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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高影响因子
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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BIORESOURCE TECHNOLOGY
·
2024
·
IF 9.7
Huanhuan Zhang,Liutao Hou,Weihong Zhang,Yucheng Lin,Xueli Liu,Shiqiang Zhao,Chun Chang
The purpose of this study is to design and investigate two coupling processes for acid-catalyzed hydrolysis of corncob, achieving the simultaneous preparation of biomass-based furfural and levulinic acid (LA). Meanwhile, high concentration and yield of LA were obtained through a situ feeding strategy of pretreated furfural residue with high solids loading (20%, w/v). In Scenario A, 2-methyltetrahydrofuran was selected as the solvent for the LA extraction process compared with the neutralization process in Scenario B. Techno-economic assessment results show that Scenario A is technically feasible and cost-competitive, with an internal rate of return of 21.92%, a net present value of 121 million US dollars, a carbon efficiency of 72%, an environmental factor of 4.38, and a process mass intensity of 32.19. This study will provide new insights for fully utilizing lignocellulosic biomass to prepare renewable energy resources, comprehensively evaluating the economic feasibility, and promoting green and low-carbon development.
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PubMed
高影响因子
FUEL
·
2024
·
IF 6.7
Yaqi Duan,Conghao Ku,Yuping Lv,Yantao Wang,Weiran Yang
Due to its unique physical and chemical properties, applying activated carbon nanomaterials as catalysts gradually become a hot research topic. Herein, the synergistic catalytic effect of activated carbon nanoparticles and CaO for highly selective oxidation of levulinic acid to citramalic acid was first reported. Among various activated carbons tested (commercially available and biomass-derived), the one obtained from Nanjing Chemical Reagent Co., Ltd. exhibits the best catalytic activity due to its large surface area, suitable pore structure, abundant active sites, and excellent O 2 activation ability. The levulinic acid conversion and citramalic acid selectivity respectively reached 100 % and 82.8 % at 90 °C for 0.5 h under 0.5 Mpa O 2 . Further, the 3D flower-like CaO/carbon composite (CaO/CF) was developed, which also showed excellent catalytic activity for the selective oxidation of levulinic acid to citramalic acid, with 91 % levulinic acid conversion and 81.8 % citramalic acid selectivity under otherwise the same reaction condition. The mechanistic study indicated that superoxide anion radical ( O 2 – ), Ca 2+ and OH – all play a crucial role in levulinic acid oxidation. This work may promote the application of activated carbon nanomaterial as an effective catalyst for selective oxidation reactions.
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高影响因子
FUEL
·
2022
·
IF 8.035
Puxiang Yan,Haiyong Wang,Yuhe Liao,Pengyao Sun,Chenguang Wang
Catalytic valorization of biomass into chemicals and fuels plays a key role in order to achieve net-zero greenhouse gas emissions. Herein, a series of hierarchical ZSM-5 zeolites were synthesized by the post-treatment method to transform furfural alcohol (FAL) to levulinic acid (LA). ZSM-5 obtained from tandem alkaline treatment (0.2 M NaOH) and acid washing (0.1 M HCl), denoted as ZSM-5-OH 0.2 -H, exhibited the highest activity, affording 76.2% LA yield in 9:1 acetone–water mixed solvents at 393 K for 0.5 h. The enhanced adsorption capacity and acid accessibility of FAL on zeolite mediated by the introduction of mesopores, as well as the reduced secondary reactions of the generated LA due to few Al atoms in straight and sinusoidal channels (as confirmed by UV–vis diffuse reflectance), were responsible for the outstanding catalytic performance of ZSM-5-OH 0.2 -H. The structure–activity relationship revealed that regulating the porous structure and Al distribution of ZSM-5 was an effective strategy to enhance its hydrolytic performance of FAL to LA. Moreover, ZSM-5-OH 0.2 -H could be reused for three reaction cycles without significant loss in catalytic activity.
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高影响因子
Molecular Catalysis
·
2022
·
IF 5.089
Canshuo Gu,Lungang Chen,Yong Liu,Xinghua Zhang,Jianguo Liu,Qi Zhang,Chenguang Wang,Longlong Ma
The production of furanic biofuel 2-methyltetrahydrofuran (2-MTHF) has been studied by hydrodeoxygenation of biomass-derived levulinic acid (LA) over bimetallic NiCo/γ-Al 2 O 3 catalyst. The contents of Ni and Co in NiCo/γ-Al 2 O 3 were investigated. The Ni 5 Co 25 /γ-Al 2 O 3 catalyst gave high activity in hydrodeoxygenation of LA with a 73.4% yield of 2-MTHF under optimal conditions. The crystal phase, valence states, acidity and basicity of catalysts were measured by multiple characterizations to understand the relationships among 2-MTHF yields and catalyst properties. XPS characterization revealed that the number of metal oxides increased on bimetallic catalysts while the reduced metals occupied on monometallic catalysts. The bimetallic catalysts also presented increased acidity than that of monometallic catalysts. These distinct properties were also observed among bimetallic catalysts with different contents of Ni and Co, which were responsible for different performances. Besides, the solvent effect on the structure of 1,4-pentanediol, which was further converted to 2-methyltetrahydrofuran, was disclosed by molecular dynamics simulations.
