Cu_2O@HKUST-1前驱物法合成CuO中空管状超级结构及其CO催化氧化性能

以Cu_2O@HKUST-1(HKUST-1=Cu_3(BTC)2,BTC~(3-)=均苯三甲酸离子)线状核@壳结构为前驱体,通过在碱性条件下原位水解HKUST-1壳、氧化刻蚀Cu_2O核的方法得到了一种新型的、由相互交错的CuO纳米片构筑的、中空管状的超级结构,并研究了其对CO氧化的催化活性。结果表明,这种中空的CuO管状超级结构具有较大的比表面积(56.3 m~2/g)和可观的催化活性,催化剂对CO的完全转化温度为200℃,190℃时转化效率为17.3 mmolCO/(gCuO·h)。     

Favorable hydrogen storage properties of M(HBTC)(4,4'-bipy).3DMF (M = Ni and Co)

Two metal-organic frameworks of M(HBTC)(4,4'-bipy).3DMF (M = Ni and Co; H 3BTC = 1,3,5-benzenetricarboxylic acid; 4,4'-bipy = 4,4'-bipyridine; DMF = N,N'-dimethylformamide) were synthesized by a one-pot solution reaction and a solvothermal method, respectively. The as-prepared samples have high specific surface areas of 1590 m (2)/g and 887 m (2)/g. The activation at different temperatures for the guest removal prior to gas loading obviously affects the gas sorption process. Ni(HBTC)(4,4'-bipy).3DMF shows high hydrogen storage capacities of 1.20 wt % at room temperature and 3.42 wt % at 77 K. Co(HBTC)(4,4'-bipy).3DMF shows capacities of 0.96 wt % at 298 K and 2.05 wt % at 77 K. The hydrogen adsorption heats in the two compounds decrease slightly as a function of the amount adsorbed, and it confirms that the H 2 molecules are combined with stronger sites preferentially. Research on the kinetics of hydrogen adsorption shows a fast saturation process (80 s) and no obvious capacity loss after 20 cycles.     

Statistically Optimum HKUST-1 Synthesized by Room Temperature Coordination Modulation Method for the Adsorption of Crystal Violet Dye

Due to its excellency and versatility, many synthesis methods and conditions were developed to produce HKUST-1 ([Cu₃(BTC)₂(H₂O)₃]_n). However, the diversity of HKUST-1 was actually generated both in terms of characteristics and morphologies. Hence, the consistency of HKUST-1 characteristics and morphologies needs to be maintained. The statistical analysis and optimization provide features to determine the best synthesis condition. Here, a room-temperature coordination modulation method was proposed to maintain the morphology of HKUST-1 while reducing energy consumption. In addition, response surface methodology (RSM) was used to demonstrate the statistical analysis and optimization of the synthesis of HKUST-1. The molar ratio of ligand to metal, reaction time, and acetic acid concentration were studied to determine their effects on HKUST-1. The optimum HKUST-1 was obtained by the synthesis with a molar ratio of ligand to metal of 0.4703 for 27.2 h using 5% v/v acetic acid concentration. The statistical analysis performed a good agreement with the experimental data and showed the significance of three desired parameters on HKUST-1. The optimum HKUST-1 had the adsorption capacity of 1005.22 mg/g with a removal efficiency of 92.31% towards CV dye. It could be reused up to 5 cycles with insignificant decrease in performance.     

Stability improvement of Cu3(BTC)2 metal-organic frameworks under steaming conditions by encapsulation of a Keggin polyoxometalate

Cu(3)(BTC)(2) with an incorporated Keggin polyoxometalate was demonstrated to be stable under steaming conditions up to 483 K, while the isostructural HKUST-1 degrades and transforms into [Cu(2)OH(BTC)(H(2)O)](n)·2nH(2)O from 343 K onwards.     

Co(Ⅱ)-Zn(Ⅱ)掺杂配位聚合物的 合成及物理性能

采用均苯三甲酸配体、 硝酸锌与硝酸钴反应, 一步合成了钴掺杂的锌配位聚合物Zn_1-xCo_x(BTC)·(OH)(H₂O)₃(NMP)(DMF)(H₂O)_1.5(H₃BTC为1,3,5-均苯三酸, NMP为1-甲基-2-吡咯烷酮, DMF为N,N'-二甲基甲酰胺, x=0~0.8). 该化合物结构经X射线单晶衍射确定, 属于立方晶系, 空间群P2₁3, 晶胞参数a=1.43863(20) nm. 利用元素分析、 能量散色光谱(EDS)、 UV-Vis光谱、 X射线粉末衍射(XRD)、 热重分析(TGA)、 氮气吸附和磁性分析等表征手段对样品的物理性质进行了表征. 氮气吸附实验结果表明, 该配位聚合物具有良好的微孔吸附特性, Langmiur比面积为832 m ²/g, 孔径为0.84 nm; 元素分析结果表明, 钴/锌摩尔比为1∶1时, 在37~300 K温度范围内其磁性表现为反铁磁性, 并满足Curie-Weiss定律.     

