Hydrolysis of mechanically pre-treated cellulose catalyzed by solid acid SO_4~(2-)-TiO_2 in water–ethanol solvent

An efficient catalyst SO_4~(2-)-TiO_2(ST) from industrial metatitanic acid has been successfully prepared to catalyze hydrolysis of ball-milling cellulose. The results show that the highest catalytic efficiency is obtained for ST calcined at 450 °C(ST-450) with the yield of 21.8% glucose, 13.0% 5-HMF and 4.2% furfural at 200 °C for30 min. The ball milling of cellulose and solid acid catalyst significantly enhances the cellulose hydrolysis. The high Lewis to Br?nsted acid sites ratio for ST-450 induced by bidentate ligands between SO_4~(2-)and TiO_2 benefits high organics yield, and high total acid sites contribute to the high cellulose conversion. The large pore volume of0.29 cm~3·g~(-1) and appropriate pore size of 7.35 nm of ST-450 also contribute to the high performance. High reaction temperature over 200 °C exhibits negative effect on glucose and 5-HMF yield due to undesired side reactions, while furfural product is stable in the reaction system. The bidentate ligands between SO_4~(2-)and TiO_2 are considered as active acid sites for cellulose hydrolysis in water–ethanol solvents.     

Postsynthetic acid modification of amino-tagged metal-organic frameworks: Structure-functionrelationship for catalytic 5-hydroxymethylfurfural synthesis

Developing an efficient and selective catalyst for the dehydration of fructose to 5-hydroxymethylfurfural(HMF) is significant for biomass conversion. Herein, a metal-organic framework(MOF) with acidity and strong hydrophobicity is first reported by the condensation of amino-tagged MOFs with mercapto carboxylic acids and subsequent oxidation. The hydrophobic acidic MOFs possess acid densities ranging from 0.2-1.0 mmol·g^-1, H₂O contact angles of 114°-125°, and specific surfac...     

Functionalized metal–organic frameworks with strong acidity and hydrophobicity as an efficient catalyst for the production of 5-hydroxymethylfurfural

In the dehydration of fructose to 5-hydroxymethyl furfural(HMF), in situ produced water weakens the acid strength of the catalyst and causes the rehydration of HMF, causing unsatisfactory catalytic activity and selectivity. In this work, a class of benzenesulfonic acid-grafted metal–organic frameworks with strong acidity and hydrophobicity is obtained by the direct sulfonation method using 4-chlorobenzenesulfonic acid as sulfonating agent. The resultant MOFs have a specific surface area of greater than 250 m~2·g~(-1), acid density above 1.0 mmol·g~(-1), and water contact angle up to 129°. The hydrophobic MOF-Ph SO_3 H exhibits both higher catalytic activity and selectivity than MOF-SO_3 H in the HMF synthesis due to its better hydrophobicity and olephilicity. Moreover, the catalyst has a high recycled stability. At last, fructose is completely converted, and 98.0% yield of HMF is obtained under 120 °C in a DMSO solvent system. The successful preparation of the hydrophobic acidic MOF provides a novel hydrophobic catalyst for the synthesis of HMF.     

缺陷UiO-66对水中塑化剂的吸附

金属有机骨架材料（metal-organic frameworks,MOFs）是一种具有骨架结构的新型多孔材料。本研究合成了金属有机框架化合物UiO-66和有缺陷的UiO-66（UiO-66-1）,并研究了其作为吸附剂吸附塑化剂邻苯二甲酸二甲酯（DMP）的性能及其吸附动力学,最后通过拟合吸附等温线和吸附动力学模型拟合了吸附剂的最大吸附量和最快吸附时间。实验结果表明,UiO-66-1对DMP有更好的吸附性能,在5~10min内快速达到吸附平衡,pH在3~10吸附率仍可保持稳定;分析测试结果表明,引入缺陷的UiO-66-1的比表面积比UiO-66大,达到了1438m²/g,孔容为0.58cm³/g,晶体的尺寸也明显增大,吸附量增大了近一倍,最大吸附量可达到404mg/g,且循环利用率高;通过吸附等温线模型和吸附动力学模型的拟合研究表明,UiO-66-1的吸附过程比较符合Langmuir模型和拟二级动力学模型。     

