RENEWABLE ENERGY
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2020
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IF 6.274
Han Chen,Qiong Xu,Du Zhang,Wenzhu Liu,Xianxiang Liu,Dulin Yin
A series of mesoporous nickel catalysts with different molar ratios of citric acid and nickel nitrate were synthesized via a simple two-step method by solid-state grinding and in-situ reduction; these catalysts were further employed for the catalytic transfer hydrogenation of levulinate esters to γ-valerolactone (GVL) with 2-propanol as the hydrogen donor. The effects of C 6 H 8 O 7 /Ni molar ratios , catalyst dosage, reaction temperature and time on the catalytic performance were investigated. An excellent GVL selectivity of 99.1% and an ethyl levulinate (EL) conversion of 100% could be achieved at 180 °C in 6 h over Ni-1.0 catalyst with a 1.0:1 M ratio of C 6 H 8 O 7 /Ni. The characterization results showed that the Ni-1.0 catalyst was composed of mesoporous metallic Ni bulk and a surface Ni–NiO composite, and the acid sites of NiO played a synergistic catalytic role in producing GVL from EL. The superior mesoporous structure and large surface area of Ni-1.0 increased the atomic utilization rate of nickel metallic active centers. Moreover, Ni-1.0 catalyst could be easily separated and reused ten times, with an EL conversion above 95% remaining in each recycle. This work provids a highly efficient and environmentally friendly catalytic procedure for the conversion of biomass into GVL, a fuel additive compound.
研究领域:
化学工程
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可再生资源与环境科学
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DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
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2021
·Vol. 45
·期 12
·5526-5539
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IF 3.591
Zhi Zhang,Zhihang Huang,Hong Yuan
KCC-1/Al–SO3H solid acids with different Si/Al molar ratios were prepared by sulphonic acid functionalisation using fibrous nanoporous silica particles (KCC-1/Al) as carriers. Field emission scanning electron and transmission electron microscopy measurements revealed that the sulphonation did not change the spherical morphology and fibrous structure of KCC-1/Al. The Brunauer–Emmett–Teller (BET) analysis indicated that the BET surface area of KCC-1/Al–SO3H could reach 293–372 m2 g−1, while the average pore size was 7.31–7.43 nm. In addition, pyridine adsorption infrared profiles showed that KCC-1/Al–SO3H contained abundant Lewis–Brønsted acid sites, while based on ammonia temperature-programmed desorption characterisation, a total ammonia desorption quantity of 91 cm3 g−1 could be achieved using a Si/Al molar ratio equal to 5. The efficiency of the prepared KCC-1/Al–SO3H was examined in the synthesis of ethyl levulinate (EL) from cellulose in a mixture of ethanol and toluene. Among them, 5KCC-1/Al–SO3H exhibited superior performance, affording EL in 28.8 mol% yield under the optimal reaction conditions (200 °C, 6 h). Furthermore, a mechanism demonstrating the synergistic effect of the Lewis–Brønsted acid sites was proposed based on the reaction activity of different biomass sugars at the acidic sites.
