Enhancing the Cycle Performance of Lithium-Sulfur Batteries by Coating the Separator with a Cation-Selective Polymer Layer.

Lithium-sulfur batteries are believed to possess the feasibility to power electric vehicles in the future ascribed to the competitive energy density. However, soluble polysulfides continuously shuttle between the sulfur electrode and lithium anode across the separator, which dramatically impairs the battery's capacity. Herein, the surface of a polypropylene separator (PP film) is successfully modified with a delicately designed cation-selective polymer layer to suppress the transport of polysulfides. In principle, since bis-sulfonimide anions groups on the backbone of the polymer are immobilized, only cations can pass through the polymer layer. Furthermore, plenty of ethoxy chains in the polymer can facilitate lithium-ion mobility. Consequently, in addition to obstructing the movement of negatively charged polysulfides by the electrostatic repulsive force of fixed anions, the coated multi-functional layer on the PP film also guarantees the smooth conduction of lithium ions. The investigations demonstrate that the battery with the pristine PP film only delivers 228.5 mAh g-1 after 300 cycles at 2 C with a high capacity fading rate of 60.9 %. By contrast, the polymer-coated sample can release 409.4 mAh g-1 under the identical test condition and the capacity fading rate sharply declines to 43.2 %, illustrating superior cycle performance.

A review on biomass-derived levulinic acid for application in drug synthesis.

Levulinic acid (LEV) has been identified as a key building block chemical produced entirely from biomass. Its derivatives can be used to synthesize a variety of value-added chemicals, such as 2-butanone, 2-methyltetrahydrofuran, and so on. LEV has carbonyl and carboxyl functional groups, which makes it flexible, diverse, and unique during drug synthesis. It also reduces the cost of drug synthesis and makes the reaction cleaner and, not the least, has untapped potential in the field of medicine. This article reviews the application of LEV in cancer treatment, medical materials, and other medical fields. Overall, LEV can be used in the following ways: (1) Used as a raw material to directly synthesize drugs; (2) Used to synthesize related derivatives, which can be more specifically used in drug synthesis, and derivatives can achieve the corresponding release of drugs, such as paclitaxel (PTX)- LEV, polymer-betulinic acid (BA)-LEV after amidation; (3) It can modify chemical reagents or act as linkers to connect pharmaceutical reagents with carriers to form pharmaceutical intermediates, a pharmaceutical intermediate skeleton, and so on. (4) It can acylate and esterify to form: acetylpropionate and levulinyl, the indole, pyridazine, and other medicinally active functional groups can be synthesized by a long chain, which can reduce the cost of drug synthesis and simplify the tedious synthesis steps. (5) To form the protective group of levulinic acid, the hydroxyl or carboxyl position is first protected, and then the protective group is removed after the corresponding reaction, in order to participate in drug synthesis.

Selective hydrogenation of vanillin over a graphene-encapsulated nitrogen-doped bimetallic magnetic Ni/Fe@NDC nano-catalyst.

One of the main obstacles to the development of sustainable biomass feedstocks today is the research of selective hydrogenation of biomass platform compounds for the synthesis of high-value chemicals. This work reports on the synthesis of a Ni/Fe bimetallic catalyst with nitrogen-doped carbon serving as the carrier, hydrogen serving as the primary donor, and isopropanol serving as the reaction medium and serving as a secondary donor. Vanillin was catalytically hydrogenated to produce 4-methylguaiacol, a complete hydrogenation product, under a reaction temperature of 200 °C for four hours. A single product with a good yield (95.26% conversion and selectivity up to 99%) was achieved by the moderate conditions, offering a potential route for the catalytic hydrogenation of biomass platform compounds.

Graphene Encapsulated Low-Load Nitrogen-Doped Bimetallic Magnetic Pd/Fe@N/C Catalyst for the Reductive Amination of Nitroarene Under Mild Conditions.

