Solvothermal Conditions Research Articles

Preparation of Zr-MOF for the removal of norfloxacin from an aqueous solution

Zr-MOF was prepared under solvothermal conditions using zirconium acetate as the metal ion and 2,5-dihydroxyterephthalic acid as the organic ligand. It was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and thermogravimetry (TG). Zr-MOF was used as an adsorbent to remove norfloxacin from aqueous solutions. The experimental results were fitted, and the results showed that the pseudo-second-order kinetics model was appropriate for studying the removal of norfloxacin. We investigated the adsorption capacity of Zr-MOF under different masses, concentrations, and pH values. At pH 10, the maximum adsorption capacity after 5 h was 134.5 mg/g.Compared with another adsorbent,the adsorption capacity of Zr-MOF was higher.The removal of norfloxacin from an aqueous solution using Zr-MOF was feasible, inexpensive, and effective. Our findings indicate that Zr-MOF has broad application prospects for the purification of an aqueous solution.

Sensitive detection of chloramphenicol and efficient adsorbent for conge red of lanthanide complexes based on lactam carboxylic acid ligands

Two lanthanide metal complexes [M(H4L)Cl(OH) (H2O)2]n [M = La (1), Ce (2)] were constructed via lactam carboxylic acid ligand (2-(5-amino-2,5-dihydro-1H-imidazole-4-yl)-4-oxo-3,4-dihydroquinazoline-7-carboxylic acid) (H5L) under solvothermal condition. Complexes 1 and 2 could sensitively, selectively and repeatedly detect chloramphenicol (CAP) through the fluorescence quenching effect with a quenching constant (Ksv) of 1.87 × 103 and 1.52 × 104 Μ−1, respectively, and the detection limit (LOD) were 1.23 × 10−6 and 2.03 × 10−7 M, respectively. Density functional theory (DFT) calculations indicate that the LUMO energy level of the CAP quenched was lower than that of the ligand, so the photoelectron energy transfer (PET) between complexes and CAP leads to fluorescence quenching. Moreover, 1 and 2 exhibited excellent adsorption performance to Congo red (CR) and adsorption capacity were 3448.3 mg g−1 and 1886.5 mg g−1, respectively. Adsorption kinetics experiments showed that this kind of adsorption belonged to chemisorption, the hydrogen bonding and π-π interactions between the complex host and CR guest molecules resulted in high adsorption capacity.

Highly sensitive fluorescence detection of nitrofurazone and nitrofurantoin in milk and honey using a hydrostable Cd(Ⅱ) metal-organic framework

A new and water-stable Cd (II) metal-organic framework, namely [Cd(mba)(bpdb)0.5] (MOF 1), was successfully designed and synthesized by a mixed ligand of H2mba and bpdb under solvothermal condition (bpdb = 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene, H2mba = 4-(carboxymethyl)benzoic acid). Single crystal X-ray structural analysis suggests that MOF 1 crystallized in the monoclinic system with the P21/c space group and exhibits a 3D framework based on the infinite [CdO5N] chain. Fluorescence sensing experiments show that MOF 1 can be used as a fluorescence sensor to selectively, sensitively and quickly detect Nitrofurazone (NFZ) and Nitrofurantoin (NFT) antibiotics with very low detection limits of 0.116 μM and 0.123 μM, respectively. More importantly, MOF 1 was able to detect the NFT and NFZ antibiotics in milk and honey samples with good recovery rates. Additionally, the possible fluorescent quenching reasons for NFZ and NFT antibiotics were mainly caused by the fluorescence resonance energy transfer (FRET) and photoelectron electron transfer (PET) mechanism.

In-situ confinement of ultra-small NaYF4:Yb3+/Er3+ UCNPs as multifunctional ratiometric thermometer and optical heater