研究领域:
化学工程
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催化材料科学
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DOI
高影响因子
JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
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2019
·Vol. 94
·期 10
·3093-3101
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IF 2.659
Jiaming Wu,Yuewen Shao,Guojian Jing,Zhanming Zhang,Zhengmao Ye,Xun Hu
Background Graphene oxide (GO) has abundant oxygen-containing functionalities such as hydroxyl groups and carboxyl groups with distinct acidities. This feature makes GO a potential solid acid catalyst for the acid-catalyzed reactions such as the production of ethyl levulinate (EL), a platform chemical, from the acid-treatment of furfuryl alcohol (FA). The structure and functionalities of GO are closely related to its catalytic performance, and thus it is necessary to establish the relationship between the chemical structure and the catalytic properties of GO. To achieve this aim, in this work, the GO catalysts were designed by a facile one-pot synthetic route with no subsequent modification. By controlling the parameters of oxidation process in preparation, multiple functional groups were immobilized onto graphitic substrate, significantly impacting the catalytic activity of GO in the conversion of FA to EL in an ethanol (EtOH) medium. Results The results showed that, the oxidation process significantly influenced the distribution of oxygen-containing functionalities on the surface of GO. The amount of the oxygen-containing functionalities can be adjusted by the oxidation parameters such as oxidizing agent equivalent, reaction time and temperature, while the organosulfate can only be remained at a moderate oxidation temperature. The existence of the synergistic effect between the oxygen-containing functionalities and the organosulfate functionalities promoted the catalytic activity of GO for the acid-catalyzed conversion of FA to EL. Conclusions This work provides a new strategy of design and development of functional graphene-based catalysts for the acid-catalyzed reactions, and lays foundation of the practicability of GO in biomass conversion. © 2019 Society of Chemical Industry
研究领域:
化学工程
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催化科学
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材料科学
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DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
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2018
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IF 4.521
Zhenzhen Lin,Mengting Luo,Yindi Zhang,Xiaoxue Wu,Yanghe Fu,Fumin Zhang,Weidong Zhu
Heterogeneous catalytic conversion of biomass-derived methyl levulinate (ML) to γ-valerolactone (GVL) is highly attractive as a sustainable route to mitigating the dependence on nonrenewable fossil resources. However, this route is limited by its low selectivity toward GVL and severe reaction conditions. Here, we present a synergistic catalytic process that offers exclusive GVL selectivity with complete ML conversion under mild conditions (80 °C, 0.5 MPa of H 2 pressure). This is achieved over a dual-functionalized catalyst of Ru nanoparticles (Ru-NPs) and Brønsted acid SO 3 H groups in a Cr-based metal-organic framework (MIL-101). The Ru-NPs served as metal sites for the hydrogenation of ML to methyl-3-hydroxyvalerate (MHV) and the acidic SO 3 H moieties promoted the cyclization of MHV to generate GVL via lactonization. In contrast, GVL production was significantly suppressed over the physically mixed congener (2.0 wt% Ru/MIL-101 + MIL-101-SO 3 H). This result demonstrates an unrivalled advantage of the dual integration of metal/acid sites in a single MOF crystal, and the relative amount of sulfonic acid groups in the catalyst can exert significant influence on the overall catalytic performances. The activation energies for the hydrogenation and lactonization steps with the developed catalyst were 29.5 and 42.1 kJ/mol, respectively, which are much lower than those observed with the traditional 5.0 wt% Ru/AC catalyst.
研究领域:
化学工程
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催化科学
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DOI
高影响因子
Molecular Catalysis
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2023
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IF 4.6
Bo Li,Haijun Guo,Zhen Xiong,Lian Xiong,Shimiao Yao,Mengkun Wang,Hairong Zhang,Xinde Chen
γ-valerolactone (GVL) is a sustainable chemical, which can be obtained by hydrogenation of levulinic acid (LA) and levulinate. Herein, we reported a solvent-free hydrogenation of butyl levulinate (BL) to GVL and 1,4-pentanediol (1,4-PDO) over a skeletal Cu-Al-Zn catalyst. The skeletal Cu-Al-Zn catalyst was prepared from Devarda's alloy by alkali leaching and the catalyst was characterized by different analysis methods. The aluminum in the Devarda's alloy was dissolved by sodium hydroxide in the leaching process and many active Cu atoms were generated on the catalyst surface and the skeletal Cu-Al-Zn exhibited many micrometer-scale irregular particles with rough surface. The skeletal Cu-Al-Zn catalyst showed the excellent performance in the solvent-free hydrogenation of BL to GVL under constant hydrogen pressure (5 wt% catalyst loading, 180°C, 6 MPa of H 2 , 6 h): the LA conversion was 100%, the GVL yield was 74.75% and the 1,4-PDO yield was 25.63%. Moreover, the catalyst showed stable performance and it was reusable up to 5 times without apparent loss of activity. A stable hydrogen pressure with Zn would suppressed the dehydration of 1,4-PDO.
