INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2023
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IF 4.2
Rongrong Li,Wenqi Liu,Huibin Liu,Hongyu Niu,Quan Zhou,Changhai Liang,Xiao Chen
One-pot hydrogenation of biomass-derived furfural with multiple reduction sites requires suitable metal sites to achieve a high value-added chemical in high yield. In this work, nonprecious Ni–Fe bimetallic catalysts with high efficiency derived from FexNiy/MgAl-LDH hydrotalcite precursors are prepared for one-pot sequential hydrogenation of furfural to tetrahydrofurfuryl alcohol at mild conditions. Through fine adjustment of metallic Fe/Ni molar ratios in hydrotalcite precursors, bimetallic FexNiy/MgAlO catalysts can be constructed. The topological transformation of hydrotalcite precursors provides a mesoporous structure for bimetallic supported catalysts. Due to the formation of the Ni–Fe alloy, there is an electron transfer from Fe to Ni in the catalyst due to the higher electronegativity of Ni than that of Fe, which greatly influences the adsorption of furfural on the surface of catalysts. Comparing the structures and catalytic performances of monometallic Ni/MgAlO and Fe/MgAlO catalysts, the Ni-rich Fe1Ni4/MgAlO catalyst with the dual active sites of metallic Ni and FeNi3 alloy presents high efficiency in sequential hydrogenation of the C═O bonds and C═C bonds of furfural to tetrahydrofurfuryl alcohol with the yield of 90.3% under 3 MPa H2 and 80 °C for 3 h, which can be an alternative for noble metal catalysts. Additionally, the Ni-rich Fe1Ni4/MgAlO catalyst presents excellent cycling stability. This design strategy for nonprecious NiFe bimetallic catalysts not only provide promising candidates for effective utilization of biobased furfural but also extend the application of bimetallic catalysts derived from hydrotalcite precursors for one-pot hydrogenation reactions.
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高影响因子
INDUSTRIAL CROPS AND PRODUCTS
·
2019
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IF 4.191
Xiaoyun Li,Rui Xu,Qingling Liu,Min Liang,Jiaxin Yang,Shuangchun Lu,Guangbi Li,Lefu Lu,Chuanling Si
A one-step process was proposed for valorization of corn stover into furfural and levulinic acid catalyzed by SAPO-18 zeolites. With the aim to produce furfural and levulinic acid, the Brønsted to Lewis acid site ratios of SAPO-18 were modified. The influence of reaction temperature, time and the ratios of Brønsted to Lewis acid site on the valorization of corn stover were investigated. At the fixed catalyst concentration of 20 g/L, a furfural yield of 95.1% was observed at 205 °C for 40 min using SAPO-18 with Brønsted to Lewis acid site ratio of 0.11, and a levulinic acid yield of 70.2% achieved at 190 °C for 80 min using SAPO-18 with Brønsted to Lewis acid site ratio of 0.17. The Brønsted to Lewis acid site ratios of SAPO-18 were adjusted by altering the framework Si/Al ratio of SAPO-18. The SAPO-18 with lower Brønsted to Lewis acid site ratios showed higher activity for furfural production from corn stover and that with higher ratios exhibit superior catalytic effect for levulinic acid formation. The kinetic models considering the effect of Brønsted to Lewis acid site ratios agreed with the experiment values well, which provided detailed insights on the conversion of hemicellulose and cellulose fraction of corn stover into furfural and levulinic acid.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2017
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IF 6.216
Qiong Wang,Xinshu Zhuang,Wen Wang,Xuesong Tan,Qiang Yu,Wei Qi,Zhenhong Yuan
In order to minimize hemicellulose (or cellulose) waste upon the simultaneous production of furfural and 5-hydroxymethylfurfural (or furfural and levulinic acid) from the hydrolysis of lignocellulose in one-pot acid/organic solvent systems, we have developed a novel pressurized phosphoric acid-acetone-water system (PPAWS) to convert hemicellulose into furfural with a high retention of cellulose. In the PPAWS (acetone/water = 7:3, v / v ) at 150 °C under 1.5 MPa nitrogen, furfural production (yield 45.8%), delignification (lignin removal rate 89.8 wt%), and cellulose-rich residue extraction (retention rate 72.9 wt%, purity 92.5 wt%) from sugarcane bagasse were achieved simultaneously in just 5 min. Gas chromatography–mass spectrometry analysis of the liquid products revealed that pressure significantly inhibits the generation of aldol condensation products, i.e., acetone self-condensation products and 4-(2-furyl)-3-buten-2-one from the condensation of acetone and furfural, and acetone was retained in large quantities. In addition, kinetic analysis revealed that the “xylose → furfural → degradation products” pentose-hydrolysis path occurs in the PPAWS and that the rate constant of the “xylose → furfural” step is significantly increased, which is a clear departure from the reaction conducted without additional pressure. Furfural degradation experiments confirmed that adding pressure also inhibits the degradation of furfural in the initial stage of the reaction. The PPAWS exploits the benefits of acetone for lignin removal and the promotion of furfural production, and can be easily integrated into advanced jet fuel production from the aldol condensation of furans and ketones.
