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1.
Metal–organic frameworks (MOFs) have been demonstrated to be desired candidates for sensing definite species owing to their tunable composition, framework structure and functionality. In this work, the NH2-MIL-101 series was utilized for sensing specific amino acids. The results show that cysteine (Cys) can significantly enhance the fluorescence emission of NH2-MIL-101-Fe suspended in water, while NH2-MIL-101-Al exhibits the ability to sense lysine (Lys), arginine (Arg) and histidine (His) in aqueous media via turn-on fluorescence emission. Titration experiments ensure that NH2-MIL-101-Fe and NH2-MIL-101-Al can selectively and quantitatively detect these amino acids. The sensing mechanism was examined and discussed. The results of this study show that the metal centers in MOFs are crucial for sensing specific amino acids.  相似文献   

2.
Yin  Sheng  Chen  Yong  Hu  Qingsong  Li  Ming  Ding  Yi  Di  Jun  Xia  Jiexiang  Li  Huaming 《Research on Chemical Intermediates》2020,46(7):3311-3326

Photoactive metal–organic frameworks (MOFs) have proven to be a promising porous material in the field of catalysis. Controllable integration of these MOFs with inorganic semiconductor materials may endow new multifunctional hybrid materials with preferable photocatalytic properties. In this research, NH2-MIL-125(Ti) nanoplates modified Bi2WO6 microspheres was prepared via a simple solvothermal method. The photocatalytic behaviors of the acquired catalysts was evaluated via the degradation of tetracycline hydrochloride (TC) under visible light. The experimental results showed that NH2-MIL-125(Ti)/Bi2WO6 composites display higher photocatalytic activity than that of single Bi2WO6, and the ideal incorporation amount of NH2-MIL-125(Ti) was around 5 wt%. The steady state fluorescence spectrum, transient photocurrents and electrochemical impedance spectroscopy verified that the introduction of NH2-MIL-125(Ti) could accelerate the separation and transfer of photogenerated carriers and thus improve the photocatalytic activity of Bi2WO6. The photocatalytic mechanism was explored in detail. This work extends the knowledge of integrating MOFs with traditional photocatalysts to form new composite materials in the area of environmental purification.

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3.
Rational design and engineering of high-performance molecular sieve membranes towards C2H4/C2H6 and flue gas separations remain a grand challenge to date. In this study, through combining pore micro-environment engineering with meso-structure manipulation, highly c-oriented sub-100 nm-thick Cu@NH2-MIL-125 membrane was successfully prepared. Coordinatively unsaturated Cu ions immobilized in the NH2-MIL-125 framework enabled high-affinity π-complexation interactions with C2H4, resulting in an C2H4/C2H6 selectivity approaching 13.6, which was 9.4 times higher than that of pristine NH2-MIL-125 membrane; moreover, benefiting from π-complexation interactions between CO2 and Cu(I) sites, our membrane displayed superior CO2/N2 selectivity of 43.2 with CO2 permeance of 696 GPU, which far surpassed the benchmark of other pure MOF membranes. The above multi-scale structure optimization strategy is anticipated to present opportunities for significantly enhancing the separation performance of diverse molecular sieve membranes.  相似文献   

