CN114292414A - Vacancy type polyacid-based metal organic framework molecular material and application thereof in selective catalytic reduction of nitrobenzene - Google Patents
Vacancy type polyacid-based metal organic framework molecular material and application thereof in selective catalytic reduction of nitrobenzene Download PDFInfo
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Abstract
The invention relates to a novel vacancy type polyacid-based metal organic framework molecular material, which has the molecular formula as follows: c54H36N18O51SiW11Zn3.5The chemical formula is { [ HZn (TPT) SiW11O39)] [Zn(TPT)(H2O)3][Zn(H2O)4][Zn0.5(TPT)(H2O)]}·4H2O, ZnW-TPT for short (TPT =2,4,6-tri (4-pyridoyl) -1,3, 5-triazine). The compound belongs to a monoclinic system,P2 1 /cand (4) space group. The novel metal organic framework molecular material can be used as a photocatalyst for catalytic reductionNitrobenzene selectively produces aniline.
Description
Technical Field
The invention belongs to the technical field of preparation of metal organic framework compounds, and particularly relates to a vacancy type polyacid-based metal organic framework molecular material, a synthesis method and application of the vacancy type polyacid-based metal organic framework molecular material as a photocatalyst in catalytic selective reduction of nitrobenzene to aniline.
Background
Energy shortage and environmental pollution are two of the most important problems facing mankind in the 21 st century, which are closely related to human health and socioeconomic development. Due to the enormous potential solar radiation has for environmental remediation and chemical energy generation, photocatalysis has become the most promising green solution, where chemical reactions caused by photocatalysis can be applied in a variety of areas, including energy, environmental and industrial chemistry. Aniline is often used as a raw material for manufacturing many products such as dyes, pigments, rubbers, and medicaments in industrial chemistry, and is also a potential intermediate for the industrial synthesis of fine chemicals, pesticides, and medicines. In general, aniline derivatives are obtained by hydrogenation reaction of gold, platinum and other noble metal catalysts to reduce nitroaromatic hydrocarbons, however, although the yield is high, the reaction process still has some disadvantages such as low selectivity, high cost and harsh reaction conditions (high temperature and high pressure H)2) The need for fossil fuels as a source of hydrogen, etc. Therefore, the method has great prospect in both basic research and application research.
Metal organic framework Materials (MOFs) have been increasingly studied in various application fields because they have excellent photoelectrochemical properties and can be optimized in function by selecting organic bridging ligands. 2,4,6-tri (4-pyridyl) -1,3,5-triazine (TPT) has a nano-grade conjugated surface, good light absorption performance and special electrical conductivity, and is a good photosensitizer candidate material. Importantly, TPT can be irradiated with light to generate triplet diradicals in the solid state, and two reversible reduction peaks (E) are found in TPT by cyclic voltammetry1= -1.72 V，E2= 1.25V vs Ag/AgCl), indicating that TPT can undergo two-step reversible reduction, and therefore addition of TPT to MOFs has good photocatalytic performance.
Polyoxometallates (POM) are a class having a high oxidation state (e.g., Mo)6+、W6+、V5+) The molecular-based semiconductor composed of the transition metal has the advantages of structural diversity, reversible redox activity, easy functionalization and the like. In general terms, the term "a" or "an" is used to describe a device that is capable of generating a signalThe redox potential of the polyacid can be controlled by adjusting its structural and compositional elements. In recent years, in basic chemical research and industrial applications, a large number of polyacid-based heterogeneous photocatalytic materials have unique photochemical properties and high catalytic activity, and in particular, polyacids can accommodate multiple electrons and protons without changing the structure, thereby promoting a multiple-electron redox reaction and a photoreduction of nitrobenzene.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a vacancy type polyacid-based metal organic framework molecular material, a synthesis method and application of the vacancy type polyacid-based metal organic framework molecular material as a photocatalyst in catalyzing and selectively reducing nitrobenzene to aniline.