Aniline is a group of important platform molecules that has been widely used in the synthesis of other high-value chemicals and pharmaceutical products. How to produce high-value anilines as the high-value chemical intermediates more efficiently and environmentally has always been a research topic in the industry. Catalytic hydrogenation is an environmentally friendly method for preparing halogenated anilines. Traditional noble metal catalysts face the problems of cost and noble metals residue. To improve the purity of the product as well as the activity and recyclability of the catalyst, we prepared a Pd/Fe magnetic bimetallic catalyst supported on N-doped carbon materials to reduce nitrobenzene to aniline under mild conditions. The catalyst has a low Pd loading of 2.35%. And the prepared bimetallic Pd/Fe@N/C catalyst showed excellent catalytic reactivity with the nitrobenzene conversion rate of 99%, and the aniline selectivity of 99% under mild reaction conditions of 0.8 MPa H2 and 40 °C. A variety of halogenated and aliphatic nitro compounds were well tolerated and had been transformed to the corresponding target amine products with excellent selectivity. In addition, the novel N-doped graphene-encapsulated bimetallic magnetic Pd/Fe@N/C catalyst not only had magnetic physical properties, which was easy to separate, recover, and used for the recycling of the catalyst without metal leaching but also catalyzed highly selective reductive amination of aromatics was a green, economical and environmentally friendly reaction with the only by-product of H2O. Supplementary Information: The online version contains supplementary material available at 10.1007/s10562-023-04273-7.

Highly selective photocatalytic oxidation of alcohols under the application of novel metal organic frameworks (MOFs) based catalytic system.

Carboxylic acid is one of the most crucial and widely used organic chemicals in daily human life activities. Hence preparation of this important chemical was performed under the application of the highly selective photo-catalysts through oxidation of alcohols to carboxylic acids. Herein, we have designed and disclosed a binary NH2-MIL-125(Ti)/ NaBr) catalyst system to realize the effective transformation of alcohols into carboxylic acids under visible light irradiation. Hence, derivatives of benzyl alcohol containing either electron withdrawing and donating groups as well as aliphatic primary alcohols were effectively converted into the corresponding carboxylic acids. Based on our findings, NH2-MIL-125(Ti) based photocatalytic system has shown efficient and highly selective activities for oxidation of alcohol especially the in-situ conversion of co-catalyst NaBr into the corresponding free radical can enhance the alcohol oxidation performance of the catalytic system.

Exploring carbohydrate extraction from biomass using deep eutectic solvents: Factors and mechanisms.

Deep eutectic solvents (DESs) are increasingly being recognized as sustainable and promising solvents because of their unique properties: low melting point, low cost, and biocompatibility. Some DESs possess high viscosity, remarkable stability, and minimal toxicity, enhancing their appeal for diverse applications. Notably, they hold promise in biomass pretreatment, a crucial step in biomass conversion, although their potential in algal biomass carbohydrates extraction remains largely unexplored. Understanding the correlation between DESs' properties and their behavior in carbohydrate extraction, alongside cellulose degradation mechanisms, remains a gap. This review provides an overview of the use of DESs in extracting carbohydrates from lignocellulosic and algal biomass, explores the factors that influence the behavior of DESs in carbohydrate extraction, and sheds light on the mechanism of cellulose degradation by DESs. Additionally, the review discusses potential future developments and applications of DESs, particularly extracting carbohydrates from algal biomass.

Ru-MnOx Interaction for Efficient Hydrodeoxygenation of Levulinic Acid and Its Derivatives.

Metal-oxide interaction was widely observed in supported metal catalysts, playing a significant role in tuning the catalytic performance. Here, we reported that the interaction of Ru and MnOx was able to facilitate the hydrodeoxygenation of levulinic acid (LA) to 2-butanol with a high turnover frequency (1.99 × 106 h-1), turnover number (4411), and yield (98.8%). Moreover, this catalyst was capable of removing the hydroxymethyl group of lactones and diol with high yields of products. The high activity of the Ru-MnOx catalyst was due to the strong Ru-MnOx interaction, which facilitated reduction of Ru oxide to Ru0 and Mn oxide to Mn2+. The increased fractions of Ru0 and Mn2+ provided metal and Lewis acid sites, respectively, and therefore facilitated LA hydrodeoxygenation. A linear correlation between the hydrodeoxygenation activity of the Ru-MnOx catalyst and [Mn2+]ln([Ru0]) was observed.

Production of aromatic hydrocarbons from lignin derivatives by catalytic cracking over a SiO2-Al2O3 catalyst.

