A High-Quality Mixed Matrix Membrane with Nanosheets Assembled and Uniformly Dispersed Fillers for Ethanol Recovery.

A high-quality filler within mixed matrix membranes, coupled with uniform dispersity, endows a high-efficiency transfer pathway for the significant improvement on separation performance. In this work, a zeolite-typed MCM-22 filler is reported that is doped into polydimethylsiloxane (PDMS) matrix by ultrafast photo-curing technique. The unique structure of nanosheets assembly layer by layer endows the continuous transfer channels towards penetrate molecules because of the inter-connective nanosheets within PDMS matrix. Furthermore, an ultrafast freezing effect produced by fast photo-curing is used to overcome the key issue, namely filler aggregation, and further eliminates defects. When pervaporative separating a 5 wt% ethanol aqueous solution, the resulting MCM-22/PDMS membrane exhibits an excellent membrane flux of 1486 g m-2 h-1 with an ethanol separation factor of 10.2. Considering a biobased route for ethanol production, the gas stripping and vapor permeation through this membrane also shows a great enrichment performance, and the concentrated ethanol is up to 65.6 wt%. Overall, this MCM-22/PDMS membrane shows a high separation ability for ethanol benefited from a unique structure deign of fillers and ultrafast curing speed of PDMS, and has a great potential for bioethanol separation from cellulosic ethanol fermentation.

Efficient Electrosynthesis of Urea over Single-Atom Alloy with Electronic Metal Support Interaction.

Urea electrosynthesis from carbon dioxide (CO2) and nitrate (NO3 -) is an alternative approach to traditional energy-intensive urea synthesis technology. Herein, we report a CuAu single-atom alloy (SAA) with electronic metal support interaction (EMSI), achieving a high urea yield rate of 813.6 µg h-1 mgcat -1 at -0.94 V versus reversible hydrogen electrode (vs. RHE) and a Faradaic efficiency (FE) of 45.2 % at -0.74 V vs. RHE. In situ experiments and theoretical calculations demonstrated that single-atom Cu sites modulate the adsorption behavior of intermediate species. Bimetallic sites synergistically accelerate C-N bond formation through spontaneous coupling of *CO and *NO to form *ONCO as key intermediates. More importantly, electronic metal support interaction between CuAu SAA and CeO2 carrier further modulates electron structure and interfacial microenvironment, endowing electrocatalysts with superior activity and durability. This work constructs SAA electrocatalysts with EMSI effect to tailor C-N coupling at the atomic level, which can provide guidance for the development of C-N coupling systems.

Single Cobalt Atoms Immobilized on Palladium-Based Nanosheets as 2D Single-Atom Alloy for Efficient Hydrogen Evolution Reaction.

Single-atom alloys (SAAs) display excellent electrocatalytic performance by overcoming the scaling relationships in alloys. However, due to the lack of a unique structure engineering design, it is difficult to obtain SAAs with a high specific surface area to expose more active sites. Herein, single Co atoms are immobilized on Pd metallene (Pdm) support to obtain Co/Pdm through the design of the engineered morphology of Pd, realizing the preparation of ultra-thin 2D SAA. The unsaturated coordination environments combined with the unique geometric and electronic structures realize the modulation of the d-band center and the redistribution of charges, generating highly active electronic states on the surface of Co/Pdm. Benefiting from the synergistic interaction and spillover effect, the Co/Pdm electrocatalyst exhibits outstanding hydrogen evolution reaction (HER) performance in both acid and alkaline solutions, especially with a Tafel slope of 8.2 mV dec-1 and a low overpotential of 24.7 mV at 10 mA cm-2 in the acidic medium, which outperforms commercial Pt/C and Pd/C. This work highlights the successful preparation of 2D ultra-thin SAA, which provides a new strategy for the preparation of HER electrocatalyst with high efficiency, activity, and stability.

Synthesis of AuX (X = Ni, Ga, Mo, Zn, and Cr) Alloy Aerogels as High-Performance Electrocatalytic CO2 Reduction Reaction Catalysts.

