Molecular Catalysis
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2024
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IF 3.9
Xing Gao,Wenna Zhang,Yingying Ruan,Shihao Zhang,Sheng Wei,Yiwen Zhang,Pengfei Liu,Dong Tian,Yihu Dai,Yanhui Yang
The conversion of biomass-based compounds into highly value-added chemicals has received extensive attention in recent years. This work reports the liquid-phase selective hydrogenation and furan ring-rearrangement of furfural (FFL) into cyclopentanone (CPO) and cyclopentanol (CPL) over Pd/Co 4 Al 1 -HTs catalysts and water as the solvent. The specific reaction rate of the optimal catalyst at 160 °C reaches 538 h –1 , and the selectivity of CPO/CPL is 77.5 %. By adopting the ion-exchange and formamide treatment methods, the type of the interlayer anions and interlayer spacing for the CoAl-HTs supports can be regulated, which can affect the state of the supported Pd sites and their catalytic activity and selectivity towards the ring-rearrangement products. Furthermore, the H 2 /D 2 exchange experimental results demonstrate that the presence of the interlayer NO 3 – anions of CoAl-HTs support promotes the activation and dissociation of H 2 , thereby accelerating the hydrogenation of FFL to cyclic compounds.
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高影响因子
FUEL
·
2024
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IF 6.7
Xiao Chen,Rongrong Li,Zhengwen Hu,Ying Zhong,Deng Hu,Changhai Liang
The selective activation of targeted bonds within renewable biomass-derived furanic compounds for the production of high-value alkyl diols holds significant importance for biomass upgrading, necessitating well-defined catalysts and clearly defined catalytically active sites. Herein, 1,5-pentanediol is synthesized through the selective hydrogenolysis of furfural-derived tetrahydrofurfuryl alcohol utilizing Ni-Co/La(OH) x bimetallic catalysts. The La(OH) x with abundant defect sites polarizes Ni-Co alloy for heterocracking of H 2 , as well as leads to expose more interfacial NiCo-O V -La 3+ sites. By harnessing the synergistic interplay between the alloy sites and the interfacial sites, the optimized Ni 4 Co 1 /La(OH) x bimetallic catalyst markedly enhances the adsorption of –OH groups in tetrahydrofurfuryl alcohol and facilitates the selective assault of active H species on the C-O-C bonds within tetrahydrofuran rings. This approach markedly elevates the selective hydrogenolysis of tetrahydrofurfuryl alcohol to 1,5-pentanediol, attaining an exceptional selectivity of 88.6 % with a conversion of 98.1 % for tetrahydrofurfuryl alcohol. Furthermore, the Ni 4 Co 1 /La(OH) x bimetallic catalyst demonstrates exceptional performance in the one-pot hydrogenation-hydrogenolysis of furfural to 1,5-pentanediol, exhibiting a low activation energy of 17.77 kJ/mol and a high turnover frequency of 192.1 h −1 . Notably, the Ni 4 Co 1 /La(OH) x bimetallic catalyst showcases remarkable stability. This outcome provides invaluable insights for the advancement of a sustainable process to produce diol monomers from renewable resources with a low carbon footprint.
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高影响因子
JOURNAL OF VINYL & ADDITIVE TECHNOLOGY
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2025
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IF 3.6
Huajun Duan,Ruian Li,Yuan Gao,Jiangtao Geng,Yuan Chen,Ya Li,Weipeng Liu,Huiru Ma
Epoxy resin (EP) is a thermosetting resin of significant commercial value. However, it is afflicted by inherent defects, including flammability and non-self-extinguishing properties. Consequently, it is imperative to modify EP with flame retardant additives. Currently, the majority of flame retardants are characterized by complexity and a cumbersome preparation process, which is not conducive to environmental sustainability. Consequently, there is a growing demand for eco-friendly bio-based flame retardants. In this paper, bio-based reactive flame retardants (HGD) with hydroxymethyl and phenolic hydroxyl groups were prepared in a one-step method by bulk reaction using the bio-based materials 5-hydroxymethylfurfural, guaiacol, and DOPO as raw materials, and were added into EP as co-curing agents to prepare flame retardant epoxy resins (FREPs). Comprehensive evaluation revealed fire safety improvements in HGD-modified EP systems. Specifically, the