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.
研究领域:
催化
·
化学工程
·
材料科学
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2021
·
IF 5.909
Putrakumar Balla,Prem Kumar Seelam,Ravi Balaga,Rajendiren Rajesh,Vijayanand Perupogu,Tong Xiang Liang
Sustainable catalysis is the key for the future progress toward biorefinery and bioeconomy. In this work, we designed and developed an inexpensive and eco-friendly Ni@C catalyst for selective hydrogenation of biomass-based platform molecules. A facile synthesized Ni nanoparticles encapsulated in a stabilized carbon support derived from a sacrificial agent copolymer-gel was investigated in the hydrogenation of furfural (FA) to tetrahydrofurfuryl alcohol (THFOL) and levulinic acid (LA) to γ-valeralactone (GVL). The aim is to study the two different reactions over a highly stabilized Ni nanoparticles embedded in the carbon matrix. The Ni@C was found to be active and selective in multi-catalyzed hydrogenation reactions. The Ni nanoparticles with small and ultra-fine sizes are highly dispersed over the carbon matrix. This was concluded through high-resolution micrography images (SEM, TEM) and XRD patterns. In both reactions, a complete conversion of furfural and levulinic acid was achieved with maximum selectivity over the Ni@C catalyst. The effect of reaction temperature, solvent type, reaction time, and H 2 pressure were also studied. Overall, optimized reaction conditions were determined, and the Ni@C is easily reusable and exceptionally durable in the studied reaction cycles. The apparent activation energies for FA hydrogenation to THFOL and LA hydrogenation to GVL are 15.4 kJ/mol and 33.6 kJ/mol, respectively.
研究领域:
催化化学
·
可再生资源与环境科学
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2022
·
IF 4.654
Zhen Ge,Hongye Cheng,Guojin Zhang,Linsheng Wang,Zhiwen Qi
To achieve maximum usage and economically upgrade light cycle oil, it is necessary to separate light cycle oil components into nonaromatic and aromatic fractions. A deep eutectic solvent composed of tetrabutylphosphonium bromide and levulinic acid exhibited excellent extraction performance in separating light cycle oil components. In this work, the mechanisms of deep eutectic solvent formation and light cycle oil separation are investigated using characterization analysis and molecular dynamics simulations. Both Fourier-transform infrared spectra and molecular dynamics simulation results indicate that the main driving force for deep eutectic solvent formation is hydrogen-bonding interactions between the Br– anion of tetrabutylphosphonium bromide and the carboxyl group (−COOH) of levulinic acid. On the other hand, while the TBP+ cation of tetrabutylphosphonium bromide and the carbonyl group (−C═O) of levulinic acid are less likely to contribute to deep eutectic solvent formation, they are more likely to interact with the aromatic ring of tetralin via CH−π and π–π interactions, respectively. The results suggest that each functional group of tetrabutylphosphonium bromide and levulinic acid plays an essential role either in deep eutectic solvent formation or in aromatic compound extraction, which provides insights into the mechanism of extractive separation of light cycle oil components using deep eutectic solvents.
研究领域:
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CELLULOSE
·
2019
·Vol. 27
·期 3
·1451-1463
·
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
·
可再生资源化学
✓ 已验证
产品关联
DOI
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.
研究领域:
生物化学
·
可再生资源与环境工程
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Rulu Huang,Yue Wang,Feiyi Chen,Huai Liu,Rui Zhang,Wenlong Jia,Lincai Peng,Yong Sun,Junhua Zhang
The sluggish kinetic of the hydrogen transfer reaction pose a significant challenge in developing efficient catalytic transfer hydrogenation (CTH) system for upgrading biomass-derived platform molecules. In this contribution, for the first time, hafnium (Hf) species have been found to coordinate with the hydroxyl groups on halloysite nanotubes surface to construct a single-atom Hf catalyst (Hf@HNTs) with unsaturated-coordinated structure at room temperature. Especially, the Hf(1.7)@HNTs delivered an impressive catalytic performance for the CTH of levulinic acid (LvA) to gamma-valerolactone (GVL) with high turn-over frequency (TOF) of 43.1 h −1 at 160 °C, considerably exceeding that of coordination-saturated HfO 2 and state-of-art Hf-based catalysts. Experimental and density functional theory (DFT) studies revealed that Hf(1.7)@HNTs possessed unsaturated-coordinated and atomically-dispersed Hf-O Lewis acid-base pairs, which favored the adsorption and activation of LvA. Moreover, DFT calculations explicitly demonstrated that the energy barriers for the hydrogen transfer between the LvA and hydrogen donor were significantly reduced on the Hf(1.7)@HNTs than that of HfO 2 .
