Catalytic dehydration of glucose to 5‐hydroxymethylfurfural with a bifunctional metal‐organic framework

Glucose conversion to 5‐hydroxymethylfurfural (HMF) generally undergoes catalytic isomerization reaction by Lewis acids followed by the catalytical dehydration to HMF with Brönsted acid. In this work, a sulfonic acid functionalized metal‐organic framework MIL‐101(Cr)‐SO₃H containing both Lewis acid and Brönsted acid sites, was examined as the catalyst for γ‐valerolactone‐mediated cascade reaction of glucose dehydration into HMF. Under the optimal reaction conditions, the batch heterogeneous reaction gave a HMF yield of 44.9% and selectivity of 45.8%. Reaction kinetics suggested that the glucose isomerization in GVL with 10 wt % water follows the second‐order kinetics with an apparent activation energy of 100.9 kJ mol^?1. Continuous reaction in the fixed‐bed reactor showed that the catalyst is highly stable and able to provide a steady HMF yield. This work presents a sustainable and green process for catalytic dehydration of biomass‐derived carbohydrate to HMF with a bifunctional metal‐organic framework. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4403–4417, 2016     

氨基酸金属有机框架的研究进展

氨基酸金属有机框架是指含有氨基酸单元的有机配体与金属离子共同参与合成的具有周期性结构的材料。氨基酸作为蛋白质的组成成分,具有绿色环保、生物相容性良好、种类多样、价格低廉等优点,将其引入金属有机框架（MOFs）可以赋予材料特殊的柔性结构、丰富的活性位点、优良的应用性能等特征。该文综述了氨基酸MOFs的结构维度分类,介绍了氨基酸MOFs的主要合成方式,包括溶剂热法、机械化学合成法、微波加热辅助法,进一步阐述了材料的性能调控,重点介绍了这类材料在手性拆分、催化、吸附等领域的应用。最后,通过分析当前氨基酸金属有机框架材料存在的稳定性不好、结构难以预测等问题,对其未来在生物医药领域的研究重点进行了展望。     

Synthesis and Characterization of New Organometallic Hybrid Material LCP-1 Based on MOF (Metal–Organic Framework) and Maghnite-H<Superscript>+</Superscript>, a Protons Exchanged Montmorillonite Clay,as Catalytic Support

In this work, a new 3D crystalline metal–organic framework formulated as [Zn₂(BTC)₄, (BTC: 1,2,4,5-Benzenetetracarboxylate)] and called LCP-1 (LCP: Laboratoire de Chimie des Polymères), with unsaturated coordinated Zn(II) sites as metal ion and pyromellitic acid (H₄BTC: 1,2,4,5-Benzenetetracarboxylic acid) as organic ligand, has been successfully synthesized under solvothermal conditions. In-Situ polymerization of this material was also carried out using an amount of clay called Maghnite-H⁺, an acid-exchanged montmorillonite, as an eco-catalyst with the aim to respect the principles of green chemistry, to give a new hybrid composite material LCP-1/Mag-H⁺ with a better yield, a significantly reduced time and temperature reaction than those of LCP-1. LCP-1 and LCP-1/Mag-H⁺ have been structurally characterized and established by fourier transform infrared spectroscopy (FT-IR). The morphology of these compounds was studied by the X-ray diffraction (XRD) and revealed a highly crystalline and ordered structure for both LCP-1 and LCP-1/Mag-H⁺. FT-IR and XRD spectra showed also that the stability and structural integrity of LCP-1 and LCP-1/Mag-H⁺ was maintained even after being evacuated from the DMF solvent molecules. The thermal stability identified by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) showed that Maghnite-H⁺, as inorganic support, has also improved the thermal stability of LCP-1 compound.     

Supramolecular approach to metal–organic gels using excess organic ligand as building units

A metal–organic gels containing Ag(4,4′-bipyridine)NO₃ metal–organic framework and 4,4′-bipyridine units were hydrothermally synthesized using excess 4,4′-bipyridine ligand as building units. The metal–organic gels structure was characterized by various spectroscopic methods and a mechanism of assembly was discussed on the basis of the obtained data. The metal–organic gels retained the characteristics of both the metal–organic framework and gels; furthermore, the reversible hydration/dehydration, reversible anion exchange, and responsive properties were also investigated.     