研究领域:
催化
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绿色化学
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可持续化学
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高影响因子
Molecular Catalysis
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2023
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IF 4.6
Xiaoqing Gao,Shanhui Zhu,Hongyan Zheng,Feng Wang,Wanjun Li,Huifang Wang,Yulan Niu
In order to relieve greenhouse effect, it is highly urgent to convert carbon-neutral biomass to value-added chemicals and liquid fuels by designing new process. 96.5% yield of biofuel alkyl levulinate was achieved in the alcoholysis of furfuryl alcohol with ethanol over highly active Ag + exchanged H 3 PW 12 O 40 (AgPW) catalyst at low temperature. In situ XRD, 31 P MAS NMR, XPS and NH 3 -TPD results confirm that AgPW contains large amounts of strong acid sites and stable Keggin structure, resulting in the excellent performance. Subsequently, new process was developed to synthesize biofuel 2-methyl-1,3-dioxolanes (MDL) with ∼70% yields via a tandem furfuryl alcohol alcoholysis and acetalization reaction over AgPW. Additionally, MDL can be availably obtained from furfural, xylose and hemicellulose by an integrated multi-step process.
研究领域:
化学工程
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可再生能源
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催化化学
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DOI
高影响因子
CATALYSIS LETTERS
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2023
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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
研究领域:
生物质化学
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催化化学
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可持续化学
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DOI
高影响因子
JOURNAL OF SUPERCRITICAL FLUIDS
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2024
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IF 3.4
Dongjie Zhang,Yue Zhang,Yifei Li,Zanhong Wang,Yin Zhang,Haitao Li
This study reports a novel method for γ-valerolactone (GVL) production from ethyl levulinate (EL) utilizing non-noble metal catalysts within a supercritical isopropanol (IPA) system. Nickel-loaded nickel–aluminum oxide nanosheets (Ni X Al-R) were fabricated via hydrothermal treatment of Ni–Al layered double hydroxide precursors, followed by hydrogen reduction at 550 °C for 1.5 h. Using Ni X Al-R as the catalyst and IPA as the hydrogen donor , we achieved notable results: 82.7% EL conversion, 73.6% GVL yield, and 1.178 mol GVL g −1 h −1 reaction efficiency after 1.5 h in supercritical IPA. The catalytic activity of Ni X Al-R remained stable over five catalytic cycles. The surface of Ni X Al-R exhibits abundant oxygen vacancies and unsaturated Al species (Al x+ ), which promote the initial transfer hydrogenation of EL to form the ethyl 4-hydroxypentanoate (4-HPE) intermediate. Simultaneously, the supercritical IPA environment overcomes mass transfer limitations at the solid–liquid interface between 4-HPE and the catalyst, thereby facilitating the Al x+ -catalyzed intramolecular esterification of 4-HPE into GVL.
研究领域:
化学工程
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催化科学
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可再生化学品合成
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DOI
高影响因子
Catalysts
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2024
·Vol. 14
·期 12
·924
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IF 3.8
Yu Yue,Guozhi Zhu,Min Liu,Yue Zhu,Weilong Ji,Xiaoqin Si,Tianliang Lu
As an important biomass resource, γ-valerolactone (GVL) shows considerable potential for applications in biofuel production, organic synthesis, polymer, and food industries. Herein, an effective method was presented for synthesizing GVL through the catalytic transfer hydrogenation (CTH) of ethyl levulinate (EL) under mild conditions. Using isopropanol as a hydrogen donor, a 100% conversion of ethyl levulinate and an 88.7% yield of GVL were achieved over 2%Zr-Beta-7d catalyst at 110 °C for 8 h. The acidic sites of synthesized Zr-Beta via hydrothermal methods easily adjusted and offered high catalytic activity and selectivity. The Lewis (L) acid sites on the zeolite serve as the active centers for the conversion of EL. Characterization results indicate that the amounts of L acid sites on Zr-Beta increased with the Zr content and crystallization time rose, thus enhancing the selectivity for GVL. Additionally, the influences of catalyst dosage, reaction temperature, and time on catalytic performance are studied, as well as calculations of kinetic parameters such as reaction rate constants and activation energies. The 2%Zr-Beta-7d catalyst retains its high performance after five cycles. The current research may present an efficient approach for the conversion of EL to GVL under mild conditions.