Lanthanide-doped upconversion (UC) nanomaterials with zero background auto-fluorescence are of extensive interest in optical fields. Here, a NaYF4:Yb3+/Er3+@Zr-UiO-66 nanostructure was prepared by simultaneously encapsulating NaYF4:Yb3+/Er3+ nanoparticles (NPs) and promoting the nucleation of UiO-66 under solvothermal condition. Traditional nanosize-surface induced defects and grain boundaries of NaYF4:Yb3+/Er3+ upconversion nanoparticles (UCNPs) were greatly minimized; enabling a highly efficient energy transfer confirmed by the prolonged fluorescence lifetime and enhanced UC emission of NaYF4:Yb3+/Er3+@Zr-UiO-66 nanocomposite. The optical thermometry property of nanocomposite was investigated based on the fluorescence intensity ratio (FIR) technique in the temperature range of 303–393 K. The maximum relative temperature sensitivities (Sr) were calculated to be 1.02 and 0.73% K−1 based on a pair of thermally coupled energy levels (TCLs) of (2H11/2 → 4I15/2, 4S3/2 → 4I15/2) and another pair of non-thermally coupled energy levels (NTCLs) of (2H11/2 → 4I15/2, 4F9/2 → 4I15/2), respectively. Besides, it exhibited effective internal optical heating property due to the thermal excitation between the two adjacent TCLs of 2H11/2 and 4S3/2 in NaYF4:Yb3+/Er3+ UCNPs as heated by increasing the laser power. This work demonstrates a feasible confined synthesis of NaYF4:Yb3+/Er3+@Zr-UiO-66 nanocomposite with extreme UC emitting performance, and it holds great potential acting as both ratiometric thermometer and optical heater for multifunctional applications.

Acidity of Carboxylic Acid Ligands Influences the Formation of VO2(A) and VO2(B) Nanocrystals under Solvothermal Conditions.

Vanadium dioxide (VO2) can adopt many different crystal structures at ambient temperature and pressure, each with different, and often desirable, electronic, optical, and chemical properties. Understanding how to control which crystal phase forms under various reaction conditions is therefore crucial to developing VO2 for various applications. This paper describes the impact of ligand acidity on the formation of VO2 nanocrystals from the solvothermal reaction of vanadyl acetylacetonate (VO(acac)2) with stoichiometric amounts of water. Carboxylic acids examined herein favor the formation of the monoclinic VO2(B) phase over the tetragonal VO2(A) phase as the concentration of water in the reaction increases. However, the threshold concentration of water required to obtain phase-pure VO2(B) nanocrystals increases as the pKa of the carboxylic acid decreases. We also observe that increasing the concentration of VO(acac)2 or the concentration of acid while keeping the concentration of water constant favors the formation of VO2(A). Single-crystal electron diffraction measurements enable the identification of vanadyl carboxylate species formed in reactions that do not contain enough water to promote the formation of VO2. Increasing the length of the carbon chain on aliphatic carboxylic acids did not impact the phase of VO2 nanocrystals obtained but did result in a change from nanorod to nanoplatelet morphology. These results suggest that inhibiting the rate of hydrolysis of the VO(acac)2 precursor either by decreasing the ratio of water to VO(acac)2 or by increasing the fraction of water molecules that are protonated favors the formation of VO2(A) over VO2(B).

Exceptionally high charge mobility in phthalocyanine-based poly(benzimidazobenzophenanthroline)-ladder-type two-dimensional conjugated polymers

Two-dimensional conjugated polymers (2DCPs), composed of multiple strands of linear conjugated polymers with extended in-plane π-conjugation, are emerging crystalline semiconducting polymers for organic (opto)electronics. They are represented by two-dimensional π-conjugated covalent organic frameworks, which typically suffer from poor π-conjugation and thus low charge carrier mobilities. Here we overcome this limitation by demonstrating two semiconducting phthalocyanine-based poly(benzimidazobenzophenanthroline)-ladder-type 2DCPs (2DCP-MPc, with M = Cu or Ni), which are constructed from octaaminophthalocyaninato metal(ii) and naphthalenetetracarboxylic dianhydride by polycondensation under solvothermal conditions. The 2DCP-MPcs exhibit optical bandgaps of ~1.3 eV with highly delocalized π-electrons. Density functional theory calculations unveil strongly dispersive energy bands with small electron–hole reduced effective masses of ~0.15m0 for the layer-stacked 2DCP-MPcs. Terahertz spectroscopy reveals the band transport of Drude-type free carriers in 2DCP-MPcs with exceptionally high sum mobility of electrons and holes of ~970 cm2 V−1 s−1 at room temperature, surpassing that of the reported linear conjugated polymers and 2DCPs. This work highlights the critical role of effective conjugation in enhancing the charge transport properties of 2DCPs and the great potential of high-mobility 2DCPs for future (opto)electronics.

