乙酸调控MIL-53(Fe)的形貌演变及其高效选择性氧化H2S性能

硫化氢(H2S)广泛存在于以煤、石油和天然气等为原料的化工生产过程中,不仅腐蚀管道和设备,而且还会对健康和环境造成危害.因此,高效脱除H2S已成为工业废气减排的重点.在各种方法中,H2S选择性氧化技术(H2S+(1/2)O2→(1/n)Sn+H2O)由于具有设备需求低、反应不受热力学平衡限制、理论转化率可达100%等优点展现出了巨大的应用前景.实现这一过程的关键在于发展高效稳定的催化剂.作为一类新兴的多孔材料,金属-有机骨架材料(MOFs)由于其独特的结构和性质吸引了广泛的研究兴趣.与传统的脱硫材料相比,MOFs的优势主要体现在:1)高度分散的金属原子可作为催化活性中心;2)超高比表面积和规则的孔结构有利于反应物与活性位点之间的接触;3)结构可调变性高,通过在合成过程中有目的地引入配体或调控剂可产生额外的活性位点,满足特定催化的需求.基于以上特点可知,MOFs是一类有潜力的催化剂,但目前将其应用于H2S选择性氧化领域的研究尚处于起步阶段.本文以典型的铁基MOFs MIL-53(Fe)为研究对象,在制备MIL-53(Fe)过程中添加乙酸(HAc)作为调控剂,通过控制HAc的量,得到一系列具有不同形貌的MIL-53(Fe)-xH样品,并将其应用于H2S选择性氧化反应.SEM结果表明,在MIL-53(Fe)的合成过程中引入乙酸可以显著影响样品的形貌和尺寸.活化前后样品的XRD结果表明,HAc具有与对苯二甲酸(H2BDC)相似羧基基团,二者均可与Fe–O团簇配位.此外,TG-DSC结果证实,随着HAc加入量的提高,与Fe^3+形成配位的HAc/H2BDC比值随之增加.FT-IR和Raman结果进一步证明HAc成功地配位到MIL-53(Fe)的框架中,并且参与配位的HAc可通过真空活化移除从而暴露出Fe^3+不饱和位点.H2S选择性氧化测试表明,MIL-53(Fe)-xH的脱硫活性随着HAc含量的提高先增加然后降低,其中MIL-53(Fe)-5H活性最优.此外,MIL-53(Fe)-5H催化剂在连续运行55 h后仍能保持100%H2S转化率和86%硫选择性,性能远优于传统的Fe2O3催化剂.吡啶原位红外光谱结果表明,HAc的引入可以产生额外的Lewis酸性位点(LAS),LAS含量的不同是造成催化剂活性差异的主要原因.     

苯部分加氢制环己烯新型Ru-B/MOF催化剂

制备了多种金属-有机骨架(MOF)材料,采用浸渍-化学还原法制备了非晶态Ru-B/MOF催化剂,考察了它们在苯部分加氢反应中的催化性能.催化性能评价结果表明,这些催化剂的初始反应速率(r0)顺序为Ru-B/MIL-53(Al)Ru-B/MIL-53(Al)-NH2Ru-B/UIO-66(Zr)Ru-B/UIO-66(Zr)-NH2Ru-B/MIL-53(Cr)Ru-B/MIL-101(Cr)Ru-B/MIL-100(Fe),环己烯初始选择性(S0)顺序为Ru-B/MIL-53(Al)≈Ru-B/MIL-53(Cr)Ru-B/UIO-66(Zr)-NH2Ru-B/MIL-101(Cr)Ru-B/MIL-53(Al)-NH2Ru-B/UIO-66(Zr)≈Ru-B/MIL-100(Fe).催化性能最好的Ru-B/MIL-53(Al)催化剂上的r0和S0分别为23 mmol·min-1·g-1和72%.采用多种手段,对催化性能差异最为显著的Ru-B/MIL-53(Al)和Ru-B/MIL-100(Fe)催化剂的物理化学性质进行了表征.发现MIL-53(Al)载体能够更好地分散Ru-B纳米粒子,粒子的平均尺寸为3.2 nm,而MIL-100(Fe)载体上Ru-B纳米粒子团聚严重,粒径达46.6 nm.更小的粒径不仅能够提供更多的活性位,而且也有利于环己烯选择性的提高.对Ru-B/MIL-53(Al)催化剂的反应条件进行了优化,在180°C和5 MPa的H2压力下,环己烯得率可达24%,展示了MOF材料用作苯部分加氢催化剂载体的良好前景.     

