Bioinspired and biomolecular catalysts for energy conversion and storage

Abstract

Metalloenzymes are remarkable for facilitating challenging redox transformations with high efficiency and selectivity. In the area of alternative energy, scientists aim to capture these properties in bioinspired and engineered biomolecular catalysts for the efficient and fast production of fuels from low‐energy feedstocks such as water and carbon dioxide. In this short review, efforts to mimic biological catalysts for proton reduction and carbon dioxide reduction are highlighted. Two important recurring themes are the importance of the microenvironment of the catalyst active site and the key role of proton delivery to the active site in achieving desired reactivity. Perspectives on ongoing and future challenges are also provided.

Artificial Photosynthesis for Regioselective Reduction of NAD(P)+ to NAD(P)H Using Water as an Electron and Proton Source

“…Rapid consumption of fossil fuels has resulted in its depletion, causing unacceptable environmental problems such as the greenhouse effect, which may lead to climatic disaster. , Since fossil fuels are the products of photosynthesis, it is highly desired to achieve artificial photosynthesis to produce solar fuels that can replace fossil fuels in future. − The stoichiometry of photosynthesis is given by eq 2 NADP + + 2 H 2 normalO → hv 2 NADPH + 2 H + + O 2 where nicotinamide adenine dinucleotide phosphate (NADP + ) is reduced to 1,4-dihydro form (NADPH) with water that acts as a reductant under visible light irradiation. − In artificial photosynthesis, solar-driven water splitting to produce H 2 and O 2 as well as CO 2 reduction has been extensively studied using photoconductor heterogeneous catalysts. − Photocatalytic regioselective reduction of NAD(P) + to produce NAD(P)H has been achieved using sacrificial electron donors such as triethylamine and triethanolamine. − However, the stoichiometry of photosynthesis, that is, production of NAD(P)H and its analogues utilizing water as an electron and proton source (eq ) has yet to be achieved because of the instability of NAD(P)H with photoconductor catalysts under photoirradiation.…”

Nobel symposium #168 Visions of bio‐inorganic chemistry: metals and the molecules of life

“…This encompasses distances we are unused to thinking about in the biochemical context, for example, cable bacteria that conduct electrons over cm-distances to connect electron donors and acceptors in aquatic sediments. Bren and Casini [17,18] provide examples of applications of bioinorganic and bioinspired systems. Bren considers the key current issue of energy storage by finding inspiration for proton and carbon dioxide reduction in nature.…”