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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Kinetic insight into glucose conversion to 5-hydroxymethyl furfural and levulinic acid in LiCl⋅3H2O without additional catalyst

Jinghua Wang,Hongyou Cui,Jiangang Wang,Zhihe Li,Ming Wang,Weiming Yi

Conversion of glucose to 5-hydromethyl furfural (HMF) and levulinic acid (LA) was systematically investigated in LiCl·3H 2 O without additional catalyst. Based on the experimental investigations by using glucose, fructose and HMF as the reaction substrate separately, corresponding reaction kinetics in LiCl·3H 2 O were modelled by first-order assumption. Kinetic analysis demonstrates that high temperature favors the formation of LA, while low temperature facilitates to selectively form humins. To achieve high LA yield, at least a temperature of 140 °C is required. Without additional catalyst converting glucose to LA in LiCl·3H 2 O, humins was predominantly derived from glucose and HMF, and glucose isomerization is the reaction rate-determining step. The activation energies of the main reactions are 160.96 kJ/mol (glucose to HMF), 139.20 kJ/mol (fructose to HMF), and 71.81–76.48 kJ/mol (HMF to LA) respectively. The activation energies for humins formation were 23.45 kJ/mol from glucose, 49.54 kJ/mol from fructose, and 42.15–65.85 kJ/mol from HMF, respectively. It is verified that LiCl·3H 2 O, as compared to aqueous medium, is an excellent reaction medium for converting glucose to LA as it can provide the active centers for fructose to HMF reaction and HMF to LA reaction, but lack of highly efficient Lewis acid for glucose isomerization. With the addition of Lewis acid (such as AlCl 3 and FeCl 3 ), as high as 83.4% of LA yield can be obtained respectively when directly converting glucose, with the total selectivities of LA and HMF of 95%.

研究领域: 生物化学 · 催化化学
✓ 已验证 DOI 高影响因子
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Systems Microbiology and Biomanufacturing · 2022 · IF 0

Characterization of acid-resistant aldo–keto reductases capable of asymmetric synthesis of (R)-CHBE from Lactobacillus plantarum DSM20174

Zhu Jiufeng,Bai Yajun,Fan Tai-Ping,Zheng Xiaohui,Cai Yujie

Ethyl ( R )-4-chloro-3-hydroxybutyrate (( R )-CHBE), as a chiral intermediate, is widely used in the synthesis of various chiral drugs. In this study, we screened two aldo–keto reductases (LP-AKRs) from the probiotic Lactobacillus plantarum DSM20174, both with a molecular weight of approximately 31 kDa. Both enzymes could reduce 4-chloroacetoacetic acid ethyl ester (COBE) to produce ( R )-CHBE with an enantioselectivity value of 99%. When determining the kinetic parameter, the K m , K cat , and V max of LP-AKR5 and LP-AKR9 were 9.5 mM, 7.6 U/mg, 3.96 s −1 and 8.7 mM, 8.59 U/mg, 4.47 s −1 , respectively. Both LP-AKR5 and LP-AKR9 had an optimal reaction pH of 6 and could maintain a high level of stability at pH 6, allowing them to perform well in an acidic environment. LP-AKR5 and LP-AKR9 had optimal reaction temperatures of 30 °C and 40 °C, respectively. Metal ions had minimal influence on LP-AKR5 and LP-AKR9 enzyme activities. This series of enzymatic properties showed that LP-AKR5 and LP-AKR9 mined from Lactobacillus plantarum DSM20174 could asymmetrically catalyze the synthesis of ( R )-CHBE under weakly acidic circumstances, which could maintain product stability and provide a good foundation for industrial production.

