CN110358102B - A class of polyacid-based metal-organic framework crystal materials, preparation method and application of catalytic synthesis of parabens - Google Patents
A class of polyacid-based metal-organic framework crystal materials, preparation method and application of catalytic synthesis of parabens Download PDFInfo
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Abstract
本发明属于催化化学技术领域，具体涉及一类多酸基金属有机框架晶体材料、制备方法及其催化合成对苯琨类化合物的应用，该材料可以作为非均相催化剂，在催化烷基酚、烷氧基苯以及2‑甲基萘氧化合成相应对苯琨的反应中具有优异的催化性能，尤其是在催化2,3,6‑三甲基苯酚氧化合成2,3,5‑三甲基苯琨的反应中，在10‑20min内，几乎可以实现底物的完全转化，苯琨的产率高达96％‑99％，且其转化频率也高达300‑600h‑1；此外该催化剂可以重复使用，且结构和催化活性都没有发生变化；该材料的制备工艺简单、产品纯度高，在催化领域中具有潜在的应用前景。
The invention belongs to the technical field of catalytic chemistry, and in particular relates to a type of polyacid-based metal organic framework crystal material, a preparation method and application thereof for catalyzing synthesis of p-benzoquinone compounds. The material can be used as a heterogeneous catalyst in catalyzing alkylphenol, It has excellent catalytic performance in the reaction of alkoxybenzene and 2-methylnaphthalene oxidation to synthesize corresponding p-benzene kun, especially in catalyzing the oxidation of 2,3,6-trimethylphenol to synthesize 2,3,5-trimethylphenol In the reaction of benzene kun, in 10-20min, almost can realize the complete conversion of substrate, the productive rate of benzene kun is up to 96%-99%, and its transformation frequency is also up to 300-600h -1 ; In addition this catalyst can repeat It can be used, and the structure and catalytic activity have not changed; the preparation process of the material is simple, the product purity is high, and the material has potential application prospects in the field of catalysis.
Description
Technical Field
The invention belongs to the technical field of catalytic chemistry, and particularly relates to a preparation method of a polyacid-based metal organic framework crystal material and application of the polyacid-based metal organic framework crystal material in catalyzing and oxidizing alkylphenol, alkoxy benzene and 2-methylnaphthalene to efficiently synthesize a hydroquinone compound.
Background
The p-benzoquinone compounds are important intermediates for synthesizing medicaments, health products and fine chemicals, and play an important role in a plurality of biological systems. The selective oxidation of synthetic raw materials (such as phenol, aromatic hydrocarbon and the like) in a low oxidation state is a main way for preparing hydroquinone compounds. Conventional oxidation processes typically use stoichiometric amounts of metal oxidizing agents (CrO)3，MnO2，V2O5) And strong acid solutions, but always with the production of large amounts of hazardous waste and over-oxidized by-products. Use of environmentally friendly O in reactions2Or H2O2Oxidants are receiving increasing attention. At present, some transition metal salts or coordination compounds are present in O2Or H2O2As the catalyst for oxidizing various phenols and alkoxyaromatics under the conditions mentioned above, for example, cupric chloride, Co-Schiff base complex, titanosilicate, methyltrioxorhenium, ruthenium and iron compounds, etc. are mentioned. However, these catalysts have problems of poor stability, low selectivity to hydroquinone, low utilization efficiency of an oxidizing agent, and the like. Therefore, the development of highly active, highly selective and stable catalysts for synthesizing p-benzoquinones remains a significant challenge.
Polyoxometallates (polyacid for short, POMs) have shown a certain application value in liquid phase oxidation of various organic substances due to good redox property and stability. Heteropoly acid H with Keggin structure in catalyzing oxidation of alkyl phenol/aromatic hydrocarbon into corresponding quinonenXM12O40(M ═ W or Mo; X ═ P or Si; n ═ 3or 4) and transition metal-substituted heteropolyacids such as TBA4H[γ-PW10V2O40]And TBA8[{γ-SiW10Ti2O36(OH)2}2(μ-O)2]Have been used as homogeneous catalysts (Shimizu, m., Orita, h., Hayakawa, t., Takehira, k.,tetrahedron Lett.1989,30, 471-; ivanchikova, i.d.; maksimchuk, n.v.; maksimovskaya, r.i.; maksimov, g.m.; kholdeva, o.a. acs catal.2014,4, 2706-. Although these homogeneous catalysts generally have high catalytic activity, separation and recycling of the catalyst and purification of the product still face major difficulties. Therefore, the development of heterogeneous polyacid catalysts for synthesizing p-benzoquinone compounds is still a subject of urgent research.