optimized EP/HGD-7.5 formulation demonstrated reductions in key combustion parameters compared to unmodified EP: 35.7% decrease in peak heat release rate (pHRR), 34.0% reduction in total heat release (THR), 24.3% lower average effective heat of combustion (Av-EHC), and 16.8% suppression of total smoke production (TSP). Meanwhile, the modified composites exhibited concurrent mechanical enhancement. At 7.5% HGD loading, flexural strength and modulus increased by 21.1% and 20.0%, respectively, while tensile performance optimization occurred at 5.0% loading with 20.6% strength improvement and 24.5% modulus elevation. Notably, HGD-modified EP systems maintained superior thermal stability. The glass transition temperature ( T g ) of EP/HGD-7.5 is 154.2°C, exceeding that of EP. This investigation successfully demonstrates a sustainable approach for developing multifunctional epoxy composites with enhanced fire resistance and mechanical performance through bio-based modification.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Shanguang Xu,Xin Han,Fan Zhang,Zhengyang Sun,Ruiying Chai,Fei Xu,Shanguo Du,Xiuling Jiao,Dairong Chen,Jie Zhang
The development of efficient catalysts for the selective hydrogenation of furfural (FAL) to furfuryl alcohol (FOL) is of great importance for sustainable chemical production. In this study, a highly efficient Cu/Al 2 O 3 catalyst was developed for the selective hydrogenation of FAL to FOL, achieving 100 % conversion and 100 % selectivity at 85 °C and 1.0 MPa H 2 with the optimal 7Cu/Al 2 O 3 -AIP catalyst, which was tailored by modulating the surface acidity of Al 2 O 3 and the distribution of Cu species. Evaluation of Cu-supported varying Al 2 O 3 catalysts revealed a near-linear correlation between the density of medium-strong acidic sites and catalytic activity, unequivocally demonstrating that medium-strong acidic sites on the alumina surface serve as the active sites for the reaction, which was further corroborated by competitive adsorption experiments involving pyridine and furfural. Furthermore, the density of Cu 0 sites was varied by adjusting the copper loading and conducting N 2 O selective oxidation experiments. Notably, a linear increase in catalytic activity was observed with the Cu 0 /(Cu 0 + Cu + ) ratio on the catalyst surface. Advanced characterization techniques, combined with experimental results, elucidated that the Cu 0 species act as the primary active sites for H 2 activation, while acidic sites are crucial for FAL adsorption, leading to the exceptional catalytic performance by the synergistic catalysis. This study underscores the synergistic effect between Cu 0 species and acidic sites, providing profound mechanistic insights into the FAL hydrogenation process and establishing a strategic foundation for the rational design of highly efficient Cu-based catalysts.
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高影响因子
Molecular Catalysis
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2019
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IF 2.938
Wenke Li,Zhe Cai,Hang Li,Yu Shen,Yongqiang Zhu,Haichao Li,Xubin Zhang,Fumin Wang
One-pot conversion of furfural to the target product γ-valerolactone (GVL) is a challenging and meaningful part of biomass exploitation. Development of heterogeneous catalysts with both Brønsted and Lewis acid properties has proved to be promising and useful because they offer an efficient way to tandem cascade reactions from furfural to GVL. Herein, we successfully synthesized sulfated DUT-67(Hf), a novel bifunctional catalyst, via a post-synthetic modification method. The prepared sulfated DUT-67(Hf) was characterized by XRD, SEM, TEM, N 2 adsorption-desorption, Elemental (N, C, H, S) analyses, situ infrared spectra of pyridine adsorptions, XPS, FT-IR, TG, and NH 3 -TPD. The acidity of the catalysts could be adjusted by submersion in different concentrations of aqueous sulfuric acid, giving 0.01 mol/L sulfuric acid for 0.42 mmol/g acidity to 0.1 mol/L sulfuric acid for 2.16 mmol/g acidity. Sulfated DUT-67(Hf) possessed by 0.06 mol/L aqueous sulfuric acid exhibited optimal catalytic activity and showed an 87.1% yield of GVL under the conditions of 180 °C after 24 h of reaction. Moreover, the mechanism of introducing Brønsted acid sites into DUT-67(Hf) and the better hydrogen donors was also investigated through contrasting experiments.
