초록
<P>Unlocking the potential of the hydrogen economy requires breakthroughs in production, storage, distribution, and infrastructure. Here we demonstrate an <I>in vitro</I> artificial enzymatic pathway that can produce hydrogen at extremely high rates by splitting water energized by carbohydrates (<I>e.g.</I>, starch). This fifteen hyperthermophilic enzymes pathway comprises ATP-free starch phosphorylation, an NAD-based pentose phosphate pathway, and a biomimetic electron transport chain consisting of a diaphorase, an electron mediator benzyl viologen (BV), and a [NiFe]-hydrogenase, whereas fast electron transfer was facilitated by utilizing a BV-conjugated diaphorase. The highest reaction rate of 530 mmol H<SUB>2</SUB> per L per h was accomplished at 80 °C. Two NAD-conjugated dehydrogenases were further applied to enable nine-day hydrogen production with a total turnover number of NAD of over 100 000, along with hyperthermophilic enzymes. This biohydrogen production system characterized by the highest chemical-energy efficiency and an exceptionally-high reaction rate addresses challenges associated with cost-effective, distributed hydrogen production, off-board hydrogen storage, and infrastructure.</P><P>Graphic Abstract</P><P>Ultra-rapid biohydrogen production from water splitting energized by a natural energy storage compound starch with an artificial enzymatic biosystem.<BR/><IMG SRC='http://pubs.rsc.org/services/images/RSCpubs.ePlatform.Service.FreeContent.ImageService.svc/ImageService/image/GA?id=c8ee00774h'/><BR/></P>