研究领域: 生物化学 · 分子生物学 · 工业微生物学
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RSC Sustainability · 2024 · IF 0

Catalytic synthesis of renewable 2-methylfuran from furfural

Yuanyuan Han,Xing Zhang,Wei Wang,Shaobo Guo,Xiaohui Ji,Guangyi Li

Biomass energy stands at the forefront of remedial strategies for the current energy deficit and has garnered considerable attention. The deployment of highly efficient catalysts is pivotal to the success of this energy form. Prevailing literature established that high-valent metal presence contributed significantly to the hydrogenation of furfural to prepare 2-methylfuran. In this study, we elucidated the efficacy of a monometallic catalyst consisting solely of cobalt and its oxides, denoted as Co/CoOx, in the catalytic transformation of furfural derived from lignocellulosic biomass into 2-methylfuran. Leveraging the economical Co/CoOx catalyst, in conjunction with minimal addition of hydroquinone, we accomplished the selective hydrodeoxygenation of furfural, culminating in an augmented yield of 2-MF up to 73%. This investigation is the inaugural confirmation that minuscule quantities of hydroquinone can efficaciously mitigate side reactions such as the polymerization of furfural within the selective hydrodeoxygenation process. The Co/CoOx catalyst was characterized through an array of analytical techniques, including XRD, H2-TPR and N2-adsorption. These characterization studies unveiled that the optimal selectivity for 2-methylfuran was achieved when the ratio of Co0 : Co2+ in the catalyst approached approximately 95%.

研究领域: 生物质能 · 催化化学 · 有机合成
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APPLIED SURFACE SCIENCE · 2021 · IF 6.707

High-performance hard carbon anode prepared via an ingenious green-hydrothermal route

Jing Wang,Wenjie Lv,Qingjuan Ren,Lei Yan,Lijun Zhang,Zhiqiang Shi

Phenolic resin, as a synthetic polymer precursor of hard carbon, has become the core anode precursor of sodium-ion batteries (SIBs). However, the carcinogenic formaldehyde is normally adopted in the synthesis of conventional phenolic resins. Meanwhile, the synthetic process is multifarious and prolonged, which is detrimental to mass production. In this paper, an eco-friendly phenolic resin was prepared by an efficient hydrothermal synthesis process using gentle and slightly toxic glyoxylic acid instead of notorious carcinogen formaldehyde. By adjusting the carbonization temperature of as-obtained phenolic precursor, the acquired optimal hard carbon anode material equipped a splendid reversible capacity of 325 mAh g −1 and a high initial coulombic efficiency (ICE) of 88.59%. Besides, it displayed an outstanding rate performance of 161.4 mAh g −1 for 300 cycles at 5 C with the capacity retention rate of 93.31%. When matched against the appropriate cathode, the full battery can provide a high energy density of 239 Wh kg −1 , displaying excellent rate capability and cycling stability. The participation of “green” aldehyde monomer in hydrothermal synthesis process for acquiring phenolic resin is an efficient and scalable approach for obtaining higher energy storage anode, which can pave environmentally-friendly way for the realization of large-scale energy storage application.

研究领域: 材料科学 · 能源存储 · 环境科学
✓ 已验证 DOI 高影响因子
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Food Packaging and Shelf Life · 2020 · IF 4.244

Preparation of cinnamaldehyde-loaded polyhydroxyalkanoate/chitosan porous microspheres with adjustable controlled-release property and its application in fruit preservation