Au基MOFs双功能催化剂的制备及其催化CO2与苯胺/H2反应性能

以UiO-66(Zr)、MIL-100(Fe)、MIL-100(Cr)、MIL-101(Cr)、NH 2-MIL-101(Al)为载体,Au为活性组分,制备Au/UiO-66(Zr)、Au/MIL-100(Fe)、Au/MIL-100(Cr)、Au/MIL-101(Cr)、Au/NH 2-MIL-101(Al)双功能催化剂。采用XRD、BET、NH 3-TPD、HRTEM等表征催化剂的结构,在釜式反应器中评价催化剂对CO 2与苯胺/H 2反应生成N-甲基苯胺与N,N-二甲基苯胺的N-甲基化反应性能,考察反应条件对催化剂催化性能的影响。结果表明,催化剂的XRD特征衍射峰与相应MOFs的模拟特征峰基本一致;负载Au后催化剂仍具有高的比表面积和大的孔容、孔径;不同MOFs负载Au的催化剂具有不同的酸强度和酸量;Au纳米粒子的分散性很好,粒径为(3~7)nm。制备的催化剂均具有催化CO2与苯胺/H2的N-甲基化反应性能,其中质量分数2%Au/MIL-101(Cr)催化剂催化性能最好,苯胺转化率为45.26%,N-甲基苯胺和N,N-二甲基苯胺选择性分别为73.50%和26.50%,重复使用性能优异。     

锆基MOFs的合成和表征及催化制备生物柴油

采用不同有机配体（对苯二甲酸，2-硝基对苯二甲酸、2-氨基对苯二甲酸、2-羟基对苯二甲酸），利用剂热合成法合成锆基MOFs结构UiO-66及其衍生物，添加不同的调节剂（甲酸、乙酸、苯甲酸和盐酸）调节锆基MOFs结构。采用XRD、SEM和FT-IR等对锆基MOFs材料进行表征，研究不同的调节剂和添加量对锆基MOFs形貌特征和结构性质的影响。研究发现调节剂的不同对锆基MOFs结构形成产生不同影响，盐酸和乙酸混合调节剂能显著提高UiO-66的结晶度，当n(调节剂)∶n(ZrCl4)=30∶1时，苯甲酸调节剂可以获得尺寸为500 nm结构规整的UiO-66八面体晶体，甲酸调节剂将UiO-66的比表面积由1173.3 m2/g提高到1973.8 m2/g。选择3种锆基MOFs作为酯化反应催化剂，UiO-66-NH2催化活性较好，其游离脂肪酸转化率为50.7%，用KOH催化酯化油反应得到的生物柴油产率为51.6%，脂肪酸甲酯含量达99%以上。     

功能化Zr-MOF强化混合基质膜CO2分离

混合基质膜（MMMs）在气体分离领域具有良好的应用前景,金属有机框架（MOFs）由于具有高孔隙率和有机连接基团,常被用作填料制备MMMs。但由于MOFs与聚合物的界面相容性问题,MMMs的气体分离性能提升受到限制。本文合成了功能化的Zr-MOF（UiO-66-AC）,并利用其与聚醚共聚酰胺（Pebax）共同制备了混合基质膜。填料中引入的羰基和羧基等基团提供了MOFs与聚合物基质之间较强的界面相互作用。与纯Pebax膜相比,UiO-66-AC/Pebax MMMs的气体渗透性能得到了显著提高。当填料质量分数为6%时,膜的CO₂渗透系数为102.4 Barrer,CO₂/N₂和CO₂/CH₄选择性分别为90.6和26.0,CO₂/N₂分离性能突破了Robeson上限(2008),表明该混合基质膜在CO₂的分离应用上具有潜力。     

Defective NH2-UiO-66 (Zr) effectively converting CO2 into cyclic carbonate under ambient pressure,solvent-free and co-catalyst-free conditions

In this study, a series of metal–organic frameworks (MOFs) NH₂-UiO-66-xHAc catalysts were synthesized by solvothermal method using acetic acid (HAc) as a modulator, and were applied to the cycloaddition of CO₂ and epichlorohydrin (EPIC) under ambient pressure. Influences of the modulation by HAc on morphologies and structures of the MOFs are demonstrated via PXRD, FESEM, FTIR, N₂ adsorption–desorption, XPS and ¹H NMR characterizations. The results show that the MOFs containing mesoporous pores can be prepared by adjusting the concentration of HAc. By optimizing the amount of HAc added, the specific surface area of NH₂-UiO-66-8HAc is as high as 879.17 m²·g^-1, which is 28.3% higher than that of the original MOFs. And the evaluation of catalytic performance showed that HAc modulation enhanced the activity of NH₂-UiO-66-xHAc under mild conditions. The exposure of Lewis acid sites, increased specific surface area and porosity via the modulation of HAc defective ligand can be supposed the key factors to determine the enhanced catalytic activities. In addition, considering the influence of gas concentration on the reaction, the concept of TOP (Turnover of Pressure, defined as the mass of conversions of a unit mass catalyst under unit pressure and unit time) was first proposed in this article.     

