CARBOHYDRATE RESEARCH
·
2022
·
IF 2.975
Huifang Ren,Xiao-Yang Yue,Wen-Sheng Dong
We propose a new approach for the synergistically catalytic conversion of cellulose to levulinic acid (LA) in water by SO 3 H-functionalized ionic liquid (SFIL) and lanthanide chloride (LnCl 3 ). Compared with using 1-methyl-3-(3-sulfopropyl)imidazolium chloride ([MIMPS]Cl) only, the LA yield using [MIMPS]Cl and ErCl 3 increased by 14.4% and 13.6% at 50 mol% of IL and 30 mol% of IL, respectively. Moreover, the combined [MIMPS]Cl and ErCl 3 system can tolerate high concentrations of substrates and maintain high activity at eleven runs. We also investigated the effects of the cation structure of ionic liquids (alkyl chain length, hydroxyl groups on the side chains, and aromatic properties) on LA production. The observations can provide useful information for designing efficient ionic liquid catalysts for biomass utilization.
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PubMed
高影响因子
Materials
·
2022
·Vol. 15
·期 21
·7464
·
IF 3.748
Ying Yang,Suoying Zhang,Lin Gu,Shijie Hao
Herein, we report a stable catalyst with Ru single atoms anchored on a one-dimensional carbon fiber@graphitic carbon nitride hierarchy, by assembling wet wipes composed of fiber-derived carbon fiber (CF), melamine-derived graphitic carbon nitride (g-C3N4) and RuCl3 before NaBH4 reduction. The atomically dispersed Ru species (3.0 wt%) are tightly attached via N-coordination provided by exterior g-C3N4 nanosheets, and further stabilized by the interior mesoporous CF. The obtained CF@g-C3N4–Ru SAs catalyst can be cycled six times without notable leaching of Ru or loss of GVL yield in the acidic media. This catalyst is more stable than Ru nanoparticles supported on CF@g-C3N4, as well as Ru single atoms anchored on CF and g-C3N4, and proves to be one of the most efficient metal catalysts for aqueous LA hydrogenation to γ-valerolactone (GVL). The isolated Ru atoms by strong N-coordination, and their enhanced electron/mass transfer afforded by the one-dimensional hierarchy, can be responsible for the excellent durability of CF@g-C3N4–Ru SAs under harsh reaction conditions.Keywords:Ru single atom;one-dimensional hierarchy;levulinic acid;γ-valerolactone;stability
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高影响因子
BIORESOURCE TECHNOLOGY
·
2022
·
IF 11.889
Shanta Dutta,Qiaozhi Zhang,Yang Cao,Chunfei Wu,Konstantinos Moustakas,Shicheng Zhang,Ka-Hing Wong,Daniel C.W. Tsang
Lignocellulosic paper waste constitutes a major waste stream globally, which should be valorised for chemical production. However, paper properties ( e.g. , feedstock composition, cellulosic crystallinity, and thermal stability/degradability) vary with raw materials and pulping processes. This study investigated levulinic acid (LA), hydroxymethylfurfural (HMF), and furfural production by H 2 SO 4 and FeCl 3 catalysed conversion of nine types of paper wastes in a green solvent system (1:1 γ‐valerolactone/water). At 160–180 °C for 1–20 min, ∼23–27 wt% LA yield was achieved from sanitary papers, tracing/parchment paper, and paper food box mainly containing crystalline cellulose, while a lower LA yield (∼10–20 wt%) was obtained from other paper wastes with high contents of ash and lignin. A higher selectivity towards HMF (∼12 mol%) was achieved in the presence of FeCl 3 . A furfural yield of ∼ 4–7.5 wt% was also obtained from the hemicellulose content. This study elucidates crucial factors and desirable characteristics of paper waste for catalytic valorisation.
