The photoreforming of lignocellulose is a novel method to produce clean and sustainable H 2 energy. However, the catalytic systems usually show low activity under ultraviolet light; thus, this reaction is very limited at present. Visible light-responsive metal-free two-dimensional graphite-phased carbon nitride (g-C 3 N 4 ) is a good candidate for photocatalytic hydrogen production, but its activity is hindered by a bulky architecture. Although reported layered g-C 3 N 4 modified with active functional groups prepared by the chemical exfoliation enhances the photocatalytic activity, it lost the intrinsic structure and thus is not conducive to understand the structure−activity relationship. Herein, we report an intrinsic monolayer g-C 3 N 4 (∼0.32 nm thickness) prepared by nitrogenprotected ball milling in water, which shows good performance of photoreforming lignocellulose to H 2 driven by visible light. The exciton binding energy of g-C 3 N 4 was estimated from the temperature-dependent photoluminescence spectra, which is a key factor for subsequent charge separation and energy transfer. It is found that monolayer g-C 3 N 4 with smaller exciton binding energy increases the free exciton concentrations and promotes the separation efficiency of charge carriers, thereby effectively improving its performance of photocatalytic reforming of lignocellulose, even the virgin lignocellulose and waste lignocellulose. This result could lead to more active catalysts to photoreform the raw biomass, making it possible to provide clean energy directly from locally unused biomass.

A lignin amphoteric surfactant and betaine could enhance the enzymatic hydrolysis of lignocellulose and recover cellulase. The effects of lignosulfonate quaternary ammonium salt (SLQA) and dodecyl dimethyl betaine (BS12) on enzymatic hydrolysis digestibility, ethanol yield, yeast cell viability, and other properties of high-solid enzymatic hydrolysis and fermentation of a corncob residue were studied in this research. The results suggested that SLQA and 1 g/L BS12 effectively improved the ethanol yield through enhancing enzymatic hydrolysis. SLQA had no significant effect on the yeast cell membrane and glucose fermentation. However, 5 g/L BS12 reduced the ethanol yield as a result of the fact that 5 g/L BS12 damaged the yeast cell membrane and inhibited the conversion of glucose to ethanol. Our research also suggested that 1 g/L BS12 enhanced the ethanol yield of corncob residue fermentation, which was attributed to the fact that lignin in the corncob adsorbed BS12 and decreased its concentration in solution to a safe level for the yeast.

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Due to the poor enzyme thermal stability, the efficient conversion of high crystallinity cellulose into glucose in aqueous phase over 50 °C is challenging. Herein, an enzymeinduced MOFs encapsulation of β-glucosidase (β-G) strategy was proposed for the first time. By using various methods, including SEM, XRD, XPS, NMR, FTIR and BET, the successful preparation of a porous channel-type flower-like enzyme complex (β-G@MOFs) was confirmed. The prepared enzyme complex (β-G@MOFs) materials showed improved thermal stability (from 50 °C to 100 °C in the aqueous phase) and excellent resistance to ionic liquids (the reaction temperature was as high as 110 °C) compared to the free enzyme (β-G). Not only the catalytic hydrolysis of cellulose by single enzyme (β-G) in ionic liquid was realized, but also the high-temperature continuous reaction performance of the enzyme was significantly improved. Benefiting from the significantly improved heat resistance, the β-G@MOFs exhibited 32.1 times and 34.2 times higher enzymatic hydrolysis rate compared to β-G for cellobiose and cellulose substrates, respectively. Besides, the catalytic activity of β-G@MOFs was retained up to 86 % after five cycles at 110 °C. This was remarkable because the fixation of the enzyme by the MOFs ensured that the folded structure of the enzyme would not expand at high temperatures, allowing the native conformation of the encapsulated protein wellmaintained. Furthermore, we believe that this structural stability was caused by the confinement of flower-like porous MOFs.

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