Very large breathing effect in the first nanoporous chromium(III)-based solids: MIL-53 or Cr(III)(OH) x [O(2)C-C(6)H(4)-CO(2)] x [HO(2)C-C(6)H(4)-CO(2)H](x) x H(2)O(y)

The first three-dimensional chromium(III) dicarboxylate, MIL-53as or Cr(III)(OH) x [O(2)C-C(6)H(4)-CO(2)].[HO(2)C-C(6)H(4)-CO(2)H](0.75), has been obtained under hydrothermal conditions (as: as-synthesized). The free acid can be removed by calcination giving the resulting solid, MIL-53ht or Cr(III)(OH) x [O(2)C-C(6)H(4)-CO(2)]. At room temperature, MIL-53ht adsorbs atmospheric water immediately to give Cr(III)(OH) x [O(2)C-C(6)H(4)-CO(2)] x H(2)O or MIL-53lt (lt: low-temperature form, ht: high-temperature form). Both structures, which have been determined by using X-ray powder diffraction data, are built up from chains of chromium(III) octahedra linked through terephthalate dianions. This creates a three-dimensional structure with an array of one-dimensional large pore channels filled with free disordered terephthalic molecules (MIL-53as) or water molecules (MIL-53lt); when the free molecules are removed, this leads to a nanoporous solid (MIL-53ht) with a Langmuir surface area over 1500 m(2)/g. The transition between the hydrated form (MIL-53lt) and the anhydrous solid (MIL-53ht) is fully reversible and followed by a very high breathing effect (more than 5 A), the pores being clipped in the presence of water molecules (MIL-53lt) and reopened when the channels are empty (MIL-53ht). The thermal behavior of the two solids has been investigated using TGA and X-ray thermodiffractometry. The sorption properties of MIL-53lt have also been studied using several organic solvents. Finally, magnetism measurements performed on MIL-53as and MIL-53lt revealed that these two phases are antiferromagnetic with Néel temperatures T(N) of 65 and 55 K, respectively. Crystal data for MIL-53as is as follows: orthorhombic space group Pnam with a = 17.340(1) A, b = 12.178(1) A, c = 6.822(1) A, and Z = 4. Crystal data for MIL-53ht is as follows: orthorhombic space group Imcm with a = 16.733(1) A, b = 13.038(1) A, c = 6.812(1) A, and Z = 4. Crystal data for MIL-53lt is as follows: monoclinic space group C2/c with a = 19.685(4) A, b = 7.849(1) A, c = 6.782(1) A, beta = 104.90(1) degrees, and Z = 4.     

Effect of NH2 and CF3 functionalization on the hydrogen sorption properties of MOFs

The hydrogen adsorption capacity and heat of adsorption at 77 K have been evaluated for several porous metal terephthalate MOFs (MIL-53(Fe), MIL-125(Ti) and UiO-66(Zr)), as well as in their -NH(2) and -(CF(3))(2) functionalized isoreticular structures. The capacity of hydrogen is basically related to the textural properties of the solids and not to their composition. The heats of adsorption at low coverage are on the whole close to those usually reported for MOFs (6-7 kJ mol(-1)), except for the UiO-66(Zr) and MIL-53(Fe)-(CF(3))(2) analogues, whereas the presence of Lewis acid sites and/or a confinement effect enhances significantly the strength of interaction with hydrogen.     

