Efficient Water Reforming of Biomass to H2 via Well‐Organized Redox‐Neutral Cleavage of C−C, O−H and C−H Bonds

Abstract Hydrogen (H 2 ) is a clean and environmentally friendly energy carrier. The depletion of fossil fuels makes renewable H 2 production highly desirable. Water reforming of renewable biomass to hydrogen, with a relay of natural photosynthesis to biomass, would be an indirect pathway to realize the ideal but extremely challenging photocatalytic overall water splitting to hydrogen, with favorable thermodynamics. Since the seminal work of water reforming of biomass in 1980, great endeavors have been made. Nevertheless, hitherto, the entire kinetic pathway has been elusive, which seriously limits the reforming processes. Using a designed well‐organized redox‐neutral cleavage of C−C, O−H and C−H bonds enabled by photoelectrocatalysis, here, we show the efficient water reforming of biomass to hydrogen at room temperature, with a yield up to 93 %. The clear insights into the kinetic pathway with oxidation of carbon radicals to carbon cations as the indicated rate‐determining step, would cast brightness for efficient and sustainable hydrogen production to accelerate the hydrogen economy.