研究领域:
化学工程
·
材料科学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Ying Zhu,Furui Hu,Zi Yu,Yongxin Liang,Tao Gan,Huayu Hu,Zuqiang Huang,Yanjuan Zhang
The activation of reaction system for high-efficiency hydrogenation of levulinic acid (LA) into γ-valerolactone (GVL) is significant for sustainable development of biomass. Herein, based on a strategy of tourmaline (TM)-activated aqueous-phase system, a Cu-Ni/ZrO 2 @TM/C catalyst was facilely constructed by a totally solid-phase method. Cu-Ni/ZrO 2 @TM/C exhibited outstanding catalytic performance, benefiting from the spontaneous polarization and far-infrared radiation characteristics of tourmaline and the strong metal–metal and metal–support interactions. Under the optimum reaction conditions of 180 °C, 150 min, and 1.5 MPa H 2 , 100.0 % of LA conversion and 93.0 % of GVL yield were achieved. A variety of tests and theoretical calculations confirm that tourmaline with spontaneously polarized electric field and far-infrared radiation can break intermolecular hydrogen bonds to form small water clusters for activating aqueous-phase environment, facilitating the transport of active species as well as greatly reducing the hydrogenation barrier. The activating water effect of tourmaline, the acid sites and oxygen vacancies of ZrO 2 , and the alloying structure of Cu-Ni bimetal can synergistically benefit the transport of active species for reinforcing water-assisted proton hopping. Moreover, a reasonable tourmaline-activated aqueous-phase system was proposed to explain the enhanced aqueous hydrogenation of LA. This study innovatively illuminates the construction of functional non-precious metal catalysts for efficient aqueous-phase hydrogenation of biomass-derived chemicals.
研究领域:
化学工程
·
催化科学
·
可再生资源转化
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Yun Wang,Haimei Wu,Jiale Wang,Kaiyue Zhang,Yingxin Liu,Zuojun Wei
A highly effective transformation from renewable biomass and its derivatives into high-value-added chemicals and biofuels is important and challenging. Herein, a N-doped mesoporous carbon (NMC)-supported Ru catalyst developed by an incipient wetness impregnation method was reported for the reductive amination of levulinic acid (LA)/esters with amines to N-substituted 5-methyl-2-pyrrolidinones. A complete conversion of LA with a 99.8% yield of N-hexyl-5-methyl-2-pyrrolidinone (HMP) was achieved over 0.05 mol % Ru/NMC under mild conditions of 120 °C and 1.5 MPa H2 for 4 h, giving a high turnover frequency (3667 h–1). Furthermore, Ru/NMC exhibited superior stability and recyclability (reusable 21 cycles without loss of activity). The excellent performance of the Ru/NMC catalyst was mainly attributed to the introduction of N species to the mesoporous carbon, which not only improved the anchoring and the dispersion of Ru nanoparticles on the catalyst surface but also provided moderate basic sites and transferred electrons from NMC to Ru nanoparticles, as revealed by detailed characterizations. Additionally, the developed Ru/NMC catalytic system was applicable to LA/esters and various amines to afford the corresponding N-substituted 5-methyl-2-pyrrolidinones with excellent yields (80–99%).
研究领域:
催化化学
·
可再生化学
·
材料科学
✓ 已验证
DOI
高影响因子
JOURNAL OF MOLECULAR LIQUIDS
·
2025
·
IF 5.2
Zi-Quan Wang,Ya-Peng Du,Xiao-Ping Zheng,Yu Chai,Yu-Cang Zhang,Yan-Zhen Zheng
The direct conversion of raw lignocellulosic waste into specialty chemicals such as levulinic acid (LA) has the potential to significantly enhance biorefinery profitability. Here, we demonstrated that incorporating γ-valerolactone (GVL) as a co-solvent during the SO 3 H-functionalized ionic liquid-catalyzed conversion of bagasse in water markedly enhanced reaction rates and catalytic activity, achieving a LA yield as high as 76.1 % with a 1:1 vol ratio of GVL to water. This catalytic system also effectively converted other lignocellulosic waste to LA. Reaction constants and activation energies for the bagasse dehydration process to LA were obtained. Comprehensive characterization via Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray diffraction (XRD) elucidated significant changes in functional groups, surface morphology, and crystallinity index of solid residues over extended reaction times. Notably, hemicellulose and cellulose were converted within 4 h, with lignin remaining in the solid residues and forming by-products after prolonged reaction times. This efficient one-pot conversion method showed promise as a sustainable approach to transform agricultural waste into LA, offering new opportunities for eco-friendly resource utilization.
