“…Long-period evolution endows organisms with the capability to convert abundant simple substrates (H 2 O, CO 2 , and N 2 ) into diverse and more complex molecules through specific mechanisms of individual biocatalytic enzymes . Due to their capacity to operate at nearly ambient temperatures and pressures in an aqueous environment, biocatalysts are gaining more attention as key components of solar-to-chemical conversion systems for synthesizing valuable products such as H 2 , alcohol, acetic acid, and ammonia. , Generally, biocatalysts are classified into two types: free enzymes and whole cells . Although free enzymes can directly receive excited electrons and possess higher catalytic activities compared with whole-cell biocatalysts, they are very delicate in adverse environments, limiting their reuse and long-term and large-scale applications.…”