Reaction Kinetics Mechanisms and Catalysis
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2021
·Vol. 134
·期 2
·777-792
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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.
研究领域:
化学工程
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有机化学
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生物质转化
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催化
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DOI
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.
研究领域:
化学工程
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环境科学
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生物质能
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DOI
PubMed
高影响因子
Materials
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2022
·Vol. 15
·期 21
·7464
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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
研究领域:
催化化学
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材料科学
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产品关联
DOI
PubMed
高影响因子
GREEN CHEMISTRY
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2021
·Vol. 23
·期 23
·9669-9682
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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
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化学工程
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2026
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IF 7.6
Qian Wang,Rong Chen,Limei Sheng,Ai Liu,Agen Huang
The esterification of levulinic acid with ethanol to produce ethyl levulinate represents a promising biomass valorization route, yet solid acid catalysts are constrained by an inherent trade-off between activity and stability. Herein, we report a rationally designed HPW10@UiO-66/PIL ternary hybrid catalyst that overcomes this long-standing dilemma. The catalyst is constructed by confining phosphotungstic acid clusters within a poly(ionic liquid)s network anchored to defect-engineered UiO-66, enabling synergistic electrostatic and hydrogen-bonding stabilization. Under optimized conditions (LA/EtOH molar ratio = 1:6.8, 70 °C, 6 h), the catalyst achieved an exceptional ethyl levulinate yield of 98.4% with 99% selectivity. ICP analysis confirmed negligible HPW leaching (<0.5 wt %) during the reaction. The catalyst retained 97% of its initial yield after five cycles, demonstrating superior recyclability. Mechanistic studies reveal that the PIL network not only ensures high dispersion and leaching resistance of HPW clusters but also reconstructs their spatial intimacy with unsaturated Zr centers, enabling substantive Brønsted–Lewis acid synergy. This work provides a paradigm for addressing the activity–stability paradox in heterogeneous acid catalysis through rational interfacial engineering.
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DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2026
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IF 3.9
Jintao Liu,Dekun Duan,Monan Wang,Jinghan Wang,Weixue Zhang,Yue Zhang,Qiuli Zhang,Gan Ye
Abstract Catechol-functionalized UiO-66(Zr) holds considerable promise for targeted catalytic transformations owing to its distinctive electronic and structural properties. However, the direct synthesis of such frameworks has remained a persistent synthetic challenge. Herein, we report a rational, solvent-free, one-pot synthetic strategy enabling precise control over catechol functionalization in UiO-66(Zr) (UiO-66(Zr)-(OH)2) with well-defined hierarchical porosity. The optimized UiO-66(Zr)-0.25(OH)2 displays markedly improved catalytic performance in the esterification of levulinic acid (LA) with primary alcohols to yield alkyl levulinates. This superior activity arises synergistically from three key features: (i) increased Brønsted acidity imparted by the ortho-dihydroxyphenyl groups; (ii) a hierarchical pore architecture that enhances mass transport and substrate accessibility; and (iii) strong adsorptive affinity for both LA and alcohol substrates. Under standardized 12 h batch reactions with an alcohol-to-LA molar ratio of 20 and 50 mg of catalyst, UiO-66(Zr)-0.25(OH)2 achieves LA conversions of 98.9, 97.9, 95.6, and 94.3% with methanol, ethanol, 1-propanol, and 1-butanol, respectively, while maintaining >99.9% selectivity for the corresponding products of alkyl levulinates at optimally tuned reaction temperatures (60, 70, 80, and 100 °C). This work establishes a practical and environmentally sustainable synthetic strategy for the rational design of functionalized metal–organic frameworks, enabling high-efficiency, heterogeneous catalysis in targeted reactions.
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DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
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2024
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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
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材料科学
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产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL THERMODYNAMICS
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2024
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IF 2.2
Dongmei Xu,Hailin Sun,Nan An,Jun Gao,Lianzheng Zhang,Yixin Ma,Yinglong Wang
Levulinic acid (LA) is a crucial bio-based chemical with extensive industrial applications. Due to its significant share in the cost of production, the development of efficient techniques for the separation of LA is essential. Traditional separation using sulphuric acid raises environmental and cost concerns, making liquid–liquid extraction a more sustainable and cost-effective alternative. liquid–liquid equilibrium (LLE) investigation was carried out for two ternary mixtures of water + LA + isopropyl ether / methyl tert -butyl ether (MTBE) at two temperatures and 101.3 kPa. The results indicated that the solvent MTBE, as an extractant, showed a higher partition coefficient and selectivity for LA than isopropyl ether, demonstrating its superior effectiveness in recovering LA. The interaction insights between LA and the extractants were explored using quantum chemistry calculations, which aligned well with the collected results. The ascertained LLE data was modeled using the NRTL equation, achieving the RMSD values below 0.01, demonstrating a good concordance between the collected data and computed values. The fitted NRTL model parameters are conducive to the designing and optimizing the LA separation process.