In order to achieve the purpose, the invention adopts the following technical scheme:
a novel vacancy type polyacid-based metal organic framework molecular material has a molecular formula as follows: c54H36N18O51SiW11Zn3.5The chemical formula is { [ HZn (TPT) SiW11O39)][Zn(TPT)(H2O)3][Zn(H2O)4][Zn0.5(TPT)(H2O)]}·4H2O, abbreviated ZnW-TPT, TPT =2,4,6-tri (4-pyridil) -1,3,5-triazine, chemically named 2,4, 6-tris (4-pyridine) 1,3, 5-triazine. The compound belongs to the monoclinic system, P21/cAnd (4) space group. The material can efficiently and selectively reduce nitrobenzene into aniline.
The method for synthesizing the defect type polyacid-based metal-organic framework molecular material comprises the step of reacting Zn (CH)3COO)2·2H2O、K8[β2-SiW11O39] ·14H2Mixing O and TPT in solvent, adjusting pH to 4-5 (preferably 4.2), transferring to a reaction kettle, reacting at 110-130 deg.C for 60-84 h (preferably at 120 deg.C for 72 h), cooling to room temperature, separating out crystal, washing, and drying.
In particular to a synthesis method of the defect type polyacid-based metal organic framework molecular material, namely Zn (CH)3COO)2·2H2O、K8[β2-SiW11O39]·14H2The mass ratio of O to TPT is 6: 4: 1.
in the method for synthesizing the vacancy type polyacid-based metal organic framework molecular material, the solvent is formed by mixing distilled water and acetonitrile in any proportion.
The invention provides an application of the vacancy type polyacid-based metal organic framework molecular material as a catalyst in photocatalytic reduction of nitrobenzene. Furthermore, the application mainly comprises the step of preparing aniline by selectively reducing nitrobenzene through photocatalysis.
Compared with the prior art, the invention has the following beneficial effects:
1) the vacancy type polyacid-based metal organic framework material can accurately analyze the crystal structure characteristics through X-ray single crystal diffraction, and provides theoretical support for further conjecturing the interaction between an active center and a reaction substrate and researching the catalytic reaction mechanism of the vacancy type polyacid-based metal organic framework material;
2) the vacancy type polyacid-based metal organic framework material has the characteristics of an n-type semiconductor, has a LUMO energy level (-1.29V vs. NHE) with high reduction potential and a HOMO energy level (1.74V vs. NHE) with high oxidation potential, and can realize the organic conversion from nitrobenzene to aniline;
3) the invention is beneficial to developing a photoreduction reaction synthesis strategy with the characteristics of atom economy, high efficiency and the like. The catalytic system abandons the traditional method with high cost, secondary pollution, complex manufacturing process and low efficiency, directly carries out reduction catalytic reaction on nitrobenzene under 365nm light irradiation, and accords with the development concept of green chemistry;
4) the invention realizes high-efficiency catalysis by designing and adjusting reasonable matching of three-dimensional and electronic effects between the catalytic active sites and the substrate. The catalysis process is heterogeneous, the catalyst can be recovered through filtration or centrifugal separation, the cyclic utilization for multiple times is realized, and the catalysis efficiency is not obviously reduced after the multiple cycles, so that the multifunctional vacancy type polyacid-based metal organic framework material provides a good theoretical basis for the selective reduction of nitrobenzene to generate aniline under the catalysis of non-noble metal.
