CATALYSIS LETTERS
·
2023
·
IF 2.8
Xiang Yuchen,Zhang Huiming,Zhang Jingyi,Xu Qiong,Liu Xianxiang,Yin Dulin
Comprehensive use of available biomass, especially low-cost forestry waste to produce bioenergy, materials have great meaning for realization of green and sustainable chemical processes. In this work, forestry sawdusty waste (SD) was used to produce biochar (SDBC-P) via a H 3 PO 4 assisted hydrothermal carbonization method. And a novel zirconium-coordinated biochar catalyst Zr-SDBC-P has been prepared by self-assembly method. Characterization results revealed that hydrothermal carbonization in the presence of H 3 PO 4 promoted the formation of oxygen-containing functional groups (–COOH, Ar–OH) which were used as ligand to obtain high contents of Lewis acid − base sites (Zr 4+ –O 2− ). Zr-SDBC-P-4 showed satisfactory catalytic activity in synthesis of bioderived γ-valerolactone (GVL) from ethyl levulinate (EL). EL conversion of 98.2% and GVL selectivity of 85.4% were obtained within 5 h at 170 °C. In addition, Zr-SDBC-P-4 displayed outstanding chemical stability. There was no obvious decrease of GVL yield after being used for six cycles. Overall, this work offered a viewpoint to design catalyst from value-added utilization of biomass waste. Graphical Abstract
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高影响因子
ACS Catalysis
·
2023
·
IF 12.9
Xugang Yang,Zaihao Yuan,Minghao Zhou,Feng Chen,Bo-Qing Xu,Hui Shi
Lewis acidic heterogeneous catalysts are known to be active for transfer hydrogenation of carbonyl compounds, which occur naturally or can be derived from renewable feedstocks. While previous studies have explored a myriad of Zr-based catalytic systems toward the Meerwein–Pondorf–Verley (MPV) reductions, few have determined intrinsic, site-specific rates under strict kinetic control across a sufficiently wide range of process conditions, causing misconceptions about the true potentials of these catalysts for the targeted transformations. Here, we present a quantitative assessment on the intrinsic activities of four types of Zr catalysts that are purportedly promising candidates for the MPV reductions; the selected catalysts contain active Zr sites within diversified local coordination and secondary solvating environments. A comprehensive kinetic study of ethyl levulinate (EL) MPV reduction in 2-butanol, combined with in situ quantitative titration of the active sites by selective poisoning with alkylphosphonic acid titrants of Lewis acid sites during the reaction, reveals dramatic differences in the relative fraction of active sites (13–78% of total Zr) and turnover rates (>300-fold) among the studied catalysts. Mechanistically, the hydride shift invariably remains as the sole rate-limiting step, regardless of the catalyst; the free energy barriers in both first-order and zero-order kinetic regimes and kinetic isotope effects, however, differ significantly among the catalysts. Through mechanism-based rate equations and transition-state-theory treatments, we further delineate that the wide variations in enthalpic and entropic components not only suggest disparate transition state structures and energetics but also reflect varying adsorption thermodynamics that are influenced by both reactant coordination at and solvent restructuring near the active sites.
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FUEL
·
2023
·
IF 7.4
Wenqi Zhao,Xiaowei Bai,Xiangrui Lin,Yalkunjan Tur sun,Mei Zhong,Zhenghua Dai,Jian Li
Biomass-derived furfural and its derivatives are promising feedstocks for producing valuable C 5 diols by catalytic hydrolysis. However, this process requires selective ring opening of tetrahydrofurfuryl alcohol (THFA) to 1,5-pentanediol, which is challenging. Here we report efficient route for this conversion using Ni-La(OH) 3 catalysts prepared by a green co-precipitation-hydrothermal method. We show that these catalysts can achieve up to 91.7% yield and 94.6% selectivity of 1,5-pentanediol from THFA under mild conditions. We elucidate the key role of the La(OH) 3 phase, the basic sites and the Ni n+ -O-La 3+ structure of the catalysts in promoting the selective hydrogenolysis and ring opening of THFA. We also demonstrate that the co-dehydrogenation of secondary alcohols enables lower reaction pressure and longer catalyst lifetime. Our work provides a sustainable and environmentally benign approach for producing 1,5-pentanediol from biomass-based furfural and its derivatives, which has potential applications in polymer synthesis and green chemistry.
