Photocatalytic Carbon Dioxide Reduction Using Nickel Complexes as Catalysts

Abstract

Nickel complexes have been investigated as catalysts in visiblelight-driven photocatalytic CO 2 reduction for a long time. In this minireview, discrete molecular Ni catalysts are described to shed light on the utility in the reaction in relevance to metalloenzymes for CO 2 fixation. In contrast to the cases of Ru catalysts, Ni catalysts for the CO 2 reduction should be of importance due to high selectivity in CO formation.

Photo‐Mediated Reduction of Carbon Dioxide to Formic and Other Carboxylic Acids by Ni‐Catalysis with Chelating Ligand

“…and visible light as energy source with earth abundant transition metal Ni paved the way for flourishing sustainable chemistry. The most abundant feature of photosensitized Ni‐catalyzed CO 2 reduction reactions is the selective production of CO [9b] . But performance of Ni catalysis to produce other two‐electron‐reduced product of CO 2 such as formic acid or carboxylate is also impressive.…”

Homogeneous Systems Containing Earth‐Abundant Metal Complexes for Photoactivated CO2 Reduction: Recent Advances

“…À 0.81 [f] 0.77 [f] [78] Ru(phen) 3 (PF 6 ) 2 610 1.26 [f] À 1.36 [f] À 0.87 [f] 0.82 [f] [78] fac-Ir(ppy) 3 494 0.77 [f] À 2.19 [f] À 1.73 [f] 0.31 [f] [78] Ir(dFppy) 3 476 0.94 [f] À 1.87 [f] À 1.28 [f] 0.36 catalysts used in photocatalytic CO 2 reduction have been reviewed, focusing on their reactivity and selectivity. [19] In general, homogeneous molecular catalysts based on 3dtransition metals can convert CO 2 to two-electrons reduction products, CO and HCO 2 (H). Rarely methane or methanol have been observed in photoactivated CO 2 -reduction by means of these molecular catalysts.…”

“…As well, the first CO 2 reduction catalyst that presented outstanding efficiency in terms of turnover number (TON) and frequency (TOF) was also a Ni(II)‐based N‐heterocyclic‐carbene complex [18] . Recently, discrete molecular nickel catalysts used in photocatalytic CO 2 reduction have been reviewed, focusing on their reactivity and selectivity [19] . In general, homogeneous molecular catalysts based on 3d‐transition metals can convert CO 2 to two‐electrons reduction products, CO and HCO 2 (H).…”

N-Heterocyclic Carbene Gold Complexes in a Photocatalytic CO2 Reduction Reaction

“…GC samples were prepared by taking headspace samples (300 μL) using a VICI gas-tight syringe, compressing the sealed sample to 250 μL, then submerging the tip of the sealed gas tight syringe in diethyl ether, opening and closing the valve to adjust the pressure in the syringe to atmospheric pressure, and injecting the sample into the GC instrument (see Figure S10 for a representative GC trace). Formate analysis was conducted as previously described by 1 H NMR spectroscopy (see Figure S11 for a representative formate analysis 1 H NMR trace). 40 Formate analysis was only performed at the end of the photocatalytic reaction as it requires significant reaction volume.…”