Electrocatalytic CO2 reduction reaction (eCO2RR) into value-added chemicals is highly desirable to mitigate the global warming effect and energy crisis. Metal aerogels, as featured by a self-supporting structure, large specific surface area, outstanding conductivity, and a hierarchical porous structure, are ideal electrocatalysts in eCO2RR. Herein, we report a simple and general strategy for constructing a series of Au-based alloy aerogels which contain Au with another metal including Ga, Ni, Mo, Zn, and Cr, respectively. For the first time, the electrocatalytic activities of AuGa aerogels, AuNi aerogels, and AuMo aerogels for CO2RR were studied in detail. The resultant Au81Ga19 aerogel achieves a 95.2% Faradaic efficiency (FE) at -1.16 V versus reversible hydrogen (vs RHE) in H-cells. Impressively, a total 99.4% FE for C1 products (CO + HCOOH) with a current density of 100 mA cm-2 at -0.6 V vs RHE and a large current density of 228 mA cm-2 can be achieved at -0.9 V with a 72.3% FE for the C1 product in a flow cell. Electrochemical characterization and theoretical calculations further revealed that the outstanding performance of the Au-based aerogels was derived from the large specific surface area, abundant grain boundaries, low interfacial charge transfer resistance, and synergetic effect. Overall, this study provides a promising alternative to engineer alloy aerogel electrocatalysts for highly efficient CO2 electroreduction.

The Ultrafast and Continuous Fabrication of a Polydimethylsiloxane Membrane by Ultraviolet-Induced Polymerization.

The polydimethylsiloxane (PDMS) membrane commonly used for separation of biobutanol from fermentation broth fails to meet demand owing to its discontinuous and polluting thermal fabrication. Now, an UV-induced polymerization strategy is proposed to realize the ultrafast and continuous fabrication of the PDMS membrane. UV-crosslinking of synthesized methacrylate-functionalized PDMS (MA-PDMS) is complete within 30 s. The crosslinking rate is three orders of magnitude larger than the conventional thermal crosslinking. The MA-PDMS membrane shows a versatile potential for liquid and gas separations, especially featuring an excellent pervaporation performance for n-butanol. Filler aggregation, the major bottleneck for the development of high-performance mixed matrix membranes (MMMs), is overcome, because the UV polymerization strategy demonstrates a freezing effect towards fillers in polymer, resulting in an extremely high-loading silicalite-1/MA-PDMS MMM with uniform particle distribution.

Simultaneous acetone-butanol-ethanol fermentation, gas stripping, and full-cell-catalyzed esterification for effective production of butyl oleate.

In this study, aiming to improve the economic feasibility of acetone-butanol-ethanol (ABE) fermentation process, generate valuable products and extend the product chain, esterification catalyzed by Candida sp. 99-125 cells was hybrid with the ABE fermentation-gas-stripping integration system. The gas-stripping condensate that contained concentrated ABE products was directly used for esterification without the participation of toxic organic solvents. Full-cell catalysis temperature and the cell dosage rate on oleate production were evaluated and optimized in the esterification process. Under the optimized conditions (35 °C, 8% of cells), ~ 68% of butyl oleate and ~ 12% of ethyl oleate were obtained after 4 h of esterification. The Candida sp. 99-125 cells were able to be reused for at least four cycles. The novel cascade process showed environmental benefits, which also showed promising in improving the economic feasibility of the conventional ABE fermentation process.

Towards an energy-friendly and cleaner solvent-extraction of vegetable oil.

The extraction of vegetable oils is an energy-intensive process. It has moreover a significant environmental impact through hexane emissions and through the production of organic-loaded wastewater. A rice bran oil process was selected as the basis, since full data were available. By using Aspen Plus v8.2 simulation, with additional scripts, several improvements were examined, such as using heat exchanger networks, integrating a Vapor Recompression Heat Pump after the evaporation and stripping, and examining a nitrogen stripping of hexane in the rice bran meal desolventizing unit followed by a gas membrane to recover hexane. Energy savings by the different individual and combined improvements are calculated, and result in a 94.2% gain in steam consumption and a 73.8% overall energy saving. The power consumption of the membrane unit reduces the overall energy savings by about 5%. Hexane separation and enrichment by gas membranes facilitates its condensation and re-use, while achieving a reduction of hexane emissions by over 50%. Through the considerable reduction of required steam flow rates, 61% of waste water is eliminated, mostly as organic-loaded steam condensate. Through overall energy savings, 52% of related CO2 emissions are eliminated.