Structural transformation and magnetic properties of Co(II) coordination polymers with pyrazole-3,5-dicarboxylate and pyrazine

A two-dimensional (2D) Co(II) coordination polymer with rectangular channel, namely {[Co2(Hpzdc)2(pyz)(CH3OH)(H2O)2]⋅3H2O}n (1) was synthesized under the solvothermal condition (Hpzdc = pyrazole-3,5-dicarboxylate and pyz = pyrazine). Both Co(II) centers exhibit octahedral geometry. The coordinated methanol and all water molecules in 1 can be removed by heating to give rise to the amorphous phase of desolvated 1 (1a). After 1a was immersed in the mixture of water and methanol, a new isostructural {[Co2(Hpzdc)2(pyz)(H2O)3]⋅3H2O}n (2) was obtained. The replacement of water for methanol in 1 leads to an alteration in the intermolecular packing, which gives rise to the color variations. The single-crystal to amorphous to single-crystal transformations accompanied by the color changes were confirmed by single crystal X-ray structure analysis, XRPD, TGA, elemental analysis, and spectroscopic techniques. The magnetic properties of 1 and 2 exhibit the antiferromagnetic interaction and spin–orbit coupling of octahedral high-spin Co(II) ion.

Controllable synthesis of blue-emitting CsPbBr3 nanoplates via a SnBr2-mediated solvothermal reaction method

Blue-emitting CsPbX3 (X = Cl, Br, I) nanocrystals (NCs) have potential applications in white light illumination and full-color luminescent displays. However, current methods for synthesizing blue-emitting CsPbX3 NCs face challenges in poor controllability, low photoluminescence quantum yields (PLQYs), and the harmful effects of short-wavelength blue light. In this work, we report on a SnBr2-mediated solvothermal method for the controllable synthesis of blue-emitting CsPbBr3 nanoplates (NPLs) that exhibit high optical purity within the harmless blue light range. The pioneering use of SnBr2 as a mediator in solvothermal reactions plays a crucial role in the controllable synthesis process. By increasing the amount of SnBr2, the as-prepared products gradually transform from CsPbBr3 NCs to mixed CsPbBr3/Cs4PbBr6 NCs, and finally to CsPbBr3 NPLs. By further adjusting the solvothermal reaction conditions, CsPbBr3 NPLs with controlled thickness (2.34–3.53 nm), regulated blue-light emission (459.4–466.6 nm) and a high PLQY up to 63.17% can be obtained. This study provides a feasible method for the controllable synthesis of perovskite NPLs and opens up new possibilities for the application of perovskite blue light-emitting devices.

Functionalized Metal-organic Frameworks for White Light Emission and Highly Sensitive Sensing of PA and Fe3+/Al3+①

Three isomorphic Ln-MOFs [Ln(bcbob)(H2O)(DMF)] (Ln = Tb for 1, Eu for 2, Gd for 3; DMF = N,N-dimethylformamide) have been constructed from a semi-rigid V-shaped organic linker 3,5-bis((4΄-carboxylbenzyl)oxy)benzoilate acid (H3bcbob) under solvothermal conditions. X-ray single-crystal diffraction analysis reveals that they exhibit a two-dimensional (2D) layered structure. Compounds 1~3 show the characteristic green and red emissions of Ln3+ and blue emission arising from the organic ligand, respectively. Based on their photoluminescence properties, the white-light emitting materials 4 and 5 with longer fluorescence lifetime (ms grade) and higher quantum yield (e.g. 40.61% for 4) are fabricated. Remarkably, 1 exhibits good sensing ability on nitroaromatic compounds, especially for picric acid (PA). In addition, 1 is still a highly selective sensing material for Fe3+ and Al3+.