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Bioresources and Bioprocessing
·
2022
·Vol. 9
·期 1
·1-10
·
IF 4.983
Zhai Siyu,Zhang Lihe,Zhao Xi,Wang Qian,Yan Yin,Li Cui,Zhang Xu
The current energy crisis has prompted the development and utilization of renewable energy and energy storage material. In this study, levulinic acid (LA) and 1,4-butanediol (BDO) were used to synthesize a novel levulinic acid 1,4-butanediol ester (LBE) by both enzymatic and chemical methods. The enzymatic method exhibited excellent performance during the synthesis process, and resulted in 87.33% of LBE yield, while the chemical method caused more by-products and higher energy consumption. What’s more, the thermal properties of the obtained LBE as a phase change material (PCM) were evaluated. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) showed that the melting temperature, latent heat of melting, and pyrolysis temperature were 50.51 °C, 156.1 J/g, and 150–160 °C, respectively. Compared with the traditional paraffin, the prepared PCM has a superior phase transition temperature, a higher latent heat of melting, and better thermal stability. The thermal conductivity could be increased to 0.34 W/m/k after adding expanded graphite (EG). In summary, LBE has great potential in the application of energy storage as a low-temperature phase change energy storage material. Graphical Abstract
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高影响因子
Reaction Kinetics Mechanisms and Catalysis
·
2021
·Vol. 134
·期 2
·777-792
·
IF 2.081
Liu Yingxin,Zhang Kaiyue,Zhang Liang,Wang Yun,Wei Zuojun
The selective reductive amination of levulinic acid (LA) into pyrrolidone derivatives is regarded as one of the most promising reactions in the fields of biomass conversion into high value-added chemicals. Herein, we report a one-pot synthesis of N -substituted-5-methyl-2-pyrrolidones by reductive amination of LA/ester with nitriles over several commercial catalysts. Among the catalysts texted, Pd/C was found to be the most efficient for the reductive amination of LA/ester with various nitriles to give high yields of pyrrolidones (up to 92%) under mild reaction conditions (80 °C, 1.6 MPa H 2 , tetrahydrofuran solvent). And the catalyst showed good reusability.
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高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Yaowei Lu,Yongxing Wang,Qinghu Tang,Qiue Cao,Wenhao Fang
The synergistic effect in a bimetallic oxide usually plays a vital role in determining the behavior of supported-metal catalysts. We show the unique synergy in a Sn x Mn 1 O y oxide, which can boost the hydrogenation catalysis of supported Pt nanoparticles for selective conversion of levulinic acid (LA) to γ-valerolactone (GVL). On a series of Pt/Sn x Mn 1 O y catalysts with a similar Pt loading ( ca. 0.44 wt%) and a controlled Pt size ( ca. 2.7 nm), the intrinsic TOF presents a volcano-like dependence on Pt 0 sites and Lewis acidity, which is determined by the variable synergistic effect between MnO y and SnO y . The optimal Pt/Sn 0.8 Mn 1 O y catalyst exhibits a high i TOF of 2709 h −1 and achieves 100% selectivity to GVL at 99% conversion of LA at 120 ℃ and 2 MPa of H 2 . DFT calculations demonstrate that the incorporation of Sn can provide a lower energy barrier for the crucial elementary reactions.
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ENERGY & FUELS
·
2019
·
IF 3.021
Mingxue Su,Wenzhi Li,Qiaozhi Ma,Song Li,Tao Yang,Xiaomeng Dou
A water-tolerant, basic, and hierarchical MFI zeolite catalyst was synthesized and applied in the aldol condensation reaction between biomass-derived furfural and levulinic acid. The results showed that the addition of poly(diallyl dimethylammonium chloride) significantly affected the textural and acid–base properties of hierarchical zeolite, which subsequently influenced the catalytic performance of hierarchical zeolite. In the aqueous phase, potassium-modified, hierarchical MFI zeolite (K/H-MFI-n) was more active for aldol condensation between furfural and levulinic acid than the potassium-modified, conventional MFI zeolite (K/MFI). This was ascribed to higher basic sites density and improved diffusion limitation of K/H-MFI-n. A 70.6% yield of aldol condensation product was achieved with a complete conversion of furfural at 100 °C for 9 h by K/H-MFI-0.6. However, only 27.4% yield of aldol condensation product with 55.1% furfural conversion was obtained by K/MFI at the same condition. Two major isomeric aldol products, β-furfurylidenelevulinic acid and δ-furfurylidenelevulinic acid (β-FDLA and δ-FDLA), were obtained after acidification. K/H-MFI-n displayed an enhanced selectivity (54.9%) to δ-FDLA, owing to the stronger basicity of K/H-MFI-n. However, K/MFI showed a preferred selectivity to β-FDLA (42.7%), owing to the dominant Lewis acidity. Recyclability research showed that the catalytic performance of potassium-modified, hierarchical MFI zeolite was acceptable after five runs.