研究领域:
生物质化学
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催化化学
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DOI
高影响因子
RENEWABLE ENERGY
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2025
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IF 9.1
Yingfu Tian,Tianliang Lu,Hongjin Qu,Xiaomei Yang,Lipeng Zhou
Efficient conversion of ethyl levulinate (EL) in high concentration to γ-valerolactone (GVL) at moderate temperature via catalytic transfer hydrogenation strategy is highly desirable. In this work, hydrothermally synthesized Sn-β zeolite with high Sn content was employed as a catalyst to realize this aim. Fully crystallized Sn-β zeolite with high Sn content ( n Si / n Sn = 60) was successfully synthesized within 12 days using MgCl 2 as a promoter. The synthesized zeolites were characterized by XRD, SEM, UV-vis spectroscopy, FT-IR spectroscopy and XPS. The L acid density of Mg-Sn-β-60-12d increased to 90 μmol g −1 compared to Mg-Sn-β-100-7d (56 μmol g −1 ). 92% yield of GVL was achieved on Mg-Sn-β-60-12d using high concentration of EL (1.2 mol L –1 ) as reactant at 130 o C for 8 h. The performance of Mg-Sn-β is better than that of Sn-β with same n Si / n Sn . The reaction mechanism over Mg-Sn-β was discussed. In addition, Mg-Sn-β-60-12d showed excellent stability and reusability during five runs.
研究领域:
化学工程
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催化材料科学
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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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高影响因子
JOURNAL OF CATALYSIS
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2026
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IF 6
Xiang Li,Wei Li,Ling Wang,Siqi Xu,Tete Xie,Xiu Xiu Zou,Peng Wang,Peng Huang,Shangxing Chen,Zongde Wang,Wenyuan Han,Aliaksandr Tsyhanau,Qiang Deng
Developing a cost-effective catalyst for the selective tandem conversion of furfural (FFA) to ethyl levulinate (EL) is important for synthesizing biofuels and fine chemicals from biomass. However, traditional catalysts prefer the hydrogenation-dehydration-hydrolysis pathway and are slow due to high activation energy requirement. Herein, a NiCoP/LaPO 4 catalyst was prepared via calcination of layered double hydroxide (LDH) precursor, followed by hydrogen reduction, and phosphating. When applied to the tandem of FFA for EL production, it exhibited a high selectivity of 90.1% at 160 °C under ethanol and water via acetalization–hydrogenolysis–hydrolysis route. Catalytic mechanism investigation indicated that in situ hydrogen spillover from NiCoP nanoparticles to the LaPO 4 support, leading to the formation of H + –H − pairs. These H + –H − pairs not only provide Brønsted acid sites to drive FFA acetalization and 2-ethoxymethyl furan (EMF) hydrolysis but also activate the C–O bonds of the key intermediate 2-diethoxymethyl furan (DEMF) via the S N 2 mechanism, markedly accelerating the hydrogenolysis step. Moreover, the NiCoP/LaPO 4 catalyst shows remarkable catalytic versatility for the synthesis of different alkyl levulinates from a range of alcohols (i.e., methanol, propanol, isopropanol, butanol and benzyl alcohol). This study presents an efficient bifunctional catalysis approach for complex tandem reaction pathways aimed at synthesizing alkyl levulinate by hydrogen spillover to generate transient H + –H − pairs.
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高影响因子
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