Development of an Ionic Porphyrin-Based Platform as a Biomimetic Light-Harvesting Agent for High-Performance Photoenzymatic Synthesis of Methanol from CO₂

Abstract

NADH is a required cofactor for enzymatic hydrogenation of CO 2 to methanol, but the high costs of NADH deter its large-scale application. Photocatalytic reduction of NAD + to NADH is a promising solution that utilizes limitless solar energy. The success of photocatalytic reduction of NAD + depends on the use of a photosensitizer that must enable efficient electron transfer from the photosensitizer to the catalyst. Among the evaluated photosensitizers, ionic porphyrin (ZnTPyPBr) was found to be the most efficient photosensitizer for in situ NADH regeneration. Compared to the free system (control), methanol concentration was increased sevenfold when a membrane was used as a support to integrate cascade enzymatic reaction and NADH regeneration.

Replacing Ru complex with carbon dots over MOF-derived Co3O4/In2O3 catalyst for efficient solar-driven CO2 reduction

“…11 Among these, the addition of photosensitizer, which can boost the charge transfer efficiency and provide more active sties to activate photocatalytic molecules, has, so far, been widely investigated. 12–15 Inspired by molecular catalysis, noble metal complexes ( e.g. , [Ru(bpy) 3 ]Cl 2 and Ir(ppy) 3 ) coupled with stable semiconductor catalysts often possess high CO 2 conversion efficiencies.…”

Improving the Enzymatic Cascade of Reactions for the Reduction of CO2 to CH3OH in Water: From Enzymes Immobilization Strategies to Cofactor Regeneration and Cofactor Suppression

“…In fact, the porphyrin ring acting as the harvesting site can effectively absorb photons and transfer electrons to the electron mediator. Zhang et al [ 68 ] used an ionic porphyrin for cofactor regeneration, achieving an increase in NADH yield of about 18% with the porphyrin derivative ZnTPyPBr.…”

“… Regeneration Method Type of Regenerator Yield/Key Outcome Ref. Enzymatic regeneration GDH Y MeOH reached 127% [ 48 ] Enzymatic regeneration GDH Y MeOH reached up to 95.3% [ 72 ] Enzymatic regeneration PTDH or GlyDH PTDH is 4 times more active than GlyDH , [CH 3 OH] increases from 0.1 mM without PTDH to 0.9 mM with PTDH [ 18 ] Enzymatic regeneration PTDH The multienzymatic cascade reaction, along with PTDH , yielded 3.28 mM methanol [ 64 ] Enzymatic regeneration GCDH Yield of methanol reached 100% after coupling GCDH regeneration [ 68 ] Enzymatic regeneration GCDH-XDH XDH for NADH regeneration was found to be more efficient than GCDH producing at least 8 mM CH 3 OH yield [ 65 ] Enzymatic regeneration GDH Yield of methanol was increased 64-folds compared to the reaction without a regeneration system …”

Dehydrogenase-Functionalized Interfaced Materials in Electroenzymatic and Photoelectroenzymatic CO2 Reduction

“…Toward selective methanol production from CO 2 reduction, photosynthesis driven by the NAD + reduction to NADH and a cascade reduction to methanol requires photosensitizers for the transfer of electrons by solar energy irradiation . In this process, a dehydrogenase-immobilized electrode can transform a photoenzymatic CO 2 reduction into a selective methanol formation. , In this process, the FDH enzyme conformation, low-energy binding of CO 2 on FDH, and NADH regeneration efficiency play significant roles . Obtaining CH 3 OH from CO via 6H + /6e – reduction requires highly selective homogeneous and heterogeneous systems including single atoms through their dynamic behavior, which requires atomic-level resolution and highly sensitive surface spectroscopic techniques. , …”