4.
Infrared spectra of K2Zn(SeO4)2·6H2O and (NH4)2Zn(SeO4)2·6H2O containing SO42? guest ions and those of K2Zn(SO4)2·6H2O and K2Zn(SeO4)2·6H2O containing NH4+ guest ions are presented and discussed in the region of the stretching modes ν3 and ν1 of the sulfate ions and in the region of asymmetric bending modes ν4 of the NH4+ ions, respectively. The SO42? ions matrix-isolated in the selenate matrices (approximately 2 mol%) exhibit three bands for ν3 and one band for ν1 in agreement with the low site symmetry C1 of the selenate host ions. The NH4+ guest ions included in the potassium sulfate matrix are characterized also with three site symmetry components of ν4. However, the ammonium ions in (NH4)2Zn(SeO4)2·6H2O as well as those included in K2Zn(SeO4)2·6H2O display four infrared bands corresponding to ν4 probably due to some kind of disorder of the ammonium ions. The extent of energetic distortion of the isomorphously included sulfate ions as deduced from the values of Δν3 (site-group splitting) and Δνmax (the difference between the highest and the lowest wavenumbered components of the stretching modes) are commented. The spectroscopic experiments reveal that the SO42? guest ions are weaker distorted in the potassium selenate matrix than the same ions in the neat potassium sulfate due to the larger unit-cell volumes of the selenate compounds. However, the SO42? guest ions are stronger distorted in the ammonium selenate matrix as compared to the same ions in the neat ammonium sulfate owing to the formation of hydrogen bonds between the SO42? guest ions and the NH4+ host ions. The analysis of the spectra shows that the band positions of the water librations in the host potassium compounds are affected by the included ammonium cations. The formation of the hydrogen bonds between the NH4+ guest ions and the XO42? host ions leads to a decrease in the proton acceptor capabilities of the anions (anti-cooperative or proton acceptor competitive effect) and as a result the hydrogen bonds formed by the water molecules weaken on going from the neat potassium compounds to the mixed crystals K1.8(NH4)0.2Zn(SO4)2·6H2O and K1.8(NH4)0.2Zn(SeO4)2·6H2O (the bands corresponding to water librations are broadened and shifted to lower frequencies).  相似文献   

5.
采用简单的溶剂热法制备金属有机框架化合物MIL-125(Ti)和NH_2-MIL-125(Ti)材料,并通过X射线衍射仪、扫描电子显微镜、傅氏转换红外线光谱分析仪和比表面积测试仪对所得样品进行表征。将2种材料修饰构建为石英晶体微天平传感器,测试其在11%~97%RH相对湿度范围内的湿度感测性能。实验结果表明,基于MIL-125(Ti)和NH_2-MIL-125(Ti)构建的传感器对湿度具有灵敏度高、重复性好、响应/恢复快等特点。相对于没有氨基修饰的MIL-125(Ti),NH_2-MIL-125(Ti)材料修饰的传感器对湿度表现出更高的响应性能。在环境湿度约52%时,NH_2-MIL-125(Ti)传感器对11%RH湿度响应值比MIL-125(Ti)湿度传感器的大57 Hz,说明氨基功能化对MIL-125(Ti)的湿敏性能有显著的增强作用。此外,通过Materials Studio模拟计算获得了水分子与MIL-125(Ti)及NH_2-MIL-125(Ti)作用的吸附焓,也证明氨基功能化对MIL-125(Ti)的湿度敏感性能具有增强作用。  相似文献   