Metal-organic frameworks with exceptionally high capacity for storage of carbon dioxide at room temperature

Metal-organic frameworks (MOFs) show high CO2 storage capacity at room temperature. Gravimetric CO2 isotherms for MOF-2, MOF-505, Cu3(BTC)2, MOF-74, IRMOFs-11, -3, -6, and -1, and MOF-177 are reported up to 42 bar. Type I isotherms are found in all cases except for MOFs based on Zn4O(O2C)6 clusters, which reveal a sigmoidal isotherm (having a step). The various pressures of the isotherm steps correlate with increasing pore size, which indicates potential for gas separations. The amine functionality of the IRMOF-3 pore shows evidence of relatively increased affinity for CO2. Capacities qualitatively scale with surface area and range from 3.2 mmol/g for MOF-2 to 33.5 mmol/g (320 cm3(STP)/cm3, 147 wt %) for MOF-177, the highest CO2 capacity of any porous material reported.     

Alkali metal cation doping of metal-organic framework for enhancing carbon dioxide adsorption capacity

Metal-organic frameworks （MOFs） have attracted much attention as adsorbents for the separation of CO2 from flue gas or natural gas. Here, a typical metal-organic framework HKUST-I（also named Cu-BTC or MOF-199） was chemically reduced by doping it with alkali metals （Li, Na and K） and they were further used to investigate their CO2 adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction （XRD）, thermo-gravimetric analysis （TGA） and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO2 storage capacity of HKUST-1 doped with moderate quantities of Li＋, Na＋ and K＋, individually, was greater than that of unmodified HKUST-1. The highest CO2 adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11% increase in adsorption capacity at 298 K and 18 bar as compared with HKUST- 1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO2 than those of N2. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO2 after 10 cycles.     

金属有机骨架材料/聚酰亚胺混合基质膜的制备及气体分离性能

合成了3种不同结构、 粒径和气体吸附性能的金属有机骨架材料(MOFs): 微米级Cu₃(BTC)₂、 亚微米级ZIF-8和S-Cu₃(BTC)₂. 氮气吸附等温线分析结果表明, ZIF-8和Cu₃(BTC)₂具有较大比表面积(1653和1439 m²/g), S-Cu₃(BTC)₂的比表面积为171.4 m²/g. 用共混法将MOFs直接引入聚酰亚胺中制备了MOFs/聚酰亚胺混合基质膜(MMMs). X射线衍射(XRD)和全反射红外光谱(FTIR-ATR)分析结果表明, MOFs在混合基质膜中保持物理和化学稳定. 气体渗透测试结果表明, MOFs的加入使膜的气体渗透分离性能明显提高, S-Cu₃(BTC)₂使渗透系数增加了1.75倍; ZIF-8和Cu₃(BTC)₂使渗透系数增加了3倍左右; 同时, 膜的气体分离系数变化很小.     

The Role of Multiwall Carbon Nanotubes in Cu‐BTC Metal‐Organic Frameworks for CO2 Adsorption

The discovery of natural gas fields with a high content of CO₂ in world gas reservoirs poses new challenges for CO₂ capture. This work investigates the use of the metal‐organic framework (MOF) Cu‐BTC and hybrid MWCNTs@Cu‐BTC for CO₂ adsorption. Cu‐BTC and hybrid MWCNTs@Cu‐BTC were synthesized by the solvothermal method. The results of imaging of intact MOF pores in Cu‐BTC and hybrid MWCNTs@Cu‐BTC nanocrystals by high‐resolution transmission electron microscopy (HRTEM) under liquid nitrogen conditions are presented. Physical characterizations of the solid adsorbents were made by using a selection of different techniques, including field‐emission scanning electron microscopy (FESEM), X‐ray powder diffraction (XRD), Fourier transform infrared (FT‐IR) spectroscopy, thermogravimetric analysis (TGA), Brunauer–Emmet–Teller (BET) surface area, and CO₂ adsorption and physisorption measurements. HRTEM and FESEM confirmed that Cu‐BTC has an octahedral shape and that the surface morphology of Cu‐BTC changes by the intercalation of MWCTNs. The results show that the modified Cu‐BTC improved the CO₂ adsorption compared to pure Cu‐BTC. The increase in the CO₂ uptake capabilities of hybrid MWCNTs@Cu‐BTC was ascribed to the intercalation of MWCNTs with Cu‐BTC crystals. The CO₂ sorption capacities of Cu‐BTC and hybrid MWCNTs@Cu‐BTC were found to increase from 1.91701 to 3.25642 mmol/g at ambient conditions.     