研究领域:
化学工程
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环境科学
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产品关联
DOI
高影响因子
CELLULOSE
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2019
·Vol. 27
·期 3
·1451-1463
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IF 3.917
Zhou Lipeng,Gao Dongting,Yang Jingru,Yang Xiaomei,Su Yunlai,Lu Tianliang
Abstract Conversion of cellulose to chemicals is an economic and environmental route for biomass utilization. In this work, efficient conversion of cellulose to alkyl levulinates and levulinic acid was realized by oxidation pretreatment combined with alcoholysis over Al 2 (SO 4 ) 3 catalyst. Proper pre-oxidation conditions including oxidation temperature and time are important. By pre-oxidation, part of hydroxymethyl groups on cellulose was converted to carboxyl groups which provide the Brønsted acid sites near the glycosidic bonds to improve the depolymerization of cellulose to monosaccharide. Al 2 (SO 4 ) 3 ·18H 2 O can play both Brønsted and Lewis acid roles in methanol and catalyze the conversion of monosaccharide to alkyl levulinates and levulinic acid. After pre-oxidation at optimized conditions, cellulose can be converted into methyl levulinate and levulinic acid over Al 2 (SO 4 ) 3 in methanol efficiently, and total yield of methyl levulinate and levulinic acid can reach 66.8% at 180 °C for 3 h. Furthermore, the simple and cheap Al 2 (SO 4 ) 3 catalyst is recyclable which is important for the practical application. Graphic abstract
研究领域:
生物化学
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可再生资源化学
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DOI
高影响因子
Journal of Environmental Chemical Engineering
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2021
·
IF 5.909
Xi Cheng,Qingge Feng,Dachao Ma,Hongcheng Chen,Xu Zeng,Feifan Xing,Jiayang Teng
To eco-friendly catalyze glucose to levulinic acid, recyclable acid catalyst has been researched. The synthesis process of propyl sulfonic acid functionalized SBA-15 was improved and the hydrophobic treatment was performed. The structure and functional groups of materials were characterized by X-ray diffraction, transmission electron microscopy , N 2 adsorption–desorption isotherms, elemental analysis, Fourier transform infrared spectroscopy , X-ray photoelectron spectroscopy and simultaneous thermal analysis. The catalytic activity , recyclability and hydrothermal stability of CH 3 -SBA-15-SO 3 H material were researched. The highest yield of levulinic acid at 61.56% was obtained at 180 ℃ for 2.5 h in γ-GVL-water solvent system, and the yield of levulinic acid was only decreased by 2% after 4 times reuse. The high degree of silicon polycondension and hydrophobic surface of CH 3 -SBA-15-SO 3 H were the key to maintain the hydrothermal stability. The CH 3 -SBA-15-SO 3 H solid acid had great potential in development and utilization of biomass resources .
研究领域:
化学工程
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生物质资源开发
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2020
·Vol. 22
·期 13
·4240-4251
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IF 9.48
Jinghua Wang,Hongyou Cui,Yong Wang,Rongrong Zhao,Yujiao Xie,Ming Wang,Weiming Yi
An efficient approach for the synthesis of levulinic acid (LA) by converting cellulose in a biphasic system consisting of molten salt hydrate (MSH), (LiCl·3H2O) and methyl isobutyl ketone (MIBK) using NbOPO4/HZSM-5 as the catalyst was reported. A series of molten salt hydrates (LiBr·3H2O, LiCl·3H2O, ZnCl2·3H2O, CaCl2·3H2O and Ca(NO3)2·3H2O) were evaluated in terms of their cellulose dissolvability and catalytic activity without any additional catalyst in the conversion of cellulose to LA. Among them, LiBr·3H2O, LiCl·3H2O and ZnCl2·3H2O were capable of dissolving and swelling cellulose and demonstrated excellent performance in cellulose conversion to LA even without any additional catalyst. High temperature favors the formation of LA while low temperature is beneficial to saccharides and 5-hydroxymethylfurfural (HMF). Using NbOPO4/HZSM-5, an efficient conversion of cellulose to LA was achieved in a biphasic system, affording a LA yield as high as 94.0%. The partition coefficient of HMF between the MIBK and LiCl·3H2O phases increased notably when the temperature was increased, proving that a biphasic solvent restrained the secondary reaction of HMF to humins. The reaction mechanism study based on the investigation of converting glucose, fructose and HMF to LA found that the side reactions of saccharides to humins are the key factors affecting the selectivity of LA in the investigated reaction system. Therefore, it is crucial to match the cellulose hydrolysis reaction with the subsequent reactions to maintain saccharides including glucose and fructose at low concentrations for highly efficient conversion of cellulose to LA.
研究领域:
化学工程
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生物质转化
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产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2012
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IF 2.237
Weina Liu,Yucui Hou,Weize Wu,Zhenyu Liu,Qingya Liu,Shidong Tian,Kenneth N. Marsh
Cellulose is the most widely distributed source of biomass, and its efficient conversion to a variety of chemicals is important for a sustainable future. In this work, sulfur dioxide (SO2) dissolved in hot water has been demonstrated to be an efficient catalyst for the selective conversion of cellulose to chemicals such as glucose and levulinic acid. The selectivity of products can be tuned by the SO2 concentration, temperature, and reaction time. SO2 acts both as a supply of H+ ions through ionization of H2SO3 when dissolved in water and as a Lewis acid catalyst that breaks the hydrogen bonds in cellulose. Importantly, SO2 in the reaction mixture can be recovered completely by stream stripping, thus avoiding the formation of acidic wastewater. This work provides a new, efficient, and environmentally benign way to convert cellulose to chemicals.
研究领域:
化学工程
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可持续化学
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生物质转化
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）