6.
Zusammenfassung Untersucht wird ein Isokonzentrationsschnitt in bezug auf Schwefelsäure im Dreistoffsystem (NH4)2SO4–Fe2(SO4)3–H2O bei 25 °C. Es wird ein Kristallisationsbereich von anomalen Mischkristallen auf der Basis (NH4)2SO4 bei einem Eisen(III)-sulfatgehalt von 1,5% des Ammoniumsulfatgehalts ermittelt. Außerdem wird ein Kristallisationsbereich von Mischkristallen auf der Basis NH4Fe(SO4)2·12 H2O, ein Kristallisationsbereich von reinem NH4Fe(SO4)2·12 H2O und ein Kristallisationsbereich von Fe2(SO4)3·9 H2O festgestellt. Die Anwesenheit von Schwefelsäure in der Lösung vermindert die Löslichkeit aller Phasen im obigen System.Untersucht wird teilweise das Dreistoffsystem NH4Fe(SO4)2–H2SO4–H2O bei 25 °C. Es wird ein Kristallisationsbereich von NH4Fe(SO4)2·12 H2O, welches als feste Phase bis etwa 12% Schwefelsäure in der Lösung existiert, ermittelt. Es wird bewiesen, daß die anomalen Mischkristalle auf der Basis (NH4)2SO4 metastabile, mit der Zeit langsamen Veränderungen unterliegende Systeme sind.
An isoconcentration section with respect to sulphuric acid of the ternary system ammonium sulphate-ferric sulphate-water at 25 °C
The system (NH4)2SO4–Fe2(SO4)3–H2O was investigated at 25 °C with an excess of H2SO4. The crystallization ranges of the anomalous mixed crystals based on ammonium sulphate, the mixed crystals on the basis of the double-salt NH4Fe(SO4)2· ·12 H2O, the crystallization ranges of Iron(III)-ammonium sulphate and Fe2(SO4)3·9 H2O were determined. The presence of H2SO4 in the solution lowers the solubilities of the different phases occurring in the said system. The system NH4Fe(SO4)2–H2SO4–H2O was partially studied at 25 °C. The crystallization range of iron-ammonium alum existing as a solid phase at equilibrium at sulphuric acid concentrations up to ca. 12% in the solution is described. It was shown that the anomalous mixed-crystals based on ammonium sulphate undergoe slow changes with time.
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7.
The four ternary limiting isotherms of the system K+− NH4+ CrO4−− SO4−− H2O are given for 25° C. In the systems K2SO4 (NH4)2SO4 H2O and K2SO4 K2CrO4 H2O only one solid phase has been encountered; both systems belong to the type I of the ROOZEBOOM classification. A miscibility gap is present in the systems (NH4)2CrO4 K2CrO4 H2O and (NH4)2CrO4 (NH4)2SO4 H2O; they belong to ROOZEBOOM'S type V.  相似文献   

8.
Photocatalytic utilization of CO2 in the production of value-added chemicals has presented a recent green alternative for CO2 fixation. In this regard, three FeNbO4/NH2-MIL-125(Ti) composites of different mole ratios were synthesized, characterized using Powder X-ray diffraction (PXRD), UV–vis diffuse reflectance spectroscopy (UV-Vis DRS), Brunauer–Emmett–Teller (BET), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX). PXRD patterns confirm the co-existence of the parent components in the prepared composites. Moreover, the surface area increased as the mole percent of NH2-MIL-125(Ti) in the composites increased due to the large surface area of NH2-MIL-125(Ti). Prepared composites were investigated for the photocatalytic insertion of CO2 into propylene oxide. FeNbO4(75%)/NH2-MIL-125(Ti)(25%) showed the highest percent yield of 52% compared to the other two composites. Results demonstrate the cooperative mechanism between FeNbO4 and NH2-MIL-125(Ti) and that the reaction proceeded photocatalytically.  相似文献   

9.
An aerial humidity-induced solid-phase hydrolytic transformation of the [Zn(NH3)4]MoO4@2H2O (compound 1@2H2O) with the formation of [(NH4)xH(1−x)Zn(OH)(MoO4)]n (x = 0.92–0.94) coordination polymer (formally NH4Zn(OH)MoO4, compound 2) is described. Based on the isostructural relationship, the powder XRD indicates that the crystal lattice of compound 1@2H2O contains a hydrogen-bonded network of tetraamminezinc (2+) and molybdate (2−) ions, and there are cavities (O4N4(μ-H12) cube) occupied by the two water molecules, which stabilize the crystal structure. Several observations indicate that the water molecules have no fixed positions in the lattice voids; instead, the cavity provides a neighborhood similar to those in clathrates. The @ symbol in the notation is intended to emphasize that the H2O in this compound is enclathrated rather than being water of crystallization. Yet, signs of temperature-dependent dynamic interactions with the wall of the cages can be detected, and 1@2H2O easily releases its water content even on standing and yields compound 2. Surprisingly, hydrolysis products of 1 were observed even in the absence of aerial humidity, which suggests a unique solid-phase quasi-intramolecular hydrolysis. A mechanism involving successive substitution of the ammonia ligands by water molecules and ammonia release is proposed. An ESR study of the Cu-doped compound 2 (2#dotCu) showed that this complex consists of two different Cu2+(Zn2+) environments in the polymeric structure. Thermal decomposition of compounds 1 and 2 results in ZnMoO4 with similar specific surface area and morphology. The ZnMoO4 samples prepared from compounds 1 and 2 and compound 2 in itself are active photocatalysts in the degradation of Congo Red dye. IR, Raman, and UV studies on compounds 1@2H2O and 2 are discussed in detail.  相似文献   