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JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2023
·
IF 2.6
Jian Chen,Mei Dong,Wenjing Shi,Danni Zhao,Wensheng Li,Haoran Liu,Weiping Luo
In this study, the solubility of isophthalic acid (IPA) and m-toluic acid (m-TA) in eight monobasic alcohols, methanol, ethanol, 1-propanol, iso-propanol, 1-butanol, iso-butanol, tert-butanol, and 2-butanol is measured under 101.3 kPa by the method of laser dynamics. The experimental temperature range is 294.35–360.75 K. The measured data showed that the solubility of IPA and m-toluic acid increased with the increase of temperature in the measured temperature range. At the same temperature, the solubility of m-toluic acid in the same pure solvent is higher than that of IPA. The solubility of IPA and m-toluic acid in eight solvents decreased with the increase of the number of carbon atoms of the solvent. At the same temperature, the solubility ratio of m-toluic acid to IPA in iso-butanol is the highest in the same solvent, and the ratio was greater than 70, making it the best solvent for separating IPA and m-toluic acid. The Apelblat model, the Buchowski–Ksiazczak λh model, and the modified nonrandom two-liquid activity coefficient model were used to correlate the experimental data, and the calculated solubility was in good agreement with the measured result. The calculated solubilities were in good fit with the measured results. The thermodynamic properties were calculated, and the main contributor of the standard molar Gibbs energy of IPA and m-toluic acid in eight alcohols is enthalpy, about 55.40 to 82.86%.
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ACS Sustainable Chemistry & Engineering
·
2023
·
IF 8.4
Guoxing Liu,Huai Liu,Junhua Zhang,Rui Zhang,Heng Zhang,Yong Sun,Lincai Peng
Catalytic conversion of concentrated carbohydrates and raw biomass into 5-hydroxymethylfurfural (HMF), an important and value-added platform chemical, is highly desirable for industrial applications but challenging. In this work, the tin pyrophosphate-oxide (SnP2O7–SnO2) catalyst has been designed to efficiently produce HMF from various concentrated carbohydrates and raw biomass. Especially, a high HMF yield of 67.8% was implemented over the SPC4 catalyst from concentrated glucose (36 wt %) in a biphasic solvent system of water and methyl isobutyl ketone. Moreover, the SPC4 catalyst disclosed a wide range of universality for converting various concentrated carbohydrates and raw biomass to HMF with satisfactory yields (45.9–79.5%). To the best of our knowledge, this is the first example of accomplishing appreciable HMF yields from carbohydrates and raw biomass at such a high substrate concentration. It has been demonstrated that the superior catalytic performance of the catalyst should originate from its balanced Lewis and Brønsted acidity and superhydrophilicity property. This work invents a highly promising heterogeneous catalyst for efficiently valorizing renewable lignocellulose-related compounds into versatile furans.
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ACS Omega
·
2023
·
IF 4.1
Yuzhu Li,Kangzhuo Yang,Zhanglan He,Zhipeng Liu,Jialing Lu,Dong Zhao,Jia Zheng,Michael C. Qian
Electronic nose (E-nose) technology is frequently attempted to simulate the human olfactory system to recognize complex odors. Metal oxide semiconductors (MOSs) are E-noses’ most popular sensor materials. However, these sensor responses to different scents were poorly understood. This study investigated the characteristic responses of sensors to volatile compounds in a MOS-based E-nose platform, using baijiu as an evaluation system. The results showed that the sensor array had distinctive responses for different volatile compounds, and the response intensities varied depending on the sensors and the volatile compounds. Some sensors had dose–response relationships in a specific concentration range. Among all the volatiles investigated in this study, fatty acid esters had the greatest contribution to the overall sensor response of baijiu. Different aroma types of Chinese baijiu and different brands of strong aroma-type baijiu were successfully classified using the E-nose. This study provided an understanding of detailed MOS sensor response with volatile compounds, which could be further applied to improve the E-nose technology and its practical application in food and beverages.