Drawings
FIG. 1 is a diagram of (a) the coordination environment of compound ZnW-TPT; (b) is a three-dimensional network structure of a compound { ZnW-TPT } (color code: Zn, brown; C, gray; O, red; W, green; N, blue, partial hydrogen atoms are omitted for clarity);
FIG. 2 is a chart of the infrared spectrum of compound ZnW-TPT;
FIG. 3 is an XRD spectrum of compound ZnW-TPT;
in FIG. 4, (a) is the solid UV spectrum of ZnW-TPT; (b) is the band gap of ZnW-TPT compound; (c) a Mott-Schottky plot of ZnW-TPT; (d) fluorescence quenching for the ZnW-TPT compound; (e) transient photocurrent response for ZnW-TPT compound; (f) is an electrochemical AC impedance plot of ZnW-TPT compound;
FIG. 5 is an excitation-emission spectrum fluorescence spectrum (E) of compound ZnW-TPTX=398)；
FIG. 6 is a thermogravimetric analysis of compound ZnW-TPT;
FIG. 7 shows the main product aniline1H NMR spectrum;1H NMR (500 MHz, DMSO) δ 7.11 – 6.95 (m, 2H), 6.63 – 6.52 (m, 2H), 6.48 (dd, J = 10.4, 4.1 Hz, 1H), 4.97 (s, 2H)；
FIG. 8 is a PXRD pattern of the catalyst after three cycles of catalysis of compound ZnW-TPT;
FIG. 9 is an FT-IR spectrum of the catalyst after three cycles of catalysis of compound ZnW-TPT;
FIG. 10 is a graph showing the reaction cycle test of the photoreduction of nitrobenzene.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
Example 1
A vacancy type polyacid-based metal organic framework material has a molecular formula as follows: c54H36N18O51SiW11Zn3.5The chemical formula is { [ HZn (TPT) SiW11O39)][Zn(TPT)(H2O)3][Zn(H2O)4][Zn0.5(TPT)(H2O)]} ·4H2O, process for synthesizing the same, and kitThe synthesis of the ligand and the catalyst comprises the following steps:
1) synthesis of ligand 2,4,6-tri (pyridine-4-yl) -1,3,5-triazine (TPT)
The synthesis can be carried out in particular by reference to the literature (Yanagiya, K.; Yasumoto, M.; Kurabayashi, M. Bulletin of the Chemical Society of Japan 1973, 46(9), 2809-2814).
2）K8[β2-SiW11O39]·14H2And (3) synthesis of O:
reference is made in particular to the literature (Tez, A.; Herv, G.Inorg. Syn. 1990, 2790.) was synthesized.
3) Synthesis of Compound ZnW-TPT
The compound { ZnW-TPT } is prepared by self-assembly under hydrothermal conditions, and specifically comprises the following steps: weighing Zn (CH)3COO)2·2H2O 60 mg (0.27 mmol)、K8[β2-SiW11O39]·14H2O40 mg (0.012 mmol) and TPT 10 mg (0.032 mmol) in a volume ratio of 2: 1, placing the mixture in a mixed solvent of distilled water and acetonitrile at room temperature, stirring for 12 h to mix uniformly, then adjusting the pH =4.2 by using 1M hydrochloric acid, then transferring the mixture to a high-pressure reaction kettle, slowly heating the mixture in an oven, reacting the mixture at 120 ℃ for 72 h, slowly cooling the mixture to room temperature, separating out colorless crystals, washing the crystals with water and drying the crystals to obtain the compound ZnW-TPT, wherein the yield is 70% (based on K)8[β2-SiW11O39]·14H2O）。
The chemical formula of the above compound ZnW-TPT: c54H36N18O51SiW11Zn3.5Elemental analysis and ICP (%): calculated for compound: c: 16.08 of; h: 0.90; si: 0.67; n: 6.25; w: 50.15 of; zn: 5.7. experimental values: c: 16.15 of; h: 0.11; si: 0.75; n: 7.15 of; w: 50.80, respectively; zn: 6.4.
crystal structure analysis: the compound ZnW-TPT was subjected to crystal testing and analysis, and the results were as follows.
TABLE 1 crystallographic data for Compound ZnW-TPT
As can be seen in table 1: compound ZnW-TPT belongs to the monoclinic system,P21/cand (4) space group. As can be seen from a in fig. 1: compound ZnW-TPT consisting of 1 Zn2+Substituted single-defect eggin type anion [ Zn (TPT) (SiW)11O39)]6−1 of [ Zn (TPT) (H)2O)3]2+1 of [ Zn (H) ]2O)4]2+1 of [ Zn ]0.5(TPT)(H2O)]+1 equilibrium proton and 4 crystalline water molecules. There are four crystallographically independent zinc ions in the crystal. Zn (1) occupies [ SiW11O39]8−And coordinated to a TPT molecule. Zn (2) is penta-coordinated, a twisted tetragonal pyramid configuration formed by one bridging oxygen of POM, one N atom of TPT molecule and three O atoms of coordinating water molecule. Zn (3) is hexacoordinated, having a distorted octahedral geometry, coordinated by one terminal oxygen of the POM, one N atom of the TPT molecule and four oxygen atoms coordinating water molecules. Zn (4) is a six-coordinate distorted octahedral geometry coordinated by two terminal oxygen atoms of the POM, two N atoms of the TPT molecule and two oxygen atoms of the coordinating water molecule. The pi-pi interaction between TPTs is 3.35-3.52A.
