RENEWABLE ENERGY
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2022
·
IF 8.634
Yiwei Tang,Xiaoning Liu,Ran Xi,Le Liu,Xinhua Qi
As one of the important chemical feedstocks and biofuels, ethyl levulinate (EL) can be produced from biomass-derived furfural by consecutive hydrogenation, etherification and ring-opening reactions. However, this process normally requires two separate steps in different reaction systems, which is complex and energy consumption. Herein, Nb–Ni bifunctional ordered mesoporous carbons (Nb/ [email protected] ) were synthesized by a two-step process where [email protected] was firstly synthesized by a solvent evaporation induced self-assembly (EISA) process using F127 as a template agent, polyphenol gallic acid as carbon precursor and Ni 2+ as cross-linker, following with the supporting of Nb species in the [email protected] by an incipient wetness impregnation method. The as-synthesized Nb/ [email protected] samples were applied for the one-pot catalytic transformation of furfural to EL, and exhibited good activity with the highest EL yield of 83% under an optimized condition. Two possible pathways for the one-pot production of EL were proposed according to two intermediates: (1) hydrogenation of furfural to form furfuryl alcohol (FFA) that is then etherified with ethanol to form 2-(ethoxymethyl)furan (2-EMF); and (2) acetalization and etherification of furfural with ethanol to produce 2-(diethoxymethyl)furan (2-DMF). Then both 2-DMF and 2-EMF are converted to EL through acid catalyzed ring opening reaction. The dominant reaction pathway varied with the properties of the catalyst and the applied reaction conditions.
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高影响因子
ENERGY & FUELS
·
2022
·
IF 4.654
Kaifeng Lu,Yifan Wang,Caidi Jin,Robert Liao,Weihong Tan,Jun Ye,Lingjun Zhu,Shurong Wang
The conversion of biomass-derived monosaccharides to value-added platform compounds, regarded as the alternative biofuels precursors, has attracted increasing attention. This work provides a novel approach on developing efficient and recyclable catalyst for biorefining. Herein, a titania-supported tungstophosphoric acid (TPA-TiO2) nanocomposite catalyst with advantages in acidity flexibility and catalytic stability was proposed for the efficient dehydration of xylose to furfural. The loading of the active component of TPA played an important role in the acidity and Lewis/Brønsted acids distribution of the catalyst. The structure characterization of the catalyst showed that the TPA particles were distributed well in TiO2 support. After the optimization of catalytic reaction conditions, the xylose conversion could approach to 96.12% while the furfural yield of 76.71% was obtained at 190 °C for 60 min catalyzed by TiO2-TPA-3 in a methyl isobutyl ketone (MIBK)–water biphasic solvent system. It was still about 80% of the initial yield after the fifth recycling of the TiO2-supported heteropolyacids catalyst. Furthermore, the reaction kinetics of xylose dehydration to furfural was investigated. The catalytic system in this work had a lower activation energy for xylose dehydration, and the decrease in furfural yield was mainly caused by the side reaction of furfural with intermediates. This work provides a novel approach on developing efficient and recyclable catalyst for biorefining.
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高影响因子
RENEWABLE ENERGY
·
2022
·
IF 8.634
Yuewen Shao,Jie Wu,Zhiyuan Zheng,Mengjiao Fan,Kai Sun,Félix Mérimé Bkangmo Kontchouo,Lijun Zhang,Shu Zhang,Guangzhi Hu,Xun Hu
Production of cyclopentanone (CPO) from biomass-derived furfural is attractive but challenging, as deep hydrogenation or ring-opening of furan ring in furfural over Co-based catalysts hinders the formation of the targeting products. In this study, alloying Co with Fe species in Co–Fe–Al catalysts is proposed for selective conversion of furfural to CPO in water. The formation of CoFe alloy in Co–Fe–Al catalyst weakened the interaction between Co species and the alumina carrier, lowered the adsorption/activation of H 2 , suppressed the formation of especially Brønsted acidic sites, facilitated the electron transfer from Co 0 to Fe species, increased the activation energy for hydrogenation of furfural (from 17.2 kJ mol −1 over Co–Al to 33.4 kJ mol −1 over 1.5Co-1.5Fe-1.0Al), and weakened the adsorption of C C and C–O–C functionalities in furan ring of furfuryl alcohol (FA) on metallic sites. These factors together suppressed deep hydrogenation of furan ring in FA or ring-opening of FA to diols, producing CPO and CPL with total yield of 91.5%, which was attributed to the synergy between hydrogenation and Brønsted acidic sites. In addition, the presence of Fe in Co–Fe–Al catalysts also enhanced the structural stability of Co species, preventing the phase transformation and aggregation of Co species, and rendering the catalyst with superior reusability .
