Reaction pathways and selectivity in the chemo-catalytic conversion of cellulose and its derivatives to ethylene glycol:A review

Biomass-to-ethylene glycol is an effective means to achieve high-value utilisation of cellulose but is hindered by low conversion efficiency and poor catalyst activity and stability.Glucose and cellobiose are derivatives of cellulose conversion to ethylene glycol,and it is found that studying the reaction process of both can help to understand the reaction mechanism of cellulose.It is desirable to develop a reusable,highly active catalyst to convert cellulose into ethylene glycol.This ideal catalyst might have one or more active sites described the conversion steps above.Here,we discuss the catalyst development of celluloseto-ethylene glycol,including tungsten,tin,lanthanide,and other transition metal catalysts,and special attention is given to the reaction mechanism and kinetics for preparing ethylene glycol from cellulose,and the economic advantages of biomass-to-ethylene glycol are briefly introduced.The insights given in this review will facilitate further development of efficient catalysts,for addressing the global energy crisis and climate change related to the use of fossil fuels.

Sn nucleation and growth from Sn(II)dissolved in ethylene glycol:Electrochemical behavior and temperature effect

Thermodynamic and kinetic aspects of Sn nucleation and growth processes onto a glassy carbon electrode from SnCl2·2H2O dissolved in ethylene glycol solutions were studied.Typical reduction and oxidation peaks observed in voltammograms have demonstrated the capability of ethylene glycol solutions to electrodeposit Sn.The temperature-dependence of diffusion coefficient values derived from potentiodynamic and potentiostatic studies helped to determine and validate estimations of the activation energy for Sn(II)bulk diffusion.Chronoamperometric results have identified that,the suitable model to describe the early stage of Sn electrodeposition could be composed of Sn three-dimensional nucleation and diffusion-controlled growth and water reduction contributions,which was duly validated by theoretical and experimental approaches.From the model,typical kinetic parameters such as the nucleation frequency of Sn(A),number density of Sn nuclei(N_(0)),and diffusion coefficient of Sn(II)ions(D),were determined.The presence of Sn nuclei with excellent quality and their structures were verified using SEM,EDX,and XRD techniques.

Analysis of Ethylene Glycol Degumming Process and Characterization of Hemp Fibers

To overcome the shortcomings of traditional degumming process,an efficient and environmentally friendly ethylene glycol(EG) degumming process was adopted to degum hemp fibers.The surface morphology,chemical composition,chemical structures,and mechanical properties of the fiber samples were analyzed to explore the mechanism of the degumming process.It was found that the EG degumming process could be divided into the main degumming stage(heating) and the supplementary degumming stage(insulation).The removal rates of hemicellulose and lignin in the main degumming stage were 70.56% and 60.17%,respectively.In the supplementary degumming stage,9.95% hemicellulose and 25.39% lignin were removed.It is confirmed that EG can separate hemp fibers effectively with less damage,which holds great potential for the biomass fiber separation technology.

Study of Thermal,Phase Morphological and Mechanical Properties of Poly(L-lactide)-b-Poly(ethylene glycol)-b-Poly(L-lactide)/Poly(ethylene glycol)Blend Bioplastics

A poly(L-lactide)-b-poly(ethylene glycol)-b-poly(L-lactide)(PLLA-PEG-PLLA)block copolymer has great potential for use as a flexible bioplastic.Highly flexible bioplastics are required for flexible packaging applications.In this work,a PEG was incorporated into block copolymer as a plasticizer by solvent casting.PLLA-PEG-PLLA/PEG blends with different blend ratios were prepared,and the plasticizing effect and miscibility of PEG in block copolymer were intensively investigated compared to PLLA/PEG blends.The results indicated that the PEG was an effective plasticizer for the block copolymer.The blending of PEG decreased glass-transition temperature and accelerated the crystallization of both the PLLA and PLLA-PEG-PLLA matrices.The PEG was completely miscible when blended with block copolymer and it improved thermal stability of the block copolymer matrix but not of the PLLA matrix.Film extensibility of PLLA-PEG-PLLA/PEG blends steadily increased as the PEG ratio increased.These non-toxic and highly flexible PLLA-PEG-PLLA/PEG bioplastics are promising candidates for several applications such as biomedical devices,tissue scaffolds and packaging materials.