Design of PDMS/PAN composite membranes with ultra-interfacial stability via layer integration.

The interfacial interaction between the selective layer and porous substrate directly determines the separation performance and service lifetime of functional composite membranes. Till now, almost all reported polymeric selective layers are physically in contact with the substrate, which is unsatisfactory for long-term operation. Herein, we introduced a functional composite membrane with ultra-interfacial stability via layer integration between the polydimethylsiloxane selective layer and polyacrylonitrile substrate, where a facile light-triggered copolymerization achieved their covalent bonding. The critical load for the failure of the selective layer is 45.73 mN when testing the interfacial adhesion, i.e., 5.8 times higher than that before modification and significantly higher than previous reports. It also achieves superior pervaporation performance with a separation factor of 9.54 and membrane flux of 1245.6 g m-2 h-1 feeding a 1000 ppm phenol/water solution at 60 °C that is significantly higher than the same type of polymeric ones. Not limited to pervaporation, such a strategy sheds light on the design of highly stable composite membranes with different purposes, while the facile photo-trigged technique shows enormous scalability.

Sequential catalytic lignin valorization and bioethanol production: an integrated biorefinery strategy.

BACKGROUND: The effective valorization of lignin and carbohydrates in lignocellulose matrix under the concept of biorefinery is a primary strategy to produce sustainable chemicals and fuels. Based on the reductive catalytic fractionation (RCF), lignin in lignocelluloses can be depolymerized into viscous oils, while the highly delignified pulps with high polysaccharides retention can be transformed into various chemicals. RESULTS: A biorefinery paradigm for sequentially valorization of the main components in poplar sawdust was constructed. In this process, the well-defined low-molecular-weight phenols and bioethanol were co-generated by tandem chemo-catalysis in the RCF stage and bio-catalysis in fermentation stage. In the RCF stage, hydrogen transfer reactions were conducted in one-pot process using Raney Ni as catalyst, while the isopropanol (2-PrOH) in the initial liquor was served as a hydrogen donor and the solvent for lignin dissolution. Results indicated the proportion of the 2-PrOH in the initial liquor of RCF influenced the chemical constitution and yield of the lignin oil, which also affected the characteristics of the pulps and the following bioethanol production. A 67.48 ± 0.44% delignification with 20.65 ± 0.31% of monolignols yield were realized when the 2-PrOH:H2O ratio in initial liquor was 7:3 (6.67 wt% of the catalyst loading, 200 °C for 3 h). The RCF pulp had higher carbohydrates retention (57.96 ± 2.78 wt%), which was converted to 21.61 ± 0.62 g/L of bioethanol with a yield of 0.429 ± 0.010 g/g in fermentation using an engineered S. cerevisiae strain. Based on the mass balance analysis, 104.4 g of ethanol and 206.5 g of lignin oil can be produced from 1000 g of the raw poplar sawdust. CONCLUSIONS: The main chemical components in poplar sawdust can be effectively transformed into lignin oil and bioethanol. The attractive results from the biorefinery process exhibit great promise for the production of valuable biofuels and chemicals from abundant lignocellulosic materials.

Rapid fractionation of corn stover by microwave-assisted protic ionic liquid [TEA][HSO4] for fermentative acetone-butanol-ethanol production.

BACKGROUND: The use of ionic liquids (ILs) to fractionate lignocelluloses for various bio-based chemicals productions is in the ascendant. On this basis, the protic ILs consisting of triethylammonium hydrogen sulfate ([TEA][HSO4]) possessed great promise due to the low price, low pollution, and high efficiency. In this study, the microwave-assistant [TEA][HSO4] fractionation process was established for corn stover fractionation, so as to facilitate the monomeric sugars production and supported the downstream acetone-butanol-ethanol (ABE) fermentation. RESULTS: The assistance of microwave irradiation could obviously shorten the fractionation period of corn stover. Under the optimized condition (190 W for 3 min), high xylan removal (93.17 ± 0.63%) and delignification rate (72.90 ± 0.81%) were realized. The mechanisms for the promotion effect of the microwave to the protic ILs fractionation process were ascribed to the synergistic effect of the IL and microwaves to the depolymerization of lignocellulose through the ionic conduction, which can be clarified by the characterization of the pulps and the isolated lignin specimens. Downstream valorization of the fractionated pulps into ABE productions was also investigated. The [TEA][HSO4] free corn stover hydrolysate was capable of producing 12.58 g L-1 of ABE from overall 38.20 g L-1 of monomeric sugars without detoxification and additional nutrients supplementation. CONCLUSIONS: The assistance of microwave irradiation could significantly promote the corn stover fractionation by [TEA][HSO4]. Mass balance indicated that 8.1 g of ABE and 16.61 g of technical lignin can be generated from 100 g of raw corn stover based on the novel fractionation strategy.

