Catalysis Science & Technology
·
2020
·Vol. 10
·期 14
·4684-4692
·
IF 5.721
Pilan Zhang,Jie Yang,Hualei Hu,Danxin Hu,Jiang Gan,Yexin Zhang,Chunlin Chen,Xiaoqiang Li,Lei Wang,Jian Zhang
The self-etherification of 5-hydroxymethylfurfural (HMF) to 5,5′(oxy-bis(methylene))bis-2-furfural (OBMF) was investigated on ZSM-5, MCM-22, beta and hierarchical micro–mesoporous ZSM-5 (HMZ) catalysts. The hierarchically structured zeolites exhibited a superior intrinsic activity and good resistance to carbonaceous deposit; the latter could be ascribed to the lower mass transfer barrier in the mesopores of the HMZ catalysts. The structure–activity correlation showed that the catalytic activity mainly originated from one or several specific Brønsted acid sites, providing key clues to design efficient zeolite catalysts for producing OBMF.
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Catalysts
·
2026
·Vol. 16
·期 4
·312
·
IF 4.5
Xuelai Zhao,Wuyu Wang,Zhenjing Jiang,Xinghua Zhang,Xiuzheng Zhuang,Qi Zhang,Longlong Ma
The homogeneous nature of L-proline organocatalysts restricts their application in aldol condensation due to poor recyclability and stability. Herein, L-proline was heterogenized by ionic intercalation into Mg–Al layered double hydroxides (LDHs), yielding a series of proline-intercalated catalysts with tunable layer structures. Co-precipitation and memory-effect reconstruction strategies were employed to regulate interlayer spacing and proline loading. The resulting catalysts exhibited efficient performance in the aldol condensation of furfural with ketones under mild conditions. The reconstructed catalyst re-Mg4Al1P achieved a furfural conversion of 88.67% and a total product yield of 85.54% at room temperature, with product selectivity exceeding 95%. Structural characterizations confirmed that proline was stabilized within the LDH interlayers via R–COO—Mg electrostatic interaction while preserving the secondary amine active site. Mechanistic analysis indicated that the reaction proceeded through enamine- or enol-mediated pathways depending on water content, while the layered LDH framework imposed geometric confinement that suppressed side reactions. Catalyst deactivation in aqueous systems was mainly attributed to proline leaching rather than structural collapse.
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Molecular Catalysis
·
2023
·
IF 4.6
Shuxing Zhang,Jiali Zheng,Zhihui Li,Xiaoshu Ding,Yanji Wang
Herein, we reported a green catalytic reaction system for the synthesis of 5-amino-1-pentanol with furfural and ionic liquid hydroxylamine salt as the initial raw material. In addition, the method can obtain 2-furonitrile and furfurylamine in high yields. The reaction system comprises three new reactions, including the reaction of furfural with ionic liquid hydroxylamine salt to synthesize 2-furonitrile, the hydrogenation of 2-furonitrile to prepare furfurylamine, and the hydrogenolysis of furfurylamine to prepare 5-amino-1-pentanol. For the synthesis of 2-furonitrile, ionic liquid hydroxylamine salt (NH 2 OH) 2 ·[HSO 3 - b - mim ]·HSO 4 was prepared. The ionic liquid as co-solvents, catalysts, and hydroxylamine stabilizer has recovery and reusability. For the hydrogenation of 2-furonitrile to furfurylamine, high-efficiency Ru/g-C 3 N 4 catalyst was prepared. For the hydrogenolysis of furfurylamine to 5-amino-1-pentanol, high-efficiency Pt/ZrO 2 catalyst was prepared. Finally, the yield of 5-amino-1-pentanol based on furfural was 48.7%. A potential pathway for preparing drugs from biomass has been identified in this work.
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DALTON TRANSACTIONS
·
2022
·Vol. 51
·期 45
·17441-17453
·
IF 4.569
Yuewen Shao,Mingzhu Guo,Mengjiao Fan,Kai Sun,Guoming Gao,Chao Li,Félix Mérimé Bkangmo Kontchouo,Lijun Zhang,Shu Zhang,Xun Hu
One-pot conversion of furfural, a biomass-derived platform chemical, to gamma-valerolactone (GVL), a fuel additive and green solvent, involves multiple steps of hydrogenation. Among these reactions, the deep hydrogenation of the furan ring in furfural interrupts GVL formation over Ni or Co-based catalysts. In this study, a method of alloying Ni and Co with Fe over a ZSM-5 support was proposed for tackling excessive activity of the catalyst for hydrogenation. The results indicated that the formation of binary NiFe and CoFe alloys in Ni–Co–Fe/ZSM-5 enhanced the dispersion of metallic species, reduction of metal oxides, formation of more Lewis acidic sites, and the adsorption of the C–O functionality of the furan ring, while lowering the capability for adsorption/activation of H2 and the adsorption of the CC group of the furan ring. These factors together reduced the activity for the hydrogenation of the furan ring in furfural, but enhanced the hydrogenation of the CO in ethyl levulinate (EL). The kinetic study confirmed that the hydrogenation of EL was the rate-determining step. The coordination of the dual alloys, NiFe and CoFe, in the bifunctional Ni–Co–Fe/ZSM-5 catalyst rendered superior activity for selective one-pot conversion of furfural to GVL with a yield of 85.7%.
