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The photocatalytic reforming of lignin for H2 evolution can simultaneously overcome environmental and energy issues. However, the photocatalytic activity is still far from useful, considering lignin's complex structure. Therefore, this poses a huge challenge for the design of photocatalysts via ingredient/heterojunction regulation synergistic effects. Herein, in situ Mo-doped and metallic Ni-supported ZnIn2S4-wrapped NiMoO4 step-scheme (S-scheme) heterojunctions (NMO@M–ZIS–N) were developed via a reduction strategy assisted by thermal dissolution. The introduction of NMO can significantly inhibit the agglomeration of ZIS and expose more active sites. The close contact of the two phases helps to form a S-scheme heterojunction, which effectively promotes the separation and transport of photogenerated electron–hole pairs. Due to its unique structural design, the optimal hybrid heterojunction can exhibit excellent photocatalytic hydrogen evolution reaction (HER) activity (5.14 mmol h−1 g−1 for TEOA and 0.53 mmol h−1 g−1 for lignin). The superior photocatalytic performance can be mainly attributed to the synergistic effect of S-scheme heterojunctions coupled with Mo doping and metallic Ni supports to broaden the light absorption, enhance the kinetic process of charge transport, and retain strong redox ability, thereby promoting the photocatalytic HER activity. [ABSTRACT FROM AUTHOR]

In order to reduce the enzyme cost of lignocellulosic enzymatic hydrolysis, upper critical solution temperature (UCST) additives are used to recover and reuse cellulase by regulating the temperature. A sulfobetaine polymer, PSPE, showed a sensitive UCST response in buffer, and its UCST-performance was optimised by adjusting the molecular weight of the polymer. PSPE-3 (Mw = 355.1 kDa) was added to the cellulase buffer at 50 °C, and PSPE-3 and cellulase were co-precipitated by cooling to the room temperature of 25 °C. PSPE-3 and cellulase co-precipitated mainly through hydrophobic interactions via cooling. Compared with octadecyl sulfobetaine (SB3–18), PSPE-3 had a more sensitive UCST response and stronger cellulase recovery ability. Adding only 40% PSPE-3 (accounting for the mass fraction of cellulase) can save more than 50% cellulase in the enzymatic hydrolysis system of eucalyptus chips pre-treated with dilute acid (Eu-DA). However, for the Eu-DA system, adding 100% SB3–18 can only save about 30% of cellulase. In this work, efficient recycling of cellulase was achieved at room temperature by adding UCST-type PSPE. The process is green without consuming acid and alkali, and this work provides a new idea for reducing the production cost of cellulosic ethanol. [ABSTRACT FROM AUTHOR]

This study evaluated maleic acid (MA) as a green hydrotrope for efficient wood fractionation at atmospheric pressure and ≤100 °C. MA hydrotropic fractionation (MAHF) resulted in esterified lignin with a low degree of condensation and a very light color. 2D 1H–13C HSQC and HMBC NMR analyses of reaction products of a lignin model compound guaiacylglycerol-beta-guaiacyl ether with MA identified bonding through the γ-OH group. The surface charge of lignocellulosic MAHF water insoluble solids (WIS), induced by lignin esterification (carboxylation), enhanced enzymatic sugar yield by reducing nonproductive cellulase binding to lignin through pH-mediated electrostatic repulsion and also enhanced the lubrication effect of lignin in mechanical nanofibrillation for producing cellulose nanofibrils from WIS. Preliminary studies indicated that disssolved xylan can be dehydrated into furfural by MA in the fractionated liquor at a good yield of 70% and MA can be reused for repeated fractionation with minimal loss of less than 5%. [ABSTRACT FROM AUTHOR]

The conversion of lignocelluloses into fermentable sugars by enzymatic hydrolysis is a key step in biorefining. However, there are still some bottleneck problems such as low hydrolysis efficiency, high cost of cellulase and low utilization of lignin. In this work, the nonionic surfactant monomethoxy polyethylene glycol (MPEG) was grafted on enzymatic hydrolysis lignin (EHL) to obtain a pH-responsive polymer (EHL-MPEG). EHL-MPEG could achieve rapid dissolution–precipitation conversion by the ionization and protonation of carboxyl groups. By adjusting the grafting amount of MPEG, EHL-MPEG could not only enhance the enzymatic hydrolysis of lignocelluloses, but also efficiently recover cellulase after hydrolysis. Adding 3 g L−1 EHL-MPEG40 (the mass ratio of MPEG to EHL was 40%) could increase the glucose yield of corncob residue (CCR) and pretreated eucalyptus from 79.4% and 48.3% to 92.5% and 89.5%, respectively, which was comparable to the effect of the nonionic surfactant PEG4600. By simply adjusting the pH of solutions, more than 85% of cellulase proteins could be recovered by EHL-MPEG40 with almost complete recovery of β-glycosidase, exoglucanase V and xylanase. Compared with a pH-responsive lignin amphoteric surfactant (pH-LAS) obtained by grafting ionic groups on lignin, EHL-MPEG40 had a more sensitive pH response and a stronger cellulase recovery ability. In the enzymatic hydrolysis of CCR, a pH-LAS could save about 50% of cellulase, while EHL-MPEG40 could save more than 60% of cellulase. Furthermore, approximately 96% of EHL-MPEG40 could be reused. This new method can not only evade the process of immobilization, but also avoid the activity loss and component change of cellulase through immobilization. Using recyclable EHL-MPEG to improve glucose yield and recover cellulase during lignocellulosic hydrolysis is of great significance for improving the enzymatic saccharification process, reducing the cost of cellulase and realizing comprehensive utilization of lignocelluloses. [ABSTRACT FROM AUTHOR]

In order to enhance the enzymatic hydrolysis of lignocelluloses and recycle surfactants after enzymatic hydrolysis, a pH-responsive lignin amphoteric surfactant (SLQA) was prepared by the quaternization of sulfonated lignin (SL). Compared with SL, SLQA could much more effectively enhance the enzymatic hydrolysis of lignocelluloses. With an increase in the quaternization degree, enhancement of the enzymatic hydrolysis of lignocelluloses by the SLQA gradually increased. Adding 2 g L−1 SLQA-80 (mass radio of quaternizing agent to SL was 80%) could increase the enzymatic digestibility of pretreated eucalyptus and corncob residues (CCR) from 36.7% and 37.8% to 84.3% and 90.5%, respectively. The adsorption of SLQA on lignin film was larger than that of SL, and the lignin film became more hydrophilic after adsorbing SLQA. Thus, SLQA could cause more effective steric hindrance and form a hydration layer to reduce the non-productive adsorption of cellulase on lignin. The purified SLQA-80 exhibited sensitive pH-responsive property, and 90.8% of SLQA-80 could be recycled by adjusting the pH of hydrolysate after enzymatic hydrolysis. Adding recyclable SLQA could not only obviously enhance the enzymatic hydrolysis of lignocelluloses, but could also enable the comprehensive utilization of lignocelluloses. This method is of great significance to reducing the cost of cellulosic ethanol. [ABSTRACT FROM AUTHOR]