Adjacent [ Zn (TPT)) (SiW11O39)]6−The unit takes Zn (2) and Zn (3) atoms as nodes, and TPT as an organic bridging ligand to form a two-dimensional (2D) network structure. The two-dimensional network is then further connected by Zn (4) ions, forming a three-dimensional infinite extension structure (b in fig. 1). The porosity of the one-dimensional channel by PLATON analysis was about 12.0% (9514.1 a 3), indicating that: ZnW-TPT has the potential to adsorb nitrobenzene within its pores.
Infrared spectrum: the IR spectrum of compound ZnW-TPT is shown in FIG. 2. As can be seen from the figure: 3400cm−1The left and right broadband absorption peaks are attributed to H2And O stretching and contracting vibration. In TPT, the triazine ring is at 1372 cm−1Exhibits telescopic vibration at 1519 cm−1The resonance is the telescopic absorption of pyridine ringAnd (5) peak collection. 800-−1Then the characteristic absorption peak of the polyacid is obtained.
Powder diffraction of radiation: the X-ray powder diffraction pattern of compound ZnW-TPT is shown in FIG. 3, where Simulation shows the pattern obtained by Simulation, and Experiment shows the pattern obtained by Experiment. The comparison shows that the peak types and the peak positions of the two are basically completely matched, which indicates that the sample is pure and has few impurities.
Ultraviolet-visible diffuse reflectance spectrum: ZnW-TPT has an ultraviolet-visible spectrum as shown in a in figure 4, and shows strong light absorption concentrated at 350 nm, which shows that the TPT has strong absorption in the ultraviolet region and has potential application prospect in the aspect of solar energy utilization. Under air illumination with a 300W xenon lamp, the crystal sample rapidly turned deep blue due to electrons from the excited TPT٠-Transfer of free radicals to POM results in heteropolyblue (POM)red). POMred was reoxidized by air, especially at 20 minutes of darkness. ZnW-TPT has good photochromic properties to facilitate photocatalysis. Here, the bandgap of ZnW-TPT was calculated using the Kubelka-Munk function:
αhν = A(hν-Eg) n/2
wherein α, hv, a and Eg represent absorption coefficient, photon energy, constant and band gap, respectively. In the function, the value of n is determined by the type of optical transition in the semiconductor (n =1 for a direct transition; n =4 for an indirect transition), and n =4 for compound ZnW-TPT for an indirect transition. Thus, the bandgap Eg of Cd-TIPA is 3.03 eV (b in FIG. 4). In addition, the energy level change of compound ZnW-TPT was confirmed by the profile. As shown, the flat band potential of compound ZnW-TPT was measured to be-1.49 eV (vs. Ag/AgCl). The conduction band potential (E) was calculated by the following formulaCB)：ECB = E (vs. Ag/AgCl) + 0.2V. Therefore, the conduction band potential of compound ZnW-TPT was-1.29V. According to formula EVB = ECB + EgCombining UV-visible absorption spectroscopy with electrochemical test results to obtain E of compound ZnW-TPTVBThe value was 1.74eV (c in FIG. 4). The results show that the Eb potential ratio C of the compound6H5NO2/C6H5NH2The standard redox potential of (0.50 eV vs. NHE) is more negative, which is theoretically confirmedIt is clear that ZnW-TPT is feasible as a photocatalyst to catalyze the nitrobenzene reduction process.
