Fine-Tuning the Electrocatalytic Regeneration of NADH Cofactor Using [Rh(Cp*)(bpy)Cl]<sup>+</sup>-Functionalized Metal–Organic Framework Films
Weiwei Li, Chunhua Zhang, Ziman Zheng, Xiaoyu Zhang, Lin Zhang, Alexander Kuhn
Abstract
Electrochemical regeneration of the reduced form of the nicotinamide adenine dinucleotide (NADH) cofactor catalyzed by immobilized [Rh(Cp*)(bpy)Cl]+ is a promising approach for the enzymatic synthesis of many valuable chemicals with NAD-dependent dehydrogenases. However, rational control of the efficiency is often limited by the irregular structure of the electrode/electrolyte interface and the accessibility of the molecular catalyst. Here, we propose an electrochemical system for NADH cofactor regeneration, based on highly ordered three- dimensional (3D) metal–organic framework (NU-1000) films. [Rh(Cp*)(bpy)Cl]+ is incorporated at the zirconium nodes of NU-1000 via solvent-assisted ligand incorporation (SALI), leading to a diffusion-controlled behavior, associated with an electron hopping mechanism. Varying the ratio of redox-active [Rh(Cp*)(bpy)Cl]+ and inactive postgrafting agents enables the elaboration of functional electrodes with tunable electrocatalytic activity for NADH regeneration. The exceptionally high faradic efficiency of 97%, associated with a very high turnover frequency (TOF) of ∼1400 h–1 for NADH regeneration, and the total turnover number (TTN) of over 20000 for the enzymatic conversion from pyruvate to l-lactate, when coupled with l-lactate dehydrogenases (LDH) as a model reaction, open up promising perspectives for employing these electrodes in various alternative bioelectrosynthesis approaches.