Shenyu Yang,Qiuju Miao,Yiping Huang,Peishan Jian,Xiaoping Wang,Mei Tu

Cinnamaldehyde (Ci) is a highly effective natural broad-spectrum antibacterial agent and preservative, but its strong volatility and short duration have a negative impact on its application in the field of agriculture and food. In order to improve these properties, porous PHA/CS microspheres were prepared by using polyhydroxyalkanoate (PHA) and chitosan (CS) as basic materials based on Poiseuille flow principle, and PHA/CS scaffolds were obtained by sintering the microspheres at low temperature. The effect of the ratio of PHA and CS on the particle size and charge of microspheres was studied. It was found that the particle size increased with the increase of the ratio of PHA and CS, while the surface charge changed from negative to positive. The SEM results showed that the microspheres exhibit a porous structure, and the CS adsorb on the surface of microspheres resulted in the reduction of surface pores. FTIR spectrum confirmed that there was only physical interaction between PHA and CS. PHA-based microspheres exhibited high encapsulation efficiency and loading capacity for Ci. Ci-loaded PHA-based microspheres and scaffolds had different release rates, and the release time can be adjusted in the range of 7–60 days. Antimicrobial activity and fruit preservation ability of the loaded Ci microspheres showed that it can effectively inhibit the growth of bacteria and extend the shelf life of the strawberry. This novel Ci carrier with good biocompatibility, biodegradability and adjustable release rate would have a broad application in the field of food preservation and antibacterial.

研究领域: 食品科学 · 材料科学 · 微生物学
✓ 已验证 DOI 高影响因子
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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

Sec-amine grafted D301 resin catalyzed fixed-bed process for continuous preparation of methacrolein via Mannich reaction

Gang Wang,Zengxi Li,Liu Fan,Chunshan Li,Suojiang Zhang

S ec -amines catalyzed two-step Mannich reaction for preparation of methacrolein from propionaldehyde and formaldehyde was more attractive than the C 4 selective oxidation route. Herein, a novel continuous fixed-bed process was developed for direct preparation of methacrolein from above stocks with catalysis of sec -amine grafted D301 resin. The effect of resin, sec -amine structure and grafting percentage on catalytic performance of the modified resin were detailed investigated and demonstrated by using FT-IR, TG-DTA, titration and solid-state NMR characterization methods before the optimal conditions were obtained. The grafting percentage of amine with abundant sec -amino groups onto D301 resin could reach 93.7% at optimal condition. With this new strategy, the yield and selectivity of methacrolein could attain 40.2% and 99.3%. In addition, the Mannich reaction step with activation energy of 66.3 kJ/mol was determined as the rate-controlling step through mechanism-based kinetic calculation.

研究领域: 有机化学 · 催化化学
✓ 已验证 DOI 高影响因子
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GENOME BIOLOGY · 2024 ·Vol. 25 ·期 1 ·1-26 · IF 10.1

Early-life ruminal microbiome-derived indole-3-carboxaldehyde and prostaglandin D2 are effective promoters of rumen development

Sun Daming,Bian Gaorui,Zhang Kai,Liu Ning,Yin Yuyang,Hou Yuanlong,Xie Fei,Zhu Weiyun,Mao Shengyong,Liu Junhua

Background The function of diverse ruminal microbes is tightly linked to rumen development and host physiology. The system of ruminal microbes is an excellent model to clarify the fundamental ecological relationships among complex nutrient–microbiome–host interactions. Here, neonatal lambs are introduced to different dietary regimes to investigate the influences of early-life crosstalk between nutrients and microbiome on rumen development. Results We find starchy corn-soybean starter-fed lambs exhibit the thickest ruminal epithelia and fiber-rich alfalfa hay-fed lambs have the thickest rumen muscle. Metabolome and metagenome data reveal that indole-3-carboxaldehyde (3-IAld) and prostaglandin D2 (PGD2) are the top characteristic ruminal metabolites associated with ruminal epithelial and muscular development, which depend on the enhanced ruminal microbial synthesis potential of 3-IAld and PGD2. Moreover, microbial culture experiment first demonstrates that Bifidobacterium pseudolongum is able to convert tryptophan into 3-IAld and Candida albicans is a key producer for PGD2. Transcriptome sequencing of the ruminal epithelia and smooth muscle shows that ruminal epithelial and muscular development is accompanied by Wnt and Ca 2+ signaling pathway activation. Primary cell cultures further confirm that 3-IAld promotes ruminal epithelial cell proliferation depending on AhR-wnt/β-catenin signaling pathway and PGD2 accelerates ruminal smooth muscle cell proliferation via Ca 2+ signaling pathway. Furthermore, we find that 3-IAld and PGD2 infusion promote ruminal epithelial and musculature development in lambs. Conclusions This study demonstrates that early-life ruminal microbiome-derived 3-IAld and PGD2 are effective promoters of rumen development, which enhances our understanding of nutrient–microbiome–host interactions in early life.