Surfactant-assisted dilute ethylenediamine fractionation of corn stover for technical lignin valorization and biobutanol production.

In this study, a surfactant-assisted diluted ethylenediamine (EDA) fractionation process was investigated for co-generation of technical lignin and biobutanol from corn stover. The results showed that the addition of PEG 8000 significantly enhanced cellulose recovery (88.9 %) and lignin removal (68.9 %) in the solid fraction. Moreover, the pulp achieved 86.5 % glucose yield and 82.6 % xylose yield in enzymatic hydrolysis. Structural characterization confirmed that the fractionation process promoted the preservation of active ß-O-4 bonds (35.8/100R) in isolated lignin and functionalized the lignin through structural modification using EDA and surfactant grafting. The enzymatic hydrolysate of the pulps yielded a sugar solution for acetone-butanol-ethanol (ABE) fermentation, resulting in an ABE concentration of 15.4 g/L and an overall yield of 137.2 g/Kg of dried corn stalk. Thus, the surfactant-assisted diluted EDA fractionation has the potential to enhance the overall economic feasibility of second-generation biofuels production within the framework of biorefinery.

Real time monitoring of on-chip coenzyme regeneration with SPR and DPI.

We report in this work real time characterization of enzyme-coenzyme binding by using surface plasmon resonance (SPR) and dual polarization interferometry (DPI) analyses. Results showed that diaphorase (DP) and lactate dehydrogenases (LDH) had distinct binding selectivity and preference over reduced and oxidized states of coenzyme NAD(H). On the basis of that, DP and LDH were chosen as indicator enzymes to distinguish the specific state of surface-bound NAD(H). The transformation between NADH and NAD(+) during enzyme-catalyzed redox reactions was therefore transduced into variation in interaction signals as indicated via the binding status of the indicator enzymes as detected with both SPR and DPI. This real time molecule-specific detection strategy revealed quick and direct reflection of the state and reactivity of the coenzyme, promising a unique way of precise molecular interaction analysis.

Preparation of poly(phthalazinone-ether-sulfone) sponge-like ultrafiltration membrane.

Poly(phthalazinone-ether-sulfone) (PPES) polymer is a relatively newly developed material with a bis(4-fluorodiphenyl) sulfone group. The formation of the PPES membrane by wet-phase inversion can proceed according to a slow or fast gelation method. These formation mechanisms were studied experimentally. The resulting membrane morphology was investigated using both optical and scanning electron micrography. The effects of PPES concentration and two additives, polyvinylpyrrolidone (PVP) and oxalic acid (OA), on the apparent viscosity and gelation rate of PPESK/NMP solutions and membrane performance have also been investigated. It was found that the gelation rate is important to obtain a sponge-like membrane structure, however favored by a fast gelation rate. The membrane obtained by a fast gelation rate showed a high pure water flux and rejection of bovine serum albumin (BSA), contrary to previous findings. On the basis of the experimental results, the actual membrane structure and pure water flux were related, and in agreement with the optical micrograph and gelation rate, respectively. The current results provide a fundamental insight in this novel copolymer, useful in future applications, especially in the membrane formation process.

Electroenzymatic Reduction of Furfural to Furfuryl Alcohol by an Electron Mediator and Enzyme Orderly Assembled Biocathode.