研究领域:
生物化学
·
可再生能源
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Mengli Zhou,Sichan Li,Haojie Tian,Xinyu Liu,Zhimin Wu,Qiying Liu,Jianchun Jiang
Levlinic acid (LA) and its derived γ-valerolactone (GVL) are the two important biomass derived platform molecules, which showed wide application in the fields of fine chemicals, drug and liquid fuel industrials. Considering the coupling of sequential steps for glucose to LA and GVL, selective production of LA and GVL via glucose one-pot conversion in water is an open challenge. Herein, we used metal chlorides as the acidic catalyst for glucose conversion to LA, obtaining the high yield of 77.8 C-mol% over SnCl 4 . Moreover, using the SnCl 4 and Ru/C as the combined catalyst, glucose or cellulose could be converted to GVL with the high yield of 60.1 or 57.9 C-mol% in the case of in situ hydrogenation by formic acid (the by-products during LA formation) decomposition. The formation of LA was responsible for the cooperative effect of BAS (Bronsted acid sites) and LAS (Lewis acid sites) of SnCl 4 for accelerating glucose isomerization, fructose dehydration followed by 5-hydroxymethyl furfural (HMF) rehydration, while the GVL production is relative to the highly efficient formic acid decomposition to H 2 followed by LA hydrogenation to GVL over Ru/C. This study provided an avenue for facile and highly efficient conversion of biomass and the derivatives to LA and GVL using commercial catalysts.
研究领域:
催化化学
·
生物质能源
·
绿色化学
·
可再生化学品
·
多相催化
✓ 已验证
产品关联
DOI
高影响因子
Journal of Cleaner Production
·
2025
·
IF 10
Hongguang Zhang,Zi Yu,Yongxin Liang,Tao Gan,Zuqiang Huang,Huayu Hu,Yanjuan Zhang
The utilization of organic molecules as in-situ hydrogen donors for producing γ-valerolactone (GVL) biofuel from biomass-derived levulinic acid (LA) represents one of the promising sustainable approaches. However, this process still faces challenges, including the difficult activation of the hydrogen source and the transport limitations of active hydrogen species. Herein, a Co-MnO/spontaneously polarized ceramic-carbon (Co-MnO/SPCE-C) composite catalyst, featuring a unique spontaneous polarization effect, was developed for catalytic transfer hydrogenation (CTH) of LA to GVL in the isopropanol/H 2 O (volume ratio = 1/19) cosolvent system. Co-MnO/SPCE-C contributed to an outstanding LA conversion of 99.9% and a favorable GVL yield of 93.5%, surpassing the performance achieved by comparative catalysts. Various characterization techniques demonstrate that SPCE with far-infrared emission and surface electric field increased the oxygen vacancies, thereby promoting hydrogen spillover and enhancing the properties of CoO x –MnO acidic sites. The 17 O NMR spectra reveal that SPCE activated water clusters by weakening the hydrogen bonding network. Moreover, D 2 O experiments show that SPCE facilitated the participation of water in the reaction. This work provides valuable insights into the development of an efficient strategy for producing GVL from LA. Before the catalyst can be considered for commercial applications, the focus in the future should be on a comprehensive computational analysis, long-term evaluation of catalyst stability, and additional industrial-scale testing.
研究领域:
化学工程
·
材料科学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Guangyue Xu,Chuang Li,Tianyu Deng,Chenguang Wang,Ying Zhang,Yao Fu
The conversion of levulinic acid (LA) to γ-valerolactone (GVL) is one of the most important reactions from biomass-derived platform chemicals to value-added chemicals. In this work, bimetallic PdRu/TiO2 catalyst compared to monometallic Ru/TiO2 was designed for the conversion of LA to GVL at ambient H2 pressure. The highly dispersed Pd affected the reaction by two antagonistic effects: (I) increasing the reaction rate by promoting the activation of H2; (II) decreasing the reaction rate by lowering the activation ability of carbonyl group over Ru. The kinetic analysis refined by H2 concentration showed much lower apparent activation energy over 0.2Pd1Ru/TiO2 than that over Ru/TiO2. Finally, the catalysts were evaluated by both GVL productivity and catalyst cost to show increasing benefit of Pd addition at lower H2 pressure. This study offers both theoretical foundation and application instructions for high efficiency conversion of LA to GVL under mild conditions, especially ambient H2 pressure.
研究领域:
催化化学
·
生物质能
·
绿色化学
✓ 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）