CATALYSIS LETTERS
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2022
·Vol. 152
·期 12
·3537-3547
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IF 2.936
Liu Zonghui,Zhang Zhongze,Wen Zhe,Xue Bing
Development of simple and high performance solid catalysts for the utilization of biomass has become an important research topic in heterogeneous catalysis and sustainable chemistry. Herein, a highly efficient catalytic system was studied for the catalytic transfer hydrogenation of furfural to high value furfuryl alcohol over a series of acidic or basic oxides catalysts. Among those oxides, acidic Al 2 O 3 is identified as the most effective for FAL production, giving a FUR conversion as high as 40% (FUR consumption rate was 186 mmol g cat −1 h −1 ) and FAL selectivity of 99% after only 5 min at 150 °C using 2-propanol as the H-donor and solvent. Furthermore, the as prepared Al 2 O 3 give an Ea value of 15.2 kJ/mol, which is much lower than other complex catalysts in the literatures. Correlating the catalyst performance with its physical and chemical properties uncovers that the large specific surface area and high acidity of Al 2 O 3 would be the key to the catalyst performance. Graphical Abstract
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高影响因子
FUEL
·
2022
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IF 8.035
Bin Hu,An-shuai Cheng,Wen-luan Xie,Ji Liu,Yao-bing Huang,Ling-jun Zhu,Bing Zhang,Ming-xiao Li,Li Zhao,Ti-peng Wang,Qiang Lu
Pyrolysis is a promising thermal conversion technique of biomass to tackle the energy crisis and environmental pollution. Furfural (FF) is an important pyrolysis product from biomass-based materials and a crucial platform compound for energy and fuels. In the present study, we developed a new and green approach to selectively produce FF through the oxalic acid-assisted fast pyrolysis (OAFP) of corncob (CC). The FF yield was up to 16.5 wt% (based on raw CC) through the fast pyrolysis of the solid mixture of CC and OA with a ratio of 1:4 (CC/OA) at 400 °C during the micro-pyrolysis coupled with online-detection experiments. The corresponding FF selectivity was 56.5% (based on raw CC). Under similar experimental parameters, a yield of 10.0 wt% (based on raw CC) was achieved with a lab-scale setup. Experiment and density functional theory (DFT) calculation results suggested that OA played a catalyst-like role in the selective formation of FF from hemicellulose (mainly xylose units) of CC and meanwhile decomposed during the pyrolysis process. The formic acid (FA) decomposed from OA had a similar but lighter effect than OA. With the assistance of OA, the energy barriers of the FF formation reactions decrease dramatically and the competitiveness of the pathways is also altered, which contributes a lot to the FF selective generation. FF is mainly generated in a chain propagation pattern from the acyclic reducing end and unsaturated (C4 C5 bond) non-reducing end of the xylan chain.
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JOURNAL OF MEMBRANE SCIENCE
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2022
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IF 10.53
Yaqi Wang,Tanlong Xue,Zhihao Si,Chang Liu,Shuai Yang,Guozhen Li,Yan Zhuang,Peiyong Qin
Recently, the preparation of polymeric membranes by UV-induced polymerization is encouraged due to the ultrafast curing and controllable operation. However, the long-period exposure under UV light has a great threat to both the environment and operators. Herein, we developed the visible-light-induced polymerized PDMS membrane for the pervaporative separation of furfural . The differences among photoinitiator ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate (TPO-L), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO) and 2-hydroxy-2-methylpropiophenone (1173) in the polymerization kinetics , membrane structure and separation performance are compared. Results show that the absorbance of TPO-L matches 405 nm of the visible light region; and it can be well dispersed and compatible with PDMS and obtain high initiation efficiency. Furthermore, the conditions including TPO-L concentration and PDMS viscosity are optimized, and the prepared membrane has an outstanding pervaporation performance containing 1299.5 g m −2 h −1 of total flux and 40.2 of furfural separation factor. Importantly, the ultrafast and continuous preparation process of membrane is operated by a home-made machine, indicating the wonderful potential for its large-scale application.