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高影响因子
Journal of Bioresources and Bioproducts
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2021
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IF 0
Jingwen Shao,Yong Ni,Lifeng Yan
Furfural is an alternative feedstock and has been used for the production of maleic acid (MA) and fumaric acid (FA) by an oxidation process. Deep eutectic solvents (DESs) were used as the green solvents while sodium chlorate was used as an oxidant and vanadium pentoxide was used as the catalyst at 70–90 °C under atmospheric pressure. It was found that several acidic DESs are valid, such as acetic acid/choline chloride (AA/ChCl) and propionic acid/choline chloride (PA/ChCl), and AA/ChCl DES was selected as the solvent for the conversion. The optimal DES is AA/ChCl, and the effect of the amount of oxidant, time, and temperature on the yield of the MA and FA has been systematically studied, and the conversion of furfural can reach 100% while the yield of the MA and FA reached 66.5% under reaction temperature of 80 °C for 12 h, which provides a new green route to synthesis valuable monomers from furfural.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2021
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IF 3.764
Hongyu Niu,Yuan Cheng,Chuang Li,Shaojie Li,Jingjie Luo,Changhai Liang
Rational design of promising Cu catalyst requires better understanding of the Cu–support perimeter for reactions such as hydrogenation rearrangement of furfural─a pivotal and alternative transformation to produce cyclopentanol. Herein, a series of Cu catalysts with constructed Cu-M-Ox interfaces (M = Zn or Al) have been synthesized. In freshly reduced Cu/ZnO-Alx samples, aluminum species was enriched surrounding Cu. The Cu-Al-Ox contacting interface was formed, and the CuAl2O4 spinal structure was detected as a combining consequence only if Zn and Al species coexisted. The specific metal–support synergistic interaction and Cu-Al-Ox contacting interface simultaneously aroused the enhanced redox property and large number of surface acid sites, facilitating the adsorption/activation of hydrogen and reactants. During the reaction, Al2O3 retreating from the Cu-Al-Ox interface caused the replacement of Cu-Al-Ox by new Cu-Zn-Ox interface, which was directly correlated with the irreversibly changed chemical structure and decreased cyclopentanol yield, although the furfural conversion was well sustained. In this work, we confirmed that supported copper catalysts were competent for the activation and conversion of furfural, with the turnover frequency reaching 28.1 h–1 by the Cu/ZnO-Al3 sample at temperatures as low as 90 °C. The further transformation of cyclopentanone to cyclopentanol was largely depending on the maintenance of a steady Cu-Al-Ox contacting interface.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2021
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IF 13.273
Jinghua Wang,Hongyou Cui,Jiangang Wang,Zhihe Li,Ming Wang,Weiming Yi
Conversion of glucose to 5-hydromethyl furfural (HMF) and levulinic acid (LA) was systematically investigated in LiCl·3H 2 O without additional catalyst. Based on the experimental investigations by using glucose, fructose and HMF as the reaction substrate separately, corresponding reaction kinetics in LiCl·3H 2 O were modelled by first-order assumption. Kinetic analysis demonstrates that high temperature favors the formation of LA, while low temperature facilitates to selectively form humins. To achieve high LA yield, at least a temperature of 140 °C is required. Without additional catalyst converting glucose to LA in LiCl·3H 2 O, humins was predominantly derived from glucose and HMF, and glucose isomerization is the reaction rate-determining step. The activation energies of the main reactions are 160.96 kJ/mol (glucose to HMF), 139.20 kJ/mol (fructose to HMF), and 71.81–76.48 kJ/mol (HMF to LA) respectively. The activation energies for humins formation were 23.45 kJ/mol from glucose, 49.54 kJ/mol from fructose, and 42.15–65.85 kJ/mol from HMF, respectively. It is verified that LiCl·3H 2 O, as compared to aqueous medium, is an excellent reaction medium for converting glucose to LA as it can provide the active centers for fructose to HMF reaction and HMF to LA reaction, but lack of highly efficient Lewis acid for glucose isomerization. With the addition of Lewis acid (such as AlCl 3 and FeCl 3 ), as high as 83.4% of LA yield can be obtained respectively when directly converting glucose, with the total selectivities of LA and HMF of 95%.
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高影响因子
APPLIED CATALYSIS A-GENERAL
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2021
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IF 5.706
Qingrui Peng,Haijun Wang,Yongmei Xia,Xiang Liu
A multifunctional Zr-containing catalyst (FM-Zr-ARS) was successfully synthesized by a modulated hydrothermal synthesis route. Systematic characterization results supported the presence of robust porous inorganic-organic frameworks stabilized by the strong coordination interaction of Zr 4+ with oxygen-rich functional groups in Alizarin red S (ARS). Moreover, the -O-Zr-O- network in the FM-Zr-ARS structure formed a rich content of acid-base sites. In addition, the inherent sulfonic groups in ARS made the FM-Zr-ARS hybrids possess Brønsted acid sites. Therefore, under the synergistic catalysis of the multiple functional sites, FM-Zr-ARS showed remarkably high catalytic activity for γ-valerolactone (GVL) production from levulinate esters and furfural. Finally, 72.4 % and 97.7 % yields of GVL were obtained in the conversion of furfural and ethyl levulinate, respectively, after 8 h of reaction at 433 K. On the basis of the role of different functional sites, a plausible catalytic mechanism was presented for the conversion of biomass-derived furfural to GVL.