Preparation and Thermo-Responsive Properties of Poly(Oligo(Ethylene Glycol)Methacrylate)Copolymers with Hydroxy-Terminated Side Chain

Thermo-responsive random copolymers,poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-(ethylene glycol)methyl ether methacrylate)(P(EO_(2)-co-EO_(4/5)))and poly(2-(2-methoxyethoxy)ethoxyethyl methacrylate-co-ethylene glycol methacrylate(P(EO2-co-EG4/5))are synthesized via atom transfer radical polymerization(ATRP).The successful synthesis and the narrow polydispersity index(PDI)of two copolymers are indicated by 1H nuclear magnetic resonance(1H-NMR)and gel permeation chromatography(GPC)analyses.The transition behaviors of polymers in the aqueous solution are demonstrated by changes in turbidity and particle sizes.The transition behavior of P(EO2-co-EG4/5)is found to be milder than that of P(EO2-co-EO4/5).Moreover,the presence of hydrogen bonds without thermo-responsive properties established by hydroxyl groups in the end-side chain of P(EO_(2)-co-EG_(4/5))hinders the dehydration at the transition temperature(TT).Attenuated total reflection Fourier transform infrared spectrometry(ATR-FTIR)analysis along with contact angle measurements reveals that both P(EO_(2)-co-EO_(4/5))and P(EO_(2)-co-EG_(4/5))films undergo phase transitions from hydrophilicity to hydrophobicity above TT.By examining the swelling and collapse behaviors of the polymer films during phase transitions,it can be concluded that the end hydroxyl groups may establish hydrogen bonds with neighboring ether groups within the films,which remain intact throughout the phase transition process due to their strong bonding interactions.This leads to an increase in steric hindrance within swollen films thereby impeding dehydration processes and inducing hysteresis during phase transitions.

The HY5 transcription factor negatively regulates ethylene production by inhibiting ACS1 expression under blue light conditions in pear

Ethylene is the main factor controlling fruit ripening of pear(Pyrus ussuriensis).Ethylene production rate is negatively correlated with fruit shelf life;therefore,it is important to decrease the ethylene levels for optimal fruit storage.Here,we observed that blue light treatment could inhibit ethylene production and promote the expression of ELONGATED HYPOCOTYL 5(PuHY5),a basic leucine zipper domain(bZIP)transcription factor.The following studies showed that PuHY5 could bind to the promoter of ACC synthase 1(PuACS1),a rate-limiting enzyme in ethylene biosynthesis,and inhibit its expression.For pears in which Pu HY5 was silenced,the ethylene production and PuACS1 expression were much higher than those in the control fruit.These results demonstrated that blue light inhibited ethylene production through the induction of Pu HY5 in pear.Our finding provides a new method for prolonging fruit shelf life.

Significance of Nanoparticles Aggregation with Cattaneo-Christov Heat Flux on the Water and Ethylene Glycol Mixture Based MWCNTs-Nanofluid Flow over a Stretching Cylinder

This work aims to analyze the flow of electrically conducting MWCNTs-nanofluid over a stretching cylinder with the aggregation and non-aggregation effects of nanoparticles. The working fluid comprised a combination of water and ethylene glycol, with volumetric proportions of (50:50) considered. Convective boundary constraints and modified Fourier law are implemented in heat transmission assessment. The mathematical flow model is formulated in the form of PDEs and is transformed into ODEs via similarity transformation. Numerical outcomes will be obtained with the use of the bvp4c technique and will be displayed with the help of graphs and tables. The results show that the surface drag coefficient is enhanced in the case of aggregation of nanoparticles whereas heat transfer rate is enhanced in the non-aggregation effect of nanoparticles. Furthermore, the temperature distribution enhances the increasing values of particle volume fraction in the case of aggregation effects of nanoparticles whereas temperature distribution lowers in the case of non-aggregation effect of nanoparticles. .

Revealing the roles of components in glucose selective hydrogenation into 1,2-propanediol and ethylene glycol over Ni-MnO_x-ZnO catalysts

MnOx-promoted Ni-based catalyst supported by ZnO was developed to selectively hydrogenate glucose into polyols in water at 523 K with a yield of 64.9%. Using glucose, sorbitol, glycerol and LA as the rawmaterials, the roles of nickel, ZnO and MnOx were investigated. The results show that nickel provided a new pathway of glucose to sorbitol and played an important role in the hydrogenation of C3 intermediates to 1,2-propanediol(1,2-PDO). The high yield of 1, 2-PDO was attributed to effective C–C bond cleavage performance of ZnO support promoted by MnOx. ZnO and MnOx contribute to the conversion of glycerol to lactic acid(LA) and LA to 1, 2-PDO, respectively. A concise pathway for hydrogenation of glucose over Ni-based catalyst was proposed.