Stable Co(II)-based coordination polymer as fluorescence sensor for the discriminative sensing of biomarker methylmalonic acid

Three novel Co-based coordination polymers including {[Co(L)(μ3-O)1/3]2}n (1), {[Co(L)(bimb)]}n (2) and {[Co(L)(bimmb)1/2]}n (3) (H2L = 2,6-di(4-carboxylphenyl)-4-(4-(triazol-1-ylphenyl))pyridine), bimb = 1,4-bis(lmidazol) butane, bimmb = 1,4-bis(imidazole-1-ylmethyl)benzene) were successfully prepared under solvothermal conditions and characterized. Single-crystal X-ray diffraction analyses revealed that 1 possesses a 3D architecture composed of a trinuclear cluster [Co3N3(CO2)6(μ3-O)], 2 exhibits a 2D new topological framework with the point symbol (84·122)(8)2, whereas 3 shows a unique six-fold interpenetrated 3D framework with a (63·82·10)2(63)2(8) topology. Impressively, all of them can function as a highly selective and sensitive fluorescent sensor for the biomarker methylmalonic acid (MMA) via fluorescence quenching. The low detection limit, reusability and high anti-interference performance together make 1–3 become promising sensors for the practical detection of MMA. Furthermore, the successful application of MMA detection in urine sample was demonstrated, which may be a potential candidate for the further development of clinical diagnostic tools.

High-Concentration Self-Assembly of Zirconium- and Hafnium-Based Metal-Organic Materials.

Metal-organic frameworks (MOFs) are crystalline, porous solids constructed from organic linkers and inorganic nodes that are promising for applications in chemical separations, gas storage, and catalysis, among many others. However, a major roadblock to the widespread implementation of MOFs, including highly tunable and hydrolytically stable Zr- and Hf-based frameworks, is their benchtop-scalable synthesis, as MOFs are typically prepared under highly dilute (≤0.01 M) solvothermal conditions. This necessitates the use of liters of organic solvent to prepare only a few grams of MOF. Herein, we demonstrate that Zr- and Hf-based frameworks (eight examples) can self-assemble at much higher reaction concentrations than are typically utilized, up to 1.00 M in many cases. Combining stoichiometric amounts of Zr or Hf precursors with organic linkers at high concentrations yields highly crystalline and porous MOFs, as confirmed by powder X-ray diffraction (PXRD) and 77 K N2 surface area measurements. Furthermore, the use of well-defined pivalate-capped cluster precursors avoids the formation of ordered defects and impurities that arise from standard metal chloride salts. These clusters also introduce pivalate defects that increase the exterior hydrophobicity of several MOFs, as confirmed by water contact angle measurements. Overall, our findings challenge the standard assumption that MOFs must be prepared under highly dilute solvothermal conditions for optimal results, paving the way for their scalable and user-friendly synthesis in the laboratory.

Coordination Assembly of Tetrahedral Ti4(embonate)6 Cages with Alkaline-Earth Metal Ions

Recently, the tetrahedral Ti4L6 cage (L = embonate) has been applied as the starting material to realize coordination assembly with transition and rare-earth ornoble metal ions through a two-step reaction. In this work, by employing the Ti4L6 cages to assemble with alkaline-earth metal ions (such as Mg2+, Ca2+ and Ba2+) under different solvothermal conditions, a series of Ti4L6-based structures from simple cages to 1D chain, 2D layer and 3D framework have been synthesized and structurally characterized. In addition, thermal stability, phase purity, UV-vis absorption spectrum, the fluorescent and third-order nonlinear-optical properties are also investigated.

Construction of a Novel TiO2‐Covalent‐Organic‐Framework Heterojunction for Highly Selective Photo‐Oxidation Coupling of Amines under Visible Light Irradiation

AbstractA novel heterojunction material constructed with titanium dioxide nanoparticles and covalent organic frameworks, TiO2@COF‐5 NPs, was designed and synthesized successfully from HHTP, PBBA and TiO2 under solvothermal conditions. Notably, the TiO2@COF‐5 heterojunction demonstrated excellent photocatalytic performance for the aerobic oxidative coupling reaction of benzylamines to N‐benzyl‐1‐phenyl methanimines under visible light irradiation, and both high conversions (up to 99 %) and high selectivity (99 %) were achieved for various benzylamines. The ameliorated photocatalytic performance might owe much to establishing the systematic coupling between the TiO2 nanoparticles and covalent organic frameworks, which could effectively extend the wavelength range of visible light absorption and increase more reactive active sites. This study might provide a versatile approach to combining covalent organic frameworks with inorganic semiconductors to give full play to the synergistic effect of catalysis.