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RSC Advances
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2022
·Vol. 12
·期 19
·11843-11852
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IF 4.036
Qi Guo,Xinglong Hou,Wei Xu,Junli Liu
Ni3Co1/ELAC catalyst, prepared by the enzymatically hydrolyzed lignin activated carbon as a carrier and a 3 : 1 ratio content of nickel and cobalt, can selectively convert furfural to cyclopentanol (CPL) in aqueous solution. We used activated carbon prepared by the phosphoric acid method as the carrier, and investigated the effect of the carrier on the catalyst activity. The ratio of bimetal (Ni, Co) content and reaction conditions (reaction temperature, reaction time, initial H2 pressure) have also been investigated in the furfural hydrogenation. With the optimal Ni3Co1/ELAC catalyst, the conversion rate of furfural and the selectivity of CPL were 100% and 94.1%, respectively. In this process, some important catalysts were studied by XRD, XPS, ICP-AES, BET and TEM characterization. Through experimental results and other people's research, we deduced a reasonable reaction path and verified it by replacing the reaction substrate and solvents. Finally, the experiment proved that the formation of CPL by furfural required the occurrence of a rearrangement reaction and the participation of aqueous solution.
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PubMed
高影响因子
Biomass Conversion and Biorefinery
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2022
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IF 4.05
Xiao Yaoxin,Zhang Jun,Zhu Lingjun,Shan Rui,Yuan Haoran,Chen Yong
A series of inexpensive electroplating sludge-derived magnetic copper-containing catalysts were developed for the selective hydrogenation of biomass-based furfural (FFR) into furfuryl alcohol (FA) and 2-methylfuran (MF). The specific structural characteristics of as-prepared magnetic copper-containing samples were clearly identified through various techniques, including XRD, XPS, N 2 adsorption–desorption, NH 3 -TPD, SEM and so on. The characterizations revealed that the hydrogen pre-activated magnetic catalysts supplied metallic Cu species, medium acidity and porosity for the catalytic upgrading of FFR in hydrogen atmosphere. As for FFR-to-FA as well as FFR-to-MF transformations, the magnetic copper-containing catalyst with calcination temperature of 800 °C exhibited excellent performance towards the formation of FA and MF, wherein desirable FA yield of 98.5 mol% and MF yield of 71.3 mol% were achieved at reaction temperatures of 160 °C and 240 °C, respectively. The reuse experiments indicated that the recycled catalysts still maintained excellent activity and stability even after four-time recycling. The present study thus highlights a new approach for the resource utilization of electroplating sludge, which also supplies low-cost and efficient catalytic materials for the selective upgrading of various biomass-derived platform molecules.
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高影响因子
FUEL
·
2022
·
IF 8.035
Wansi Lin,Yuan Cheng,Huai Liu,Junhua Zhang,Lincai Peng
The design of high-efficiency heterogeneous catalyst plays a central role for catalytic transfer hydrogenation (CTH) of biomass-derived furfural (FAL) into furfuryl alcohol (FOL). Herein, a novel zirconium doped polyacrylonitrile (PAN) nanofiber (Zr@PAN) was assembled via electrospinning technology. Systematic characterizations revealed that the high catalytic activity for CTH of FAL into FOL was provided by the cooperative effect between Lewis acid and Lewis base sites due to the chelation effect between zirconium ions and cyano-groups on PAN. Besides, a kinetic model specifying this reaction has been set up and showed a good correlation (R 2 > 0.94) between the measured and predicted data, which can effectively monitor the process and tailor the reaction conditions to attain the desired product. Although the activity of Zr-20@PAN decreased after three cycles of recovery, the introduction of bridging agent, such as lignin and tea polyphenol, can solve the recovery defect well due to their abundant hydroxyl group or carboxyl group.