Calcium-based coordination polymers from a solvothermal synthesis of HKUST-1 in 3D printed autoclaves

A mixed-metal 1D coordination polymer [CaCu(HBTC)₂(H2O)₈]_n (where H₃BTC – benzene-1,3,5-tric arboxylic acid) was obtained in a solvothermal synthesis of a well-known copper-containing metal–organic framework [Cu₃(BTC)₂(H₂O)₃]_n (HKUST-1) in autoclaves 3D-printed from commercial polypropylene. This material was a source of calcium ions, apparently, leaking from a colorant (calcium carbonate) promoted by glacial acetic acid as a modulator used to produce large single crystals of HKUST-1. This finding was confirmed by elemental analysis and a model experiment that resulted in a new calcium-based 1D coordination polymer [Ca(H₂BTC)₂(H₂O)₅]_n under the same solvothermal conditions with no copper or calcium salts put into a 3D-printed autoclave.     

Controlled Synthesis of Porous Coordination‐Polymer Microcrystals with Definite Morphologies and Sizes under Mild Conditions

Herein, we report a facile and convenient method for the synthesis of the porous coordination polymer MOF‐14 [Cu₃(BTB)₂] (H₃BTB=4,4′,4′′‐benzene‐1,3,5‐triyl‐tribenzoic acid) as microcrystals with definite shapes and crystal facets controlled by the reaction medium at room temperature. The amount of sodium acetate added to the reaction system plays a crucial role in the shape evolution of MOF‐14 from rhombic dodecahedrons to truncated rhombic dodecahedrons and cubes with truncated edges and then to cubes. The addition of a base could accelerate the formation rate of crystal growth and increase the supersaturation of crystal growth, thus resulting in the formation of MOF‐14 cube crystals with high‐energy crystal facets. The morphological evolution was also observed for HKUST‐1 [Cu₃(BTC)₂] (H₃BTC=1,3,5‐benzenetricarbocylic acid) from octahedrons to cubes, thus verifying the probable mechanism of the morphological transformation. The gas‐adsorption properties of MOF‐14 with different shapes were studied and reveal that the porous coordination‐polymer microcrystals display excellent and morphology‐dependent sorption properties.     

Cu2O@HKUST-1核壳结构材料的制备及其抗氧化性能

以球状纳米Cu_2O为核心,直接牺牲其表面的部分Cu_2O,与溶液中的均苯三羧酸(H_3BTC)配体反应,原位生成具有核壳结构的Cu_2O@HKUST-1材料。采用O_2程序升温脱附(O_2-TPD)、H_2程序升温还原(H2-TPR)及CO氧化反应对Cu_2O@HKUST-1核壳材料的抗氧化能力进行了研究,证明金属-有机框架材料(MOFs)HKUST-1对反应气体起到富集、缓释作用,保护Cu_2O核不被氧化,显著提高了其抗氧化能力。     

高被引文章

A Cu₃(BTC)₂ (copper(Ⅱ) benzene 1, 3, 5-tricarboxylate) metal organic framework (MOF) catalyst was successfully prepared through an electrochemical route and used for selective catalytic reduction of nitrogen oxide (NO_x) with NH₃ for the first time. After systematically optimizing the reaction conditions such as solvents, voltage, electrolyte concentration, and reaction time, pure Cu₃(BTC)₂ with high crystallinity was obtained in 97.2% yield. The physicochemical properties of the catalyst were determined using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Raman spectroscopy, in situ Fourier transform infrared (FTIR) spectroscopy, temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). TGA results indicated that the framework was stable up to 310℃. The catalytic activity of Cu₃(BTC)₂ was evaluated using NO conversion as a model reaction. The Cu₃(BTC)₂ activation temperature significantly affected the catalytic activity. The Cu₃(BTC)₂ sample activated at 240℃ had the best catalytic activity and gave NO conversion of 90% at 220-280℃. A reaction mechanism was proposed based on the in situ FTIR spectroscopy results.     