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JOURNAL OF CHEMICAL TECHNOLOGY AND BIOTECHNOLOGY
·
2022
·Vol. 97
·期 10
·2805-2814
·
IF 3.709
Shuaibin Zhang,Bochao Yan,Zhihui Chen,Suping Zhang
BACKGROUND Levulinic acid, an important platform compound, is extensively used in textiles, dyes, antifreeze, animal feed, solvents and food additives. However, the use of lignocellulosic biomass to produce levulinic acid is difficult because of poor accessibility to cellulose and low hydrolytic yield. Thus a viable hydrolysis strategy and a suitable catalyst must be developed. RESULTS In this study, a bifunctional solid acid catalyst (HTC-SO 3 H) containing both cellulose binding sites ( Cl, COOH and OH) and catalytic sites ( SO 3 H) was prepared by a carbonization–grafting–oxidization method. X-ray photoelectron spectroscopy and Fourier transform infrared characterization confirmed the existence of Cl and the successful modification of the SO 3 H grafted hydrothermal carbon. The hydrogen bonds formed between cellulose and the binding sites ( Cl, OH and COOH) in the catalyst showed synergistic effects with the catalytic sites ( SO 3 H), leading to efficient hydrolysis of the furfural residue. A total of 74.81% (non-magnetic) and 70.18% (magnetic) levulinic acid yields were obtained after hydrolysis at 190 °C and 180 min in γ-valerolactone–H 2 O (1:1, v/v). Magnetic catalysts were synthesized using a co-precipitation method. Catalysts were recycled without any obvious reduction in catalytic activity. CONCLUSION Using sucralose as a raw material, the as-synthesized bifunctional solid acid catalyst improved the accessibility to cellulose and increased levulinic acid yield. Moreover, the grafted SO 3 H formed by hydroxyl hydration condensation exhibited superior stability. This study provides a valuable strategy for the efficient hydrolysis of lignocellulosic biomass. © 2022 Society of Chemical Industry (SCI).
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CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Qiuli Fu,Ximeng Xu,Rongrong Miao,Minli Wang,Huajing Zhou,Liang He,Qingqing Guan
Using some metals and their oxides modified biochar adsorbents to purify copper-containing wastewater is effective. However, the degraded reuse performance of waste adsorbents prevented their large-scale application. Thus, in this work, a MnO x -modified porous biochar was firstly obtained by KMnO 4 activation of rubber seed shell wastes for Cu(II) ions removal, and then the waste adsorbent was skillfully constructed to Cu-Mn bimetallic catalyst for efficient selective hydrogenation of furfural, realizing the proper disposal of waste adsorbent. The adsorption experiments showed that the optimized Mn-modified biochar (i.e. Mn 18% - rss BC) had a good purification capacity for the Cu(II)-containing wastewater with a wide pH range and high strong resistance to some common coexisting ions, and the maximum adsorption capacity of Cu(II) could be up to 200.59 mg/g. The characterization results showed that the oxygen-containing functional groups and a large number of MnO x particles on the surface of Mn 18% - rss BC could form stable complexes with Cu(II), making it exhibit efficient and spontaneous multilayer adsorption behavior. In addition, after the reduction of the waste adsorbent, the Cu and Mn species on the surface were uniformly dispersed in the porous carbon in the form of electron-rich nano-polycrystalline aggregates at about 3.5 nm. Under the optimized conditions, the obtained catalyst (i.e., Cu 14.3 Mn 16.5 - rss BC) had high catalytic efficiency, which can achieve 100% of furfural conversion and 87.06% of furfuryl alcohol selectivity. In conclusion, this work provided a composite solution for the reuse of copper-containing waste adsorbent, the resource recovery of agricultural and forestry wastes and the efficient transformation of biomass platform compounds.