Fluorescence emission spectrum: fluorescence emission spectrum the luminescence spectrum of the photocatalyst was investigated to determine its charge separation activity, as shown in d in fig. 4. The intensity of the ZnW-TPT fluorescence spectrum decayed by more than 80% under the continuous irradiation of a 300W xenon lamp (d in FIG. 4). In general, fluorescence quenching indicates a low rate of photogenerated electron-hole recombination. Here, fluorescence quenching is considered to be the electron transfer from the excited TPT-The free radicals are transferred to the electron acceptor POM, thereby inhibiting the recombination of ZnW-TPT photogenerated electron holes. Thus, it is believed that during irradiation, a sequential charge transfer process occurs between the ZnW-TPT components through coordination bonds and π - π interactions. FIG. 5 is an excitation-emission spectrum fluorescence spectrum (E) of compound ZnW-TPTX=398)。
Photoelectric property research: to further investigate the photocatalytic activity of ZnW-TPT, transient photocurrent response and electrochemical impedance spectroscopy tests (e, f in FIG. 4) were performed, respectively. ZnW-TPT has a higher transient photocurrent than TPT, demonstrating superior photoelectron and hole separation efficiency (e in FIG. 4). Meanwhile, the low resistance of ZnW-TPT under illumination further illustrates that ZnW-TPT has excellent photocatalytic activity (f in FIG. 4).
Thermogravimetric analysis: thermogravimetric analysis of the compound { ZnW-TPT } As shown in FIG. 6, ZnW-TPT was investigated in N by thermogravimetric analysis (TGA)2Thermal behavior at 25-800 ℃ under atmosphere. Before 580 ℃, the TG curve of ZnW-TPT shows two weight loss phases, related to the loss of lattice and coordinated water molecules, respectively. TGA shows that ZnW-TPT has higher thermal stability and meets the requirement of heterogeneous catalysis.
Example 2: experiment of photocatalytic application
Photocatalytic reduction reaction of heavy metal ions: in a typical reduction experiment, 0.5 mmol of the substrate nitrobenzene was dissolved in 0.5 mL of H2O and 2 mL acetonitrile CH3CN, 10 mg of catalyst (compound ZnW-TPT) was then added, with hydrazine hydrate as the catalytic hydrogen donor (substrate: hydrazine hydrate molar ratio 1: 4). Placing the mixture in a 10W 365nm LED lampAt room temperature N2The irradiation was carried out for 6 h. ZnW-TPT was removed by centrifugation, dried over anhydrous sodium sulfate and then dried under vacuum at 40 ℃. For products1Qualitative analysis by H NMR and quantitative analysis by gas chromatography (Agilent 8860). The recovery experiment was performed by collecting the centrifuged catalyst, washing with distilled water, and drying in a vacuum oven at 60 ℃. FIG. 7 shows the main product aniline1H NMR spectrum.
Study of photocatalytic Properties
To evaluate the photocatalytic activity of ZnW-TPT, ZnW-TPT was studied under 10W, 365nm light irradiation with N2H4·H2O is a hydrogen donor in CH3CN/H2In the O system, ZnW-TPT is used as a catalyst to reduce nitrobenzene into corresponding aniline.
As a model reaction, nitrobenzene was reduced to aniline after 6h, the conversion and selectivity reached 99% (entry 1 in Table 1), and then the reaction was continued for 12 h, with no by-product observed (entry 2 in Table 1), indicating that ZnW-TPT has a higher selectivity to aniline. Higher conversion indicates that: ZnW-TPT at N2H4·H2Has stronger photoreduction ability in the presence of O. Then, the reaction conditions were optimized with CH3CN/H2O instead of CH3CN、CH3OH、CH2Cl2And isopropanol as solvent, gave better conversion (entries 3-6 in Table 1), probably due to H2The addition of O increases the solubility of the system. Whereas a lower conversion was observed when white light was used instead of 365nm light (entry 7 in table 1), probably because the TPT was well excited under 365nm light, which matched the uv-visible solid absorption spectrum of ZnW-TPT.
Table 1: research on catalytic reduction of nitrobenzene by ZnW-TPT (terephthalic acid) under different conditionsa
aStandard conditions: substrate 0.5 mmol, ZnW-TPT 10 mg, CH3CN/H2O (4:1, v/v) 2.5 mL, N2H4·H2O (2 mmol)，N2(1 atm), 10W 365nm LED lamp, room temperature, 6 h.bConversion, determined by nuclear magnetism and gas phase.cSelectivity to aniline.dWhite light was used instead of 365nm light.