Investigation of the synthesis, activation, and isosteric heats of CO2 adsorption of the isostructural series of metal-organic frameworks M3(BTC)2 (M = Cr, Fe, Ni, Cu, Mo, Ru)

The synthesis, activation, and heats of CO(2) adsorption for the known members of the M(3)(BTC)(2) (HKUST-1) isostructural series (M = Cr, Fe, Ni, Zn, Ni, Cu, Mo) were investigated to gain insight into the impact of CO(2)-metal interactions for CO(2) storage/separation applications. With the use of modified syntheses and activation procedures, improved BET surface areas were obtained for M = Ni, Mo, and Ru. The zero-coverage isosteric heats of CO(2) adsorption were measured for the Cu, Cr, Ni, Mo, and Ru analogues and gave values consistent with those reported for MOFs containing coordinatively unsaturated metal sites, but lower than for amine functionalized materials. Notably, the Ni and Ru congeners exhibited the highest CO(2) affinities in the studied series. These behaviors were attributed to the presence of residual guest molecules in the case of Ni(3)(BTC)(2)(Me(2)NH)(2)(H(2)O) and the increased charge of the dimetal secondary building unit in [Ru(3)(BTC)(2)][BTC](0.5).     

Reconciling the discrepancies between crystallographic porosity and guest access as exemplified by Zn-HKUST-1

There are several compounds for which there exists a disconnect between porosity as predicted by crystallography and porosity measured by gas sorption analysis. In this paper, the Zn-based analogue of Cu(3)(btc)(2) (HKUST-1), Zn(3)(btc)(2) (Zn-HKUST-1; btc = 1,3,5-benzenetricarboxylate) is investigated. Conventional analysis of Zn-HKUST-1 by powder X-ray diffraction and gas sorption indicates retention of crystalline structure but negligible nitrogen uptake at 77 K. By using positron annihilation lifetime spectroscopy, a densified surface layer preventing the entry of even small molecular species into the crystal framework is revealed. The material is shown to have inherent surface instability after solvent removal, rendering it impermeable to molecular guests irrespective of handling and processing methods. This previously unobserved surface instability may provide insight into the failure of other microporous coordination polymers to exhibit significant porosity despite crystal structures indicative of regular, interconnected, microporous networks.     

Alkali metal cation doping of metal-organic framework for enhancing carbon dioxide adsorption capacity

Metal-organic frameworks (MOFs) have attracted much attention as adsorbents for the separation of CO₂ from flue gas or natural gas. Here, a typical metal-organic framework HKUST-1(also named Cu-BTC or MOF-199) was chemically reduced by doping it with alkali metals (Li, Na and K) and they were further used to investigate their CO₂ adsorption capacities. The structural information, surface chemistry and thermal behavior of the prepared adsorbent samples were characterized by X-ray powder diffraction (XRD), thermo-gravimetric analysis (TGA) and nitrogen adsorption-desorption isotherm analysis. The results showed that the CO₂ storage capacity of HKUST-1 doped with moderate quantities of Li⁺, Na⁺ and K⁺, individually, was greater than that of unmodified HKUST-1. The highest CO₂ adsorption uptake of 8.64 mmol/g was obtained with 1K-HKUST-1, and it was ca. 11% increase in adsorption capacity at 298 K and 18 bar as compared with HKUST-1. Moreover, adsorption tests showed that HKUST-1 and 1K-HKUST-1 displayed much higher adsorption capacities of CO₂ than those of N₂. Finally, the adsorption/desorption cycle experiment revealed that the adsorption performance of 1K-HKUST-1 was fairly stable, without obvious deterioration in the adsorption capacity of CO₂ after 10 cycles.     

A series of (6,6)-connected porous lanthanide−organic framework enantiomers with high thermostability and exposed metal sites: scalable syntheses, structures, and sorption properties

A series of microporous lanthanide-organic framework enantiomers, Ln(BTC)(H(2)O)·(DMF)(1.1) (Ln = Y 1a, 1b; Tb 2a, 2b; Dy 3a, 3b; Er 4a, 4b; Yb 5a, 5b, BTC = 1,3,5-benzenetricarboxylate; DMF = N,N-dimethylformamide) with unprecedented (6,6)-connected topology have been prepared and characterized. All these compounds exhibit very high thermal stability of over 450 °C. The pore characteristics and gas sorption properties of these compounds were investigated at cryogenic temperatures by experimentally measuring nitrogen, argon, and hydrogen adsorption/desorption isotherms. The studies show that all these compounds are highly porous with surface areas of 1080 (1), 786 (2), 757 (3), 676 (4), and 774 m(2)/g (5). The amounts of the hydrogen uptakes, 1.79 (1), 1.45 (2), 1.40 (3), 1.51 (4), and 1.41 wt % (5) at 77 K (1 atm), show their promising H(2) storage performances. These porous materials with considerable surface areas, high voids of 44.5% (1), 44.8% (2), 47.7% (3), 44.2% (4), and 45.7% (5), free windows of 6-7 ?, available exposed metal sites and very high thermal stability can be easily prepared on a large scale, which make them excellent candidates in many functional applications, such as, gas storage, catalysis, and so on.     