The adsorption properties of NaY zeolite for separation of ethylene glycol and 1,2-butanediol: Experiment and molecular modelling

The separation of ethylene glycol(EG)and 1,2-butanediol(1,2-BDO)azeotrope in the synthesis process of EG via coal and biomass is becoming of increasing commercial and environmental importance.Selective adsorption is deemed as the most promising methods because of energy saving and environment favorable.In this paper,NaY zeolite was used to separate 1,2-BDO from EG,and its adsorption properties was then investigated.The isotherms of EG and 1,2-BDO in vapor and liquid phases from 298 to 328 K indicated that they fitted Langmuir model quite well,and the NaY zeolite absorbent favored EG more than 1,2-BDO.The Grand Canonical Monte Carlo(GCMC)and molecular dynamics(MD)simulation techniques were conducted to investigate the competition adsorption and diffusion characteristics in different adsorption regions.It was observed that EG and 1,2-BDO molecules all have the most probable locations of the center of the 12-membered ring near the Na cations.The diffusivities of EG are lower than those of 1,2-BDO at the same adsorption concentration.At last,the breakthrough curves of the binary mixture regressed from the empirical Dose–Response model in fixed-bed column showed that the adsorption selectivity of EG could reach to as high as 2.43,verified that the NaY zeolite could effectively separate EG from 1,2-BDO.This work is also helpful for further separation of other dihydric alcohol mixtures from coal and biomass fermentation.

Solubility of Ammonia in Ethylene Glycol Between 303K and 323K under Low Pressure from 0.030 to 0.101 MPa

The solubility of ammonia in ethylene glycol is measured by an isothermal solubility equilibrium method at temperatures of （303.2, 308.2, 313.2, 318.2 and 323.2） K and total pressures of （0.030, 0.040, 0.050, 0.060, 0.070, 0.080, 9.090 and 0.101） MPa. The molality of ammonia in ethylene glycol ranges from 1.925 mol·kg-1 to 8.265 mol·kg-1. The experimental results are used to determine Henry＇s law constant of ammonia in ethylene glycol Furthermore, experimental data are correlated by applying the thermodynamic model on the basis of extended Raoult＇s law, extended Henry＇s law, corresponding-states correlations and Pitzer＇s molality scale based equation. The overall average relative deviation between the calculated data and the experimental data of Henry＇s law constant and ammonia solubility are 2.029% and 2.164% respectively.

Effect of poly(ethylene glycol) molecular weight on CO_2/N_2 separation performance of poly(amide-12-b-ethylene oxide)/poly(ethylene glycol) blend membranes

Membranes from block copolymer poly(amide-12-b-ethylene oxide)(Pebax1074) and its blends with different molecular weight poly(ethylene glycol)(PEG)(200, 400, 600, 1500, 4600 and 8000) were prepared. The thermal properties and structures of Pebax1074/PEG blend membranes were characterized by DSC and SEM, and the gas permeation properties of CO_2 and N_2 were also investigated at different temperatures. For Pebax1074/PEG blend membranes with low molecular weight PEG(MW≤ 600), higher gas permeabilities than Pebax1074 were achieved. The permeability increased with the increase of PEG molecular weight. The addition of low molecular weight PEG resulted in decrease in activation energy of permeation. For Pebax1074/PEG blend membranes with high molecular weight PEG(MW≥ 1500), due to the melt of PEO phase crystals, the gas permeation properties of blend membranes were temperaturedependent, which could be divided into crystalline region, transition region and amorphous region according to two different transition temperatures. PEG molecular weight and operation temperature determined different gas permeation properties of Pebax1074/PEG blend membranes in three regions. The activation energies of permeation in crystalline region were larger than those in amorphous region.

Electrodeposition behavior of bright nickel in air and water-stable betaine·HCl-ethylene glycol ionic liquid

The electrodeposition behaviors of nickel on glassy carbon（GC） and carbon steel（CS） electrodes were investigated in the14.3%-85.7%（mole fraction） betaine.HCl ethylene glycol（EG） ionic liquid using cyclic voltammetry and chronoamperometry.The results indicated that the reduction of Ni（Ⅱ） on CS electrode via a diffusion-controlled quasi-reversible process was much more facile and easier than that occurred on GC electrode,which followed a diffusion-controlled three-dimensional instantaneous nucleation and growth.Scanning electron microscopy was used to observe that the deposit was dense and contained fine crystallites with average size of（80±4） nm.Energy dispersive spectrometer analysis showed that the obtained deposit was metallic nickel.X-ray diffraction spectroscopy indicated that（111） plane was the most preferred crystal orientation.The nickel deposit was luminous and bright,and had good adhesion with the CS substrate.

