2022
DOI: 10.1021/jacs.2c02972
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Abstract: Bicarbonate-based electrolytes are ubiquitous in aqueous electrochemical CO 2 reduction, particularly in heterogenous catalysis, where they demonstrate improved catalytic performance relative to other buffers. In contrast, the presence of bicarbonate in organic electrolytes and its roles in homogeneous electrocatalysis remain underexplored. Here, we investigate the influence of bicarbonate on iron porphyrin-catalyzed electrochemical CO 2 reduction. We show that bicarbonate is a viable proton donor in organic e… Show more

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Cited by 46 publications
(33 citation statements)
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“…In other words, gaining control over the second coordination sphere could become a particularly important aspect of the photophysics of 3d 8 metal complexes. The influence of the second coordination sphere currently seems to be yet an underappreciated aspect in the design of new photoactive coordination compounds, at least among first-row transition metal complexes. The different extents of excited-state distortions permitted by L1 and L2 due to their different steric demand and the ensuing sizeable differences in 3 MLCT lifetimes in compounds 1 (17 ps) and 2 (48 ps) illustrate the potential of this “axial protection” design strategy. This is particularly true in comparison to 3 (0.5 ps) and many previously investigated square-planar Ni II complexes, in which this effect is absent.…”
Section: Discussionmentioning
confidence: 99%
“…In other words, gaining control over the second coordination sphere could become a particularly important aspect of the photophysics of 3d 8 metal complexes. The influence of the second coordination sphere currently seems to be yet an underappreciated aspect in the design of new photoactive coordination compounds, at least among first-row transition metal complexes. The different extents of excited-state distortions permitted by L1 and L2 due to their different steric demand and the ensuing sizeable differences in 3 MLCT lifetimes in compounds 1 (17 ps) and 2 (48 ps) illustrate the potential of this “axial protection” design strategy. This is particularly true in comparison to 3 (0.5 ps) and many previously investigated square-planar Ni II complexes, in which this effect is absent.…”
Section: Discussionmentioning
confidence: 99%
“…Apart from hydrogen-bonding interactions, proton-rich structures of MOFs or the chemical microenvironment around the active sites can also serve as proton sources (or proton donors) in ECR, which has attracted attention lately. ,, When the functional groups acting as Brønsted acid sites (e.g., hydroxyl and amino groups) are located in the vicinity of the metal sites, the intermediates of CO 2 reduction can receive protons from the adjacent Brønsted acid sites rather than directly from the electrolyte. For instance, we recently compared the performances of three polymer-coated Cu-HITP (a 2D MOF with square-planar CuN 4 nodes and interlayer Cu···Cu distance of 3.4 Å) composites, namely, Cu-HITP@PDA (HITP = 2,3,6,7,10,11-hexaiminotriphenylene; PDA = polydopamine, with rich amino groups and phenolic hydroxyl groups as proton donors), Cu-HITP@PANI (PANI = polyaniline, with only amino groups), and Cu-HITP@Poly­(p-vinylphenol) (with only phenolic hydroxyl groups) featuring different chemical microenvironments around the same catalytic sites .…”
Section: Selectivity Controlmentioning
confidence: 99%
“…Recently, Chang and co-workers reported the design and synthesis of Fe porphyrins with a urea group appended at the ortho-or the para-position of one mesophenyl substituent. [2] The two Fe porphyrins were named as Feortho-urea and Fe-para-urea, respectively (Figure 1d). Under the same conditions, Fe-ortho-urea displayed larger catalytic currents for CO 2 RR than Fe-para-urea.…”
Section: Electrocatalytic Co 2 Reduction With Metal Porphyrinsmentioning
confidence: 99%
“…By studying these functionalized Fe porphyrins as CO 2 RR model electrocatalysts, knowledge of the structure–function relationships has been accumulated, suggesting that the activity can be enhanced with intramolecular proton relays, hydrogen‐bonding groups, and positively charged groups. Particularly, recent works from Chang and co‐workers, [1,2] Aukauloo and co‐workers, [3] Dey and co‐workers, [4] and Hod and co‐workers [5] have contributed significantly to illustrating the effects of catalyst substituents on CO 2 RR activity and selectivity and, importantly, to recognizing the underlying mechanisms in CO 2 binding and activation.…”
Section: Electrocatalytic Co2 Reduction With Metal Porphyrinsmentioning
confidence: 99%
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