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高影响因子
APPLIED CATALYSIS A-GENERAL
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2017
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IF 4.339
Yong-Jian Xu,Jing Shi,Wei-Peng Wu,Rui Zhu,Xing-Long Li,Jin Deng,Yao Fu
In this paper, Cp*Ir (III) Complex and acid co-catalyst system was developed. By using Cp*Ir and γ-Al 2 O 3 (Lewis acid), 5-hydroxymethylfurfural (5-HMF) can be converted efficiently to 3-hydroxymethyl cyclopentanone (HCPN). Meanwhile, Cp*Ir and Brønsted acid can promote conversion of 5-HMF to 1-Hydroxy-2,5-hexanedione (HHD). The effect of Lewis acid and Brønsted acid on the hydrogenation of furan derivatives was studied. Mechanism of conversion of 5-HMF to HCPN was discussed in detail and mechanism proposed by our predecessors was revised. Instead of being an intermediate for the formation of HCPN, it is believed that, HHD is a product of another reaction pathway. HHD condensed via Aldol reaction to produce 3-methylcyclopenten-2-ol-1-one (MCP) instead of HCPN. Under the promotion of Lewis acid, 5-HMF firstly convert to the precursor of HHD. After that, the reaction is through 4 π-electrocyclic ring closure process and HCPN was formed ultimately. Furthermore, we found that our Cp*Ir and acid co-catalyst system is suitable for a variety of furfural compounds. By using Cp*Ir, Brønsted acid can promote conversion of furfural compounds to straight chain ketones and Lewis acid can promote the rearrangement of furfural compounds to cyclopentanone derivatives.
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高影响因子
CATALYSIS TODAY
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2014
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IF 3.309
Huiling Li,Aojie Deng,Junli Ren,Changyu Liu,Wenju Wang,Feng Peng,Runcang Sun
One of the most promising strategies for furfural production is to extract continually the target product from the aqueous solution utilizing organic solvents. With the aim to develop an ecologically viable catalytic pathway for furfural production without the addition of mineral acids, we presented a modified biphasic system using a solid acid (SO 4 2− /TiO 2 -ZrO 2 /La 3+ ) as catalyst for producing furfural from xylose. Different kinds of aprotic organic solvents (DMSO, DMF and DMI) in water phase and 2-butanol in organic phase (MIBK) were investigated as reaction media. Furfural yield and xylose conversion efficiency were dependent on the amounts of aprotic organic solvents and 2-butanol, the solid/liquid ratio, and the volume ratio of the organic phase and the aqueous phase as well as the reaction temperature and time. As a result, DMI showed the best performance on improving furfural yield during the furfural production. 3563.3 μmol of furfural/g of xylose with 97.9% xylose conversion efficiency was obtained after 12 h at 180 °C when the volume ratios of water to DMI and MIBK to 2-butanol were 8:2 and 7:3, respectively.
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高影响因子
ACS Catalysis
·
2025
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IF 13.1
Xiaorui Du,Chongshuai Gao,Jiaxin Huang,Yanbin Cui,Shijun Liu,Chenguang Wang
Controlling both the hydrogenation performance and the activation of Schiff base intermediate in catalysts is crucial for attaining high slectivity toward primary amine in the reduction amination of furfural. However, it remains pending for Pt-based catalysts, on which the reduction amination reactions rarely generate primary amines so far. In this work, we developed a Pt/TiO2 nanocluster (NC) catalyst with a size distribution independent of the reduction temperature and loading amount. The reductive amination performance was investigated by regulating the surface electronic state and the distance between Pt NCs, and the results, attractively, revealed that the catalyst with a lower loading amount exhibited a higher furfurylamine (FAM) yield. Further studies unraveled that the catalyst with a larger Pt NC proximity had more abundant effective adsorption sites for the key intermediate Schiff base, i.e., the surface Ti4+ sites adjacent to the Pt NC, promoting the transformation of the Schiff base. Meanwhile, reducing the surface density of Pt NCs helped control the intensity of hydrogen spillover, thereby inhibiting the occurrence of overhydrogenation reactions. Optimal activity for primary amine generation from furfural reductive amination was achieved with a Pt NC catalyst reduced at 500 °C and with a loading amount of only 0.1 wt %, resulting in a FAM yield exceeding 93% and a production rate of 297.9 gFAM gPt h–1. The reaction mechanism, involving the competitive relationship between NH3 and H2, was elucidated through kinetic studies and theoretical calculations. This work provides insights for the designation of catalysts with controllable hydrogenation activity and adsorption selectivity and contributes to the understanding of the mechanism of the reductive amination reaction.