UiO-66基催化剂的制备及其在CO甲烷化中的应用

煤制天然气技术具有良好的经济和环境效益,其中CO甲烷化是煤制天然气过程的重要环节之一。本研究以UiO-66材料为载体制备了一系列具有不同Ni负载量的Ni/UiO-66催化剂,采用XRD, BET, TG, SEM, TEM, XPS等表征方法对载体和催化剂的物相结构、织构性质、热稳定性和元素分布情况进行考察,并对各催化剂上CO加氢性能进行了考察。研究结果表明,Ni金属高度分散于UiO-66载体上,且对金属有机骨架材料的物相结构和晶体形貌无显著影响。在CO甲烷化反应过程中,随Ni负载量逐渐增加,各Ni/UiO-66催化剂的起活温度逐渐降低;在相同反应温度(320℃)下,不同催化剂上Ni负载量由10%增加到30%,其CO转化率由10.7%提升到89.7%;当Ni含量为20%时,催化剂在反应过程中具有良好的稳定性。同时,Ni基催化剂上CO转化率远高于具有相同金属负载量的Fe基和Co基催化剂,表明Ni作为活性金属在合成气制甲烷反应过程中具有优异的催化性能。     

硝酸胶溶剂对CuO/HZSM-5成型催化剂性能的影响

催化剂CuO/HZSM-5在氧化亚氮(N₂O)催化分解领域有着重要地位,完成对催化剂成型条件的探索是其工业实际应用的重要步骤。在CuO/HZSM-5成型过程中,胶溶剂的用量对成型催化剂的机械强度,催化活性以及其他物化性质有重要的影响。通过机械强度测定、活性评价、X射线衍射分析(XRD)、孔结构分析、氨气程序升温吸附脱附分析(NH₃-TPD)、氢气程序升温还原分析(H₂-TPR)等手段对催化剂性能进行分析。机械强度测定与NH₃-TPD分析结果显示,胶溶剂用量对成型催化剂机械强度和酸量影响较大,胶溶剂用量为体积分数2%时,机械强度最高为135.8 N·cm^-1,而催化剂酸量在胶溶剂用量为体积分数7%时最高。XRD与孔结构分析结果显示胶溶剂用量由0增长至体积分数7%,催化剂的孔容积改变幅度较小,但比表面积由277 cm²·g^-1增至293 cm²·g^-1,HZSM-5的特征峰变化较小。活性评价与H₂-TPR分析结果显示,胶溶剂用量为0的催化剂与添加胶溶剂后的成型催化剂,N₂O完全分解的温度提高幅度最大为20 ℃,活性下降,且H₂-TPR中还原峰提高幅度最大为27 ℃,可还原性变差。而胶溶剂用量由体积分数2%提高至7%,成型催化剂CuO/HZSM-5的催化活性以及可还原性差异较小。     

Ca-γ-Al2O3耦合酸溶液催化葡萄糖制5-HMF

针对以葡萄糖为原料制备5-羟甲基糠醛（5-HMF）的问题,开发了CaO杂化的γ-Al₂O₃球形颗粒[Ca-γ-Al₂O₃,粒径1.8（±0.1） mm]耦合酸溶液制备过程,采用XRD与BET对Ca-γ-Al₂O₃球形颗粒进行了表征,研究了CaO杂化量、溶剂酸浓度、溶剂中二甲基亚砜（DMSO）与水的比例、催化剂用量、反应温度与时间对反应效果的影响,并评价了Ca-γ-Al₂O₃的操作稳定性,探讨了催化机理。实验结果表明：CaO的杂化（杂化量10%）对颗粒的孔结构影响相对较小,且在Ca-γ-Al₂O₃上分布较为均匀。在0.05 mol·L^-1酸浓度、V（DMSO）/V（H₂O）=3∶1、葡萄糖与催化剂比例为2∶1（125 mg∶63 mg）、反应温度140℃与反应时间3 h下,以Ca （5%）-γ-Al₂O₃为催化剂,葡萄糖转化率为100%,5-HMF收率最高为58.6％。此外,Ca-γ-Al₂O₃循环操作（未煅烧）5次后,5-HMF收率略有降低至55％左右,同时杂化负载方式使得CaO在酸性溶液中的泄露较低,表明Ca-γ-Al₂O₃具有良好的操作稳定性。催化剂机理分析表明,Ca-γ-Al₂O₃具有良好的葡萄糖异构化能力,CaO的杂化可提高催化剂与葡萄糖的相互作用,果糖脱水过程主要依赖于酸溶液的催化。     