The electroenzymatic valorization of biomass derivatives into valuable biochemicals has a promising outlook. However, bottlenecks including poor electron transfer between the electrode surface and oxidoreductase, inefficient regeneration of cofactors, and high cost of enzymes and electron mediators hindered the realistic applications of the technique. Herein, to address the above technical barriers, a novel bio-electrocatalytic system that integrates the electrochemical NADH regeneration and enzymatic reaction was constructed, using an orderly assembled composite bioelectrode consisting of an outer immobilized enzyme layer and a sandwiched redox mediator rhodium complex layer. The as-prepared composite bioelectrode was further applied for the highly selective hydrogenation of furfural into furfural alcohol. Results indicated that the enzyme activity was significantly improved, while the furfural valorization was promoted by effective interfacial electron transition and co-factor regeneration on the composite bioelectrode. Considerable high furfural conversion (96.4%) can be achieved accompanied by a furfural alcohol selectivity of 90.0% at -1.2 V (vs Ag/AgCl). The novel composite bioelectrode also showed good stability and reusability. Up to 85.1% of the original furfural alcohol selectivity can be preserved after 10 times of recycling. This work presents a promising green alternative for the valorization of furfural, which also shows great potential extending to the valorization of other biomass compounds.

Artificial Photoenzymatic Reduction of Carbon Dioxide to Methanol by Using Electron Mediator and Co-factorAssembled ZnIn2 S4 Nanoflowers.

Increased absorption of visible light, low electron-hole recombination, and fast electron transfer are the major objectives for highly effective photocatalysts in biocatalytic artificial photosynthetic systems. In this study, a polydopamine (PDA) layer containing electron mediator, [M], and NAD+ cofactor was assembled on the outer surface of ZnIn2 S4 nanoflower, and the as-prepared nanoparticle, ZnIn2 S4 /PDA@poly/[M]/NAD+ , was used for photoenzymatic methanol production from CO2 . Because of effective capturing of visible light, reduced distance of electron transfer, and elimination of electron-holes recombination, a high NADH regeneration of 80.7±1.43 % could be obtained using the novel ZnIn2 S4 /PDA@poly/[M]/NAD+ . In the artificial photosynthesis system, a maximum methanol production of 116.7±11.8 µm was obtained. The enzymes and nanoparticles in the hybrid bio-photocatalysis system could be easily recovered using the ultrafiltration membrane at the bottom of the photoreactor. This is due to the successful immobilization of the small blocks including the electron mediator and cofactor on the surface of the photocatalyst. The ZnIn2 S4 /PDA@poly/[M]/NAD+ photocatalyst exhibited good stability and recyclability for methanol production. The novel concept presented in this study shows great promise for other sustainable chemical productions through artificial photoenzymatic catalysis.

Hydrophobic-modified metal-hydroxide nanoflocculants enable one-step removal of multi-contaminants for drinking water production.

Flocculation is a mainstream technology for the provision of safe drinking water but is limited due to the ineffectiveness of conventional flocculants in removing trace low-molecular-weight emerging contaminants. We described a synthesis strategy for the development of high-performance nanoflocculants (hydrophobic-organic-chain-modified metal hydroxides [HOC-M]), imitating surfactant-assembling nano-micelles, by integration of long hydrophobic chains with traditional inorganic metal (Fe/Al/Ti)-based flocculants. The core-shell nanostructure was highly stable in acidic stock solution and transformed to meso-scale coagulation nuclei in real surface water. In both jar and continuous-flow tests, HOC-M was superior over conventional flocculants in removing many contaminants (turbidity, UV254, and DOC: >95%; TP and NO3-N: >90%; trace pharmaceuticals [initial concentration: 100 ng/L]: >80%), producing flocs with better structural and dewatering properties, and lowering the environmental risk of metal leaching. The rationally designed nanoflocculants have large application potential, as a solution to increasing public concern about micro-pollutants and increasing water quality requirements.

A Particle-Driven, Ultrafast-Cured Strategy for Tuning the Network Cavity Size of Membranes with Outstanding Pervaporation Performance.