Moisture stability of ethane-selective Ni(II), Fe(III), Zr(IV)-based metal–organic frameworks

Metal–organic frameworks (MOFs) combined with selective adsorption capacity of ethane over ethylene and good moisture stability are highly urged by adsorption industrial community. Here, the moisture stability mechanism of Zr-bptc, UiO-66, PCN-245, and Ni(bdc)(ted)_0.5 were investigated by moisture stability experiments, and computational simulation of metal node-linker breaking energy caused by water. Results show that the moisture stability follows the order of Zr-bptc > UiO-66 > PCN-245 > Ni(bdc)(ted)_0.5. The different moisture stability for these MOFs is likely attributed to the bond strength between metal center and ligands, the coordination number of metal center, the hydrophobicity of framework, as well as the degree of interpenetrated framework. Additionally, comparing with ethylene-selective MOFs, ethane-selective MOFs have fewer coordinatively unsaturated metal sites. Breakthrough experiments indicated that Zr-bptc is the promising material for ethane/ethylene separation.     

Aluminum metal–organic framework as a new host for preparation of encapsulated metal complex catalysts

A facile strategy for encapsulation of metal complex guests into MOFs was proposed. This strategy involves pre-adsorbing metal salt on MOF, and then coordinating the metal ions with the organic ligand, as exemplified by encapsulation of tris(1,10-phenanthroline) Cu(II) complexes (CuPhen) in MIL-100(Al) (denoted as CuPhen/MIL). CuPhen encapsulated in MIL-100(Al) showed higher catalytic activity than the neat CuPhen and CuPhen encapsulated in zeolite-Y. The prepared CuPhen/MIL catalyst was stable and could be reused at least three times without significant loss in activity. This work is beneficial for the host–guest chemistry study and the development of new heterogeneous catalysts.     

Metal–organic frameworks-derived TiO2 for photocatalytic degradation of tetracycline hydrochloride

This work will change the common understanding that C doping of MIL-125(Ti)-derived TiO₂ is a key factor in improving its photocatalytic performance, and it can also help to understand the internal relationship between the structure and performance of photocatalytic materials deeply. It provides a simple synthesis method for the wider application of TiO₂ in the field of photocatalysis. Compared with previous studies, this article uses the titanium-based metal-organic framework MIL-125(Ti) to prepare the semiconductor photocatalyst M-TiO₂ by calcination in the air at a lower temperature and shorter time. After analyzing the M-TiO₂ prepared in the experiment, the results can be received that there is no obvious agglomeration and the morphology is almost unchanged, as the frame structure does not collapse at the same time. As a result, the advantages of the large specific surface area and porousness of metal–organic frameworks (MOF) as precursor derivatives are preserved. As for the changes in the micro-morphology, pore structure, and specific surface area of M-TiO₂ compared with the precursor, they are investigated seriatim. The results show that, compared with commercial TiO₂-P25, the performance of M-TiO₂ photocatalytic degradation of tetracycline hydrochloride is 5.7 times that of the precursor metal-organic framework MIL-125(Ti) and 2.2 times that of P25, and has good cycle stability.     

The effect of acid-base interaction on the thermal and transport properties of poly(etheretherketone) based composite membranes

Binary composite membranes were prepared by the solution casting method from sulfonated poly(etheretherketone) (SPEEK) and organic additives such as hydroxyquinolinesulfonicacid (HQS), 4-tertiary butylpyridine (TBP), imidazole and succinimide. Ternary composite membranes were prepared from SPEEK, inorganic phosphotungstic acid (PWA) and the same organic additives. The acid base interaction characteristics of the composite membranes were not observed by ATR-FTIR analysis. TGA results showed that the thermal stability of the composite membranes was enhanced in the temperature range up to about 400 °C by the addition of the organic additives. The acid-base interaction between SPEEK and the organic additives of HQS, TBP and imidazole decreased the water uptake, methanol permeability and proton conductivity of the binary and ternary composite membranes. However, the addition of succinimide did not decrease the water uptake, proton conductivity and methanol permeability of the composite membranes. The composite membranes containing succinimide made little acid-base interaction but made hydrogen bonding with SPEEK. The hydrogen bonding proved to be weaker than the acid-base interaction. The selectivity of the composite membranes increased by the addition of PWA, and the selectivities of the composite membranes containing succinimide were higher than those of the other composite membranes.     