A new pyrazine carboxyl derivative and its two d10 metal coordination polymers: Syntheses, characterization, DFT and property

A new pyridazine carboxyl derivative, 1-(3-carboxyphenyl)-5-methyl-4-oxo-1,4-dihydropyrida zine-3-carboxylic acid (C13H10N2O5, Mr = 274.06, abbreviate as H2(3-PDCA)) has been synthesized by ethyl 3-aminobenzoate, its structure was determined by 1H NMR, 13C NMR, FT-IR and X-ray single crystal analysis. According to density functional theory, the reaction sites of title molecule were visualized in molecular electrostatic potential maps plot. Meanwhile, two d10 metal coordination polymers had been constructed by title molecule under solvothermal conditions: [Cd(H2O)(3-PDCA)·2H2O]n (SNUT-10) and {[Zn3(H2O)10(3-PDCA)2][Zn(H2O)2(3-PDCA)2]·8H2O}n (SNUT-11). Single crystal X-ray analysis demonstrates that SNUT-10 features a 2D structure with ligands and metal atoms alternated. SNUT-11 exhibits an 2D unusual double layer architecture. In addition, the fluorescence properties of coordination polymers in the solid state were also investigated at room temperature.

Zn(II)-Based Mixed-Ligand-Bearing Coordination Polymers as Multi-Responsive Fluorescent Sensors for Detecting Dichromate, Iodide, Nitenpyram, and Imidacloprid.

Coordination polymers (CPs) are organo-inorganic porous materials consisting of metal ions or clusters and organic linkers. These compounds have attracted attention for use in the fluorescence detection of pollutants. Here, two Zn-based mixed-ligand-bearing CPs, [Zn2(DIN)2(HBTC2-)2] (CP-1) and [Zn(DIN)(HBTC2-)]·ACN·H2O (CP-2) (DIN = 1,4-di(imidazole-1-yl)naphthalene, H3BTC = 1,3,5-benzenetricarboxylic acid, and ACN = acetonitrile), were synthesized under solvothermal conditions. CP-1 and CP-2 were characterized by single-crystal X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, and powder X-ray diffraction analysis. Solid-state fluorescence analysis revealed an emission peak at 350 nm upon excitation at 225 and 290 nm. Fluorescence sensing tests showed that CP-1 was highly efficient, sensitive, and selective for detecting Cr2O72- at 225 and 290 nm, whereas I- was only detected well at an excitation of 225 nm. CP-1 detected pesticides differently at excitation wavelengths of 225 and 290 nm; the highest quenching rates were for nitenpyram at 225 nm and imidacloprid at 290 nm. The quenching process may occur via the inner filter effect and fluorescence resonance energy transfer.

Tracking the Process of Domino Ring‐Opening and Coupling of Fused Imidazole and Direct Observation of Peroxide Intermediates

Comprehensive SummaryA domino ring‐opening and coupling of imidazolyl annulated heterocycles 1 (1a: 4‐methyl‐1‐(1‐methyl‐1H‐benzo[d]imidazol‐2‐yl)‐4H‐ benzo[d]imidazo[1,5‐a]imidazole, 1b: 1‐(1,5‐dimethyl‐1H‐benzo[d]imidazol‐2‐yl)‐4,7‐dimethyl‐4H‐benzo[d]imidazo[1,5‐a]imidazole) with dioxygen was developed at solvothermal condition, leading to conjugated 1,2‐diamidoalkenes derivatives 2 ((E)‐ArCONHArC=CArNHCOAr (Ar: 1‐methyl‐1H‐benzo[d]imidazolyl (2a), 1,5‐dimethyl‐1H‐benzo[d]imidazolyl (2b))) as single crystals directly. The reaction process was tracked by electrospray ionization mass spectrometry (ESI‐HRMS) and a series of reaction intermediates are detected. 18O2 labeling experiment verified the source of oxygen in 2. Combining evidence from control experiments, nuclear magnetic resonance (NMR) tracking, and crystallography, a seven‐step reaction pathway involving oxygen addition, ring opening, Friedel‐Crafts alkylation, oxidation, and dehydration was proposed and further supported by DFT calculation.