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高影响因子
RENEWABLE ENERGY
·
2022
·
IF 8.634
Yunlong Yao,Zhiquan Yu,Chenyang Lu,Fanfei Sun,Yao Wang,Zhichao Sun,Yingya Liu,Anjie Wang
Copper catalysts showed excellent C O hydrogenation selectivity, but poor ability of hydrogen dissociation. Herein, a strategy to improve the activity of a Cu-based catalyst is developed by thermal treatment of Cu(OH) 2 at 100 °C with C 2 H 2 /Ar (0.5 vol%) followed by H 2 reduction at 300 °C. By means of X-ray diffraction (XRD), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS), it was revealed that Cu x C crystallites , in addition to Cu crystallites, were present in the prepared catalysts. In furfural hydrogenation at 60 °C and 1.0 MPa, the Cu x C-containing catalyst showed significantly higher activity than the Cu counterpart prepared from the same precursor by H 2 reduction at 300 °C. The introduction of ZnO improved the dispersion, and thus led to enhanced catalytic performance. The Cu x C-Cu-ZnO catalyst with Zn/Cu molar ratio of 0.5 showed considerably high hydrothermal stability in a 70-h run, with furfural conversion of >99.0% and the furfuryl alcohol selectivity of 100%.
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高影响因子
APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Jingjing Tan,Jing He,Kuan Gao,Shanhui Zhu,Jinglei Cui,Long Huang,Yulei Zhu,Yongxiang Zhao
The hydrogenation of furfural to furfuryl alcohol in liquid was performed over Cu/CeO 2 catalyst with different morphology that was nanorod (CeO 2 -R), nanocube (CeO 2 -C) and nanopolyhedron (CeO 2 -P), respectively. It was observed that the Cu/CeO 2 -R catalyst exposed (1 1 0) crystal plane owns more oxygen vacancies and metal sites of Cu 0 in comparison with the catalyst of Cu/CeO 2 -P and Cu/CeO 2 -C. Meanwhile, it exhibited superior catalytic performance for furfural hydrogenation to furfuryl alcohol with a high yield of 98 % at 100 °C, 2 MPa H 2 within 4 h. The structure–activity relationship demonstrated that the catalyst intrinsic activity (TOF) is positively related to the concentration of oxygen vacancies and the metal sites of Cu 0 on its surface. DFT calculations and in-situ FTIR confirmed that Cu/CeO 2 -R (1 1 0) catalyst with more oxygen vacancy is in favor of the adsorption and activation of furfural (C O) on the catalyst surface compared with Cu/CeO 2 -P (1 1 1) and Cu/CeO 2 -C (1 0 0). Accordingly, the remarkable efficiency of Cu/CeO 2 -R catalyst can be assigned to the synergistic catalysis between the surface Cu 0 and the oxygen vacancies. Cu 0 was used to adsorb and activate H 2 , whereas the oxygen vacancies facilitate the adsorption of C O by O on the surface of the catalyst.