研磨法制备金属有机框架材料的新进展

金属有机框架材料是由金属离子/团簇和具有一定刚性结构的有机配体通过配位键连接而成的多孔晶体材料,具有多孔、比表面积大、结构多样、表面易修饰等特点,在能源、化工、医药领域具有广泛的应用。机械化学合成法是指通过机械能诱导化学反应的方法,由于其绿色环保、耗时短、效率高、应用范围广、副反应少的特点近年来受到广泛关注,在制备金属有机框架材料方面同样表现出显著的优势。研磨法是机械化学合成法中重要的一种。为了解生物金属骨架材料的机械化学法合成概况及最新进展,本文介绍了研磨法制备金属有机框架材料的经典案例,尤其着重介绍了应用于医药领域的金属有机框架材料的合成,研究进展表明研磨法是一种绿色高效的合成方法,为金属有机框架材料在医药领域的广泛应用提供了可能,具有良好的发展前景。     

Antioxidant Activities of Free and Liposome-Encapsulated Green tea extracts on canola oil oxidation stability

In the present study, green tea extract was encapsulated in liposomes based on the Mozafari method (with no organic solvents) and characterized for its physicochemical properties (encapsulation efficiency, particle size, and Z-potential). Encapsulation efficiency, particles size, and Z-potential were determined to be 51.34, 419 nm, and -57 mV, respectively. Total polyphenol content of the green tea by Folin-Ciocalteu's phenol reagent was measured as 164.2 mg gallic acid/g extract. Free radical scavenging activities of free and liposomal extracts were 90.6 and 93.4%, respectively, using the DPPH method. Antioxidant activity of the ethanolic extract of green tea in free and liposomal forms with concentrations of 200, 600, and 1000 mg L⁻¹ were assessed on oxidative stability of the canola oil at 60 °C for 0, 4, 8, 12, 16, 20, 24, 28, and 32 days. Results were compared to results of synthetic antioxidant butylated hydroxytoluene at 200 mg L⁻¹. To assess antioxidant activity on canola oil stability, peroxide, thiobarbitoric acid, and anisidine values were assessed as well as the total oxidation value and rancimat test. Results showed that the liposomal green tea extract was more effective than the free extract. Furthermore, a 600 mg L⁻¹ concentration of the green tea extract showed a significant antioxidant activity, compared to other extract concentrations. Increasing storage time and various concentrations of the ethanolic green tea extracts included significant effects on canola oil stability (P ≤ 0.05). Results demonstrated that the green tea extract could be used as an effective antioxidant. Free and liposomal extract (at 600 mg L⁻¹) resulted in stronger functionality than the synthetic antioxidant butylated hydroxytoluene.     

Microencapsulation of caffeic acid and its release using a w/o/w double emulsion method: Assessment of formulation parameters

Caffeic acid (CAF)has numerous health benefits mainly due to its antioxidant, antibacterial and fungicide properties. However, its incorporation in skin care products as anti-aging and the photoprotective agent is still limited due to its solubility and stability in oily matrices or solutions balanced with the skin pH. In this research, CAF–ethyl cellulose (EC) microparticles were produced by water-in-oil-water double emulsion solvent evaporation encapsulation technique using a biocompatible polymer, EC, as a coating material and a surfactant, polyvinyl alcohol, as a stabilizer of the double emulsion. The study assessed the influence of formulation parameters as the solubility of the polymer in organic solvents and the polymer concentration on microparticles final characteristics. CAF–EC microparticles were characterized by product yield, encapsulation efficiency, mean particle size, particle size distribution and polydispersity and imaged by scanning light microscopy. In vitro release profiles were obtained in water and octanol to mimic oily based and water-based matrices balanced with the skin pH. In vitro release kinetics studies were carried out to investigate the release pattern of CAF in simulated cosmetic formulations. Both the product yield and the encapsulation efficiency were found to be dependent on the solubility of the polymer in the organic phase. The product yield was mainly affected by operational factors such as the sticking and the agglomeration of the polymer to the walls and the magnet stirring during microparticles hardening and results from the encapsulation efficiency revealed that an increase of the polymer concentration led to an increase of the encapsulation efficiency. The usage of a water-soluble solvent contributed to a decrease in the mean particle size and reduction of polydispersity with higher polymer concentrations. The polymer concentration, the polymer solubility in the organic phase and the amount of CAF entrapped shown to affect the release in water, whereas the release in octanol was mainly independent of the amount of CAF entrapped in EC microparticles. The double emulsion solvent evaporation technique and the assessment of the selected formulation conditions have given significant and innovative insights on the microencapsulation of bioactive ingredients for cosmetics formulations.     

Size-Selective Homocoupling of Arylboronic Acids Mediated by a Copper-Based Metal–Organic-Framework

Copper-based metal–organic-frameworks with open metal sites have received increasing research interest as heterogeneous catalysts for various organic transformations. A copper-based metal organic framework (1) built with L-NO₂ ligand (L-NO₂?=?4,4′-dicarboxy-4″-nitrotriphenylamine) was selected for catalyzing aerobic homocoupling of arylboronic acid toward biaryl products given its structural robustness and 1-D channels lined with rich open metal sites. The experimental results show that MOF (1) exhibits pronounced size selectivity over arylboronic acid molecules, which is only effective for short arylboronic acid molecules (e.g. phenylboronic acid, p-methylphenylboronic acid and p-fluorophenylboronic acid), giving the corresponding biaryl products in good yields. Moreover, MOF (1) also demonstrates a good recyclability which only shows a small decay in the catalytic performance after five repeated runs.