Catalytic cracking of phenolic compounds to aromatic hydrocarbons is vital to the utilization of lignin. In this work, pristine amorphous SiO2-Al2O3 was used as a catalyst to produce aromatic hydrocarbons from lignin-derived phenolics by catalytic cracking using methanol as the solvent. These catalysts were characterized by various techniques (XRD, NH3-TPD, Py-IR, etc.) and evaluated on a fixed bed reactor using guaiacol as a model compound. The effects of reaction temperature, the flow of carrier gas, the molar ratio of guaiacol to methanol, and WHSV were investigated. 33-SA (SiO2-Al2O3 with the SiO2 content of 33%) exhibited the best catalytic activity due to its high content of Lewis acid sites (168.47 µmol g-1). Co-feeding with methanol promoted the removal of oxygen atoms and improved the reaction system H/Ceff. Under the optimal conditions of 400 °C, 25 mL min-1 N2, a molar ratio of methanol to guaiacol of 25, and WHSV of 8/3 h-1, the yield of aromatic hydrocarbons reached 57.93%. The deactivating species in the transformation of guaiacol into aromatic hydrocarbons on catalysts were also studied.

Depth-dependent effects of tree species identity on soil microbial community characteristics and multifunctionality.

Soil microbes play key roles that support forest ecosystem functioning, while their community characteristics are strongly determined by tree species identity. However, the majority studies primarily focus on soil microorganisms in the topsoil, resulting in limited understanding of the linkages between tree species identity and the microbial communities that inhabit deep soils. Here we investigated the diversity, structure, function, and co-occurrence networks of soil bacterial and fungal communities, as well as related soil physicochemical properties, to a depth of two meters in dryland forests dominated by either Pinus tabuliformis, a native coniferous species, Robinia pseudoacacia, an exotic broadleaf and nitrogen-fixing species, or both. Tree species identity had stronger effects on soil multifunctionality and microbial community structure in the deep layers (80-200 cm) than in the top layers (0-60 cm). In addition, fungal communities were more responsive to tree species identity, whereas bacteria were more sensitive to soil depth. Tree species identity strongly influenced microbial network stability and complexity, with higher quantities in R. pseudoacacia than the other plantations, by affecting microbial composition and their associations. The increased in microbial network complexity and the relative abundance of keystone taxa enhance the soil multifunctionality of microbial productivity, sugar and chitin degradation, and nutrient availability and cycling. Meanwhile, the relative abundance of keystone taxa was more representative of soil multifunctionality than microbial diversity. Our study highlights that tree species identity significantly influences soil microbial community characteristics and multifunctionality, especially in deep soils, which will help us understand soil nutrients processed in plantation forest ecosystem and provide a reference for tree species selection in ecological restoration.

Biomass directional pyrolysis based on element economy to produce high-quality fuels, chemicals, carbon materials - A review.

Biomass is regarded as the only carbon-containing renewable energy source and has performed an increasingly important role in the gradual substitution of conventional fossil energy, which also contributes to the goals of carbon neutrality. In the past decade, the academic field has paid much greater attention to the development of biomass pyrolysis technologies. However, most biomass conversion technologies mainly derive from the fossil fuel industry, and it must be noticed that the large element component difference between biomass and traditional fossil fuels. Thus, it's necessary to develop biomass directional pyrolysis technology based on the unique element distribution of biomass for realizing enrichment target element (i.e., element economy). This article provides a broad review of biomass directional pyrolysis to produce high-quality fuels, chemicals, and carbon materials based on element economy. The C (carbon) element economy of biomass pyrolysis is realized by the production of high-performance carbon materials from different carbon sources. For efficient H (hydrogen) element utilization, high-value hydrocarbons could be obtained by the co-pyrolysis or catalytic pyrolysis of biomass and cheap hydrogen source. For improving the O (oxygen) element economy, different from the traditional hydrodeoxygenation (HDO) process, the high content of O in biomass would also become an advantage because biomass is an appropriate raw material for producing oxygenated liquid additives. Based on the N (nitrogen) element economy, the recent studies on preparing N-containing chemicals (or N-rich carbon materials) are reviewed. Moreover, the feasibility of the biomass poly-generation industrialization and the suitable process for different types of target products are also mentioned. Moreover, the enviro-economic assessment of representative biomass pyrolysis technologies is analyzed. Finally, the brief challenges and perspectives of biomass pyrolysis are provided.