Efficient detection of metronidazole by a glassy carbon electrode modified with a composite of a cyclotriveratrylene-based metal–organic framework and multi-walled carbon nanotubes

Constructing a sensitive and efficient sensor for determination of metronidazole (MNZ) is crucial in food field. Herein, a new cyclotriveratrylene-based metal–organic framework (MOF), namely, [Cd6L2(cyclen)2(H2O)2] (1), was constructed by self-assembly of functionalized 5,6,12,13,19,20-hexacarboxy-propoxy-cyclotriveratrylene (H6L), 1,4,7,10-tetraazacyclododecane (cyclen) and Cd(II) cation under solvothermal condition. In 1, adjacent Cd(II) cations are linked by L6− to produce a 2D polymeric structure with carboxylate and phenolic oxygen atoms. To enhance conductivity of 1, it was combined with conducting carbon materials, including mesoporous carbon (MC), reduced graphene oxide (RGO) and multi-walled carbon nanotubes (MWCNT), respectively, producing a series of composite materials. Remarkably, electrochemical tests showed that 1@MWCNT(1:1) featured a much better electrochemical detection performance for metronidazole (MNZ) than 1@MC and 1@RGO. The linear range for the detection of MNZ is up to 0.4–500 μM and the limit of detection (LOD) for MNZ reached 0.25 μM. Importantly, the fabricated sensor 1@MWCNT(1:1) was employed for the detection of MNZ in honey and egg with satisfactory result. High-performance liquid chromatography (HPLC) validated the high accuracy of the electrochemical method for the determination of honey and egg.

Metal organic frameworks based on mixed ligands: Syntheses, structures and selective detection of nitro explosive TNP, metal ions Fe3+ Cu2+ and CrO42-

Three new MOFs [Cd(2,5-bipi)(5-hip)]n (1), [Mn(2,5-bipi)(1,3-bdc)]n (2), and [Co(2,5-bipi)(1,3-bdc)(DMF)]n (3) (2,5-bipi = 2,5-bis(1-imidazoly)pyridine, 5-H2hip = 5-hydroxyisophthalic acid, 1,3-H2bdc = isophthalic acid) have been successfully synthesized under solvothermal conditions. They were characterized by elemental analysis, FT-IR spectra, X-ray single-crystal diffraction, powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA). The results suggest that the linkage of different ligands with metal ions affords a 4-connected layer. And these 2D networks are extended to the final 3D supramolecular architectures by CH∙∙∙π stacking interactions. Fluorescence sensing measurements showed that MOF 1 can detect TNP, Fe3+, Cu2+ and CrO42− ions with high selectivity and sensitivity. In addition, their possible quenching mechanisms were studied in detail.

Syntheses, crystal structure and properties of two chalcogenidoantimonates Mn(en)3Sb2S4 and Co(en)3Sb2Se4

Two chalcogenidoantimonates Mn(en)3Sb2S4 (1) and Co(en)3Sb2Se4 (2) have been synthesized in solvothermal conditions. 1 and 2 are consist of transition metal complex cations and [Sb2Q4]2- (Q = S, Se) anions. They have band gaps of 2.20 eV and 2.25 eV, respectively, indicating that they can be used as semiconductor materials. The photocurrent responses of 1 and 2 were also investigated. Photocatalytic experiments showed that both 1 and 2 could degrade methylene blue (MB) upon visible light irradiation, reaching 47 % for 1 and 30 % for 2, indicating that both compounds are good photocatalytic materials. Therefore, they present a promising potential for the photoelectric research chalcogenides.

Post-Synthetic Ligand Exchange by Mechanochemistry: Toward Green, Efficient, and Large-Scale Preparation of Functional Metal–Organic Frameworks

Green, facile, and large-scale preparation of functionalized metal–organic frameworks (MOFs) remains a challenge. Herein, we report a rapid synthesis of functionalized MOFs by the integration of post-synthetic ligand exchange (PSLE) and mechanochemistry. This mechano-PSLE approach can circumvent the hurdles of PSLE such as long reaction time, excessive solvent, and even failure of PSLE caused by redissolution and recrystallization under solvothermal conditions. More importantly, the gram-scale MOF functionalized with the chiral group can be obtained facilely and greenly. It exhibited excellent asymmetric catalytic performance (81% conversion and 92.1% ee) for α-alkylation of aldehydes irradiated by a xenon lamp, providing a basis for industrial batch production of functionalized MOFs.