Copper oxide-based cathode for direct NADPH regeneration

Kadowaki, J T; Jones, Tappey H.; Sengupta, Abhishek; Gopalan, Venkat; Subramaniam, V. V.

doi:10.1038/s41598-020-79761-6

Cited by 13 publications

(5 citation statements)

References 41 publications

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“…In each enzymatic step, one mole of NADH is oxidized to NAD + that must be converted back to NADH. This regeneration can be performed in a photoelectrochemical or photocatalytic way, in a simple system or with an electron mediators such as a ruthenium complex [ 273 , 274 ].…”

Section: Application Of Copper Oxide-based Materials In Photocatalysis and Photoelectrocatalysismentioning

confidence: 99%

Copper Oxide-Based Photocatalysts and Photocathodes: Fundamentals and Recent Advances

Baran¹,

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Busch

et al. 2021

Molecules

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This work aims at reviewing the most impactful results obtained on the development of Cu-based photocathodes. The need of a sustainable exploitation of renewable energy sources and the parallel request of reducing pollutant emissions in airborne streams and in waters call for new technologies based on the use of efficient, abundant, low-toxicity and low-cost materials. Photoelectrochemical devices that adopts abundant element-based photoelectrodes might respond to these requests being an enabling technology for the direct use of sunlight to the production of energy fuels form water electrolysis (H2) and CO2 reduction (to alcohols, light hydrocarbons), as well as for the degradation of pollutants. This review analyses the physical chemical properties of Cu2O (and CuO) and the possible strategies to tune them (doping, lattice strain). Combining Cu with other elements in multinary oxides or in composite photoelectrodes is also discussed in detail. Finally, a short overview on the possible applications of these materials is presented.

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Section: Application Of Copper Oxide-based Materials In Photocatalysis and Photoelectrocatalysismentioning

confidence: 99%

Copper Oxide-Based Photocatalysts and Photocathodes: Fundamentals and Recent Advances

Baran¹,

Visibile

Busch

et al. 2021

Molecules

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“…After termination of the reaction (Figure S27), the characteristic peaks of NADPH decreased or disappeared, which could be attributed to the specific regeneration of active 1,4-NADPH by Rh-COF Bpy + HCOF and Rh-COF Bpy @HCOF 25 in the presence of M. In the absence of M, COF Bpy @HCOF 25 partially photocatalyzes the formation of inactive isomers like 1,2-NADPH, 1,6-NADPH, and (NADP) 2 . 58…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Hollow Rh-COF@COF S-Scheme Heterojunction for Photocatalytic Nicotinamide Cofactor Regeneration

et al. 2023

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Photocatalytic regeneration of a nicotinamide cofactor, nicotinamide adenine dinucleotide phosphate (NADPH), has emerged as an ideal cascade partner for combination with enzymatic transformations, but it still suffers from low efficiency due to the recombination of photogenerated charge carriers. Herein, a hierarchical Rh-covalent organic framework (COF)@COF core–shell hollow sphere (CSHS) with S-scheme heterojunction is proposed to enhance the charge carrier transfer and utilization in photocatalysis to regenerate the expensive NADPH. The hierarchical Rh-COFBpy@ hollow spherical COF (HCOF) CSHS was prepared by simple sequential in situ growth. The turnover frequency of Rh-COFBpy@HCOF25 for NADPH regeneration reached 2.6 mmol·gRh‑COF –1·h–1, which was 3.7 times that of pure Rh-COFBpy under visible light. Density functional theory calculation and X-ray photoelectron spectroscopy analysis showed that an internal electric field directed from Rh-COFBpy to HCOF was formed in Rh-COFBpy@HCOF CSHS, which accelerated the photogenerated electron transfer from HCOF to Rh-COFBpy. In situ irradiated XPS analyses and photoirradiated Kelvin probe measurement revealed the S-scheme charge-transfer mechanism within Rh-COFBpy@HCOF. The Rh-COFBpy@HCOF photocatalytic NADPH regeneration system was further coupled with enzymatic reduction of CC, achieving a photoenzyme cascade reaction. This work provides a protocol for the design and utilization of COF-based artificial photosynthetic systems.

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“…3 ) and ESI-MS (Supplementary Fig. 4 ) 32 , 33 . The higher rate and greater yield observed with the Pt-coated catalyst is consistent with previous studies identifying Pt as a highly active 1,4-NADH regeneration catalyst 34 .…”

Section: Resultsmentioning

confidence: 99%

Bioelectrocatalysis with a palladium membrane reactor

et al. 2023

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Enzyme catalysis is used to generate approximately 50,000 tons of value-added chemical products per year. Nearly a quarter of this production requires a stoichiometric cofactor such as NAD+/NADH. Given that NADH is expensive, it would be beneficial to regenerate it in a way that does not interfere with the enzymatic reaction. Water electrolysis could provide the proton and electron equivalent necessary to electrocatalytically convert NAD+ to NADH. However, this form of electrocatalytic NADH regeneration is challenged by the formation of inactive NAD2 dimers, the use of high overpotentials or mediators, and the long-term electrochemical instability of the enzyme during electrolysis. Here, we show a means of overcoming these challenges by using a bioelectrocatalytic palladium membrane reactor for electrochemical NADH regeneration from NAD+. This achievement is possible because the membrane reactor regenerates NADH through reaction of hydride with NAD+ in a compartment separated from the electrolysis compartment by a hydrogen-permselective Pd membrane. This separation of the enzymatic and electrolytic processes bypasses radical-induced NAD+ degradation and enables the operator to optimize conditions for the enzymatic reaction independent of the water electrolysis. This architecture, which mechanistic studies reveal utilizes hydride sourced from water, provides an opportunity for enzyme catalysis to be driven by clean electricity where the major waste product is oxygen gas.

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Copper oxide-based cathode for direct NADPH regeneration

Cited by 13 publications

References 41 publications

Copper Oxide-Based Photocatalysts and Photocathodes: Fundamentals and Recent Advances

Copper Oxide-Based Photocatalysts and Photocathodes: Fundamentals and Recent Advances

Hollow Rh-COF@COF S-Scheme Heterojunction for Photocatalytic Nicotinamide Cofactor Regeneration

Bioelectrocatalysis with a palladium membrane reactor

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