CATALYSIS LETTERS
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2022
·Vol. 153
·期 3
·836-849
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IF 2.936
Jiang Haoran,Xue Changhao,Sun Weijie,Gong Zhaoxiang,Yuan Xia
The esterification of cyclohexene with formic acid is the first step in synthesizing cyclohexanol via the indirect hydration of cyclohexene. In this work, we improved the efficiency of the esterification reaction by constructing a sulfonic-acid-functionalized UiO-66 solid-acid catalyst containing defect sites. By using acetic acid as the modulator, ZrCl 4 as the zirconium source, and 2-sulfoterephthalic acid monosodium salt as the ligand, a sulfonic-acid-functionalized UiO-66-SO 3 H with defect sites was prepared using a solvothermal synthesis method. Additionally, we also prepared UiO-66 with defect sites for comparison. We then investigated the regulation effects of acetic acid addition amount on the defect structures and acidity of the as-prepared materials. The results showed that the addition of acetic acid caused lattice defects in the as-prepared materials with a missing linker, and the specific surface area, pore volume, pore size, and particle size of the material changed significantly. The number of defect sites was determined by thermogravimetric analysis. Additionally, pyridine infrared spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis indicated that the ratio of Lewis acid to Brønsted acid sites, and the total acid content in the defect materials, greatly increased compared to pure UiO-66 and UiO-66-SO 3 H, which greatly enhanced the acid catalytic performance of the material. Among these, UiO-66-SO 3 H(20), which was prepared by adding 20 mL of acetic acid, exhibited the best catalytic activity. The conversion rate of cyclohexene reached 83.4%, the selectivity toward cyclohexyl formate was 99.8%, and the catalyst could be reused three times. Graphical Abstract The purpose of this work was to improve the efficiency of the esterification reaction of cyclohexene with formic acid by constructing a sulfonic acid-functionalized UiO-66 solid acid catalyst containing defective sites. The regulation effect due to the amount of acetic acid added on the defect structure and acidity of the as-prepared materials was investigated.
研究领域:
化学
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催化材料
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DOI
高影响因子
POLYMER DEGRADATION AND STABILITY
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2011
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IF 2.594
Qin Chen,Wenjun Xiao,Lilong Zhou,Tinghua Wu,Ying Wu
Hydrolysis of chitosan in ionic liquids was carried out under microwave irradiation (MW) using sulfonic acid-functionalized ionic liquids (SFILs) as catalysts. The effect of microwave power, irradiation time, dosage of SFILs and DMSO was investigated by orthogonal tests. Under the optimal reaction conditions, the yield of total reducing sugars (TRS) reached over 90% within 2 min. The viscosity-average molecular weight of degraded chitosan was determined by viscosity method. The structures of the original and degraded chitosan were characterized by Fourier-transform infrared (FTIR) spectra, X-ray powder diffraction (XRD) analysis and carbon-13 nuclear magnetic resonance spectroscopy ( 13 C NMR). The influence of microwave power and irradiation time on the TRS and M v was further studied. This method can dramatically reduce reaction time.
研究领域:
生物化学
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材料科学
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产品关联
DOI
高影响因子
RSC Advances
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2021
·Vol. 11
·期 24
·14710-14716
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IF 3.361
Wenliang Wu,Hongshuai Gao,Bin Hai,Binqi Wang,Min Yu,Yi Nie
An effective process for synthesis of alkyl polyglycosides (APG) was developed using SO3H-functionalized ionic liquids (SFILs) as catalysts. Four SFILs, [PSmim][HSO4], [PSmim][pTSA], [PSPy][HSO4] and [PSPy][pTSA], were designed and synthesized for APG synthesis. The results indicated that [PSmim][HSO4] shows the best catalytic performance among these four SFILs, which has a great agreement with the order of their acidities. When the [PSmim][HSO4] was used as catalyst, the reaction time could be decreased from 24 h to 8 h, and molar ration of n-octanol to glucose could be decreased from 5 : 1 to 3 : 1 under the optimization reaction conditions. In addition, the [PSmim][HSO4] could be easily regenerated and recycled at least 5 times with slight decrease in catalytic activity. Moreover, the catalytic mechanism of [PSmim][HSO4] was further investigated by molecular simulation. The high catalytic activity of [PSmim][HSO4] is attributed to hydrogen bonds between [PSmim][HSO4] and glucose and n-octanol, which could accelerate the protonation of glucose and removal of hydrogen ions from the hydroxyl in n-octanol.