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RSC Advances
·
2016
·Vol. 6
·期 45
·39131-39136
·
IF 3.289
Kai Qin,Yani Yan,Yahong Zhang,Yi Tang
Cellulose without any pretreatment was directly converted into levulinic acid (LA) in a microwave-assisted acidic catalytic system with a high ionic strength. The highest LA yield could reach 67.3 mol% within 60 min even when the cellulose concentration was as high as 10 wt%. It is concluded that high ion strength and microwave irradiation were jointly responsible for the fast cellulose conversion and high LA yield, and a cooperative acceleration mechanism is finally proposed. The high ion concentration provided by alkali metal halides not only accelerated the cellulose hydrolysis but also facilitated glucose conversion into LA by shifting the weak acid ionization equilibria, and microwave irradiation further promoted this salt effect by its characteristic heating way of ion conduction. Such a one-pot catalytic system provides a possibility of practical application for direct highly efficient conversion of cellulose due to its green properties, low cost and efficient characteristics.
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GREEN CHEMISTRY
·
2017
·Vol. 19
·期 9
·2201-2211
·
IF 9.125
Wenxiu Cao,Wenhao Luo,Hongguang Ge,Yang Su,Aiqin Wang,Tao Zhang
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is a crucial reaction included in many biorefinery schemes for the production of renewable chemicals and fuels. The development of highly stable supported Ru-based catalysts in the polar protic liquid phase under hydrothermal conditions is still a major challenge. Here, we prepared a 0.85 wt% Ru/ZrO2@C catalyst using a new stabilization strategy based on the UiO-66 (Zr-MOF) material. The catalytic performance of this Ru/ZrO2@C in LA-to-GVL was tested and compared with commercial 5 wt% Ru/C at 10 bar H2, 413 K in water and also in high protic aqueous solution (pH = 1). The full conversion of LA and quantitative yield of GVL were achieved with both catalysts. However, the 5 wt% Ru/C showed poor resistance to deactivation already after the first run. ICP, XPS, HRTEM, AC-STEM, TPR and physisorption data showed that quick deactivation of Ru/C was mainly caused by the leaching of ruthenium in addition to the loss of surface area via carbonaceous deposition in micro-pores. In contrast, the self-prepared Ru/ZrO2@C catalyst showed no apparent drop in catalytic performance either in water or in high protic aqueous solution upon multiple recycling, and no leaching of ruthenium was found even under harsh conditions (pH = 1). Remarkably, in the Ru/ZrO2@C catalyst, Ru (probable single-atom) was highly dispersed on nanotetragonal ZrO2 (3.3 nm), embedded in the amorphous carbon, and no apparent Ru nanoclusters were observed even after reactions. TPR results indicated that this excellent stability might be attributed to strong metal–support interaction between Ru and nanotetragonal ZrO2.
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NEW JOURNAL OF CHEMISTRY
·
2015
·Vol. 39
·期 10
·8158-8164
·
IF 3.086
Dongshun Deng,Guoqiang Han,Yaotai Jiang
Efficient and reversible absorption of SO2 in six new deep eutectic solvents (DESs) composed of levulinic acid (LA) and quaternary ammonium salts (choline chloride, CC; choline acetyl chloride, CAC; tetraethylammonium chloride, TEAC; tetraethylammonium bromide, TEAB; tetrabutylammonium chloride, TBAC; tetrabutylammonium bromide, TBAB) was systematically investigated. The molar ratio of LA to quaternary ammonium salt was fixed at 3 : 1. The results showed that all DESs possessed satisfactory performance for SO2 absorption, with the maximum absorption capacity of 0.625 g SO2 per g DES of LA–TEAC at 293.15 K under ambient pressure. The absorbed SO2 was easily released by bubbling N2 at 323.15 K and the regenerated DES was recycled five times without obvious loss of absorption performance. The solubility of SO2 in DES of LA–CC at T = 293.15, 303.15, 313.15, and 323.15 K under subatmospheric pressures was also determined. The relative thermodynamic parameters, i.e., absorption enthalpy, absorption entropy, and absorption Gibbs free energy, were further calculated, giving results with small negative values. The influence of water content on the SO2 absorption was also investigated. According to NMR and FTIR analyses, the absorption of SO2 in DES was a physical process. Moreover, all the DESs exhibited high selectivity for SO2/CO2. The present DESs are promising absorbents for SO2 because of their high absorption capacity and good reversibility.
