Artificial thylakoid membrane assisted NiMn₂O₄@PoPDA hierarchical hollow nanospheres for photo-enzyme integrated catalysis

The selective functionalization of CO₂ is of profound significance concerning the global energy and environmental crisis. Herein, we cleverly designed and constructed a photoenzymatic system with a hierarchical hollow structure photo-enzyme integrated catalyst (nickel manganate -poly(o-phenylenediamine), NiMn₂O₄@PoPDA) by coating NiMn₂O₄ with artificial thylakoid membrane (PoPDA) to mimic the characteristics of natural thylakoid membranes and combined formate dehydrogenase (FDH) to upgrade CO₂ to formic acid. The PoPDA membrane enhances the absorption of light energy and the efficiency of electron transfer, and improves the stability of the enzyme to avoid its deactivation. Most importantly, the favorable electronic coupling and band structure between NiMn₂O₄ and PoPDA separate holes and electrons to afford a MV^•+ regeneration rate of 213.59 ± 4.91 mmol h⁻¹ g⁻¹ and a formic acid yield of 206 µmol. This work creates an efficient strategy using PoPDA as protector for enzyme stabilization to fabricate photobiocatalysts that realize highly efficient photoenzymatic catalysis. © 2023 Elsevier B.V.