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ACS Sustainable Chemistry & Engineering
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2022
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IF 9.224
Ao Xia,Dong Feng,Yun Huang,Xianqing Zhu,Zhengxin Wang,Xun Zhu,Qiang Liao
Anaerobic digestion of furfural wastewater suffers from toxicity to microbes, which reduces its performance. The toxic effects may be eliminated by a sustainable way of conductive material supplementation. In this study, the effect on anaerobic digestion of furfural (0.5–4 g/L) was investigated by adding 0–40 g/L granular activated carbon (GAC) in batch tests. The innovation of this current study is to explore the potential direct interspecies electron transfer (DIET) for the first time in furfural degradation as the sole substrate in anaerobic digestion. The results demonstrated that when furfural was the sole substrate, in the presence of GAC, the peak methane production rate was increased by 46.0%, while the specific methane yield was improved by 24.7%, compared with the control. Additionally, the electroactive Geobacter sulfurreducens abundance in biofilms attached to the surface of GAC was 19.0 folds higher than that in the control. The abundances of the related genes of methane metabolism and furfural degradation in biofilms were 1.1 and 5.8 folds higher than the control by metagenomic analysis, respectively. These lines of evidence suggested that the pathway of furfural metabolism to methane among Moorella species, G. sulfurreducens, and Methanothrix species based on DIET was likely established.
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Molecular Catalysis
·
2021
·
IF 5.062
Qian Wang,Jie Zhang,Wenlong Jia,Xin Yu,Jiahong Chen,Yong Sun,Zuojun Wei,Shuliang Yang,Xing Tang,Xianhai Zeng,Lu Lin
Generally, 5-hydroxymethylfurfural (HMF) is used as feedstock to produce 2,5-furandicarboxylic acid (FDCA). Whereas, its poor stability in alkaline environment results in low yield of FDCA. By contrast, 5-[(formyloxy)methyl]furfural (FMF), a novel platform compound derived from HMF, with higher thermal and alkaline stability than HMF, is more promising to replace HMF as substrate for the production of FDCA. In this study, FMF was successfully converted into FDCA over MoCuO x by using NaClO as oxidant, undergoing 2,5-diformylfuran (DFF) and 5-hydroxymethylfuran-2-carboxylic acid (HMFCA) as intermediates. Under optimization condition (30 min, 40 °C), 100% yield of FDCA was obtained. Furthermore, it was also demonstrated that the yield of FDCA up to 90% was gained in 5 wt % FMF concentration. Higher oxygen species mobility and lattice oxygen ratio endowed MoCuO x excellent catalytic activity. The synergy of Mo and Cu species in MoCuO x ensured an efficient conversion of HMF to FDCA through synergistic redox couple of Mo 6+ /Mo 5+ and Cu 2+ /Cu + .
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ENERGY & FUELS
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2021
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IF 3.605
Hao Xu,Shanshan Xiong,Yuan Zhao,Lingjun Zhu,Shurong Wang
Furfural is an important platform chemical that can be produced by dehydration of pentose, which is an important building block of lignocellulosic biomass. In this study, xylose was chosen as the reaction substrate, and a carbon-based solid acid prepared from pectin was used as the catalyst in a mixed solvent consisting of water and γ-valerolactone (GVL). FTIR results showed that the sulfonated catalyst had typical characteristic peaks of sulfonic groups, while the results based on NH3-TPD and elemental analysis showed that the sulfonation temperature changed the surface acid concentration and acid site intensity of the catalyst. A furfural yield of 80.4% and a xylose conversion of 100% were obtained at 170 °C for 60 min. The conversions and product yields were influenced by the reaction temperature, reaction time, solvent composition, and catalyst acidity. Different sulfonation temperatures can change the acidity of the catalyst, which determines the catalytic performance of the catalyst.
