reaction rates at operational voltages. Herein, regular arrays of linear ridges with specific microscale separations were systematically studied and correlated to the performance of the oxygen evolution reaction (OER). The dimensions of the linear ridges were proportional to the size of the oxygen bubbles, and the mass transfer processes associated with gas evolution at these ridges were monitored using a high-speed camera. Characterization of the adhered bubbles prior to detachment enabled the use of empirical methods to determine the volumetric flux of product gas and the bubble residence times. The linear ridges promoted a self-cleaning effect as one bubble would induce neighboring bubbles to simultaneously release from the electrode surfaces. The linear ridges also provided preferential bubble growth sites, which expedited the detachment of bubbles with similar diameters and shorter residence times. The linear ridges enhanced the OER in comparison to planar electrodes prepared by electrodeposition from the same high-purity nickel (Ni). Linear ridges with a separation distance of 200 µm achieved nearly a 2-fold increase in current density relative to the planar electrode at an operating voltage of 1.8 V (vs Hg/HgO). The electrodes with linear ridges having a separation distance of 200 µm also had the highest sustained current densities over a range of operating conditions for the OER. Self-cleaning surface morphologies could benefit a variety of electrocatalytic gas evolving reactions by improving the efficiency of these processes.

Heterogeneous aqueous CO2 reduction by rhenium(i) tricarbonyl diimine complexes with a non-chelating pendant pyridyl group.

Electrocatalytic CO2 reduction in water using a series of chlorotricarbonylrhenium(i) diimine complexes deposited on pyrolytic graphite electrodes is described. Two known CO2 reduction catalysts (with diimine = 4,4'-di-tert-butyl-2,2'-bipyridine or 2-(2'-quinolyl)benzimidazole), that are highly active in organic solvent, proved to be only weakly active in water. In contrast, Cl(CO)3Re(L) complexes with tridentate nitrogen-containing ligands (L = 4,4',4''-tri-tert-butyl-2,2':6',2''-terpyridine or 2,6-bis(2-benzimidazolyl)pyridine) were better CO2 reduction catalysts. In those Cl(CO)3Re(L) complexes, only two N-atoms of the ligand are coordinated to the rhenium, leaving the third arm of the ligands to support activated, CO2-bound intermediates. The 2,6-bis(2-pyridyl)pyridine (terpy) complex was the most active, with substantial activity at alkaline pH.

Heterogeneous Aqueous CO2 Reduction Using a Pyrene-Modified Rhenium(I) Diimine Complex.

The development of molecular catalysts and materials that can convert carbon dioxide (CO2) into a value-added product is a great chemical challenge. Molecular catalysts set benchmarks in catalyst investigation and design, but their incorporation into solid-state materials, and optimization of the electrochemical operating conditions, is still needed. For example, rhenium(I) diimine catalysts show almost quantitative selectivity for the conversion of CO2 to carbon monoxide (CO) in acetonitrile (MeCN), but the modification of diimine backbones can be challenging if the goal is to incorporate such molecules into materials. Presented here is a rhenium(I) complex with a 2-(2'-quinolyl)benzimidazole (QuBIm-H) ligand, where N-alkylation with a pyrene derivative allows access to a catalyst that can be adsorbed onto electrodes for aqueous CO2 reduction chemistry. The rhenium(I) catalysts are inactive for homogeneous CO2 reduction in MeCN. However, when adsorbed on edge-plane graphite, the same complexes show good activity for heterogeneous aqueous CO2 reduction, with 90% selectivity for CO. Comparative electrochemical studies between covalent and noncovalent modification of the graphite surfaces were also carried out for related rhenium(I) tricarbonyl complexes.