10.
The crosslinked structure formed by the metal coordination bonding provides excellent and new properties for rubber materials. Herein, the crosslinking of acrylonitrile‐butadiene rubber (NBR) is induced by introducing aluminum ammonium sulfate (NH4Al(SO4)2·12H2O) particles. The crosslinking behavior, morphology, mechanical properties, and the Akron abrasion resistance of NBR/NH4Al(SO4)2·12H2O composites were fully explored. The results show that the three‐dimensional crosslinking structure is held together by metal–ligand coordination bonds between the nitrile group and AI(III). The coordination crosslink density exhibits a considerable increase with the addition of NH4Al(SO4)2·12H2O. Thus, the mechanical properties and abrasion resistance of the obtained composites are better than that of NBR/sulfur system. Interestingly, the elongation at break for NBR/NH4Al(SO4)2·12H2O composites is over 2000% due to the nature of coordination bonds. The abrasion volume loss decreases to 0.4 cm3 for NBR/NH4Al(SO4)2·12H2O composites with 20 phr NH4Al(SO4)2·12H2O particles as compared to 0.75 cm3 for NBR/sulfur system. The obtained NBR composites with facile preparation and excellent mechanical properties make the composites based on metal coordination bonding attractive for practical use. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 879–886  相似文献   

11.
Double complex salts of lanthanum(III) sulphate complex anions with several cobalt(III) ammine complex cations, [Co(NH3)6][La(SO4)3]·H2O (1), (NH4)3[Co(NH3)5 H2O]-[La(SO4)3]2·2H2O (2), and (NH4)3[Co(NH3)4(H2O)2][La(SO4)3]2·2H2O (3), were prepared by the addition of hexaamminecobalt(III), pentaammineaquacobalt(III), and cis- tetra-amminediaquacobalt(III) complexes to the solution containing lanthanum(III) ion and excess ammonium sulphate. The IR spectra of sulphate groups of these double complex salts were much more complicated than those of the almost free sulphate groups such as (NH4)2SO4 and [Co(NH3)6]2(SO4)3·5H2O. Furthermore, values of activation energy in the dehydration process of 1, 2 and 3 were estimated using modified Doyle's and Wiedemann's method. They were 95.6 ± 4.3, 157.1 ± 15.5 and 163.2 ± 20.8 kJ mol?1, respectively. Here, one molecule water is released per molecule of 1, 2 and 3.  相似文献   

12.
Author index     
The thermal decomposition of N2H5Nd(SO4)2·H2O has been studied by simultaneous TG and DSC and by isothermal weight change determination. The final product and the intermediate phases have been identified by chemical analysis, X-ray powder patterns and infrared spectroscopy. The solid phases in the decomposition sequence are: N2H5Nd(SO4)2· H2O → N2H5Nd(SO4)2 → NH4Nd(SO4)2 → Nd2(SO4)3. The reactions overlap under dynamicconditions, isothermally, however, NH4Nd(SO4)2 can be obtained by 200°C.  相似文献   