研究领域:
化学工程
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催化化学
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产品关联
DOI
PubMed
高影响因子
Scientific Reports
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2017
·Vol. 7
·期 1
·1-7
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IF 4.259
Wang Xiaomei,Gu Jinyan,Tian Lei,Zhang Xu
Owing to their unique structural and surface properties, mesoporous microspheres are widely applied in the catalytic field. Generally, increasing the surface area of the specific active phase of the catalyst is a good method, which can achieve a higher catalytic activity through the fabrication of the corresponding catalytic microspheres with the smaller size and hollow structure. However, one of the major challenges in the use of hollow microspheres (microcapsules) as catalysts is their chemical and structural stability. Herein, the grape-like hypercrosslinked polystyrene hierarchical porous interlocked microcapsule (HPIM-HCL-PS) is fabricated by SiO 2 colloidal crystals templates, whose structure is the combination of open mouthed structure, mesoporous nanostructure and interlocked architecture. Numerous microcapsules assembling together and forming the roughly grape-like microcapsule aggregates can enhance the structural stability and recyclability of these microcapsules. After undergoing the sulfonation, the sulfonated HPIM-HCL-PS is served as recyclable acid catalyst for condensation reaction between benzaldehyde and ethylene glycol (TOF = 793 h −1 ), moreover, exhibits superior activity, selectivity and recyclability.
研究领域:
材料科学
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催化化学
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产品关联
DOI
PubMed
高影响因子
CATALYSIS LETTERS
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2022
·Vol. 153
·期 6
·1625-1634
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IF 2.936
Guang Binxiong,Zhang Wei,Wu Yuefeng,Xiao Yahui,Su Miaojun,Liu Yong
Dual sulfonic acid functionalized heteropolyacid-based ionic liquids were synthesized, characterized and used as novel solid acid catalysts for selective esterification of glycerol with acetic acid toward fuel-additive triacetylglycerol (TAG). The results indicated that the as-prepared [BS 2 TMEDA]HPW 12 O 40 catalyst had the highest catalytic activity and selectivity to TAG compared with commercial H 3 PW 12 O 40 , H 2 SO 4 and Amberlyst-15 catalysts, which was attribute to its medium acidity of dual-SO 3 H groups and carbon chain length. The effects of reaction temperature, catalyst amount, acetic acid to glycerol mole ratio and reaction time on glycerol conversion and selectivity to TAG were also investigated. Under the optimized reaction condition, the glycerol conversion and selectivity to TAG reach 100% and 70.9%, respectively. Moreover, no significant loss in glycerol conversion and selectivity to TAG were observed after reused four recycles, showing favorable catalytic reusability and stability. Graphical Abstract
研究领域:
化学工程
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催化材料
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DOI
高影响因子
CARBOHYDRATE RESEARCH
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2012
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IF 2.332
Liqiang Wu,Zhikui Yin
A simple and clean synthesis of per- O -acetylation carbohydrate derivatives has been accomplished by treatment of sugars with a stoichiometric quantity of acetic anhydride under solvent-free conditions in the presence of sulfonic acid functionalized nano γ-Al 2 O 3 as an efficient and environmentally benign catalyst.
