Electrostatically Driven Multielectron Transfer for the Photocatalytic Regeneration of Nicotinamide Cofactor

Abstract

Developing generic strategies that are capable of driving multielectron processes are essential to realize important photocatalytic conversions. Here, we present the idea of introducing favorable catalyst–reactant interaction in achieving efficient photocatalytic regeneration of nicotinamide (NADH) cofactor by gold nanoparticles (AuNPs). The electrostatic attraction emanating from the ligands on the surface of NP increases the channeling and local concentration of NAD+ reactants around AuNP photocatalysts, thereby enhancing the probability of the electron transfer process. Detailed kinetics- and intensity-dependent studies confirm the involvement of multiple electron transfer from the AuNP photocatalyst to the NAD+ reactant. The photocatalytic performances of AuNPs presented here are comparable to or greater than most of the catalytic systems reported based on plasmonic NP, with the added advantage of being structurally less complex. The use of electrostatics mimics the underlying force involved in various enzyme catalysis, which can serve as a generic approach for other important artificial multielectron photocatalytic reactions as well.

Bioinspired NADH Regeneration Based on Conjugated Photocatalytic Systems

“…Furthermore, interactions between photocatalysts and NAD + , such as electrostatic interaction and bridging interaction, provide new directions for engineering the novel photocatalytic NADH regeneration system. Being able to channel the negative charged NAD + onto the material surface, plasmonic gold NPs can promote the funneling of photoexcited carriers and improve the reduction selectivity [13a] …”

“…[ 10 ] For further utilizing the visible part of sun light, various elements (e.g., carbon, boron, phosphorus, and nitrogen) were doped into TiO 2 for visible‐light‐driven NADH regeneration. [ 11 ] In addition, quantum dots, [ 12 ] plasmonic metal nanoparticles (NPs), [ 13 ] and even bio‐nanohybrids [ 14 ] are also attractive candidates for photocatalytic regeneration of NADH due to the beneficial light‐harvesting capability and fair photostability. [ 15 ] Compared with inorganic counterparts, conjugated organic systems are rising rapidly recently in photocatalysis field due to the versatile and modulable photophysical and electronic properties.…”

Comparative life cycle assessment of NAD(P)H regeneration technologies

“…[13][14][15][16] Homogeneous regeneration has been dominated by the use of Rh and Ir complexes, [17][18][19][20] with photochemical regeneration using various TiO 2 -doped and 2-dimensional photocatalysts. [21][22][23][24][25] Heterogeneous regeneration has thus far applied supported Pt catalysts. 26 Whilst almost each regeneration method claims to be sustainable, green or clean (e.g., using solar energy, clean electricity or renewable H 2 ), there has not been any direct evidence or comparisons, regardless of the qualitative or quantitative nature of the analysis.…”

Intensifying Electron Utilization by Surface-Anchored Rh Complex for Enhanced Nicotinamide Cofactor Regeneration and Photoenzymatic CO 2 Reduction

“…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. Till now, the photoenzymatic catalysis has been applied for carbon dioxide (CO 2 ) reduction [ 2 – 4 ], hydrogen/oxygen (H 2 /O 2 ) evolution [ 5 – 7 ], and biomass conversion [ 8 , 9 ]. During the photoenzymatic process, the nicotinamide cofactor is predominantly used as “energy currency” to coordinate photocatalysis and enzyme catalysis.…”