     

Bond Characteristics at Pigment-Polymer Interfaces

An assessment was made of the effectiveness of bonding polymers from solution to dispersed solids by dispersive and non-dispersive forces. The polymers included neutral low density polyethylene (LDPE), a basic ethylene co-vinyl acetate (EVA) and an acidic chlorinated polyethylene (CPE). The solids included surface coated rutiles, an organic colorant and the chromatographic support Chromosorb.^® The quality of polymer-solids bonds was estimated by eluting adsorbed polymers with p-xylene under reflux. The amount of polymer recovered was a function of acid-base forces acting at the polymer-solid interface. LDPE was recovered quantitatively, as were EVA and CPE when these were adsorbed on like (acid or base) solids but recovery was limited when significant acid-base interaction occurred. These results were relevant to the stabilization of solids dispersed in polymer solutions. Sedimentation experiments noted that the absence of acid-base interactions as well as an excess of these non-dispersive forces was detrimental to the stability of dispersions. For the specific systems under study, however, it was possible to define a preferred, intermediate range of acid-base interactions for dispersion stability. The configuration of adsorbed polymer chains was suggested to be an important consideration in this regard.     

金属氧化物催化CO2与甲醇合成碳酸二甲酯的研究进展

CO₂是主要的温室气体。近年来随着工业的大力发展,CO₂的排放量迅猛增加,严重影响着人类的生存环境。将CO₂转化成有价值的化工产品,受到了研究领域的广泛关注。其中将CO₂与产能过剩的甲醇作为原料,生产碳酸二甲酯（DMC）,既能减少CO₂排放,又能产生有价值的绿色产品DMC。本文简述了影响CO₂转化的因素,即受热力学限制和CO₂活化困难;重点介绍了具有酸碱活性中心的金属氧化物ZrO₂、CeO₂以及复合金属氧化物催化剂的催化性能和反应机理,并分析了影响催化活性的主要原因：表面酸碱性能决定了催化活性;进一步分析了催化剂表面的酸碱性来源于Lewis酸碱位和Br?nsted酸性位。对于开发高效的金属氧化物催化剂未来的研究方向提出了展望: 通过调控催化剂的晶相和形貌、增加氧空位和羟基官能团、掺杂碱性或者酸性物种来改变催化剂表面的酸碱性,并且向催化系统中添加脱水剂。最后指出了由于CO₂分子的稳定性很难被活化,需进一步深入研究其活化CO₂的机理,提高CO₂的转化率。     

掺氮Y和HZSM-5分子筛结构与酸碱性能研究

以Y分子筛和HZSM-5分子筛为前驱体,以纯氨为氮源,在800 ℃焙烧制备了氮化微孔分子筛。采用元素分析、氮气吸附-脱附、X射线衍射（XRD）、原位漫反射红外光谱等技术对材料的结构与酸碱性能进行了研究。结果表明,NaY分子筛是可获得高比表面积和完整结构掺氮分子筛理想的前驱体。原位漫反射红外光谱证实了氮原子主要以-NH2-或-NH-形式进入各分子筛骨架。原位探针分子吸附漫反射红外光谱实验表明两种分子筛均含B酸位与L酸位,经高温氨处理掺氮后B酸位显著减少、L酸位变化不明显,碱性变强。     

An erbium–organic framework as an adsorbent for the fast and selective adsorption of methylene blue from aqueous solutions

The applicability of erbium–metal–organic framework (Er-MOF) in the adsorption and removal of methylene blue from aqueous solution has been studied. Er-MOF was synthesized by hydrothermal method and characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray powder diffraction. The high thermal stability, water stability and accessible nano-sized aperture for the Er-MOF could endow it with a very high potential in adsorption of dye pollutant. The adsorption isotherm, kinetic and thermodynamic investigations confirm that the adsorption behavior is based on Langmuir isotherm with an exothermic mechanism and enthalpy-driven process. The speed adsorption process (30 min), low cost, high efficiency, big surface area, selectivity and very high and rapid reusability are the main advantages of the proposed compound as a sorbent.     