BiVO_4/MOF复合材料的合成及其光催化性能

通过简单溶剂热法制备了一种新型复合光催化剂BiVO_4/M IL-53(Fe);运用XRD、SEM/EDS、FT-IR、N_2吸附-脱附和UV-vis DRS等手段对其进行表征,并对其光催化降解RhB活性进行了研究,提出了相应的光催化降解RhB的可能机理。结果表明,相较于单一BiVO_4材料,复合催化剂的比表面积增大,且其光催化效率相较于纯BiVO_4和MIL-53(Fe)也有了较大的提高;其中,BF-2复合材料的光催化活性最高,分别约为纯MIL-53 (Fe)和BiVO_4的5. 2倍和8. 1倍。同时,BiVO_4/MIL-53(Fe)复合光催化剂经过四次循环实验后,仍能保持较稳定的光催化活性和结构。     

Anti-Influenza Virus Study of Composite Material with MIL-101(Fe)-Adsorbed Favipiravir

Nanomaterial technology has attracted much attention because of its antibacterial and drug delivery properties, among other applications. Metal-organic frameworks (MOFs) have advantages, such as their pore structure, large specific surface area, open metal sites, and chemical stability, over other nanomaterials, enabling better drug encapsulation and adsorption. In two examples, we used the common pathogenic bacterium Staphylococcus aureus and highly infectious influenza A virus. A novel complex MIL-101(Fe)-T705 was formed by synthesizing MOF material MIL-101(Fe) with the drug favipiravir (T-705), and a hot solvent synthesis method was applied to investigate the in vitro antibacterial and antiviral activities. The results showed that MIL-101(Fe)-T705 combined the advantages of nanomaterials and drugs and could inhibit the growth of Staphylococcus aureus at a concentration of 0.0032 g/mL. Regarding the inhibition of influenza A virus, MIL-101(Fe)-T705 showed good biosafety at 12, 24, 48, and 72 h in addition to a good antiviral effect at concentrations of 0.1, 0.2, 0.4, 0.8, 1.6, and 3 μg/mL, which were higher than MIL-101(Fe) and T-705.     

金属有机框架@介孔分子筛复合材料的构建和性质

通过蒸汽诱导内部水解法(VIH)在介孔分子筛SBA-15孔壁上引入Al_2O_3,合成得到Al_2O_3@SBA-15复合物,随后与对二苯甲酸配体反应,从而制备得到金属有机框架化合物(MIL-53)与介孔分子筛(SBA-15)复合材料(MIL-53@SBA-15)。采用粉末X射线衍射(PXRD)、N_2吸附-脱附测试、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等技术证明成功合成了MIL-53@SBA-15复合材料。染料吸附实验结果表明,MIL-53@SBA-15复合材料相比于SBA-15、MIL-53及其物理混合样品,表现出对丁基罗丹明染料更高效吸附特性。     

A surface architectured metal–organic framework for targeting delivery: Suppresses cancer growth and metastasis

Porous nanosized metal–organic frameworks (MOFs) are becoming possible candidates as drug-delivery nanocarriers for their versatile porous structures and large loadings of drugs. However, controlling synthesis of MOFs with uniform morphology, good biocompatibility and targeting drug delivery is still a challenge, which greatly limits their clinical applications. Herein, a multifunctional nano-sized drug-delivery material MIL-101(Fe)@FU@FA with a uniform particle size about 500 nm was successfully synthesized for targeting therapeutic purposes. The targeting reagent folic acid (FA) molecules are connected on the surface of 5-FU-loaded nanoparticle MIL-101(Fe)-NH₂ by a covalent conjugation. Cytotoxicity tests showed that the synthesized nanoparticles are biocompatible and can significantly inhibit cell proliferation on SMMC-7721 cells compared with MIL-101(Fe)@FU and free 5-FU. The cell metastasis and invasion experiments proved that the nanoparticles had a good anti-metastasis ability to tumor cells. Mechanistically, MIL-101(Fe)@FU@FA induces apoptosis of SMMC-7721 cells and block cell cycle progression in the G2/M phase. Taken together, the drug-loaded nanoparticles MIL-101(Fe)@FU@FA have the effect of targeting and sustained release to achieve the therapeutic effect.     