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高影响因子
FUEL
·
2021
·
IF 6.609
Bin Hu,Wen-luan Xie,Yu-ting Wu,Ji Liu,Shan-wei Ma,Ti-peng Wang,Shu Zheng,Qiang Lu
Furfural (FF) is a promising platform compound that can be selectively produced by the fast pyrolysis of xylan-based biomass in the presence of zinc chloride (ZnCl 2 ). Whereas, the catalytic effect of ZnCl 2 and the FF formation mechanism remain uncovered. The present work aims to give a deep insight into the formation mechanism of FF under the catalysis of ZnCl 2 by combining quantum chemistry calculations and fast pyrolysis experiments. Density functional theory (DFT) calculations and fast pyrolysis experiments were conducted with xylose as the model compound. ZnCl 2 affects the pyrolysis reactions through the binding of Zn atom and O atom of xylose initially, with manifest electron exchange between Zn and O. The activation free energies of the pyrolysis reactions can be decreased when ZnCl 2 stays at the reaction center of the transition states. Both ring-opening and 1,2-dehydration can be promoted by ZnCl 2 , whereas ring-contraction is hindered by ZnCl 2 because ZnCl 2 is away from the reaction center of the ring-contraction. Due to the distinct influence of ZnCl 2 on different reactions, the rate-determining steps in some of the possible FF formation pathways are changed. Hence, the competitiveness of these pathways is altered to a great degree, which should be responsible for the selective production of FF. Xylose tends to generate FF through the acyclic d -xylose decomposition channel due to the catalysis of ZnCl 2 . The most favorable FF generation pathway involves the successive cyclization, 1,2-dehydration between 2-OH and 1-H, electrocyclic dehydration, and 1,2-dehydration between 4-OH and 5-H following the formation of a d -xylulose intermediate.
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ACS Sustainable Chemistry & Engineering
·
2020
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IF 7.632
Xiaoqi Wang,Mo Qiu,Richard Lee Smith Jr.,Jirui Yang,Feng Shen,Xinhua Qi
Ferromagnetic Ni-doped lignin-derived ordered mesoporous carbon (Ni@OMC) was synthesized in one pot by evaporation-induced self-assembly (EISA) for use as catalysts. Lignin was used to partially replace phloroglucinol (up to 80%) as the carbon precursor under conditions that allowed ordered mesoporous structures to be perfectly retained and Ni particles to be uniformly dispersed within the material. The as-synthesized Ni@OMC catalysts promoted hydrogenation of furfural, affording furfuryl alcohol (FAL) yields and selectivities as high as 91.0 and 98.6% at 180 °C for a 12 h reaction time in the presence of H2 gas. The Ni@OMC catalyst could be simply separated through application of a magnetic field and was recyclable for at least five cycles. The stability of the Ni@OMC catalyst is attributed to space confinement effects of the carbon skeleton on the doped Ni particles through coordinated interactions between lignin and metal ions (Ni2+). The proposed method allows the synthesis of metal-doped ordered porous carbons from lignin and is green and sustainable.
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2020
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IF 16.683
Wei Liu,Yusen Yang,Lifang Chen,Enze Xu,Jiaming Xu,Song Hong,Xin Zhang,Min Wei
Activation of oxygen-containing functional groups plays a key role in sustainable biomass upgrading and conversion. In this work, a NiMo intermetallic compound (IMC) catalyst was prepared based on layered double hydroxides (LDHs) precursors, which displayed prominent catalytic performance for furfural hydrodeoxygenation (HDO) to 2-methylfuran (2-MF) (yield: 99 %) at a rather low hydrogen pressure (0.1 MPa), significantly superior to NiMo alloy, monometallic Ni and other Ni-based catalysts ever reported. CO-IR, STEM, EXAFS and XANES give direct evidences that the atomically-ordered Ni/Mo sites in NiMo IMC determine the uniform bridging-type adsorption mode of C O bond in furfural whilst adsorption of furan ring is extremely suppressed. In situ FT-IR and DFT calculation further substantiate that ordered Ni-Mo bimetallic sites of IMC, in contrast to the random atomic sequence in NiMo alloy, facilitate the activation and cleavage of C OH bond in the intermediate (furfuryl alcohol, FOL), accounting for the production of 2-MF. This work demonstrates the decisive effect of atomically-ordered active sites in IMC catalyst on activation of oxygen-containing functional groups and product selectivity, which can be extended to catalytic upgrading of biomass-derived platform molecules.
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