Poly(dimethylsiloxane) (PDMS) membranes are widely used for bioethanol separation. However, the network cavity size r3 of PDMS membranes is generally smaller than the ethanol kinetic radius (0.225 nm), which limits the transport of ethanol molecules and weakens the pervaporation performance. Herein, we proposed a particle-driven, ultrafast-cured strategy to overcome the above key issue: (1) Incorporating particles into PDMS for preventing polymer chains from packing tightly, (2) freezing particles within a PDMS layer by the ultrafast UV-cross-linking for improving its distribution and increasing the chain extension of the polymer, and (3) covalently bonding particles with PDMS to enhance their compatibility. Consequently, r3 was increased to 0.262 nm, and an extremely high loading membrane (50 wt %) with an ultrashort curing time (20 s) was prepared, which is difficult to be realized by the conventional thermally driven approach. As a result, a separation factor of 13.4 with a total flux of 2207 g m-2 h-1 for separating ethanol from a 5 wt % aqueous solution at 60 °C was obtained. This strategy shows the feasibility of recovery of different bioalcohols and the large-scale continuous membrane preparation.

Selective binding of heparin oligosaccharides in a magnetic thermoresponsive molecularly imprinted polymer.

Heparin is a highly sulfated polysaccharide, applied in clinic for treatment of thrombotic diseases. The biological activity is closely related to its molecular structure e.g. compositions of disaccharides and oligosaccharides units. The classical method to isolate the oligosaccharides after depolymerization by heparinases or nitrous acid I s by size exclusion chromatography which is a time-consuming process. In this study, we explored the possibility for rapid separation of oligosaccharides using a novel polymer material. The magnetic thermoresponsive molecularly imprinted polymers (MIPs) were synthesized using heparin disaccharide as a template, AEM, NIPAAm, and AAm as functional monomer, and MBAA as crosslinker by surface radical polymerization in an aqueous media. Incubation of the MIP with hepairn oligosaccharides demonstrated specific binding to the template molecule. This binding to the targeted molecule was affected by reaction temperature with regard to binding capacity and specificity. The recognition specificity and selectivity can be modulated by varying the compositions of multi-functional monomers. The pseudo-second-order kinetic model and Langmuir isotherm model provide the best fit to the equilibrium adsorption of heparin disaccharides by MIPs. The results suggest that the new material can be used for rapid separation of di- and tetra-saccharides of heparin, which can also be adapted to the applications for isolation of oligosaccharides from other polysaccharides, e.g. heparan sulfate and chondoriting sulfate.

Bio-plasticizer production by hybrid acetone-butanol-ethanol fermentation with full cell catalysis of Candida sp. 99-125.

Hybrid process that integrated fermentation, pervaporation and esterification was established aiming to improve the economic feasibility of the conventional acetone-butanol-ethanol (ABE) fermentation process. Candida sp 99-125 cells were used as full-cell catalyst. The feasibility of batch and fed-batch esterification using the ABE permeate of pervaporation (ranging from 286.9 g/L to 402.9 g/L) as substrate were compared. Valuable butyl oleate was produced along with ethyl oleate. For the batch esterification, due to severe inhibition of substrate to lipase, the yield of butyl oleate and ethyl oleate were only 24.9% and 3.3%, respectively. In contrast, 75% and 11.8% of butyl oleate and ethyl oleate were obtained, respectively, at the end of the fed-batch esterification. The novel integration process provides a promising strategy for in situ upgrading ABE products.

Performance enhancement of a polydimethylsiloxane membrane for effective n-butanol pervaporation by bonding multi-silyl-functional MCM-41.

In the current work, MCM-41/polydimethylsiloxane (PDMS) mixed matrix membrane (MMM) was prepared for effective n-butanol pervaporation from a model aqueous solution. In order to improve the compatibility between MCM-41 and PDMS, different types of silane coupling agents including n-propyltrimethoxysilane (PTMS), n-octyltrimethoxysilane (OTMS), n-dodecyltrimethoxysilane (DTMS) and n-hexadecyltrimethoxysilane (HDTMS) were used to modify the MCM-41. The results showed that the highest n-butanol separation performance was achieved by bonding 20 wt% of PTMS-modified MCM-41 with PDMS. Under these conditions, total flux of 1476 g m-2 h-1 was obtained when separating a 1.5 wt% n-butanol aqueous solution at 55 °C. The total flux increased by nearly 40% compared to the pure PDMS membrane with no obvious changes of the n-butanol separation factor at the same time. The curing process of the casting solution was also significantly improved after MCM-41 modification.