Pilot study on production of aviation fuel from catalytic conversion of corn stover.

Aviation fuel is high energy density and is usually produced from refinery in petroleum industry. Production of renewable aviation fuel from biomass eases pressure of carbon emission regulation. The operational processes in this study include steam stripping, hydrolysis of residues, condensation reaction unit, autoclave hydrogenation, fixed-bed hydrodeoxygenation, and oil-upgrading unit. The biomass-derived aviation fuel has a low oxygen content of 0.4 %, while its high heat value is 45.5 MJ/kg. The aviation fuel ranges from C8 âˆ¼ C15, and rich in isoparaffins (50.4 %) while the n-paraffins have a selectivity of 12.2 % and other components are cycloparaffins (19.0 %), aromatic hydrocarbons (11.3 %), and alkenes (5.6 %). The mass yield for aviation fuel from corn stover reaches 10.6 %. This pilot study achieved production of aviation fuel from raw biomass corn stover.

Catalytic Conversion of Levulinic Acid to Pyrrolidone under Mild Conditions with Disordered Mesoporous Silica-Supported Pt Catalyst.

Catalytic conversion of biomass-derived levulinic acid (LA) into high-valued 5-methylpyrrolidones has become an attractive case in studies of biomass utilization. Herein, we developed a disordered mesoporous Pt/MNS catalyst for this reductive amination process under room temperature and atmospheric pressure of hydrogen. The disordered mesoporous structures in support of Pt/MNS catalyst led the formation of highly dispersed Pt species via confinement effect, providing high specific area for enhancing the catalytic sites. With the synergistic effect between highly dispersed Pt species and mesoporous structures, 5-methylpyrrolidones were successfully synthesized from biomass-derived LA and primary amines with high selectivity. Mechanism studies indicated that introducing protonic acid would promote the reductive-amination process, and enamine intermediates could be detected during the in-situ DRIFT tests. Density functional theory (DFT) calculation confirmed that the hydrogenation of enamine intermediate was more accessible than that of imide intermediates, leading the excellent performance of the Pt/MNS catalyst. This work provided a green method to produce 5-methylpyrrolidone and revealed the impact of catalyst structural characteristics on the reaction process.

Microbial oil production from corncob acid hydrolysate by Trichosporon cutaneum.

Corncob was treated by dilute H(2)SO(4). The hydrolysate contained 45.7 g sugar/l. Without concentration or adding other nutrients, the hydrolysate, after being detoxified by overliming and adsorption with activated charcoal, was used for oil production using Trichosporon cutaneum. After 8 days' growth in shake-flasks, the biomass was 22.1 g/l with a lipid content of 36%. The lipid yield per mass of sugar was 17.4% (w/w). Corncob thus is a promising raw material for microbial oil production by this yeast.

Selective Hydrogenolysis of 5-Hydroxymethylfurfural to 2-Hexanol over Au/ZrO2 Catalysts.

2-Hexanol (2-HOL) is a versatile biomass-derived platform molecule for synthesis of liquid transportation fuels, lubricants, or detergents. Herein, a one-step preparation of 2-HOL using 5-hydroxymethylfurfural (HMF) as a substrate was reported for the first time. Several Au-based catalysts supported on different metal oxides were prepared to explore the relationship between carrier and catalytic activity. The results showed that the highest 2-HOL yield of 65.8 % was obtained at complete HMF conversion over the 5 %Au/ZrO2 catalyst. The 5 %Au/ZrO2 catalyst exhibited excellent durability after five consecutive recycling runs, while confirming its remarkable ring-opening hydrogenolysis on other biomass-derived furanics, furfural, with a total yield of 1-pentanol and 2-pentanol of 67.4 %. The distinguished ring-opening hydrogenolysis performance of the Au/ZrO2 catalyst originated from a synergistic effect between the interfacial Au-O-Zr oxygen vacancies-induced Lewis acidic sites (activating C-OH/C=O bonds) and metallic Au (activating H2 ). This work provides a possibility for producing 2-HOL from HMF with high yield, expanding the sustainable application of lignocellulosic biomass.