金属有机骨架UiO-66在催化领域的应用

金属有机骨架（MOFs）经过二十多年的快速发展,已经合成了成千上万种,然而MOFs材料普遍具有较低的稳定性,在一定程度上限制了MOFs的发展。UiO-66的合成是MOFs材料稳定性的一个突破,其在催化领域的发展尤为迅速。本文首先介绍了理想及实际状态下UiO-66的结构特征,并说明了配体缺失导致的节点空位处的元素组成。然后综述了利用UiO-66特殊的结构特征或将其功能化用于催化反应的研究,包括节点空位、功能化节点空位、负载金属纳米颗粒、功能化配体等。最后,考虑到可以综合利用UiO-66的特殊结构,对UiO-66在未来多功能催化剂的设计合成领域所能发挥的作用进行展望。     

生物质转化制5-羟甲基糠醛的酸催化研究新进展

5-羟甲基糠醛（5-HMF）是一种重要的平台化合物,可转化为一系列重要有机化工原料、医药中间体、农药产品等。本文综述了近5年来国内外以纤维素、淀粉、菊糖、蔗糖、果糖、葡萄糖和农林废物等生物质为原料,在不同酸催化下制备5-羟甲基糠醛的一些特色工作,分析比较了不同酸催化反应体系的优缺点,并建议在制备5-HMF的过程中应加强催化材料的绿色设计、催化剂循环利用的工程研究和农林副产物的复合催化液化工艺的探索,以促进生物质制备5-HMF工业技术的发展。     

生物质碳磺酸的制备及其催化水解纤维素性能

对炭化温度、磺化条件以及不同碳源等因素对生物质碳磺酸的酸量、表面结构及催化纤维素水解活性的影响进行了系统研究,并采用XRD、BET、 FT-IR和SEM等对碳磺酸的微观特征进行了分析,发现合适的炭化温度和炭化程度是制备高酸量碳磺酸的关键,在相同的炭化和磺化条件下,用不同生物质碳源制备得到碳磺酸的酸量接近,微观结构不同对纤维素水解催化活性有一定影响。在本文研究的几种碳磺酸中,具有蜂窝大孔结构的竹炭碳磺酸呈现比较突出的催化活性。将竹粉在400℃炭化3 h,然后在180℃下磺化8 h,得到竹炭碳磺酸的总酸量和磺酸量分别可达5.34和1.25 mmol·g^-1。     

纤维素基生物质多孔炭的制备及其超级电容器性能研究

以棉纤维素为原料,采用硝酸盐、尿素、纤维素共混后热裂解的方法制备分级多孔炭HPC样品,通过改变煅烧温度和KOH活化处理对多孔炭比表面积及孔结构进行调控。对比三个不同温度煅烧活化处理后样品的循环伏安曲线、恒电流充放电曲线、比容量等电化学参数,结果表明,4AC@HPC800样品作为超级电容器工作电极具有优良的电化学性能,其比表面积高达2433.8 m²·g^-1,在1 A·g^-1的电流密度下比容量高达234.7 F·g^-1,在大电流密度10 A·g^-1时依然有207.6 F·g^-1的比容量,具有良好的倍率性能;电极在2 A·g^-1的电流密度下循环10000次后依然有196.1 F·g^-1的比容量,表明其具有长时工作的特性。     

UiO-66复合材料用于典型有机污染物吸附和光催化氧化的研究进展

UiO-66系列金属有机骨架（MOFs）材料因具有较高的比表面积、丰富的孔结构、优异的结构稳定性和类半导体特性而广泛应用于污染物的吸附和催化领域。文中指出：液相有机污染物主要通过物理吸附、静电、氢键、π-π相互作用被UiO-66基材料吸附去除,同时由于电性等性质差异,UiO-66基材料可从性质差异显著的多种有机污染物中选择性吸附污染物,而气相有机污染物主要通过氢键或UiO-66基材料孔道被吸附去除,同时环境中的水汽对污染物的吸附去除具有显著影响;针对光催化,由于载流子的快速复合,纯UiO-66基材料具有较低的光催化活性,通过与半导体材料复合可显著提高材料载流子分离速率,同时活性位点高度均匀分散在UiO-66基材料表面,利于光的激发及污染物与活性位点的充分接触,进而显著提高材料的光催化活性。与此同时,本文也提出了UiO-66基材料在有机污染物吸附和去除中的不足之处。最后展望了UiO-66基材料的发展前景。     