Construction of Hyaluronic Acid-Covered Hierarchically Porous MIL-nanoMOF for Loading and Controlled Release of Doxorubicin

The porous nano-sized metal–organic framework (nanoMOF) and its proper surface modification could greatly promote the drug loading capability and introduce biocompatibility, biodegradability, and targeting functions into nano-drug delivery systems. Herein, the HACD@ADA-PA/MIL-101_NH₂ (Fe)-P nanoparticle was successfully fabricated through supramolecular and coordination interactions from three building blocks, including hierarchically porous MIL-101_NH₂ (Fe)-P nanoMOF, phosphite-modified adamantane (ADA-PA), and β-cyclodextrin (β-CD)-modified hyaluronic acid (HACD). The obtained HACD@ADA-PA/MIL-101_NH₂ (Fe)-P nanoparticle was nano-sized and highly stable in physiological fluids. The porous structure of HACD@ADA-PA/MIL-101_NH₂ (Fe)-P nanoparticle could effectively load the commercial chemotherapeutic drug doxorubicin (DOX) with an encapsulation rate of 41.20 % and a loading rate of 48.84 %. The obtained drug-loaded HACD@ADA-PA/MIL-101_NH₂ (Fe)-P@DOX nanoparticle was pH-sensitive and relatively stable at neutral condition (pH 7.2) but could release DOX in a controlled way in subacid solution at pH 5.7. The simulated in vitro DOX release experiment signified that the HACD@ADA-PA/MIL-101_NH₂ (Fe)-P@DOX nanoparticle could realize the controlled release of DOX in tumor issues.     

Encapsulation of Microperoxidase-8 into MIL-101(Cr/Fe) Nanoparticles: A New Biocatalyst for the Epoxidation of Styrene

A new biocatalyst MP8@MIL-101(Cr/Fe) was prepared by immobilization of a heme octapeptide, Microperoxidase 8 (MP8) within a mixed metal MOF, MIL-101(Cr/Fe). Both MIL-101(Cr/Fe) and MP8@MIL-101(Cr/Fe) were characterized by PXRD, FTIR spectroscopy and TGA. The catalytic activity of MP8@MIL-101(Cr/Fe) for the oxidation of styrene by H₂O₂ and tBuOOH was then examined under various reaction conditions (nature of the co-solvent and of the oxidant, concentration of the oxidant and of the substrate, time, pH) and compared to that of MP8 alone. Under the best conditions used, MP8@MIL-101(Cr/Fe) was then shown to catalyze the oxidation of styrene about 3 times more efficiently than MP8 alone with approximately 50 % selectivity for styrene oxide.     

Photocatalytic Aerobic Oxidation of Biomass-Derived 5-HMF to DFF over MIL-53(Fe)/g-C3N4 Composite

A MIL-53(Fe)/g-C₃N₄ heterogeneous composite was synthesized and applied in photocatalytic oxidation of 5-hydroxymethylfurfural (5-HMF) to 2,5-diformylfuran (DFF). The systematic investigation indicated that the introduction of MIL-53(Fe) into g-C₃N₄ increased the specific surface area, broadened the visible-light response region, and promoted the separation efficiency of the photo-generated electron-hole pairs. The 10% MIL-53(Fe)/g-C₃N₄ heterogeneous composite achieved the best photocatalytic oxidation activity with 74.5% of 5-HMF conversion under simulated sunlight, which was much higher than that of pristine g-C₃N₄ and MIL-53(Fe). The MIL-53(Fe)/g-C₃N₄ composite displayed good photocatalytic reusability and stability. Based on the characterization results and photocatalytic performance, a Z-scheme photocatalytic mechanism of the MIL-53(Fe)/g-C₃N₄ composite was suggested, and a possible reaction route was deduced.     

Matrix isolation chemistry in a porous metal-organic framework: photochemical substitutions of N2 and H2 in Zn4O[(eta6-1,4-benzenedicarboxylate)Cr(CO)3]3

