Intensifying Electron Utilization by Surface-Anchored Rh Complex for Enhanced Nicotinamide Cofactor Regeneration and Photoenzymatic CO2 Reduction.

Yuqing Cheng,Yiying Sun,Zhongyi Jiang,Ziyi Cai,Yizhou Wu,Yu Chen,Xueying Wang,Jiafu Shi

doi:10.34133/2021/8175709

Abstract

Solar-driven photocatalytic regeneration of cofactors, including reduced nicotinamide adenine dinucleotide (NADH), reduced nicotinamide adenine dinucleotide phosphate (NADPH), and reduced flavin adenine dinucleotide (FADH2), could ensure the sustainable energy supply of enzymatic reactions catalyzed by oxidoreductases for the efficient synthesis of chemicals. However, the elevation of cofactor regeneration efficiency is severely hindered by the inefficient utilization of electrons transferred on the surface of photocatalysts. Inspired by the phenomenon of ferredoxin-NADP+ reductase (FNR) anchoring on thylakoid membrane, herein, a homogeneous catalyst of rhodium (Rh) complex, [Cp∗Rh(bpy)H2O]2+, was anchored on polymeric carbon nitride (PCN) mediated by a tannic acid/polyethyleneimine (TA/PEI) adhesive layer, acquiring PCN@TA/PEI-Rh core@shell photocatalyst. Illuminated by visible light, electrons were excited from the PCN core, then transferred through the TA/PEI shell, and finally captured by the surface-anchored Rh for instant utilization during the regeneration of NADH. The TA/PEI-Rh shell could facilitate the electron transfer from the PCN core and, more importantly, achieved ~1.3-fold elevation of electron utilization efficiency compared with PCN. Accordingly, the PCN@TA/PEI-Rh afforded the NADH regeneration efficiency of 37.8% after 20 min reaction under LED light (405 nm) illumination, over 1.5 times higher than PCN with free Rh. Coupling of the NADH regeneration system with formate dehydrogenase achieved continuous production of formate from carbon dioxide (CO2). Our study may provide a generic and effective strategy to elevate the catalytic efficiency of a photocatalyst through intensifying the electron utilization.

Highlights

In living organisms, enzymes are the “catalytic machine” to trigger biological reactions for ensuring the steady implementation of metabolic processes
The polymeric carbon nitride (PCN)@tannic acid/polyethyleneimine (TA/PEI)-Rh core@shell photocatalyst was prepared by anchoring Rh complex on the PCN core through polyphenol-induced adhesion method for lightdriven NADH regeneration and photoenzymatic CO2 conversion
The PCN core was excited to generate electrons, whereas the surface-anchored Rh on Tannic acid (TA)/PEI nanoshell acted as the electron utilization center toward NADH regeneration

Summary

Introduction

Enzymes are the “catalytic machine” to trigger biological reactions for ensuring the steady implementation of metabolic processes. The features of such “catalytic machine” combined with the reactivity of synthetic chemical catalyst have spawned the field of chemoenzymatic catalysis, which can be categorized into three reaction types, i.e., sequential reactions, concurrent reactions, and cooperative reactions [1]. As a typical cooperative chemoenzymatic catalysis, photoenzymatic catalysis inherits the light harvesting capability of semiconductor photocatalyst and high activity/selectivity of enzyme, which can convert ubiquitous and clean solar energy into chemical energy.

Methods

Results

Conclusion