Thermostable variants constructed via the structure-guided consensus method also show increased stability in salts solutions and homogeneous aqueous-organic media

Enzyme instability is a major factor preventing widespread adoption of enzymes for catalysis. Stability at high temperatures and in the presence of high salt concentrations and organic solvents would allow enzymes to be employed for transformations of compounds not readily soluble in low temperature or in purely aqueous systems. Furthermore, many redox enzymes require costly cofactors for function and consequently a robust cofactor regeneration system. In this work, we demonstrate how thermostable variants developed via an amino acid sequence-based consensus method also showed improved stability in solutions with high concentrations of kosmotropic and chaotropic salts and water-miscible organic solvents. This is invaluable to protein engineers since deactivation in salt solutions and organic solvents is not well understood, rendering a priori design of enzyme stability in these media difficult. Variants of glucose 1-dehydrogenase (GDH) were studied in solutions of different salts along the Hofmeister series and in the presence of varying amounts of miscible organic solvent. Only the most stable variants showed little deactivation dependence on salt-type and salt concentration. Kinetic stability, expressed by the deactivation rate constant k(d,obs), did not always correlate with thermodynamic stability of variants, as measured by melting temperature T(m). However, a strong correlation (R(2) > 0.95) between temperature stability and organic solvent stability was found when plotting T(50)(60) versus C(50)(60) values. All GDH variants retained stability in homogeneous aqueous-organic solvents with >80% v/v of organic solvent.     

Topology and porosity control on zirconium–fumarate frameworks boosting xenon/krypton separation

The designability and ultrahigh stability of zirconium–organic frameworks make them attractive adsorbents for noble gases xenon (Xe) and krypton (Kr), but their Xe/Kr separation performance needs to be further enhanced. In this study, we rationally control the topology and porosity of zirconium–fumarate frameworks by simply changing the synthesis conditions, and successfully construct an adsorbent (named as MIP-203-F) with one-dimensional pore instead of the original cage-like fcu metal–organic framework MOF-801. The Xe/Kr separation performance of MIP-203-F is thoroughly evaluated by isotherm measurements and breakthrough experiments, while the adsorption mechanism is elucidated in detail by Monte Carlo and density functional theory calculations. Due to the uniform pore with suitable size and abundant polarization groups, MIP-203-F can differentially polarize and recognize atomic Xe/Kr gases, and establishes a new record among zirconium–organic frameworks for the capture and separation of Xe/Kr.     

Material Advancements in Fabrication of Mixed‐Matrix Membranes

The mixed‐matrix membrane (MMM) is a new membrane material for gas separation and plays a vital role for the advancement of current membrane‐based separation technology. Blending between inorganic fillers like carbon molecular sieves, zeolite, metal oxides, silica and silica nanoparticles, carbon nanotubes, zeolitic imidazolate framework, metal organic framework, and glassy and rubbery polymers etc. is possible. Due to mechanical, thermal, and chemical stability, these membranes achieve high permeability and selectivity as compared to pure polymeric materials. Despite of these advantages, the MMM performances are still below industrial expectations because of membrane defects and related processing problems as well as the nonuniform dispersion of fillers in MMMs. Material selection for organic and inorganic phases, preparation techniques, material advancements, and performance of MMMs are discussed. Issues and challenges faced during MMM synthesis as well as problem solutions are highlighted.     

金属有机框架材料的绿色合成

金属有机框架化合物（Metal-organic frameworks,简称MOFs）是由金属离子（或簇）与有机配体配位并经由自组装而形成的一类多孔材料^[1]。MOFs具有极其发达的孔道结构,比表面积和孔容远超其他多孔材料。有机/无机杂化这一特点也赋予了MOFs其他材料（例如沸石、活性炭等）所不具备的无限结构功能可调性^[2]。此外,MOFs具有移除客体分子而主体框架完好保持的持久孔道或孔穴,这使得MOFs具有超乎寻常的化学及物理稳定性。正是基于以上这些特点,MOFs在许多领域有着丰富的应用^[3-4],例如催化^[5]、H₂储存^[6]、CO₂捕集^[7]、药物运输^[8]、污染物吸附^[9]、生物医学成像^[10]等方面。MOFs的商业化探索成为了目前的热点。MOFs的很多应用都与可持续发展及“绿色材料”有关,但MOFs本身的合成过程也需要考虑可持续性和环境影响。金属有机化学所面临的环境挑战是独特的,因为它将金属离子、有机配体的危害联系在一起,且合成过程大多需要大量能耗。主要介绍了金属有机框架材料的绿色可持续合成,主要分为4个方面：1）使用更安全或生物相容性的配体;2）使用更绿色、低成本的金属源;3）绿色溶剂的开发;4）无溶剂合成法。