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APPLIED SURFACE SCIENCE
·
2023
·
IF 6.7
Wen-Jing Yi,Yongzhen Gao,Jingyi Yang,Xiaotian Zhou,Zhongyi Liu,Meng Zhang
A series of CuCoAl catalysts derived from layered double hydroxides (LDHs) with adjustable Cu/Co ratios were prepared via a facile in situ structure topotactic transformation strategy. The comprehensive characterization results revealed that the introduction of Co element and the confined effect of LDHs jointly promoted the dispersion and stability of Cu species, as well as significantly increased the active specific surface area. Interestingly, Cu 1.5 Co 1.5 Al sample showed the superior performance for furfural (FF) hydrogenation to furfuryl alcohol (FA) under the synergistic effect of Cu 0 and Cu + species, as well as the interaction between Cu species and the support. It allowed for FF conversion of 97.5% and FA selectivity of 99.7% (150 °C, 3 h, 2 MPa initial H 2 pressure, isopropanol as solvent, m(FF):m(catalyst) = 60:1). Moreover, Cu 1.5 Co 1.5 Al displayed the satisfactory reusability, where the activity and selectivity kept stable after six successive recycling runs. Specially, it displayed the promising potential for the scale-up production. Furthermore, the mechanism study based on in situ Fourier transform infrared spectra indicated that the surface exposed Cu 0 species could promote the H 2 adsorption and then rapidly dissociated H 2 into the activated H atoms, whilst Cu + species were the active sites for FF selective hydrogenation in a η 1 (O)-aldehyde adsorption configuration.
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INDUSTRIAL CROPS AND PRODUCTS
·
2019
·
IF 4.191
Xiaoyun Li,Jiaxin Yang,Rui Xu,Lefu Lu,Fangong Kong,Min Liang,Lijie Jiang,Shuangxi Nie,Chuanling Si
The production of platform chemicals from lignocellulosic biomass is scientifically valuable but technologically challenging. With the aim to establish a green reaction system for the production of furfural from lignocellulosic biomass, in the current work, H-SAPO-34 was investigated for catalysis of the conversion of Eucalyptus sawdust to furfural in γ-valerolactone (GVL). H-SAPO-34 was prepared and characterized by XRD, SEM, FTIR, BET, TGA and ammonia adsorbed FTIR. H-SAPO-34 possesses Brønsted and Lewis acid sites and a large specific surface area. The average pore diameter of H-SAPO-34 was 0.86 nm, which is beneficial for the spread of xylose and furfural and the inhibition of humin production. In this work, a peak furfural yield of 99.28% from Eucalyptus was achieved at 210 °C in 120 min with 30 g/L H-SAPO-34. The Brønsted/Lewis acid bifunctionality and the solvent effect of γ-valerolactone possibly contributed to the high furfural yield from real biomass. The kinetics of the conversion of Eucalyptus sawdust to furfural was also studied, and the activation energy for furfural production was calculated. Additionally, the catalytic activity and stability of the regenerated catalyst were estimated.
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APPLIED CATALYSIS A-GENERAL
·
2018
·
IF 4.521
Junmou Du,Huihuang Fang,Hongyan Qu,Jinping Zhang,Xinping Duan,Youzhu Yuan
5-Hydroxymethyl-2-furfural (HMF) is a key platform molecule for biomass utilization. The HMF derivative 2,5-furandicarboxylic acid (FDCA) by oxidation of HMF is a promising alternative for terephthalic acid as a monomer in polyethylene terephthalate. However, due to the facile purification of dimethyl furan-2,5-dicarboxylate (DMFD), an oxidative esterification derivative of HMF, is more desirable. In this work, supported Au–Cu bimetallic catalysts with Au–CuO x ( x = 0–1) nanohybrids were prepared by a reduction–oxidation pretreatment strategy. The as-prepared catalysts were used for the oxidative esterification of HMF into DMFD under base-free conditions using oxygen as sole oxidant. Activity tests showed that the optimized Au–Cu/γ-Al 2 O 3 catalyst displayed a remarkably high DMFD yield of up to 98% and a turnover frequency (TOF) value of 243 h –1 , whereas the monometallic Au and Cu catalysts exhibited poor performance. Various characterizations confirmed the strong interaction between Au nanoparticles and CuO x species, and their synergistic effect on the enhanced performance of HMF oxidative esterification. The reduction–oxidation pretreatment promoted the dispersion of CuO x and intensified the interaction of Au nanoparticles with CuO x . A plausible reaction mechanism for the oxidative esterification of HMF over Au–Cu/γ-Al 2 O 3 was proposed. This work provided new insights into the effect of reduction–oxidation pretreatment on the fabrication of supported Au–CuO x nanohybrids for the production of DMFD by HMF oxidative esterification.