Effect of Internal Ethylene and 1-Methylcyclopropene on Ethylene Metabolism and Membrane Lipid Peroxidation in Papaya Fruit

[Objective] This study was conducted to evaluate the effect of 1-methylcy- clopropene （1-MCP） on fruit firmness, and the activity of the enzymes involved in ethylene metabolism and membrane lipid peroxidation. [Method] The nearly ripe fruits of the papaya cultivar Risheng were randomly assigned to one of four groups. Two groups were treated under hypobaric and hypoxic （HH） atmosphere condition for six hours, and immediately soaked in deionized water （HH alone）, or fumigated with 2.0 mg/L 1-MCP （HH＋I-MCP） for 24 h. The other two groups untreated under HH condition were also soaked in deionized water （negative control）, or fumigated with 2.0 mg/L 1-MCP （1-MCP alone） for 24 h. After that, the fruits of all the four treatments were stored at room temperature （23＋1） ℃. Cell membrane permeability, fruit firmness, respiration rate, ethylene release rate, SOD activity, POD activity, CAT activity, MAD content and LOX activity were measured once every three days during storage. [Result] Treatment with 1-MCP delayed the occurrence of the peaks of respiration rate and ethylene release rate, significantly reduced the accumulation of malondialdehyde （MDA）, and inhibited the decrease in papaya fruit firmness. Compared with the control, 1-MCP treatment significantly increased the SOD （su- peroxide dismutase）, POD （peroxidase） and CAT （catalase） activity, reduced the ac- tivity of lipoxygenase （LOX）, a product of lipid peroxidatlon in membranes, and in- hibited ethylene biosynthesis, thus delaying the aging process and prolonging the storage life of papaya fruits. [Conclusion] The results will provide a theoretical basis for analvzina the key factors controllinq postharvest maturity and aging of papaya fruits.

Cu_2[ethyleneglycolbis(2-aminoethy)tetraacetate·2H_2O]·2H_2O:双核铜配合物的合成和晶体结构

乙二醇双(2-氨乙基醚)四乙酸(ethylene glycol bis(2-amino ethy)tetraacetate:EGTA)和氯化铜采用溶液蒸发方法在甲醇和水的混合溶液中成功合成双核铜配合物Cu2[EGTA.2H2O].2H2O。该晶体的结构数据是在单晶衍射仪进行收集的。通过晶体结构分析,该晶体属单斜晶系,空间群为C2/c,晶胞参数如下:a=21.013(4),b=7.5503(1),c=13.577(2),β=90.877(2)°,V=2153.8(6)3。在化合物中,铜离子分别与配体的三个氧原子和一个氮原子以及一个水分子成键,采取五配位四面体构型,铜离子空间构型是畸变的四方锥。另外,游离的水分子与配体的氧原子形成氢键而构筑成超分子。

Effect of copper loading on texture,structure and catalytic performance of Cu/SiO_2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol

Cu/SiO2 catalysts prepared by a convenient and efficient method using the urea hydrolysis deposition-precipitation （UHDP） technique have been proposed focusing on the effect of copper loading.The texture,structure and composition are systematically characterized by ICP,FTIR,N 2-physisorption,N2O chemisorption,TPR,XRD and XPS.The formation of copper phyllosilicate is observed in Cu/SiO2 catalyst by adopting UHDP method,and the amount of copper phyllosilicate is related to copper loading.It is found the structure properties and catalytic performance is profoundly affected by the amount of copper phyllosilicate.The excellent catalytic activity is attributed to the synergetic effect between Cu0 and Cu ＋.DMO conversion and EG selectivity are determined by the amount of Cu0 and Cu＋,respectively.The proper copper loading （30 wt%） provides with the highest ratio of Cu ＋ /Cu0,giving rise to the highest EG yield of 95% under the reaction conditions of p=2.0 MPa,T=473 K,H2/DMO=80 and LHSV=1.0h-1.

Synthesis of Nano-sized Yttria via a Sol-Gel Process Based on Hydrated Yttrium Nitrate and Ethylene Glycol and Its Catalytic Performance for Thermal Decomposition of NH_4ClO_4

Nano-sized yttria particles were synthesized via a non-aqueous sol-gel process based on hydrated yttrium nitrate and ethylene glycol. The effects of the molar ratio of ethylene glycol to yttrium ion and calcination temperature on crystallite size of the products were studied. The catalytic performance of the as-prepared yttria for the ammonium perchlorate （AP） decomposition was investigated by differential scanning calorimetry （DSC）. The results indicate that the nano-sized cubic yttria particles with less than 20 nm in average crystallite size can be obtained after 2 h reflux at 70℃, dried at 90 ℃, forming xerogel, and followed by annealing of xerogel for 2 h, and that the addition of the nano-sized yttria to AP incorporates two small exothermic peaks of AP in the temperature ranges of 310 - 350 ℃ and 400 - 470 ℃ into a strong exothermic peak of AP and increases the apparent decomposition heat from 515 to over 1110 J·g^- 1. It is also clear that the temperature of AP decomposition exothermic peak decreases and the apparent decomposition heat of AP increases with the increase of the amount of nano-sized yttria. The fact that the addition of the 5 % nano-sized yttria to AP decreases the temperature of AP exothermic peak to 337.7℃ by reduction of 114.6℃ and increases the apparent decomposition heat from 515 to 1240 J·g^-1, reveals that nano-sized yttria shows strong catalytic property for AP thermal decomposition.

