Hydrogenases catalyze the reversible conversion of hydrogen gas into protons and electrons which is promising for industrial application.However,free hydrogenases face challenges such as oxygen sensitivity and low electron transfer rates.This review summarized the immobilization of hydrogenases by carbon materials,metals,semiconductors,polymers and metal-organic-frameworks(MOFs).Carbon materials provide the advantages of low cost and large specific surface areas,while they tend to agglomerate.Hydrogenases are immobilizated on carbon materials through adsorption,usually involving electrostatic interactions and hydrophobic interactions,and are used in bioelectrocatalysis,biofuel cells and bioreactors.Metals and semiconductors,known for high conductivity and excellent reactive activity,are expensive and less stable.Through adsorption involving electrostatic interaction and hydrophobic interaction,immobilization of hydrogenases on metals and semiconductors are normally applied in bioelectrocatalysis,biofuel cells and photoelectrocatalysis.Polymers have good biocompatibility and mechanical strength but low conductivity.Immobilization of hydrogenases on polymers can improve the stability and oxygen tolerance of hydrogenases.Immobilization on polymers is realized through adsorption and entrapment,involving hydrogen bonds,hydrophobic interactions and π-π interactions,and is often used in bioelectrocatalysis and photoelectrocatalysis.MOFs are designable and have high specific surface areas,which provide wide choices for hydrogenases immobilization.However,MOFs tend to collapse in harsh conditions.Immobilization on MOFs through adsorption and entrapment involves coordinate bonds,hydrophobic interaction,and π-π interaction.Furthermore,the prospect of immobilization of hydrogenases by novel hybrid materials was proposed which can expand the applications of immobilized hydrogenases.Immobilization of hydrogenases facilitates the stability of hydrogenases,which can be applied in efficient production and application of hydrogen,as well as biological asymmetric hydrogenation for chiral medicine preparation.Immobilization of hydrogenases provide alternative options for transforming energy structures,realizing green manufacturing and solving environmental problems.
immobilization of hydrogenasesbioelectrocatalysiscarbon materialssemiconductorspolymersmetal-organic frameworks
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