Isolation of hemoglobin with metal–organic frameworks Y(BTC)(H_2O)_6

The hierarchical metal-organic frameworks(MOFs),such as Y(BTC)(H_2O)_6,are prepared with yttrium nitrate and benzene-1,3,5-tricarboxylic acid at room temperature.The product is characterized by Fourier transform infrared(FT-IR),X-ray diffraction(XRD),scanning electron microscopy(SEM)and thermogravimetric analysis(TGA).The Y(BTC)(H_2O)_6 particles are sufficiently rigid for performing solid phase extraction and they exhibit favorable selectivity toward the adsorption of hemoglobin.The adsorption behavior of hemoglobin onto the Y(BTC)(H_2O)_6 fits the Langmuir adsorption model with a theoretical adsorption capacity of 555.6 mg g 1.An adsorption efficiency of 87.7%for 100μg mL 1hemoglobin in 1 mL sample solution(at pH 6.0)is achieved with 0.40 mg Y(BTC)(H20)6.77.3%of the retained hemoglobin is readily recovered using a 0.5%(m/v)SDS solution as the stripping reagent.Circular dichroism spectra indicated that the conformation of hemoglobin is maintained during the adsorption-desorption process.The MOFs material is applied for the isolation of hemoglobin from human blood and the purity of the obtained hemoglobin is further verified by sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE).     

Stable Isotope Dilution Analysis of Gibberellin Residues in Tomato Paste by Liquid Chromatography-Tandem Mass Spectrometry

An accurate and sensitive method for the simultaneous determination of gibberellic acid(GA₃), gibberellin A₄(GA₄) and gibberellin A₇(GA₇) residues in tomato paste was developed by coupling solid phase extraction to high performance liquid chromatography-tandem mass spectrometry(LC-MS/MS) with electrospray ionization based stable isotope dilution analysis(SIDA). The isotope labeled internal standard can compensate for the losses during the extraction and cleanup steps and for discrimination due to ion suppression. After extraction from methanol, hydrophile lipophilic balance(HLB) solid phase extraction(SPE) column was tested for the capacity of the cleanup of the tomato paste in compared with C₁₈ SPE column which is the common way to the detection of GAs, and the former gained better result. Spiked experiments were performed in the non-contaminated tomato pastes and the recoveries of GA₃, GA₄ and GA₇ were 42.6%―75.0% in external standard method(ESM) and 91.1%―103.8% in internal standard method(ISM) respectively. The validities of this method were investigated and good analytical performance for the three GAs was obtained, including low limits of method detection(2 ng/g for GA₃ and GA₄, 0.3 ng/g for GA₇), excellent linear dynamic ranges(5―500 ng/g for GA₃ and GA₄, 1―100 ng/g for GA₇) and good relative standard deviation ranges(4.8%―9.4% for the intra-day test and 3.5%―11.9% for the inter-day test).     

反相气相色谱法测定高密度聚乙烯溶解度参数

采用反相气相色谱(IGC)技术测定了高密度聚乙烯(HDPE)在303.15～343.15 K温度范围内的溶解度参数(δ2)及相关指标。以正己烷(n-C6)、正庚烷(n-C7)、正辛烷(n-C8)、正壬烷(n-C9)、三氯甲烷(CHCl3)及乙酸乙酯(EtAc)作为探针分子溶剂,经计算获得了探针溶剂的比保留体积(V0g)、摩尔吸收焓(ΔHS1)、无限稀释摩尔混合焓(ΔH∞l)、摩尔蒸发焓(ΔHv)、无限稀释活度系数(Ω∞1)以及探针溶剂与HDPE的Flory-Huggins相互作用参数(χ∞1,2)等指标。结果表明,上述6种探针溶剂在测定温度范围内均为HDPE的不良溶剂。此外,还推导出了HDPE在室温(298.15 K)下的溶解度参数δ2为19.00 (J/cm3)0.5。