研究领域: 动物科学 · 微生物学 · 分子生物学
✓ 已验证 DOI PubMed 高影响因子
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JOURNAL OF MEMBRANE SCIENCE · 2019 · IF 7.015

An experimental study on synthesis of glycolic acid via carbonylation of formaldehyde using PTFE membrane contactor

Zhihao Zhu,Guodong Kang,Ying Sun,Sha Yu,Meng Li,Jie Xu,Yiming Cao

The batch and continuous synthesis of glycolic acid via carbonylation of formaldehyde using high-temperature and high-pressure poly(tetrafluoroethylene) (PTFE) membrane contactor was demonstrated in this paper. The experiments in conventional stirred tank reactor were also conducted for comparison. The results showed that the yield of glycolic acid was significantly improved in membrane contactor system compared to the stirred tank reactor. At reaction temperature of 120 °C and reaction pressure of 5.0 MPa, the yield of glycolic acid was higher than 90% when the reaction time was 1 h, while it was only about 45% in the conventional stirred tank reactor. The enhancement of yield was due to the improvement of mass transfer or dispersion of CO in membrane contactor system, which could provide larger gas-liquid contact area and shorter mass transfer distance. The stability of PTFE hollow fibre membranes was also investigated by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), liquid entry pressure (LEP), bubble point (BP) and contact angle (CA) measurements. The characterizations indicated that PTFE membranes exhibited good chemical and thermal stability in this reaction system. This study provided new idea and reference for the carbonylation of formaldehyde and similar gas-liquid reactions.

研究领域: 化学工程 · 材料科学
✓ 已验证 DOI 高影响因子
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JOURNAL OF POROUS MATERIALS · 2024 · IF 2.5

Influence of various templates on the performance of MFI zeolite in catalytic synthesis of trioxane

Wu Wenhui,Zhao Kangrui,Xiao Kun

ZSM-5 is widely used in the field of catalysis due to its stability and tunability. Its acidity can be adjusted not only by varying the initial gel composition, but also by incorporating different types of template to enhance its performance. Both [Ga]-MFI and [Ga, Al]-MFI have demonstrated promising performance in the catalytic trioxane of formaldehyde synthesis. However, there is currently a paucity of research examining the influence of different templates on the catalytic performance of [Ga]-MFI and [Ga, Al]-MFI. The influence of different templates on the structure, morphology, and pore structure of the zeolite has been revealed through the application of characterisation techniques, including XRD, MAS NMR spectroscopy, ICP-OES, BET, and SEM. The impact of different templates on the acid properties of [Ga]-MFI and [Ga, Al]-MFI was assessed using NH 3 -TPD and Py-IR. The results of the experimental investigation into the catalytic performance of zeolites synthesised with larger molecular-structured templates indicate that these zeolites exhibit superior catalytic performance. Furthermore, the introduction of Na + ions has been observed to reduce the space-time yield of the products.

研究领域: 材料科学 · 催化化学
✓ 已验证 DOI 高影响因子
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ChemSusChem · 2021 ·Vol. 14 ·期 24 ·5499-5507 · IF 8.928

Nickel Boride/Boron Carbide Particles Embedded in Boron-Doped Phenolic Resin-Derived Carbon Coating on Nickel Foam for Oxygen Evolution Catalysis in Water and Seawater Splitting

Jilong Li,Yanhui Wang,Hongwei Gao,Shiwei Song,Bowen Lu,Xueqing Tian,Shuyu Zhou,Yungang Yuan,Jianbing Zang