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高影响因子
ACS Sustainable Chemistry & Engineering
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2017
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IF 5.951
Wanbing Gong,Chun Chen,Yong Zhang,Hongjian Zhou,Huimin Wang,Haimin Zhang,Yunxia Zhang,Guozhong Wang,Huijun Zhao
A copper-based catalyst, which was supported by sulfonate group (−SO3H) grafted active carbon (AC), was prepared and activated simultaneously by liquid phase chemical reduction method. The modified copper catalyst, Cu/AC–SO3H, displayed an enhanced catalytic performance for selective hydrogenation of furfural (FAL) to furfuryl alcohol (FOL) in liquid phase, in which almost 100% FOL yield was obtained at 378 K and 0.4 MPa of hydrogen pressure after 120 min reaction. The effect of −SO3H was evaluated and illustrated by the combination of reaction performance and physicochemical characterizations, such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectrometer (XPS) measurements. Through grafting sulfonate group on the support, better dispersion of nanoparticles, higher reduction degree of Cu, and stronger adsorption of FAL can be attained to contribute high hydrogenation performance. In addition, the effects of reaction conditions (such as reaction temperature, H2 pressure, reaction time, solvent, and catalyst to FAL mass ratio) were evaluated intensively. Also, the Cu/AC–SO3H catalyst showed an excellent catalytic performance for transfer hydrogenation of FAL, in which 2-propanol was utilized as the solvent and hydrogen donor concurrently. Cycling test proved the prepared catalyst could be recycled and reused for several times without noticeably reduced catalytic activity of hydrogenation.
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高影响因子
Molecular Catalysis
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2019
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IF 2.938
Liqin Wang,Heqin Guo,Qiang Wang,Bo Hou,Litao Jia,Jinglei Cui,Debao Li
Furfural, generally achieved from hemicelluloses and its derived pentose, is a high value-added product. The formation of furfural from cellulose and hexose remains challenging. The acid sites in zeolites are the major active sites for preparing furfural from hexose. The catalytic performance of zeolites can be improved by increasing the number of active sites for the preparation of furfural. In this work, HZ-Na free-m and HZ-Na-m zeolites were prepared through without or with adding Na + ions in the mother gels, respectively. GHB (hydrolysate of GBL) was the active site for the formation of acyclic fructose precursor (Intermediate 2). Acyclic fructose production and the following dehydration for producing furfural were favored by the middle strong and strong Brønsted acids in the channels of HZSM-5. Meanwhile, middle strong and strong Brønsted acids were favored the production of HMF from fructose and furfural from xylose. The exterior weak Lewis acid of HZSM-5 could promote the formation of soluble oligomers. The soluble oligomers were composed by HMF and furfural through condensation, etherification, nucleophilic attack and electrophilic attack. HMF molecule was easy to participate in the production of soluble oligomers than furfural molecule over exterior weak Lewis acid of HZSM-5.
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高影响因子
Molecular Catalysis
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2017
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IF 0
Hao Chen,Houhang Ruan,Xilei Lu,Jie Fu,Timothy Langrish,Xiuyang Lu
Catalytic transfer hydrogenation of furfural to furfuryl alcohol is considered to be a very important industrial process. In this work, non-noble Cu supported on MgO-Al 2 O 3 catalysts have been prepared by co-precipitation and have shown excellent catalytic performance for conversion of furfural to furfuryl alcohol in near-critical iso-propanol. The effects of the Cu state (reduction degree and dispersion) and loading in Cu/MgO-Al 2 O 3 , acidity of catalysts have been investigated by X-ray diffraction (XRD), coupled plasma optical emission spectrometry (ICP-OES), N 2 adsorption and desorption (N 2 -BET) and temperature-programmed desorption of ammonia (NH 3 -TPD), which have led to high activity for producing furfuryl alcohol. The results have shown that the selectivity of furfuryl alcohol has been influenced by the Cu state, Lewis acidity, reaction temperature and reaction time. The mechanisms, Lewis acid- and metal mediated hydrogenation, have shown that a desirable balance of Cu loading and Lewis acidity of catalyst has influenced the activity significantly. Almost 100% furfural conversion, with 89.3% furfuryl alcohol yield has been obtained. Cycling tests have shown that the prepared catalysts have been stable, where recycling the catalysts at least four times has not shown any reduction in activity.
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