Efficient conversion of lactic acid to alanine over noble metal supported on Ni@C catalysts.

Alanine (Ala), regarded as the building block for protein synthesis, has been widely used in the field of food processing, pharmaceutical, and bio-based plastic industries. Containing plenty of oxygenic functional groups, biomass-derived chemicals are proper for Ala synthesis in an economic and green way via amination. In this work, lactic acid (LA) derived from renewable biomass and waste glycerol (the major by-product of biodiesel industry) was used to produce Ala. Here, a series of magnetic catalysts M/Ni@C (M = Ru, Pt, Pd, Ir, and Rh) were synthesized by ethylene glycol reduction of metal M supported on encapsulated Ni@C. Compared with catalysts based on other M metals, Ru/Ni@C catalysts exhibited extraordinary efficiency with 91.4% selectivity for Ala synthesis from LA (63.7% yield of Ala and 69.7% conversion of LA). The results of experiments and catalyst characterization indicated that the doping of M metals could improve the dehydrogenation ability of catalysts, as well as the ability of NH3 adsorption, facilitating the reaction towards Ala. Overall, this study provides an efficient chemo-catalytic way for the production of Ala from biomass-derived substrates.

Comparative study on the hydrogenolysis performance of solid residues from different bamboo pretreatments.

Both alkaline organosolv and formaldehyde stabilization pretreatment can yield high-quality lignin by preventing condensation. For the hydrogenolysis of the pretreated solid residues, the highest yield of C2-C4 chemicals was 66.8% under alkaline organosolv pretreatment for 60 min. Specifically, the crimped fibers and residual lignin and hemicellulose increased the surface roughness of the residue by 40.6%, the crystallinity index decreased to 44.4%, and the crystal size was reduced to 2.15 nm, which in turn promoted hydrogenolysis of the residue. However, the increase of crystallinity and crystal size and the decrease in surface roughness of the formaldehyde stabilization pretreatment residue greatly hindered the conversion of polysaccharides. In addition, residual formaldehyde on the residue may also inhibit catalyst activity. Overall, this study provides novel perspectives on the full utilization of biomass, as well as new insights into the conversion of polysaccharides.

Numerical Studies on Cellulose Hydrolysis in Organic-Liquid-Solid Phase Systems with a Liquid Membrane Catalysis Model.

The catalytic hydrolysis of cellulose to produce 5-hydroxymethylfurfural (HMF) is a powerful means of biomass resources. The current efficient hydrolysis of cellulose to obtain HMF is dominated by multiphase reaction systems. However, there is still a lack of studies on the synergistic mechanisms and component transport between the various processes of cellulose hydrolysis in a complex multiphase system. In this paper, a liquid membrane catalytic model was developed to simulate the hydrolysis of cellulose and its further reactions, including the adsorption of the liquid membrane on cellulose particles, the consumption of cellulose solid particles, the complex chemical reactions in the liquid membrane, and the transfer of HMF at the phase interface. The simulations show the synergistic effect between cellulose hydrolysis and multiphase mass transfer. We defined an indicator () to characterize the sensitivity of HMF yield to the initial liquid membrane thickness at different reaction stages. decreased gradually when the glucose conversion increased from 0 to 80%, and increased with the thickening of the initial liquid membrane thickness. It was shown that the thickening of the initial liquid membrane thickness promoted the HMF yield under the same glucose conversion. In summary, our results reveal the mechanism of the interaction between multiple physicochemical processes of the cellulose liquid membrane reaction system.

Tungsten oxide decorated silica-supported iridium catalysts combined with HZSM-5 toward the selective conversion of cellulose to C6 alkanes.

