Spatial Organization of Photocatalysts and Enzymes on Janus-Type DNA Nanosheets for Efficient CO₂ Conversion

Abstract

Bioinspired photosynthetic systems composed of photocatalysts and enzymes are a notable framework for converting CO2 to high-value chemicals. However, catalyst/enzyme deactivation and poor electron transfer kinetics in multistep photochemical processes severely limit their catalytic efficiencies. In this study, Janus-type DNA nanosheets (NSs) presenting two different DNA sequences on each face were utilized as a support for the selective immobilization of a Rh complex and formate dehydrogenase (FDH) for concerted catalytic reactions for CO2 reduction. Based on the face selectivity, DNA-conjugated Rh complex and FDH were immobilized on NSs into four different configurations: Rh complex on NS (NS1), FDH on NS (NS2), Rh complex and FDH on opposite faces of NS (NS3), FDH and Rh complex on the same face of NS (NS4). The catalytic system exhibited CO2 conversion efficiencies highly dependent on the spatial organization of Rh complex and FDH, showing the reactivity for the formate production in the order of NS1 coupled with free FDH > NS3 > NS2 coupled with free Rh complex > NS4 > free Rh complex and FDH. The NS1 coupled with free FDH showed turnover number (TON) of 1360 for the formate production based on NAD+, which is the highest value reported thus far for Rh-based photocatalyst/enzyme coupled systems. The results demonstrate that the compartmentalization of photocatalysts and biological enzymes is a viable approach for improving the efficiency of CO2 conversion and provide important design rules for building efficient artificial photosynthetic systems.

Photothermal-coupled solar photocatalytic CO2reduction with high efficiency and selectivity on a MoO3−x@ZnIn2S4core–shell S-scheme heterojunction

“…1,2 So far, the prevalent CO 2 reduction methods include photocatalysis, 3 electrochemical reduction, 4 and biological immobilization. 5 Among them, photocatalysis has attracted much attention as a sustainable, green and cost-effective technique. It has been widely applied in various catalytic reactions such as CO 2 conversion, 6 pollutant degradation, 7 water splitting, 8 and nitrogen fixation.…”

Redox Biocatalysis: Quantitative Comparisons of Nicotinamide Cofactor Regeneration Methods

“…In fact, FDH‐catalyzed CO 2 reduction has been a significant target application in the area of biomimetic CO 2 remediation by harvesting solar energy using photoenzymatic systems [225] . One of the most impressive recent works in this regard has been reported by Fard et al., where the authors demonstrated photoenzymatic CO 2 reduction to formate using TEOA as the reductant [226] . The most ingenious aspect of this study was the spatial compartmentalization of immobilized FDH and an Rh complex on Janus type DNA nanosheet, which had two different DNA sequences on each side, enabling face‐selective immobilization of the FDH and the Rh catalyst to avoid mutual inactivation.…”

“…[225] One of the most impressive recent works in this regard has been reported by Fard et al, where the authors demonstrated photoenzymatic CO 2 reduction to formate using TEOA as the reductant. [226] The most ingenious aspect of this study was the spatial compartmentalization of immobilized FDH and an Rh complex on Janus type DNA nanosheet, which had two different DNA sequences on each side, enabling face-selective immobilization of the FDH and the Rh catalyst to avoid mutual inactivation. Based on the amount of formate produced, the TN cofactor reported was 1360, which, to the best of our knowledge, is the highest among photoenzymatic cofactor regeneration studies to date.…”

A Novel Non‐Fullerene D‐A Interface with Two Asymmetrical Electron Acceptors Facilitates Charge and Energy Transfer for Effective Carbon Dioxide Reduction

“…[3] Currently, the commonly employed CO 2 reduction methods encompass photocatalytic reduction process, electrochemical reduction, and biological immobilization. [4][5][6] Photocatalytic technology, inspired by plant photosynthesis, utilizes light to convert CO 2 into hydrocarbon fuels. This approach holds several advantages including environmental friendliness, mild reaction conditions, and low cost.…”