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高影响因子
MOLECULES
·
2024
·Vol. 29
·期 16
·3779
·
IF 4.2
Pan Hou,Haopeng Su,Keyan Jin,Qiang Li,Wenfu Yan
γ-valerolactone (GVL), derived from biomass, is a crucial platform compound for biofuel synthesis and various industrial applications. Current methods for synthesizing GVL involve expensive catalysts and high-pressure hydrogen, prompting the search for greener alternatives. This study focuses on a novel zirconium phosphate (ZrP)-pillared zeolite MCM-36 derivative catalyst for converting levulinic acid (LA) to GVL using alcohol as a hydrogen source. The incorporation of ZrP significantly contributes to mesoporosity and greatly enhances the acidity of the catalysts. Additionally, we employed31P MAS NMR to comprehensively investigate the influence of phosphorus species on both the acidity and the catalytic conversion of LA to GVL. By adjusting the Zr-to-P ratios, we synthesized catalysts with enhanced acidity, achieving high conversion of LA and selectivity for GVL. The catalyst exhibited high recyclability, showing only minor deactivation over the course of five cycles. Furthermore, the catalyst was successfully applied to the one-pot conversion of furfural to GVL, showcasing its versatility in biomass conversion. This study highlights the potential of the MCM-ZrP1 catalyst for sustainable biomass conversion and offers insights for future research in renewable energy technologies.
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PubMed
高影响因子
JOURNAL OF CATALYSIS
·
2024
·
IF 6.5
Xiaoqing Gao,Shanhui Zhu,Mei Dong,Hongyan Zheng,Yanfeng Xue,Xiaojing Cui,Yulan Niu,Weibin Fan
Highly efficient synthesis of valuable γ-valerolactone (GVL) by levulinic acid (LA) hydrogenation is of interest for biomass refinery, but it suffers from great challenge to design highly active Ru-based catalyst at low temperature. ZIF-8 derived ZnO@NC nanocomposite can firmly anchor Ru nanoparticles to create strong Ru-ZnO interfacial structure, as revealed by characterization techniques and DFT calculations. By optimizing Ru content and ZnO particle size, Ru/ZnO@NC achieved excellent reaction activity with a turnover frequency (TOF) of 6032 h −1 at low temperature of 40 °C, which is never reported before. After etching the accessible ZnO, the TOF value was significantly declined to 125 h −1 on Ru/ZnO@NC-HF owing to the lack of effective Ru-ZnO interface. DFT calculation results demonstrate that the Ru-ZnO interfacial structure can facilitate the activation of intermediate CH 3 CHOCH 2 CH 2 COOH* and remarkably decline the activation energy barrier of rate-determining step (CH 3 CHOCH 2 CH 2 COOH + H = HPA) from 1.28 eV to 0.82 eV, thus leading to excellent activity of LA hydrogenation at low temperature.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2026
·
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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高影响因子
ACS Sustainable Chemistry & Engineering
·
2026
·
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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高影响因子
FUEL
·
2023
·
IF 7.4
Jingyang Zhang,Yucheng Lin,Sibo Zhao,Wei Chen,Qiulin Ma,Liyang Ma,Chun Chang
Levulinic acid (LA), regarded as one of the top twelve biomass-based platform chemicals, has been extensively studied by numerous researchers. In this study, a high LA concentration and yield were obtained through an enhanced in situ feeding strategy with a high loading of furfural residue (FR). The effects of batch process, one-time feeding and two-time feeding strategy on the hydrolysis performance (LA yield and concentrations, as well as intermediate glucose yield and concentrations) were investigated. The humin-based byproducts generated during different processes were also characterized by SEM, FT-IR and XRD analysis. The best results of one-time feeding strategy were obtained at 3 wt% H 2 SO 4 , 170 °C for 60 min with an initial FR concentration of 15% supplemented to 20% at 0th min. Under these conditions, the LA concentration and yield reached 30.00 g/L and 15% (51.1 mol%), respectively. Furthermore, a hybrid model integrated with the shrinking core model and a quasi-first-order kinetic model was adopted to elucidate the kinetic behavior of LA production from highly concentrated substrates through batch and feeding processes. The results indicated that a one-time feeding strategy can lower the activation energy required for FR degradation to glucose to 96.6 kJ/mol ( R 2 > 0.97). Similarly, the activation energy for the conversion of glucose to 5-hydroxymethylfurfural (5-HMF) and the subsequent formation of LA from 5-HMF were reduced to 80.9 kJ/mol ( R 2 > 0.97) and 23.3 kJ/mol ( R 2 > 0.97), respectively. Notably, the reaction rate of glucose to form humins was slightly reduced. This research helps to optimize the LA yield and concentration directly via an enhanced in situ feeding approach, providing valuable process operation and kinetic information for the industrial LA production from FR.
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高影响因子
APPLIED ORGANOMETALLIC CHEMISTRY
·
2022
·Vol. 37
·期 1
·e6935
·
IF 4.072
Yanyun Wang,Jiehua Bao,Changjiang Zuo,Guomeng Dong,Xiaoli Sheng,Yuzhong Huang,Yiwei Zhang,Yuming Zhou
Exploration of levulinic acid (LA) hydrogenation to γ-valerolactone (GVL) contributes to the conversion from carbohydrates to valuable fuels and chemicals. Here, we obtained a series of ultra-small PtNix bimetallic composite catalysts encapsulated in silicalite-1 zeolite (S-1) via a one-pot synthesis strategy protected by tetra(p-carboxyphenyl)porphyrin (TCPP) ligands. The catalytic results showed that PtNi 3 @S-1 (TCPP) exhibited the most active catalytic performance (95.7% LA conversion and 93.8% GVL selectivity) under optimized conditions. The characterization results indicate that ligand modification and bimetallic synergy play an important role in enhancing the catalytic activity. The introduction of TCPP provides a guarantee for the homogeneous encapsulation of PtNi 3 in S-1 zeolite at sub-nanometer size. The electronic interaction of PtNi bimetallic, high dispersibility of active components, improved surface acidity and excellent stability co-contribute to the satisfactory hydrogenation activity.
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