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
·
2014
·
IF 2.129
Jinhua Zhu,Lanlan Chen,Yingying Dong,Jiazhong Li,Xiuhua Liu
In this work, the interaction of 5-Hydroxymethyl-2-furfural (5-HMF) with calf thymus DNA (ctDNA) under simulated physiological conditions (Tris–HCl buffer of pH 7.40), was explored by UV absorption spectroscopy, fluorescence spectroscopy and molecular modeling method, using ethidium bromide (EB) as a fluorescence probe of DNA. The fluorescence quenching mechanism of EB–ctDNA by 5-HMF was confirmed to be a static quenching, which derived from the formation of a new complex. The binding constants of 5-HMF with DNA in the presence of EB were calculated to be 2.17 × 10 3 , 4.24 × 10 3 and 6.95 × 10 3 L mol −1 at 300, 305 and 310 K, respectively. The calculated thermodynamic parameters, enthalpy change Δ H and entropy change Δ S , suggested that both hydrophobic interactions and hydrogen bonds played a predominant role in the binding of 5-HMF to DNA. According to the UV absorption spectroscopy and melting temperature ( T m ) curve results, the binding mode of 5-HMF with DNA was indicative of a non-intercalative binding, which was supposed to be a groove binding. The molecular modeling results showed that 5-HMF could bind into the hydrophobic region of ctDNA and supported the conclusions obtained from the above experiments.
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ACS Catalysis
·
2025
·
IF 13.1
Kaijie Han,Song Song,Yong You,Xiaoqia Fu,Xingang Li
Ru-based catalysts are widely used for the reductive amination of carbonyl compounds. However, challenges remain, particularly in achieving high catalytic activity under mild conditions. In this study, we report a strategy to simultaneously modulate the electron density of Ru0 and the RuOx/Ru0 ratio by systematically adjusting the calcination temperature. The catalyst calcined at 200 °C demonstrated remarkable performance, achieving a 97.8% yield of furfurylamine at 30 °C, significantly outperforming most previously reported catalysts. Furthermore, it showed compatibility with a range of carbonyl compounds. At 200 °C calcination, the reduced electron density of Ru0 weakened its electron-donating ability, thereby facilitating H2 activation. Meanwhile, this treatment yielded the highest RuOx content and thereby generated the greatest Lewis acid site density, enhancing the adsorption and activation of NH3, furfural, and the Schiff base. Mechanistic studies reveal that the synergistic effect between electron-deficient Ru0 and Lewis acid sites significantly reduced the apparent activation energy for the ammonolysis of Schiff base intermediates, the rate-determining step in reductive amination. This work provides an effective strategy for tuning both the electronic structure of the metal and the acid properties of the catalyst, highlighting the crucial role of metal-acid synergy in promoting Schiff base ammonolysis during reductive amination.
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JOURNAL OF CATALYSIS
·
2020
·
IF 7.888
Yanru Zhu,Jian Zhang,Xiaodan Ma,Zhe An,Shaowei Guo,Xin Shu,Hongyan Song,Xu Xiang,Jing He
Complexity of chemical linkages (C-C/C-H/C-O, C=C/C=O, or C-O-H/C-O-C) in biomass-derived molecules makes the selective activation of targeted bonds much more challenging, expecting well-defined catalysts and definite catalytically-active sites. This work demonstrates an effective gradient reduction strategy to control the definite structure of catalytically-active sites, affording defects-rich nano-twin Cu particles. This strategy just involves the reduction (calcination under H 2 ) of Cu II -containing layered double hydroxides (LDHs) simply with controlling the reduction gradient (interval time) of Cu II species in two chemical micro-environments (Cu II -O-Cu II and Cu II -O-M II/III/IV (M ≠ Cu)) in the brucite-like layer of LDHs. The nano-twin Cu particles efficiently promote the target activation of C-O and C=C in the conversion of furfural to cyclopentanone (CPO). With ~100% furfural conversion, the defects-rich nano-twin Cu particles afford a CPO selectivity of 92%, 50% higher than regular spherical Cu particles. The multi-stepped defect sites, originating from the planar defects, play a decisive role in promoting the CPO selectivity by facilitating the hydro-deoxygenation to C-O of 4-hydroxycyclopentenone (HCP) and hydrogenation to C=C of HCP or cyclopentenone.
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危险品化学品经营许可证（带存储）