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GREEN CHEMISTRY
·
2021
·Vol. 23
·期 23
·9669-9682
·
IF 10.182
Wang Yue,Lihua Zhang,Lulu Deng,Yuanlong Guo,Qinqin Xu,Wei Peng,Peng Chen,Haibo Xie,Guanglong Zou,Songmiao Liang
Facile dissolution of silk fibroin by using sustainable solvents is the first challenge to be overcome towards its value-added utilization. In this study, sustainable protic ionic liquids (PILs), which were prepared by a simple solventless neutralization reaction of 1,5-diazabicyclo [4.3.0]-5-nonene (DBN) and biomass-derived levulinic acid (Lev), were identified to have good solubility to silk fibroin at mild conditions. Furthermore, the co-dissolution of silk fibroin and cellulose was investigated, and the solute-solvent interaction was elucidated by 13C NMR spectroscopy. The findings demonstrated that the strong hydrogen bonding forming ability of [DBNH][Lev] PILs partially arose from the potential keto–enol tautomerism of levulinate and endowed it with desirable solubility of cellulose and silk fibroin. The rheological properties of cellulose/silk fibroin solutions were systematically studied, indicating that the mass feed ratio of cellulose/silk fibroin significantly affected the apparent viscosity, overlap concentration (c*), activation energy, storage modulus and loss modulus. The interaction and aggregation between cellulose and silk fibroin were further elucidated by dynamic light scattering (DLS). The solution properties provided great opportunities for regenerated cellulose/silk fibroin composited membranes and fiber preparation, and a series of composite membranes were facilely prepared by sol–gel transition using ethanol as a coagulation bath. Various techniques were employed to elucidate the corrections among the structural, morphological, thermal and mechanical properties of the composited membranes and fibers, including infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and tensile tests. It was found that composited membranes (C50S50) had the best mechanical properties, with a tensile strength of 50 MPa and oxygen permeability of 0.0055 cm3 μm (m2 day atm)−1. Moreover, the composited fiber (C80S20) has desirable tensile strength of 152 MPa and an elongation at break of up to 12.8%.
研究领域:
生物材料学
·
化学工程
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高影响因子
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
·
2024
·
IF 11.2
Hongguang Zhang,Ying Zhu,Furui Hu,Wuxiang Zhang,Fuzheng Fu,Tao Gan,Zuqiang Huang,Huayu Hu,Yanjuan Zhang
ABSTRACT Water-assisted proton hopping (WAPH) plays an important role in the aqueous-phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). In this study, based on a strategy of spontaneously polarized ceramic (SPCE)-reinforced WAPH, a Ni–Co/SPCE–C catalyst was constructed by high-temperature calcination of a dual mechanical activation-treated precursor. Ni–Co/SPCE–C with favorable structural characteristics, intimate interfacial compatibility, and unique spontaneous polarization effect enhanced the migration efficiency of active hydrogen and activated water to form small water clusters, contributing to outstanding catalytic activity for aqueous-phase hydrogenation of LA to produce GVL at relatively low reaction temperature and H 2 pressure. A LA conversion of 99.9% and a GVL yield of 92.3% were achieved at 160°C and 1.5 MPa H 2 over the Ni–Co/SPCE–C catalyst, which were significantly higher than those catalyzed by contrastive catalysts. A variety of tests and theoretical calculations reveal that SPCE with far-infrared emission and surface electric field was conducive to the reduction in the hydrogen spillover energy barrier, the stabilization of the transition state, and the facile exchange of H 2 and water for accelerating WAPH. Moreover, a reasonable SPCE-reinforced WAPH mechanism was proposed to explain the enhanced aqueous hydrogenation of LA. This research can provide valuable insights into the design and development of high-performance non-noble metal catalysts for aqueous hydrogenation applications.
研究领域:
催化化学
·
材料科学
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危险品化学品经营许可证（带存储）