Selective swelling of polysulfone/poly(ethylene glycol) block copolymer towards fouling-resistant ultrafiltration membranes

Fouling resistance of ultrafiltration(UF) membranes is critical for their long-term usages in terms of stable performance, so convenient approaches to prepare fouling-resistant membranes are always anticipated. Herein, we demonstrate the facile fabrication of antifouling polysulfone-block-poly(ethylene glycol)(PSF-b-PEG, SFEG)composite membranes. SFEG layer was coated onto macroporous supports and cavitated by immerging them in acetone/n-propanol following the mechanism of selective swelling induced pore generation. Thus-produced SFEG membranes possessed high permeance and excellent mechanical strength. Meanwhile, the structures and separation performances of the SFEG layers can be continuously tuned through simply changing swelling durations. More importantly, the hydrophilic PEG chains were spontaneously enriched onto the pore walls through swelling treatment, endowing intrinsic antifouling property to the SFEG membranes. Bovine serum albumin(BSA)/humic acid(HA) fouling tests proved the prominent fouling resistance of SFEG membranes, and the fouling resistance is expected to be long-standing because of the firm connection between PEG chains and PSF matrix by covalent bonding.

An Efficient and Stable Ionic Liquid System for Synthesis of Ethylene Glycol via Hydrolysis of Ethylene Carbonate

An ionic liquid system of [Bmim]X/[Bmim]OH(X Cl,BF4,and PF6,) was developed for the hydroly-sis of ethylene carbonate to ethylene glycol. The important parameters,such as the variety of ionic liquids,molar ratio of [Bmim]X to [Bmim]OH,amount of ionic liquid,molar ratio of water to ethylene carbonate,reaction tem-perature,pressure and reaction time,were investigated systematically. Excellent yield(>93%) and high selectivity(99.5%) of ethylene glycol were achieved. Under the optimum reaction conditions,the ionic liquid system could be reused at least five times and the selectivity of ethylene glycol remained higher than 99.5%.

Effects of cupric ions on the corrosion behavior of aluminum alloy 5A02 in ethylene glycol–water solution

The effects of cupric ions on the corrosion behavior of aluminum alloy 5A02 in ethylene glycol–water solutions were studied by potentiodynamic polarization,electrochemical noise(EN),and complementary techniques including scanning electron microscopy(SEM),atomic force microscopy(AFM),and X-ray photoelectron spectroscopy(XPS). A positive corrosion potential and increased corrosion current were observed due to the deposition of copper. The results demonstrate that the main corrosion type was pitting and the increasing cupric ion concentration augmented the pitting density. The pits became larger and deeper as a result of the embedment of copper into the surface of the alloy. Cupric ions were preferentially deposited at the defects around the secondary phase,leading to the formation of Al–Cu microgalvanic couples,which increased the corrosion rate. The corrosion rate gradually reached a stable value as the concentration of cupric ions was increased beyond 10 mmol/L.

Controlled delivery of ibuprofen from poly(vinyl alcohol)-poly(ethylene glycol) interpenetrating polymeric network hydrogels

Hydrogels composed of poly(vinyl alcohol)(PVA) and poly(ethylene glycol)(PEG) were synthesized using glutaraldehyde as crosslinker and investigated for controlled delivery of the common anti-inflammatory drug, ibuprofen(IBF). To regulate the drug delivery, solid inclusion complexes(ICs) of IBF in β–cyclodextrin(β–CD) were prepared and added to the hydrogels. The ICs were prepared by the microwave irradiation method, which is more environmentally benign. The formation of IC was confirmed by various analytical techniques and the synthesized hydrogels were also characterized. Controlled release of drug was achieved from the hydrogels containing the ICs in comparison to the rapid release from hydrogels containing free IBF.The preliminary kinetic analysis emphasized the crucial role of β–CD in the drug release process that influences the polymer relaxation, thereby leading to prolonged release. The cytotoxicity assay validated the hydrogels as non-toxic in nature and hence can be utilized for controlled delivery of IBF.