Renewable hydrogen production from steam reforming of glycerol (SRG) over ceria-modified γ-alumina supported Ni catalyst

Excess crude glycerol derived as a by-product from biodiesel industry prompts the need to valorise glycerol to value-added chemicals. In this context, catalytic steam reforming of glycerol (SRG) was proposed as a promising and sustainable alternative for producing renewable hydrogen (H₂). Herein, the development of nickel (Ni) supported on ceria-modified mesoporous γ-alumina (γ-Al₂O₃) catalysts and their applications in catalytic SRG (at 550-750 °C, atmospheric pressure and weight hourly space velocity, WHSV, of 44,122 ml·g^-1·h^-1 (STP)) is presented. Properties of the developed catalysts were characterised using many techniques. The findings show that ceria modification improved Ni dispersion on γ-Al₂O₃ catalyst support with highly active small Ni particles, which led to a remarkable catalytic performance with the total glycerol conversion (ca. 99%), glycerol conversion into gaseous products (ca. 77%) and H₂ yield (ca. 62%). The formation rate for H₂ production (14.4 × 10^-5 mol·s^-1·g^-1, TOF (H₂) = 3412 s^-1) was significantly improved with the Ni@12Ce-Al₂O₃ catalyst, representing nearly a 2-fold increase compared with that of the conventional Ni@Al₂O₃ catalyst. In addition, the developed catalyst also exhibited comparatively high stability (for 12 h) and coke resistance ability.     

介孔纳米氧化铝的制备、表征及其应用

Using aluminum isopropoxide as the aluminum source and O,O′-bis(2-aminopropyl) polypropylene glycol-block-polyethylene glycol-block-polypropylene glycol as the template,ordered worm-like mesoporous nano-alumina was prepared by sol-gel method.The characterization results showed that the surface area,average pore diameter and pore volume of the calcined mesoporous alumina were 341.1 m²·g^-1,17.4 nm and 1.54 cm³·g^-1,respectively.The catalytic properties of the mesoporous nano alumina for the dehydration of isopropanol to propylene was investigated.The results indicated that the as-prepared mesoporous nano-alumina exhibited high catalytic activity.The conversion of isopropanol and the selectivity to propylene were more than 99.0% and 98.5%,respectively,when isopropanol WHSV was 0.5 h^-1,1.0 h^-1 and 2.0 h^-1 and the corresponding reaction temperature was controlled at the range of (230-320) ℃,(250-340) ℃ and (260-350) ℃,respectively.     

Hydrophilic porous polymers based on high internal phase emulsions solely stabilized by poly(urethane urea) nanoparticles

Stable oil-in-water (o/w) Pickering high internal phase emulsions (HIPEs) having an internal phase of up to 95 vol% were prepared with a low-energy emulsification method. A poly(urethane urea) (PUU) aqueous nanodispersion was used as aqueous phase. The PUU nanoparticles of the aqueous nanodispersion acted as a mechanical barrier, and prevented droplet coalescence in the Pickering HIPEs. In addition, open porous hydrophilic polymer foams were obtained by polymerization of the Pickering HIPEs, and the morphology of the foams were tailored by changing the oil:water ratio, PUU nanoparticle and NaCl concentrations. The method used herein provides a simple way to prepare morphology controlled hydrophilic polymer foams using o/w Pickering HIPEs as template.     

W2C/AC催化快速热解松木磨木木质素

以活性炭（AC）为载体制备了不同钨负载量的W₂C/AC催化剂,将其和松木磨木木质素（MWL）机械混合后进行Py-GC/MS（快速热解-气相色谱/质谱联用）实验,考察了钨负载量、催化剂/MWL比例对产物分布的影响,并通过外标法对主要产物（芳烃类和酚类）的真实产率进行了定量分析。结果表明,W₂C/AC催化剂可有效促进木质素的热解解聚生成单酚类产物,并对酚类产物具有脱羰基、脱甲氧基、脱羟基以及加氢的效果,从而促进稳定的酚类产物（不含羰基、甲氧基和不饱和碳碳双键）和芳烃类产物的生成。在4种W₂C/AC催化剂中,10%-W₂C/AC的催化效果最佳,在催化剂/MWL比例为5时热解产物总产率达到最大值,此时芳烃类和酚类产物的总产率由无催化剂时的21.2 mg·g^-1和151.0 mg·g^-1增加至102.1 mg·g^-1和191.1 mg·g^-1。