13.
Compounds with a general formula [Cat][In(H2O) n (SO4)2] x · mH2O (where Cat = C(NH2)3, H(2,2′-Bipy), H2(4,4′-Bipy), H2[Py(CH2)3Py], and H3N(CH2)6NH3) were synthesized and identified from the elemental analysis, IR, and thermogravimetric analysis data. X-ray diffraction analysis of crystalline [C(NH2)3][In(H2O)2(SO4)2] complex showed that the polymer chains of In aquasulfate form ensembles with guanidinium ions. The structure of [H2(4,4′-Bipy)][In2(H2O)6(SO4)4] · 2H2O consists of the dimeric anions of indium sulfate. The coordination sphere of In includes three O atoms of three SO4 groups and three O atoms of water molecules. The dimers are united into framework by diprotonated Bipy cations.  相似文献   

14.
Ternary clusters (NH3)·(H2SO4)·(H2O)n have been widely studied. However, the structures and binding energies of relatively larger cluster (n > 6) remain unclear, which hinders the study of other interesting properties. Ternary clusters of (NH3)·(H2SO4)·(H2O)n, n = 0-14, were investigated using MD simulations and quantum chemical calculations. For n = 1, a proton was transferred from H2SO4 to NH3. For n = 10, both protons of H2SO4 were transferred to NH3 and H2O, respectively. The NH4+ and HSO4 formed a contact ion-pair [NH4+-HSO4] for n = 1-6 and a solvent separated ion-pair [NH4+-H2O-HSO4] for n = 7-9. Therefore, we observed two obvious transitions from neutral to single protonation (from H2SO4 to NH3) to double protonation (from H2SO4 to NH3 and H2O) with increasing n. In general, the structures with single protonation and solvated ion-pair were higher in entropy than those with double protonation and contact ion-pair of single protonation and were thus preferred at higher temperature. As a result, the inversion between single and double protonated clusters was postponed until n = 12 according to the average binding Gibbs free energy at the normal condition. These results can serve as a good start point for studies of the other properties of these clusters and as a model for the solvation of the [H2SO4-NH3] complex in bulk water.  相似文献   

15.
Phenol, having favourable physical and chemical properties, can be enclosed as the guest component in the clathrates of tetracyano complexes. Six compounds of Hofmann and similar type clathrates M(NH3)2M' (CN)4.nG and M(en)m M'(CN)4.nG were prepared and identified: Ni(NH3)2Pt.2C6H5OH; Ni(en)2Pt(CN)4.O.14C6H5OH; Ni(NH3)2Pt(CN)4.C6H5OH.H2O; Zn(NH3)2Ni(CN)4.O.1C6H5OH.H2O; Cu(NH3)2Ni(CN)4. 2C6H5OH and Fe(NH3)2Ni(CN)4.2C6H5OH. The phenol containing clathrates are more stable than clathrates containing other guest molecules. In the case of Ni(en)2 Pt(CN)4.O.14C6H5OH thermal loss of the guest molecule leaves the host lattice intact, but further heating results in the rupture of the host lattice. The compounds were capable in the solid state of sorbing other organic molecules once they had been heated to the temperature required for almost complete loss of guest molecule i.e. n→o.  相似文献   

16.
A heterogeneous distribution study with internally formed lead chromate as host and110Ag as guest indicates the existence of a new variety of lead chromate, which forms mixed crystals with silver chromate, and differs in morphology from the aged variety. It is inferred that the formation of mixed crystals is probably due to breeding of a morphologically analogous and unstable species by the guest component. By means of study of the homogeneous distribution coefficient, D, of the system consisting of KFe(SO4)2·12H2O as host and110Ag as guest, the existence of an unknown alum, AgFe(SO4)2·12H2O, in trace amounts has been demonstrated. A distribution study of the system shows that KFe(SO4)2·12H2O forms mixed crystals with110Ag up to 10°C, after which the uptake follows an adsorption pattern. The transition temperature of the guest alum, indicated by a sharp change in the D values, is found to be 10°C. Application of radioactive tracers in the study of new and unstable compounds have been stressed.  相似文献   