研究领域:
有机化学
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催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
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2015
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IF 4.097
Zhixian Liang,Haiyun Zhai,Zuanguang Chen,Haihang Wang,Shumei Wang,Qing Zhou,Xiaoting Huang
A facile and ultrasensitive sensor based on gold microclusters (AuMCs) electrodeposited on sulfonate functionalized graphene (SF-GR) was fabricated, and applied for the simultaneous determination of gallic acid (GA) and uric acid (UA). Taking advantage of the unique plane structure of the functionalized graphene (GR), the AuMCs were successfully electrodeposited on functionalized GR immobilized on the surface of a GCE. The results of scanning electron microscope (SEM) and energy spectrum analysis illustrated that AuMCs were deposited on the functionalized GR film. In comparison with the bare GCE, the pristine AuMCs and the pristine SF-GR modified electrode, AuMCs/SF-GR/GCE exhibited excellent electrochemical oxidation toward GA and UA. In addition, the two compounds were separated completely in 0.10 M citric acid-sodium citrate buffer (pH 4.0) by differential pulse voltammetry (DPV) under optimum conditions. The anodic current was linearly related with 0.05–8.0 μM GA and 0.2–50.0 μM UA, with the detection limit of 10.7 nM and 0.12 μM, respectively. Furthermore, AuMCs/SF-GR/GCE was successfully applied to the independent determination of GA in black tea and Cortex moutan as well as the simultaneous determination of GA and UA in urine samples.
研究领域:
分析化学
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生物传感器
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材料科学
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2019
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IF 6.97
Yao Zhong,Peixin Zhang,Xiaomin Zhu,Huan Li,Qiang Deng,Jun Wang,Zheling Zeng,Ji-Jun Zou,Shuguang Deng
Because H2O decreases the acidity of sulfonic acid-based catalysts and initiates catalytic side reactions, the catalytic activity and selectivity of these catalysts are often unsatisfactory in many reactions that generate H2O as a byproduct. Herein, for the first time, hydrophobic acid-functionalized biochar is prepared by a new route based on a two-step diazo grafting method using 4-aminobenzenesulfonic acid as the sulfonated agent and 4-tert-butylaniline as the hydrophobic agent. The acid density and hydrophobicity can be easily regulated by the amounts of benzenesulfonic acid and tert-butylbenzene groups, respectively. The resulting catalysts have a large specific surface area of 400–700 m2/g, high acid density of greater than 2.0 mmol/g, and strong hydrophobicity with an H2O contact angle of up to 136°. Compared with Amberlyst-15 and H2SO4-sulfonated biochar, the hydrophobic acidic biochar exhibits higher activity and selectivity in the alkylation of 4-ethylphenol with phenylmethanol and of 2-methylfuran with cyclic ketones (cyclopentanone and cyclohexanone) for the production of high-density biofuels. The successful preparation of the hydrophobic acidic biochar not only results in an efficient catalyst for reaction systems in which H2O has a deleterious effect but also paves a way for the functional modification of carbonaceous materials.
研究领域:
化学工程
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材料科学
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能源科学
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产品关联
DOI
高影响因子
ENERGY & FUELS
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2013
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IF 2.853
Jie Liu,Dandan Cheng,Yue Liu,Zhongbiao Wu
One-step synthesized sulfonic-acid-functionalized SBA-15 (denoted as αSSBA-15) impregnated with polyethyleneimine (PEI) was used for CO2 capture in this study. The resulted sorbents were characterized via a range of analytical techniques, including transmission electron microscopy (TEM), 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR), infrared (IR), thermogravimetry–differential scanning calorimetry (TG–DSC), etc. Experimental results showed that the incorporation of propanesulfonic acid groups into the inner structure of the silica support had brought dramatic improvement in CO2 adsorption capacity, of which PEI/5SSBA-15 showed the highest CO2 adsorption amount. The main reason of this increased capacity could be attributed to the enhanced CO2 diffusion into bulk networks of PEI polymers because of its better dispersion in the pores of support, where the extended propanesulfonic acid groups on the inner surface could spatially disperse the subsequent loaded PEI molecules. Furthermore, the PEI/5SSBA-15 also exhibited superior stable cyclic adsorption/desorption performance compared to PEI/SBA-15, especially after 5 cycles. This was assumed because the enhanced surface acidity of PEI/5SSBA-15 anchored the NH2/NH groups through acid–base interaction, reducing the loss of active sites.