Reaction of the microporous metal-organic framework Zn4O(BDC)3 (BDC2- = 1,4-benzenedicarboxylate) with Cr(CO)6 at 140 degrees C in a 6:1 mixture of dibutylether and THF affords Zn4O[(BDC)Cr(CO)3]3 (1). This compound retains the porous cubic structure of the parent framework, but features Cr(CO)3 groups attached in an eta6 fashion to all of the benzene rings. Compound 1 is also microporous, exhibiting a BET surface area of 2130 m2/g. It can be fully decarbonylated by heating at 200 degrees C, but the resulting gray solid (2) shows little affinity for N2 or H2 at 298 K, suggesting aggregation of the chromium atoms. In contrast, photolysis of 1 using 450-nm light in an atmosphere of N2 or H2 produces solids with infrared spectra indicative of Zn4O[(BDC)Cr(CO)2(N2)]3 (3) and Zn4O[(BDC)Cr(CO)2(H2)]3 (4). Under an N2 atmosphere, compound 4 completely converts into compound 3 over the course of 12 h, demonstrating the lability of the Cr0-H2 bond. Owing to isolation of the metal centers within the rigid, evacuable framework structures, the N2- and H2-substituted compounds show greatly enhanced stability relative to molecular analogues generated in frozen gas matrices or supercritical fluid solutions.     

Simultaneous efficient adsorption and photocatalytic degradation of methylene blue over iron(III)-based metal–organic frameworks: a comparative study

Transition Metal Chemistry - Here, we prepared a series of Fe-based metal organic frameworks (MOFs), including MIL-53(Fe), NH2-MIL-53(Fe), MIL-88B(Fe) and NH2-MIL-88B(Fe), via an oil bath process...     

The effects of electronic polarization on water adsorption in metal-organic frameworks: H(2)O in MIL-53(Cr)

The effects of electronic polarization on the adsorption of water in the MIL-53(Cr) metal-organic framework are investigated using molecular dynamics simulations. For this purpose a fully polarizable force field for MIL-53(Cr) was developed which is compatible with the ab initio-based TTM3-F water model. The analysis of the spatial distributions of the water molecules within the MIL-53(Cr) nanopores calculated as a function of loading indicates that polarization effects play an important role in the formation of hydrogen bonds between the water molecules and the hydroxyl groups of the framework. As a result, large qualitative differences are found between the radial distribution functions calculated with non-polarizable and polarizable force fields. The present analysis suggests that polarization effects can significantly impact molecular adsorption in metal-organic frameworks under hydrated conditions.     

Metal organic framework–organic polymer monolith stationary phases for capillary electrochromatography and nano-liquid chromatography

In this study, metal organic framework (MOF)–organic polymer monoliths prepared via a 5-min microwave-assisted polymerization of ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) with the addition of various weight percentages (30–60%) of porous MOF (MIL-101(Cr)) were developed as stationary phases for capillary electrochromatography (CEC) and nano-liquid chromatography (nano-LC). Powder X-ray diffraction (PXRD) patterns and nitrogen adsorption/desorption isotherms of these MOF–organic polymer monoliths showed the presence of the inherent characteristic peaks and the nano-sized pores of MIL-101(Cr), which confirmed an unaltered crystalline MIL-101(Cr) skeleton after synthesis; while energy dispersive spectrometer (EDS) and micro-FT-IR spectra suggested homogenous distribution of MIL-101(Cr) in the MIL-101(Cr)–poly(BMA–EDMA) monoliths. This hybrid MOF–polymer column demonstrated high permeability, with almost 800-fold increase compared to MOF packed column, and efficient separation of various analytes (xylene, chlorotoluene, cymene, aromatic acids, polycyclic aromatic hydrocarbons and trypsin digested BSA peptides) either in CEC or nano-LC. This work demonstrated high potentials for MOF–organic polymer monolith as stationary phase in miniaturized chromatography for the first time.     

Influence of Pore Structure and Metal-Node Geometry on the Polymerization of Ethylene over Cr-Based Metal–Organic Frameworks

Metal–organic frameworks (MOFs) have received increasing interest as solid single-site catalysts, owing to their tunable pore architecture and metal node geometry. The ability to exploit these modulators makes them prominent candidates for producing polyethylene (PE) materials with narrow dispersity index (Ð) values. Here a study is presented in which the ethylene polymerization properties, with Et₂AlCl as activator, of three renowned Cr-based MOFs, MIL-101(Cr)-NDC (NDC=2,6-dicarboxynapthalene), MIL-53(Cr) and HKUST-1(Cr), are systematically investigated. Ethylene polymerization reactions revealed varying catalytic activities, with MIL-101(Cr)-NDC and MIL-53(Cr) being significantly more active than HKUST-1(Cr). Analysis of the PE products revealed large Ð values, demonstrating that polymerization occurs over a multitude of active Cr centers rather than a singular type of Cr site. Spectroscopic experiments, in the form of powder X-ray diffraction (pXRD), UV/Vis-NIR diffuse reflectance spectroscopy (DRS) and CO probe molecule Fourier transform infrared (FTIR) spectroscopy corroborated these findings, indicating that indeed for each MOF unique active sites are generated, however without alteration of the original oxidation state. Furthermore, the pXRD experiments indicated that one major prerequisite for catalytic activity was the degree of MOF activation by the Et₂AlCl co-catalyst, with the more active materials portraying a larger degree of activation.     