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高影响因子
JOURNAL OF POROUS MATERIALS
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2022
·Vol. 29
·期 5
·1479-1487
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IF 2.523
Ye Tiantian,Liu Hanfang,Wang Fupeng,Xie Huijie,Ran Saisai,Xu Wei,Liu Jia,Li Bin,Lin Haifeng,Chai Yongming,Wang Lei
Here, we demonstrate a simple in situ synthesis of Pd@silicate-1 (S-1), using [Pd(NH 2 CH 2 CH 2 NH 2 ) 2 ]Cl 2 as a metal precursor and steam-assisted crystallization (SAC) method. The ultra-small Pd nanoparticles (NPs) (~ 1 nm) can be successfully in situ encapsulated into the silicate-1 matrix with well dispersion. The obtained Pd@S-1 catalyst possesses high crystallinity, a large specific surface area and pore volume. More importantly, Pd NPs encapsulated into silicate-1 matrix can avoid the aggregation and sintering during catalytic reaction. Meanwhile, micropores of silicate-1 can improve the selectivity of the products in the hydrogenation of biomass furfural. Consequently, Pd@S-1 catalyst shows excellent catalytic activity in the selective hydrogenation of biomass furfural with selectivity of 95.7% and activity of 83.7% in the condition of relatively low temperature (458 K). Therefore, this strategy provides a new idea for the synthesis of molecular sieve supported metal catalysts.
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高影响因子
CARBOHYDRATE POLYMERS
·
2022
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IF 10.723
Zhuang Yue,Li-Li Sun,Shao-Ni Sun,Xue-Fei Cao,Jia-Long Wen,Ming-Qiang Zhu
The alkali-soluble hemicelluloses extracted with 10% KOH solution from corn bran were further isolated with different concentrations of aqueous ethanol solutions. Herein 92.2% of the original hemicelluloses can be obtained and the cellulase enzymatic hydrolysis rate of the alkali treated corn bran can reach to 97.2%. The corn bran hemicelluloses were mainly glucuronoarabinoxylan , in which xylose (48.4–53.8%) and arabinose (27.8–33.2%) were the main components. More linear hemicelluloses with high molecular weight tended to be precipitated in low concentration aqueous ethanol solutions. Furthermore, the relationship between the structural features of these alkali-soluble corn bran hemicelluloses and their furfural yield was investigated in MIBK (methyl isobutyl ketone)/H 2 O biphasic system. Results showed that the hemicelluloses with high xylose content are benefit to the furfural production, and the highest furfural yield of 67.7% was obtained.
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DOI
PubMed
高影响因子
Molecular Catalysis
·
2022
·
IF 5.089
Zhiquan Yu,Yan Li,Yunlong Yao,Yao Wang,Ying-Ya Liu,Zhichao Sun,Chuan Shi,Wei Wang,Anjie Wang
A bifunctional Ni 3 P/γ-Al 2 O 3 catalyst with both metal site and Lewis acid site was prepared by an electroless plating method, and applied in hydrogenative ring-rearrangement of furfural to cyclopentanone. The obtained catalyst was characterized by XRD, XPS, XAS, N 2 adsorption-desorption, ICP, TEM, CO chemisorption, NH 3 -TPD and Py-FTIR. The ultrafine Ni 3 P nanoparticles (∼3.8 nm) were highly dispersed in the catalyst. The exclusive Lewis acidity of Ni 3 P/γ-Al 2 O 3 was beneficial for the aqueous-phase hydrogenative ring-rearrangement. The effects of DP time, reaction parameters (temperature, H 2 pressure, solvent composition, and reaction time) on the catalytic performance were investigated. The yield of cyclopentanone was 74.6% at furfural conversion of 99.9% at 180 °C in 1 h over Ni 3 P/γ-Al 2 O 3 catalyst using pure water as the solvent. Moreover, the kinetics of hydrogenative ring-rearrangement of furfural catalyzed by Ni 3 P/γ-Al 2 O 3 was investigated.
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高影响因子
JOURNAL OF CATALYSIS
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2022
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IF 8.047
Chuncheng Lin,Jiamin Zhou,Zhangfan Zheng,Jinzhu Chen
Tertiary amines, currently obtained from fossil resources by a multi-step synthetic method, are important compounds in both chemical industry and organic transformations. Herein, we demonstrated highly efficient and convenient strategy to various biomass-based tertiary amines in excellent yields (85–95%) by a direct and consecutive reductive amination of furfural with various amines in one-pot using rhodium phosphide (Rh 2 P) catalyst. Typically, biomass-based tris (2-furanylmethyl)amine in 92% yield was directly obtained from furfural and HCOONH 4 in one-step. Time-dependent reaction profiles suggested a consecutive amination/hydrogenation pathway with furfurylamine-derived Schiff base and secondary amine as successively detected intermediates. The superiority of Rh 2 P was ascribed to its excellent low-temperature hydrogenation activity, which is structurally attributed to an efficient electron-transfer from P atoms (on the P-terminated Rh 2 P) to their bonded and dissociated H atoms. This research thus highlights a powerful, elegant, and attractive approach to biomass-based tertiary amines for a sustainable extension of amine chemistry.