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高影响因子
INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
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2025
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IF 8.5
Yuanlong Guo,Juchun Liu,Tianlong He,Tao Wu,Tonghui Xu,Yunqi Li,Haibo Xie
Traditional phenolic resins (PF) are extremely widely applied in industrial and daily life due to their low cost and outstanding adhesion. However, they are also limited by the toxicity of phenol and formaldehyde as well as the petroleum-based origin at the same time. Herein, a comprehensive strategy for the development of formaldehyde-free lignin-based furfural resin (LFR) with dual functions for adhesive and photothermal conversion materials was presented. Firstly, a newly developed phenolated lignin was obtained via the transesterification of 3,4-dihydrocoumarin (DHC) and aliphatic hydroxyl group of lignin under organocatalysis. Then, the phenolated lignin can be regarded as a highly versatile and precise building block polymer for the design and development of LFR. LFR exhibited excellent adhesion performance from 1.12 to 2.75 MPa on various substrates. Additionally, the low-temperature and wet adhesion strength of LFR were also investigated. Different from traditional thermosetting PF, LFR was hot-melt and possessed outstanding photothermal conversion and hydrophobicity properties, which provided the possibility for its use as a photothermal power generation coating and anti/de-icing material. The maximum temperature and output voltage as well as current of LFR-2 coating could reach 154 °C, 310 mV and 43.2 mA via a thermoelectric generator, respectively. Finally, the hydrophobic, smooth and self-cleaning surface of LFR-2 could effectively help melt and remove ice even in a − 20 °C environment, which was beneficial for the utilization of photothermal material in real environment.
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PubMed
高影响因子
ChemCatChem
·
2025
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IF 3.9
Zhouxiao Zhai,Jingce Bi,Yi Wang,Ningning Liu,Linshan Wang,Xia Zhang,Zhuopeng Wang,Yide Han
Graphical In this work, a mesoporous molecular sieve with graphite carbon-coated Co NPs (Co@CN/Al-MCM-41) was successfully synthesized by vacuum-injecting the precursor solution into the MCM-41 molecular sieve and subsequent calcination. Experimental results demonstrate that Co@CN/Al0.1-MCM-41 exhibits excellent catalytic performance in the hydrogenation of FF. Its excellent catalytic performance is primarily attributed to the interaction between Co species and Al species of MCM-41, including the reduction effect, electron transfer, and enhancement of acid density. The catalytic hydrogenation of furfural (FF) to furfuryl alcohol (FOL) using metal-loaded mesoporous molecular sieves represents a significant research area. In this work, a mesoporous molecular sieve with graphite carbon-coated Co NPs (Co@CN/Al-MCM-41) was successfully synthesized by vacuum-injecting the precursor solution into the MCM-41 molecular sieve and subsequent calcination. Using Co@CN/Al 0.1 -MCM-41 as the catalyst, the selective hydrogenation of FF to FOL achieved a conversion rate of 91.2% under mild conditions at 120 °C, which is 2.85 times higher than that of Al-free Co@CN/MCM-41, with an FOL selectivity of 97.2%. The experimental results revealed a strong correlation between FF conversion and the Si/Al ratio of MCM-41 molecular sieve. Increasing the Al species content facilitated the formation of more Co NPs active sites because of the strong electrostatic interaction, thereby promoting the activation of FF and hydrogen and enhancing the catalytic activity of Co@CN/Al 0.1 -MCM-41. Additionally, Co@CN/Al 0.1 -MCM-41also exhibited stable performance over five consecutive cycles, which was attributed to the formation of graphite carbon-coated Co NPs structure during the synthesis process. This simple fabrication strategy provides a novel approach for the modification of mesoporous molecular sieves with excellent catalytic activities.
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高影响因子
APPLIED CATALYSIS A-GENERAL
·
2024
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IF 4.7
Zhiquan Cai,Zhiyan Zhang,Xuesong Wei,Xiao-Xuan Li,Yi-Si Feng
Catalysts play a critical role in the selective conversion of furfural (FAL) in the aqueous-phase hydrogenation-rearrangement tandem reaction (AP-HRT). Herein, the N-doped bimetallic Ni-Co@NOMC was synthesized by solvent volatilization self-assembly method. The morphology and structure of the APF precursors were effectively controlled through adjustments in the synthesis and the presence of numerous pore channels and the substantial specific surface areas contributed to enhancing catalytic efficiency. Furthermore, this study also examined the synergistic interaction between the acid-base sites of the novel mesoporous N-doped carbon (NOMC) carrier and metal active sites to advance the succession of the furan ring hydrogenation and rearrangement processes. Specifically, the 99.9 % conversion of 8 wt% FAL solution was successfully accomplished with the 90.5 % selectivity of cyclopentanone catalyzed by 1.2-Ni-Co@NOMC catalysts. Therefore, this research holds significant importance for advancing the sustainable utilization of biomass resources in the future.