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PubMed
高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2023
·
IF 2.6
Mei Dong,Wenjing Shi,Jian Chen,Danni Zhao,Mengmeng Yang,Wenxin Yang,Wei Deng,Wensheng Li,Weiping Luo
In this study, the solubilities of phthalic acid (PA) and o-toluic acid (o-TA) in methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, and tert-butanol were measured by the laser dynamic method at atmospheric pressure (101.3 kPa) in the range of 292.25–353.35 K. The experimental results show that the solubilities of PA and o-TA in eight alcohols are positively correlated with temperature. In the four solvents methanol, ethanol, n-propanol, and n-butanol, the solubilities of PA and o-TA decrease with the increase of the number of carbon atoms in the main chain, and the order of solubility of PA and o-TA in butanol isomers from high to low is tert-butanol, sec-butanol, n-butanol, and iso-butanol. The solubility ratio of o-TA and PA in iso-butanol is the largest, indicating that iso-butanol could best separate the two. The experimental data were correlated by using the Apelblat model, the Buchowski–Ksiazczak λh model, and the modified no n-random two liquid activity coefficient model. The calculated solubilities were in good fit with the measured results. The Akaike information criterion was used to evaluate the selected model. The thermodynamic properties were calculated, and the main contributor of standard molar Gibbs energy of PA and o-TA in eight alcohols is enthalpy, about 54.66 to 68.34%.
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FLUID PHASE EQUILIBRIA
·
2023
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IF 2.6
Xiaomin Qiu,Huaqing Qi,Mengjin Zhou,Zhaoyou Zhu,Yinglong Wang,Jingwei Yang,Hengjun Gai
Sufficient and accurate physical property data is the basis for thermodynamic analysis and process simulation analysis. Reliable thermodynamic model data is essential for the study of extractive distillation separation of azeotropic mixtures. The vapor-liquid equilibrium data of 2-butanol alcohol-ethylene glycol and cyclohexane-butyl butyrate were measured by using a reliable experimental device, namely a modified Rose vapor-recirculating-type equilibrium still. The effects of 12 solvents on the relative volatility of the azeotrope of cyclohexane, 2-butanol alcohol and water were calculated, and ethylene glycol was selected as the best solvent. On this basis, the contribution of different atom pairs and atoms to the interaction between ethylene glycol and cyclohexane/2-butyl alcohol/water was compared and studied, and the reason why ethylene glycol can separate cyclohexane-2-butyl alcohol-water was analyzed. The thermodynamic model parameters obtained from the vapor-liquid equilibrium experiment were used to simulate the extractive distillation process, and total annual cost optimization was performed to improve the process accuracy. Overall, this study improves the application potential of phase equilibrium data in azeotropic separation technology, and establishes a reliable data and model foundation for the sustainable development of 2-butyl alcohol and cyclohexane.
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JOURNAL OF MOLECULAR LIQUIDS
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2019
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IF 4.561
Xiaoqing Yuan,Zhiyong Li,Ying Feng,Yuanchao Pei,Huiyong Wang,Diandian Liu,Dayu Wang,Jianji Wang
At present, it is still a challenge for reversible regulation of phase behavior and microstructure of microemulsions with less energy input and no composition change of the system. Photo-responsive microemulsions provide a potential way to solve these problems. In this work, 10 kinds of photo-responsive ionic liquids (ILs) with azobenzene group were used as photo-responsive surfactants to form microemulsions with water and some alcohols. Factors affecting the phase behavior and sub-regions of microemulsions, such as chemical structure of the ILs, temperature, alcohols properties and UV irradiation , were studied by conductivity, small-angle X-ray scattering, dynamic light scattering and cryo-TEM techniques. It was found that azobenzene-based ILs with a more hydrophilic head group and a shorter alkyl spacer length were favor of the formation of the microemulsions. The phase behavior of the microemulsions only slightly changed after UV irradiation, however, the area of O/W and bi-continuous sub-regions of the microemulsion could be regulated by UV irradiation. At the same time, droplets size increased after UV light irradiation , and could be restored close to the initial value by alternative vis-light irradiation.
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高影响因子
GREEN CHEMISTRY
·
2019
·Vol. 21
·期 3
·606-613
·
IF 9.405
Zhenbing Xie,Bingfeng Chen,Haoran Wu,Mingyang Liu,Huizhen Liu,Jianling Zhang,Guanying Yang,Buxing Han
Transformation of biomass or biomass-based feedstocks into fuels or valuable chemicals is of great importance for the sustainable development of our society. Mesoporous Al2O3–ZrO2 with different Al : Zr molar ratios was prepared by the sol–gel method, and Cu–Ni/Al2O3–ZrO2 catalysts were fabricated by the impregnation method. The catalytic performances of the bifunctional catalysts were studied in the selective hydrogenation of levulinic acid (LA) into 2-methyltetrahydrofuran (MTHF). It was demonstrated that both Cu : Ni and Al : Zr ratios affected the selectivity to MTHF significantly. The bimetallic catalysts Cu–Ni/Al2O3–ZrO2 containing 10 wt% Ni and 10 wt% Cu gave 99.8% MTHF selectivity at full conversion of LA when the Al : Zr ratio was 9 : 1. The outstanding catalytic performance of the catalyst is related to the mesoporous structure, the acidic properties of the support and the synergistic effect between Cu and Ni. The catalyst could be reused five times without a considerable loss of catalytic activity and selectivity.