Metal-organic framework MIL-53(Al): synthesis,catalytic performance for the Friedel-Crafts acylation,and reaction mechanism

Metal-organic framework MIL-53(Al) was synthesized by a solvothermal method using aluminum nitrate as the aluminium source and 1,4-benzenedicarboxylic acid (H₂BDC) as the organic ligand. The structure of samples was characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). The catalytic activity and recyclability of MIL-53(Al) catalyst for the Friedel-Crafts acylation reaction of indole with benzoyl chloride were evaluated. The reaction conditions were optimized and a reaction mechanism was suggested. The results showed that the MIL-53(Al) catalyst exhibited good catalytic activity and recyclability for the Friedel-Crafts acylation reaction. When the molar ratio of indole and MIL-53(Al) catalyst was 1:0.06 (n ₁:n _catalyst), the molar ratio of indole and benzoyl chloride was 1:3, and the solvent was dichloromethane, the conversion of indole could reach 97.1% and the selectivity of 3-acylindole could reach 81.1% at 25 °C after 8 h. The catalyst can be reused without significant degradation in catalytic activity. After the catalyst was reused five times, the conversion of indole was 87.6% and the selectivity of 3-acylindole was 79.5%.     

Evidence of CO(2) molecule acting as an electron acceptor on a nanoporous metal-organic-framework MIL-53 or Cr(3+)(OH)(O(2)C-C(6)H(4)-CO(2))

The adsorption mode of CO(2) at low coverage in the nanoporous metal benzenedicarboxylate MIL-53(Cr) or Cr(3+)(OH)(O(2)C-C(6)H(4)-CO(2)) has been identified using IR spectroscopy; the red shift of the nu(3) band and the splitting of the nu(2) mode of CO(2) in addition to the shifts of the nu(OH) and delta(OH) bands of the MIL-53(Cr) hydroxyl groups provide evidence that CO(2) interacts with the oxygen atoms of framework OH groups as an electron-acceptor via its carbon atom; this is the first example of such an interaction between CO(2) and bridged OH groups in a solid.     

Remarkable adsorptive performance of a metal-organic framework, vanadium-benzenedicarboxylate (MIL-47), for benzothiophene

Liquid-phase adsorption of benzothiophene over isotypic MOFs such as MIL-47 and MIL-53(Al, Cr) has shown that a metal ion of a MOF-type material has a dominant role in adsorptive desulfurization and MIL-47 has a remarkable performance.     

High-throughput assisted rationalization of the formation of metal organic frameworks in the Iron(III) aminoterephthalate solvothermal system

Through the use of high-throughput methods, solvothermal reactions of FeCl 3 and 2-aminoterephthalic acid in protic as well as aprotic reaction media were systematically studied. Thus, the fields of formation of the isoreticular structures of MIL-53, MIL-88, and MIL-101 based on Fe(III) and aminoterephthalate could be identified for the first time. The resulting 3D framework materials with amino-functionalized pores have been characterized using X-ray diffraction; IR spectroscopy; and thermogravimetric, elemental, and energy dispersive X-ray analysis. Due to the applied high-throughput method, a high density of information was obtained in a short period of time, which allows the extraction of important reaction trends and contributes to a better understanding of the role of compositional as well as process parameters in the synthesis of inorganic-organic hybrid materials. We have found that the nature of the reaction medium has the most profound impact on structure formation. Furthermore, the concentration of the starting mixture (i.e., the solvent content) and the temperature have also been identified as key parameters for the formation of the different hybrid phases.