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高影响因子
ACS Catalysis
·
2022
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IF 13.7
Yichao Jin,Sarina Sarina,Hongwei Liu,Wayde Martens,Eric R. Waclawik,Erandi Peiris,Jianfeng Jia,Jing Shang,Liangzhi Kou,Cheng Guo,Huai-Yong Zhu
Production of 2,5-furandicarboxylic acid (FDCA, a platform chemical for the chemical industry in the future) by the selective aerobic oxidation of 5-hydroxymethyl-furfural is a crucial component to enable the FDCA production from sugars. The challenge is to achieve a high FDCA yield at low temperatures. Here, we report a catalyst composed of alloyed nanoparticles (containing 1.5 wt % Ag and 1.5 wt % Pd) supported on CeO2 nanofibers, which achieved an excellent FDCA yield (93%) at 20 °C. Interesting observations include yield deterioration at higher reaction temperatures; water is the source of the oxygen atom(s) added to the oxidized intermediates and product, while O2 molecules adsorbed onto the catalyst scavenge electrons, yielding OH• radicals from OH– ions in the reaction system to drive the oxidation. At 20 °C, we avoid side reactions, but there is no external energy provided for overcoming the activation barriers. The barriers for activating the alcohol groups are significant. We find that the appropriate chemisorption on the catalyst is critical for a high FDCA yield. By tuning the Ag/Pd ratio, we attained the most catalytically active sites, bimetallic surface sites, at the boundaries between Ag and Pd clusters. The chemisorption at these sites is strong enough to cause the selective oxidation of both the aldehyde and alcohol groups in HMF at 20 °C, avoiding side reactions at high temperatures. The knowledge acquired from this study is expected to have implications for other catalytic systems where competitive reactions proceed.
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高影响因子
FUEL
·
2021
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IF 6.609
Xueying Gao,Xin Yu,Lincai Peng,Liang He,Junhua Zhang
A magnetically-recoverable multifunctional catalyst (Fe 3 O 4 /ZrO 2 @MCM-41) was tailored by the impregnation of ZrO 2 supported on mesoporous MCM-41 coated Fe 3 O 4 nanoparticles, which successfully served as a monolithic catalyst for the cascade conversion of furfural (FAL) giving high yield to γ-valerolactone (GVL), a versatile platform molecule. The ordered hexagonal framework of the parent MCM-41 well reserved after the embedding of Fe 3 O 4 and ZrO 2 . The incorporation of Fe 3 O 4 could not only impart the catalyst with a strong magnetism, but also tune its acidity to promote GVL production. An impressive yield of 85% was accomplished straight from FAL processing with iso -propanol as a hydrogen donor and solvent. The kinetic study demonstrated higher activation energy for levulinate-to-GVL step (86.9 kJ/mol) than FAL transfer hydrogenation (35.0 kJ/mol) and subsequent alcoholysis process (51.0 kJ/mol). The catalyst could be fully recovered by an external magnetic field and showed good reusability. The sustainability of this conversion represents greatly improved by the process intensification based on one-pot reaction, magnetically-recoverable multifunctional catalyst, and mild operating conditions without using gaseous hydrogen.
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高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Yue Wang,Xiangyan He,Qi Zhang,Ling Luo,Tianping Lv,Xiuwu Wang,Junhua Zhang
Construction of highly efficient catalysts is crucial for the catalytic transfer hydrogenation (CTH) of bio-based carbonyls to valuable chemicals and fuels. Herein, we successfully synthesized a series of uniformly dispersed Zr(OH) 4 -Fe 3 O 4 nanoparticles with the regulation of sodium dodecyl benzene sulfonate (SDBS), which exhibited exceptional activity for the CTH of furfural (FAL) into furfuryl alcohol (FOL). Systematic characterizations revealed that SDBS effectively modified the interaction between Fe 3 O 4 and Zr(OH) 4 , thereby enhancing Lewis acidity by facilitating the construction of electron-deficient zirconium sites. Meanwhile, the presence of oxygen vacancies and surface hydroxyl groups in Zr(OH) 4 -Fe 3 O 4 -SDBS facilitated the adsorption and activation of both substrate and hydrogen donor. Thanks to these synergistic effects, a complete conversion of FAL with an impressive selectivity towards FOL was achieved, with a remarkable turn-over frequency value reaching as high as 42.5 h −1 . Encouragingly, Zr(OH) 4 -Fe 3 O 4 -SDBS also demonstrated its universality in the CTH of carbonyl compounds by exhibiting remarkable separation capability while maintaining its activity and structure after being reused for 11 cycles without significant changes.
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高影响因子
危险品化学品经营许可证（带存储）