Graphical Put on your coat : Ni x B/B 4 C particles embedded in B-doped phenolic resin-derived carbon coating on nickel foam are prepared for efficient water/seawater electrolysis by directly soaking nickel foam in a mixture of phenolic resin and B 4 C, followed by an 800 °C annealing. The coating effectively protects the catalyst from the corrosion by seawater and facilitates the transport of electrons. Electrolysis of seawater can be a promising technology, but chloride ions in seawater can lead to adverse side reactions and the corrosion of electrodes. A new transition metal boride-based self-supported electrocatalyst was prepared for efficient seawater electrolysis by directly soaking nickel foam (NF) in a mixture of phenolic resin (PR) and boron carbide (B 4 C), followed by an 800 °C annealing. During PR carbonization process, the reaction of B 4 C and NF generated nickel boride (Ni x B) with high catalytic activity, while PR-derived carbon coating was doped with boron atoms from B 4 C (B−C PR ). The B−C PR coating fixed Ni x B/B 4 C particles in the frames and holes to improve the space utilization of NF. Meanwhile, the B−C PR coating effectively protected the catalyst from the corrosion by seawater and facilitates the transport of electrons. The optimal Ni x B/B 4 C/B−C PR /NF required 1.50 and 1.58 V to deliver 100 and 500 mA cm −2 , respectively, in alkaline natural seawater for the oxygen evolution reaction.

研究领域: 材料科学 · 电化学
✓ 已验证 DOI 高影响因子
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iScience · 2023 · IF 5.8

Hydrogen co-production via nickel-gold electrocatalysis of water and formaldehyde

Zhixin Li,Yan Zhang,Qianqian Yang,Jindong Wu,Zhi Ren,Fengzhan Si,Jing Zhao,Jiean Chen

Hydrogen is one of the most promising future energy sources due to its highly efficient energy storage and carbon-free features. However, the energy input required for a hydrogen production protocol is an essential factor affecting its widespread adoption. Water electrolysis for hydrogen production currently serves a vital role in the industrial field, but the high overpotential of the oxygen evolution reaction (OER) dramatically impedes its practical application. The formaldehyde oxidation reaction (FOR) has emerged as a more thermodynamically favorable alternative, and the innovation of compatible electrodes may steer the direction of technological evolution. We have designed Au-Vo-NiO/CC as a catalyst that triggers the electrocatalytic oxidation of formaldehyde, efficiently producing H 2 at the ultra-low potential of 0.47 V (vs. RHE) and maintaining long-term stability. Integrated with the cathodic hydrogen evolution reaction (HER), this bipolar H 2 production protocol achieves a nearly 100% Faraday efficiency (FE).

研究领域: 能源科学 · 化学工程 · 材料科学
✓ 已验证 DOI 高影响因子
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RSC Advances · 2020 ·Vol. 10 ·期 4 ·1956-1965 · IF 3.119

Synthesis of a furfural-based DOPO-containing co-curing agent for fire-safe epoxy resins

Weiqi Xie,Shiwen Huang,Donglin Tang,Shumei Liu,Jianqing Zhao

A furfural-based DOPO-containing flame retardant, 6,6′-(((methylenebis(4,1-phenylene))bis(azanediyl))bis(furan-2-ylmethylene))bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) (MBF-DOPO), was synthesized and utilized as a co-curing agent of 4,4′-diaminodiphenyl methane (DDM) for fire-safe epoxy thermosets. For the cured epoxy resin containing 4.0% MBF-DOPO, the limiting oxygen index (LOI) reached 32.9% (with the V-0 rating in UL-94 test), and the peak heat release rate and total smoke production values were respectively decreased by 29.3% and 33.6%, compared to pure epoxy resin. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) results confirmed that the furfural-based flame retardant MBF-DOPO promoted the charring formation of the epoxy matrix, which effectively isolated the gas and heat transfer during combustion and thus enhanced the fire-safety performance of the epoxy thermosets. This work provides an effective route for synthesizing a furfural-based flame retardant, which possesses great potential for application in fire-safe epoxy thermosets.

研究领域: 材料科学 · 化学工程
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