17.
In two earlier papers (C.A. 117:259320(1;121:19411y) the activity coefficients of the salts in binary solid solutions at 25‡C for 38 salt pairs, in which the members of each pair differ with respect to only one kind of ion, were determined. While the activity data are correct, the conclusions regarding deviations from ideality for eight of these pairs, namely those in which there are two moles of replaceable ion per mole of salt, require modification in order to be consistent with ideal entropies of mixing. By changing the formulation of the component salts to one-half of what is usual, the inconsistencies disappear. This half-mole approach, applied to the salt pairs CU1/2(NH4/K)SO4-3H2O, Mg1/2NH4(SO4/ CrO4)-3H2O, Mg1/2NH4(SeO4/SO4)-3H4O, Mg1/2NH4(SeO4/CrO4)-3H4O, Mg1/2 (K/NH4)SeO4-3H2O, (NH4/K)(SO4)1/2, and Ba1/2(ClO3/BrO3)-1/2 H2O shows that these solid solutions exhibit positive, not negative, deviations from ideality at 25‡C. Only the system Pb1/2(C1/Br) still deviates negatively.  相似文献   

18.
In this paper, a novel improvement in the catalytic Fenton reaction system named MHACF-NH2-MIL-101(Cr) was constructed based on H2 and Pd/NH2-MIL-101(Cr). The improved system would result in an accelerated reduction in FeIII, and provide a continuous and fast degradation efficiency of the 10 mg L-1 4-chlorophenol which was the model contaminant by using only trace level FeII. The activity of Pd/NH2-MIL-101(Cr) decreased from 100% to about 35% gradually during the six consecutive reaction cycles of 18 h. That could be attributed to the irreversible structural damage of NH2-MIL-101(Cr).  相似文献   

19.
Metal–organic frameworks (MOFs) are a new class of hybrid inorganic–organic microporous crystalline materials, which possess unique properties such as high surface area, tunable pore size, and good thermal stability. These unique characteristics make MOFs interesting targets for sample pretreatment. In this work, MIL-53 material based on aluminum and containing amine functional groups (NH2-MIL-53(Al)) was synthesized and applied as an efficient sorbent for development of vortex-assisted dispersive micro-solid phase extraction for eight United States Environmental Protection Agency’s priority phenols from aqueous samples prior to analysis by high-performance liquid chromatography with photodiode-array detection. A simple extraction process was designed. The parameters affecting the extraction efficiency, such as amount of sorbent, extraction time, type of desorption solvent and its volume were investigated. The good linearity in the concentration range of 0.0015–10.0000 μg mL?1 with the coefficients of determination of greater than 0.9929, low limits of detection (0.0004–0.0133 μg mL?1) and relative standard deviations of lower than 10% were obtained. The proposed method has been successfully applied to the determination of phenol compounds in different water sample matrices including treated water, waste water, river water, sea water, lake water, drinking water and tap water. In addition, computational simulation was performed to predict the adsorption ability of NH2-MIL-53(Al) towards the studied phenolic compounds. The computational results were in agreement with the experimental studies and it has been proved that NH2-MIL-53(Al) is promising for enrichment of phenolic pollutants.  相似文献   

20.
The crystal structures of isostructural mixed-ligand fluorosulfate complex compounds of indium(III) M2[InF3(SO4)H2O] (M = K, NH4), formed of K+ cations, NH4 + respectively, and complex [InF3(SO4)H2O]2– anions are determined. In the complex anion, the indium atom surrounded by three F atoms, the oxygen atom of the coordinated H2O molecule, and two oxygen atoms of the bridging sulfate group forms a slightly distorted octahedron (CN 6). Via alternating bridging SO4 groups, the polyhedra of In(III) atoms are arranged in polymer chains. The O–H???F hydrogen bonds organize the chains in a three-dimensional network. The K+ and NH4 + cations are located in the structure framework and additionally strengthen it.  相似文献   

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