Visible‐Light Driven CO₂ Reduction to Formate with Electron Mediated Nicotinamide‐Modified Viologen in the System of Water‐Soluble Zinc Porphyrin and Formate Dehydrogenase

Abstract

Visible‐light driven CO2 reduction to formate with the system consisting of water‐soluble zinc tetraphneylporphyrin tetrasulfonate (ZnTPPS), formate dehydrogenase from Candida boidinii (CbFDH) and 1‐nicotinamidethy‐1’‐methyl‐4,4’‐ bipyridinium salt (NEMBP) in the presence of triethanolamine (TEOA) as an electron donor was investigated. NEMBP was prepared as the 4,4’‐BP with the nicotinamide‐group to promote the improvement of affinity with CbFDH. The properties of NEMBP were characterized by photochemical and electrochemical methods. In order to evaluate the affinity between cation radical of NEMBP (NEMBP+.), as a co‐enzyme and CbFDH, the energy level based on simple docking simulation and density functional theory were estimated. It was speculated that NEMBP+. could bind near the substrate binding pocket of CbFDH as well as NAD+ by docking simulation. In the visible‐light driven NEMBP reduction with the sensitization of ZnTPPS in the presence of TEOA, the yield for reduction of NEMBP to NEMBP+. was estimated to be 80%. In the CO2 reduction to formate with the system consisting of TEOA, ZnTPPS, NEMBP and CbFDH, the turnover numbers of NEMBP and CbFDH were estimated to be 0.14 and 1.53 h−1, respectively.

Porphyrins and phthalocyanines as biomimetic tools for photocatalytic H2production and CO2reduction

“…46c) and was applied as electron carrier. 220,221 The nicotinamide group was introduced in an effort to enhance the affinity of NEMBP with FDH, since the nicotinamide group is present in the structure of the natural occurring NAD + co-enzyme. However, the NEMBP derivative presented disappointing results in all kinetic parameters for CO 2 to formic acid reduction, most likely due to the unfavorable SOMO energy level.…”

Visible-light driven fumarate synthesis from pyruvate and gaseous CO2 with a hybrid system of photocatalytic NADH regeneration and dual biocatalysts

“…7,[13][14][15] In particular, many studies have reported hybrid systems of formate dehydrogenase (FDH), which catalyzes the reduction of CO 2 to formate in the presence of NADH and photoredox systems. [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] On the other hand, visiblelight driven CO 2 xation to organic molecules has also garnered much attention in the research eld of green chemistry. [7][8][9][10][11][12] For example, CO 2 as a feedstock is bound to an organic molecule as a carboxy-group based on building C-C bonds to produce a carboxylate.…”

Boosting the photocatalytic CO2conversion efficiency of MOFs using a solid electron conveyor

“…[14][15][16] Unfortunately, NAD + promotes the inverse formate oxidation as well since NAD + has an overwhelmingly higher affinity to enzymes compared with NADH. Recently, more cost-effective articial cofactors such as methyl viologen (MV 2+ ) [17][18][19] were developed, which exhibited even higher conversion rates of CO 2 . However, electron transfer by cofactor diffusion still stems from the photocatalytic efficiency.…”