Herein, WOx-decorated Ir/SiO2 (W/Ir = 0.06) and HZSM-5 were coupled to selectively convert microcrystalline cellulose (MCC) into C6 alkanes. A 92.8% yield of liquid alkanes including an 85.3% yield of C6 alkanes was produced at 210 °C. Cellulose hydrolysis, glucose hydrogenation and sorbitol hydrodeoxygenation were integrated to produce alkanes via a sorbitol route. Ir-WOx/SiO2 showed high performance for hydrogenation and hydrodeoxygenation reactions after hydrolysis catalyzed by HZSM-5. The intimate contact between WOx and Ir enhanced the synergistic interaction through the electron transfer from Ir to WOx. The interaction strengthened the reduction capability of Ir for hydrogenations, as well as improved the adsorption and activation of C-O bonds on reduced WOx for deoxygenations. The monotungstate WOx species provided moderate Lewis acids to cooperate with Ir to accelerate hydrodeoxygenations with alleviated retro-aldol condensation to yield more C6 alkanes.

A Survey of Enhanced Cold Tolerance and Low-Temperature-Induced Anthocyanin Accumulation in a Novel Zoysia japonica Biotype.

Zoysia japonica is a warm-season turfgrass that is extensively used in landscaping, sports fields, and golf courses worldwide. Uncovering the low-temperature response mechanism of Z. japonica can help to accelerate the development of new cold-tolerant cultivars, which could be used to prolong the ornamental and usage duration of turf. A novel Z. japonica biotype, YueNong-9 (YN-9), was collected from northeastern China for this study. Phenotypic measurements, cold-tolerance investigation, and whole-transcriptome surveys were performed on YN-9 and LanYin-3 (LY-3), the most popular Z. japonica cultivar in Southern China. The results indicated the following: YN-9 has longer second and third leaves than LY-3; when exposed to the natural low temperature during winter in Guangzhou, YN-9 accumulated 4.74 times more anthocyanin than LY-3; after cold acclimation and freezing treatment, 83.25 ± 9.55% of YN-9 survived while all LY-3 leaves died, and the dark green color index (DGCI) value of YN-9 was 1.78 times that of LY-3; in YN-9, there was a unique up-regulation of Phenylalanine ammonia-lyase (PAL), Homeobox-leucine Zipper IV (HD-ZIP), and ATP-Binding Cassette transporter B8 (ABCB8) expressions, as well as a unique down-regulation of zinc-regulated transporters and iron-regulated transporter-like proteins (ZIPs) expression, which may promote anthocyanin biosynthesis, transport, and accumulation. In conclusion, YN-9 exhibited enhanced cold tolerance and is thus an excellent candidate for breeding cold-tolerant Z. japonica variety, and its unique low-temperature-induced anthocyanin accumulation and gene responses provide ideas and candidate genes for the study of low-temperature tolerance mechanisms and genetic engineering breeding.

Earth-abundant Metal-catalyzed Reductive Amination: Recent Advances and Prospect for Future Catalysis.

Nitrogen-containing compounds, as an important class of chemicals, have been used widely in pharmaceuticals, materials synthesis. Transition metal-catalyzed reductive amination of an aldehyde or a ketone with ammonia or an amine has been proved to be an efficient and practical method for the preparation of nitrogen-containing compounds in academia and industry for a century. Given the above, several effective methods using transition metals have been developed in recent years. Noble transition metals like Pd, Pt, and Au-based catalysts have been predominately used in reductive amination. Because of their high prices, strict official regulations of residues in pharmaceuticals, and deleterious effects on the biological system, their industrial applications are severely hampered. With the increasing sustainable and environmental problems, the Earth-abundant transition metals including Ti, Fe, Co, Ni, and Zr have also been investigated for the reductive amination reaction and showed great potential to the advancement of sustainable and cost-effective reductive amination processes. This critical review will mainly summarize the work using Earth-abundant metals. The effects of different transition metals used in catalytic reduction amination were discussed and compared, and some suggestions were given. The last section highlights the catalytic activities of bi- and tri-metallic catalysts. Indeed, this latter family is very promising and simultaneously benefits from increased stability, and selectivity, compared to monometallic NPs, due to synergistic substrate activation. Few comprehensive reviews focusing on Earth-abundant transition metals catalyst has been published since 1948, although several authors reported some summaries dealing with one or the other part of this aspect. It is hoped that this critical review will inspire researchers to develop new efficient and selective earth-abundant metal catalysts for highly, environmentally sustainable reductive amination methods, as well as improve the pharmaceutical industry and related chemical synthesis company traditional method with the utilization of the green method widely.