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高影响因子
GREEN CHEMISTRY
·
2022
·Vol. 24
·期 5
·2240-2248
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IF 11.034
Yanlong Qi,Ruilin Feng,Shijun Liu,Long Cui,Quanquan Dai,Chenxi Bai
Functionalized monomers are of utmost importance in producing new polymers and smart materials. Herein, a two-step approach involving heterogeneous catalysis was developed to produce a functionalized monomer (2-vinylfuran) from bio-based furfural, giving an overall yield of 89%. Economic analysis suggests that this facile approach incurs much lower costs, and its practicality improves the availability of 2-vinylfuran. This is due to the delicate structure of the optimized 4Na5Ce/SiO2, where Na species are present at the oxygen vacancies of the ceria that protect the catalyst structure from collapse, and the catalyst consequently displays excellent performance. Density functional theory (DFT) calculations revealed that the reaction occurs on the Na and Ce species. The adsorption of a furan group onto Na led to side reactions, which were suppressed in the presence of Ce, resulting in higher selectivity. Finally, a polymer based on 2-vinylfuran was prepared, which shows good surface properties and thermodynamic stability.
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高影响因子
Molecular Catalysis
·
2023
·
IF 4.6
Xiqiang Tian,Yanping Dong,Muhammad Zahid
Herein, WN-TiO 2 with evenly distributed WN nanoparticles (NPs) were facilely synthesized thru one pot evaporation-induced self-assembly (EISA) and nitridation treatment method, as an active host material for precious Pt NPs. A number of characterization techniques were executed to explore the influence of the synthetic approach upon the surface and catalytic properties of the as-synthesized 2wt%Pt/TiO 2 and 2wt%Pt/WN-TiO 2 catalysts. As compared to 2wt%Pt/TiO 2 , the 2wt%Pt/WN-TiO 2 catalyst exhibited outstanding performance in the selective hydrogenation reaction of Furfural (FAL) to Furfuryl alcohols (FOL) (conversion (97.8%) and selectivity (98.6%)). The 2wt%Pt/WN-TiO 2 catalyst also exhibited an impressive recyclability performance for up to five recycles without significant deactivation in activity and selectivity. The superior catalytic hydrogenation performance can be ascribed to the specific nanostructure characteristics of the catalyst arose from the possible synergistic effect occurred between Pt and WN species of 2wt%Pt/WN-TiO 2 . Besides, the improved homogeneous dispersion of precious Pt NPs causes more exposed active sites of Pt 0 species on the surface of 2wt%Pt/WN-TiO 2 , which is very beneficial for the improved hydrogenation of FAL to FOL.
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高影响因子
Sustainable Energy & Fuels
·
2023
·Vol. 7
·期 15
·3716-3726
·
IF 5.6
Wansi Lin,Yue Wang,Junhua Zhang,Huai Liu,Lincai Peng
Lignin is a highly abundant biopolymer next to only cellulose, and its transformation into high value-added products is always of interest. It is well known to contain bounteous hydroxyl groups, which can act as natural organic ligands to assemble metal catalysts. Herein, lignin was selected to assemble well-dispersed Zr nanoparticles in polyacrylonitrile nanofiber by electrospinning technology (ZrNPs-lignin/PAN). Systematic characterizations revealed that lignin promoted the coordination between zirconium ions and PAN nanofibers to generate Lewis acid and Lewis base sites. The abundant Lewis acid–base sites confer the composite with remarkable catalytic activity in the transfer hydrogenation (TH) of furfural (FAL) into furfuryl alcohol (FOL), and a quantitative yield of 95.9% with a high TOF of 15.1 h−1 was obtained under mild conditions. ZrNPs-lignin/PAN exhibited good recycling stability and excellent universality in the CTH of a diverse array of carbonyl chemicals into their corresponding products.
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高影响因子
危险品化学品经营许可证（带存储）