研究领域:
材料科学
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环境科学
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产品关联
DOI
高影响因子
RSC Advances
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2016
·Vol. 6
·期 93
·90232-90238
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IF 3.289
Xiao-Fang Liu,Hu Li,Heng Zhang,Hu Pan,Shan Huang,Kai-Li Yang,Song Yang
Catalytic ethanolysis of furfuryl alcohol (FA) to ethyl levulinate (EL) with MIL-101(Cr)–SO3H, prepared by simple one-pot hydrothermal treatment, is presented for the first time. The as-prepared catalyst with high surface area, hydrothermal and chemical stability, good dispersion, and feasible accessibility of –SO3H Brønsted acid sites was found to show superior performance to other sulfonic acid-functionalized solid catalysts. Besides the special textural properties, the obtained good catalytic activity of 79.2% EL yield and 100% FA conversion were also dependent on the density and strength of the Brønsted acid and the reaction parameters. A slight loss of catalytic activity after five consecutive recycles and the hot filtration experiment confirmed the good stability of MIL-101(Cr)–SO3H. Two coexisting reaction paths for the ethanolysis of FA to EL catalyzed by MIL-101(Cr)–SO3H were proposed, wherein 2-ethoxymethylfuran (2-EMF) was observed to be the dominant intermediate.
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2013
·Vol. 3
·期 8
·2044-2049
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IF 3.753
Yindi Zang,Jing Shi,Fumin Zhang,Yijun Zhong,Weidong Zhu
The sulfoxy or sulfonic acid-functionalized MIL-101 catalyst was prepared by either post-functionalization or pre-modification of the organic linkers with the functionalized ligands, respectively, the latter is the so-called one-pot synthesis method. These catalysts were systemically characterized by XRD, N2 adsorption, acid–base titration, and FT-IR techniques and applied in the liquid-phase esterification of monocarboxylic acids with monohydric alcohols. The results show that the sulfonic acid-functionalized MIL-101 (S-MIL-101) prepared by the one-pot synthesis method possesses a higher catalytic activity in the esterification than its counterpart the sulfoxy acid-functionalized MIL-101 (S/MIL-101) prepared by the post-functionalized method, due to the fact that S-MIL101 has a higher acid loading and a high utilization efficiency of the functionalized acid sites. Moreover, S-MIL-101 is stable to leaching, behaves as a true heterogeneous catalyst, can be easily recovered by filtration, and can be reused five times in succession without any loss of its catalytic activity.
研究领域:
材料化学
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催化化学
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产品关联
DOI
高影响因子
GREEN CHEMISTRY
·
2014
·Vol. 16
·期 5
·2490-2499
·
IF 6.852
Jinzhu Chen,Kegui Li,Limin Chen,Ruliang Liu,Xing Huang,Daiqi Ye
A series of sulfonic acid-functionalized metal–organic frameworks (MOF-SO3H) were prepared by postsynthetic modification (PSM) of the organic linkers within the MOF with chlorosulfonic acid. The obtained MOF-SO3H, including sulfonic acid-functionalized MIL-101(Cr) [MIL-101(Cr)-SO3H], UIO-66(Zr) [UIO-66(Zr)-SO3H], and MIL-53(Al) [MIL-53(Al)-SO3H], have been systematically studied as solid acids in fructose transformation to 5-hydroxymethylfurfural (HMF). With MIL-101(Cr)-SO3H as catalyst, a HMF yield of 90% with a full fructose conversion was obtained at 120 °C for 60 min in DMSO. The concentration of –SO3H in MOF-SO3H as well as the contribution of Brønsted acidity of MOF-SO3H parallels its –SO3H grafting rate. Under a lower –SO3H grafting level, a good linear correlation between catalytic activity, in terms of turnover frequency, and sulfonic acid-site density of MOF-SO3H was found. Moreover, the sulfonic acid groups, which function as the catalytic sites, are equivalent in all MOF-SO3H for fructose-to-HMF transformation, regardless of precursor MOFs. Both conversions of fructose and selectivities towards HMF increase with the sulfonic acid-site density of MOF-SO3H at an initial stage of fructose-to-HMF transformation. Kinetics studies reveal that the MIL-101(Cr)-SO3H promoted fructose-to-HMF transformation may follow pseudo-first-order kinetics with observed activation energy of 55 kJ mol−1 under the investigated conditions. Moreover, MIL-101(Cr)-SO3H behaves as a heterogeneous catalyst and can be easily recovered and reused. The research highlights a good prospect for catalytic application of MOF-derived solid acid catalysts for biomass carbohydrate valorization.
研究领域:
化学工程
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催化科学
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生物质转化
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）