ZnW-TPT the control experiments of Table 2 show that: k8[β2-SiW11O39] ·14H2O、Zn(CH3COO)2·2H2O and TPT gave 10%, 8% and 19% of the desired product, respectively (entries 1-3 in Table 2). Furthermore, K8[β2-SiW11O39] ·14H2O、Zn(CH3COO)2·2H2A simple physical mixture of O and TPT can convert the substrate to 25% of the target product (entry 4 in Table 3). In the absence of light irradiation or in the presence of a catalyst, only a trace conversion of nitrobenzene was observed (entries 5, 6 in table 2). The necessity of ZnW-TPT in the catalytic system is illustrated.
Table 2: control experiment for photocatalytic reduction of nitrobenzenea
aStandard conditions 0.5 mmol of substrate, 10 mg of catalyst, CH3CN/H2O (4:1, v/v) 2.5 mL, N2H4·H2O (2 mmol)， N2(1 atm), 10W 365nm LED lamp, rt, 6 h.bAnd (4) conversion rate.cSelectivity to aniline.dNo light is emitted.eNo catalyst ZnW-TPT.
The stability and reusability of catalysts have been considered as important aspects for large-scale applications. Therefore, multiple catalytic reactions were performed using the same compound to understand the recoverability of the catalyst for the photocatalytic reduction of nitrobenzene by ZnW-TPT. After each cycle, the catalyst was separated by centrifugation. The resulting catalyst was washed ultrasonically with distilled water, dried at 60 ℃ for 6h, and then the recovered photocatalyst was used in the next cycle. As shown in fig. 10, the catalytic activity of compound ZnW-TPT for the reduction of nitrobenzene was tested over multiple cycles. As is clear from the experimental results of fig. 10: ZnW-TPT maintained its original crystal structure even after the third catalytic cycle, with no significant reduction in conversion. The results show that the catalyst has higher stability and heterogeneous catalytic capability.
XRD, FT-IR spectrum before and after cycle: from the XRD, FT-IR spectrum analysis before and after the cycle (fig. 8, 9), it can be concluded that: no significant change in catalyst structure occurred before and after the cycle, indicating that ZnW-TPT meets the requirements for heterogeneous catalysis.
Claims (6)
1. A vacancy type polyacid-based metal organic framework molecular material has a molecular formula as follows: c54H36N18O51SiW11Zn3.5，The chemical formula is { [ HZn (TPT) SiW11O39)][Zn(TPT)(H2O)3][Zn(H2O)4][Zn0.5(TPT)(H2O)]}·4H2O, which belongs to the monoclinic system,P21/cand (4) space group.
2. The method for synthesizing the vacancy type polyacid-based metal-organic framework molecular material of claim 1, wherein Zn (CH) is added3COO)2·2H2O、K8[β2-SiW11O39]·14H2Mixing O and TPT in solvent, adjusting pH to 4-5, transferring to reaction kettle, reacting at 110-130 deg.C for 60-84 hr, cooling to room temperature, separating out crystal, washing, and drying.
3. The method for synthesizing the vacancy type polyacid-based metal-organic framework molecular material of claim 2, wherein the Zn (CH)3COO)2·2H2O、K8[β2-SiW11O39]·14H2The mass ratio of O to TPT is 6: 4: 1.
4. the method for synthesizing the vacancy-type polyacid-based metal organic framework molecular material of claim 2, wherein the solvent is composed of distilled water and acetonitrile.
5. Use of the vacancy type polyacid-based metal organic framework molecular material of claim 1 as a catalyst in photocatalytic reduction of nitrobenzene.
6. The use of the vacancy-type polyacid-based metal organic framework molecular material of claim 5 as a catalyst in the photocatalytic reduction of nitrobenzene to produce aniline.
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| JIACHEN JIAO 等: "Photocatalytic Multielectron Reduction of Nitroarenes to Anilines by Utilizing an Electron-Storable Polyoxometalate-Based Metal-Organic Framework", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| QING HUANG 等: "A highly stable polyoxometalate-based metal–organic framework with π–π stacking for enhancing lithium ion battery performance", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| 黄远 等: "多酸基金属-有机框架的构筑及其催化性能", 《化学研究》 * |
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| CN114292414B (en) | 2023-03-24 |
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