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JOURNAL OF CHROMATOGRAPHY A
·
2019
·
IF 3.858
Zi-Meng Wang,Cheng-Xiong Yang,Xiu-Ping Yan
Chiral crystalline sponges (CCSs) are a recent class of chiral porous metal complexes potential in chiral recognition. Here we report the fabrication of polysiloxane OV-1701 incorporated CCS-3S (PSO/CCS-3S) coated capillary column as a novel stationary phase for gas chromatographic separation of diverse racemates. CCS-3S with the chiral ligand of ( S )-mandelic was selected as the model CCS. With the aid of polysiloxane OV-1701, PSO/CCS-3S coated capillary column gave improved resolution, broader enantiomers separation scope and much larger McReynolds constants than CCS-3S coated capillary column. Many racemates that cannot be separated on CCS-3S coated capillary column were well resolved on PSO/CCS-3S coated capillary column. The PSO/CCS-3S coated capillary column also gave wide linear range, low limit of detection, good repeatability and reproducibility, and fine inertness and anti-column bleeding properties for the separation of enantiomers. In addition, the PSO/CCS-3S coated capillary column presented better resolution for the studied racemates than commercial β-cyclodextrin based Cyclosil B (30 m long ×0.32 mm i.d. × 0.25 μm film thickness), β-DEX 225 (30 m long ×0.25 mm i.d. × 0.25 μm film thickness) and amino acid based Chirasil L-Val (25 m long ×0.25 mm i.d. × 0.12 μm film thickness) capillary columns. These results indicate the great potential of PSO/CCS-3S coated capillary column in separation of enantiomers.
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高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
·
2019
·
IF 2.29
Pengshuai Zhang,Yameng Wan,Chi Zhang,Rui Zhao,Jiao Sha,Yu Li,Tao Li,Baozeng Ren
The solubility of solid compounds and active pharmaceutical ingredient in different solvents is important for its crystallization and purification industry. In this work, by using a laser dynamic method, the solubility of levamisole hydrochloride in methanol (MT), ethanol (ET), isopropanol (IPA), n-propanol (NPA), n-butanol (NBA), 2-butanol (SBA), isobutanol (IBA), n-pentanol (NPT), 3-methyl-1-butanol (IAA) and n-hexanol (NHA) from (283.15 to 323.15) K, dimethyl sulfoxide (DMSO) from (293.15 to 333.15) K and water from (283.15 to 308.15) K were measured under atmospheric pressure. The measured results showed that the experimental solubility of levamisole hydrochloride increased non-linearly with the temperature in the studied pure solvents. The measured solubility data were all correlated by the Yaws model equation, non-random two liquid (NRTL) model equation, universal quasi chemical (UNIQUAC) model equation, Wilson model equation and λh equation. Besides, the logarithm of activity coefficient of levamisole hydrochloride (lnγ 1 ) were calculated with the NRTL model, Wilson model and UNIQUAC model. The maximum relative average deviation ( ARD ) was 0.2008, the maximum root-mean-square deviation ( RMSD ) was 0.0089. Basically speaking, the measured solubility data in this study can be well correlated with the five thermodynamic models . Based on the solubility data and Wilson model, the mixing entropy, mixing enthalpy and mixing Gibbs energy were evaluated. The logarithm of the solute activity coefficients l n γ 1 in the studied saturated solutions were calculated, The positive values of l n γ 1 means that the repulsive interactions exist between levamisole hydrochloride and the corresponding solvents (NBA, NPA, NHA, IPA, IBA, SBA and IAA), and the solutions system positively deviate from Raoult’s law; The negative values of l n γ 1 means that the attractive interactions exist between levamisole hydrochloride and the corresponding solvents (MT, ET, NPT, DMSO and water), and the solutions system minus deviate from Raoult’s law. This work can give fundamental data for the crystallization and purification of levamisole hydrochloride.
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