One effective strategy for obtaining heterogeneous polyacid catalysts is to combine a polyacid with a metal-organic framework material to construct a crystalline polyacid-based metal-organic framework material (POMOF) that not only integrates the advantages of both polyacid and metal-organic framework materials, but also improves the structural and thermal stability of such composites. To date, some POMOF materials have shown higher catalytic activity and good cycle stability in catalyzing ester hydrolysis, chemical warfare agent degradation, sulfide oxidation, alcohol oxidation, etc. (Du, d.y., Qin, j.s., Li, s.l., Su, z.m., Lan, y.q., chem.soc.rev.2014,43, 4615-. However, until now, no literature report exists on the selective synthesis of corresponding quinone compounds by using POMOF crystal materials for oxidizing alkylphenol or other substrates with low oxidation states, so that it is necessary to develop polyacid-based metal organic framework crystal materials with novel structures for synthesizing p-benzoquinone compounds with high activity and high selectivity.
Disclosure of Invention
The invention aims to synthesize polyacid-based metal organic framework (POMOF) crystal materials and provide a preparation method of the crystal materials, the synthesized POMOF materials can be used as efficient catalysts for catalyzing alkylphenol, alkylbenzene and 2-methylnaphthalene to be oxidized into hydroquinone compounds, and the catalysts can be repeatedly used.
The technical scheme of the invention is as follows:
polyacid-base metal-organic frame crystal material with chemical formula of H [ CuII(ttb)(H2O)3]2[CuII(ttb)Cl]2[PW12O40]·4H2O and [ ClCu6 I(trz)4][ClCu5 I(trz)4]2[CuII(H2O)][PW12O40](ii) a Wherein, Httb is 1- (tetrazole-5-yl) -4- (triazole-1-yl) benzene, and trz is 1,2, 4-triazole.
The polyacid-based metal organic framework crystal materials all belong to a monoclinic system;
when the ligand is Httb, the space group of the crystal material 1 is P21N, unit cell parameter of
β＝99.2120(10)°，
When the ligand is trz, the space group of the crystalline material 2 is C2/C, and the unit cell parameter is
β＝113.765(3)°，
The asymmetric unit in the crystalline material 1 contains half of the crystallographically independent [ PW12O40]3–Ions, two divalent copper ions, two deprotonated 1- (tetrazol-5-yl) -4- (triazol-1-yl) benzene ligands (ttb), one chloride ion and two crystalline water molecules; the two copper ions have different configurations, one is a six-coordination octahedron configuration, and the other is a five-coordination quadrate cone configuration; copper ions are connected through ttb ligand to form two structural units, namely, binuclear { Cu2(ttb)2And of four nuclei{Cu4(ttb)4}; first a binuclear subunit { Cu2(ttb)2Interconnect by common copper ions to produce a one-dimensional structure, with adjacent one-dimensional chains passing through a four-core subunit { Cu }4(ttb)4Mutually connecting, generating two-dimensional wavy metal complex layers along the c-axis direction, and enabling wave crests and wave troughs of adjacent wavy two-dimensional layers to meet to form one-dimensional pore channels, [ PW12O40]3–Anions are filled in the one-dimensional pore canal as bidentate ligands to form a three-dimensional polyacid-based metal organic framework;
half of the [ PW ] exists in an asymmetric unit of crystalline material 212O40]3-The material comprises ions, eight points of five copper ions, six 1,2, 4-triazole ligands (trz), one point of five chloride ions and half coordination water molecules; the eight-point five copper ions have three different coordination configurations, namely a three-coordination planar triangular configuration, a four-coordination planar square configuration and a five-coordination triangular bipyramid configuration; copper ions are connected through a trz ligand to form a tetranuclear subunit and an octanuclear subunit; each four-core subunit { Cu4(trz)4Cl } with four eight-core subunits Cu8(trz)8Are connected, and each eight-core subunit { Cu }8(trz)8And four-core subunits { Cu }4(trz)4Cl and four eight-core subunits Cu8(trz)8Connecting to form two-dimensional latticed metal complex layers, stacking adjacent two-dimensional layers in parallel to form a three-dimensional porous frame with one-dimensional zigzag channels, [ PW12O40]3–Anions are used as decadentate ligands and are filled in the one-dimensional pore channels through Cu-O interaction to form a three-dimensional polyacid-based metal organic framework.
The preparation method of the polyacid-based metal organic framework crystal material is synthesized by a hydrothermal method and specifically comprises the following steps:
1) synthesis of precursor K by conventional method4[PW11VVO40]·xH2O and H3PW12O42·xH2O (Domaille,P.J.,Inorg.Synth.,John Wiley&Sons.:1990；Vol.27,96-104；John,C.B. J.,Inorg.Synth.,John Wiley&Sons.:1939；Vol.1,132-133)；
2-1) adding K4[PW11VVO40]·xH2O is dissolved in water, and then copper (II) salt and Httb, where K is added4[PW11VVO40]·xH2The ratio of the amounts of O, copper (II) salt and Httb is 1: 4-4.5: 2.3; after stirring for 0.5h, adjusting the pH value to 2.0-2.8 by using dilute hydrochloric acid, continuing stirring for 0.5h, then transferring to a polytetrafluoroethylene reaction kettle, heating in an oven at 180 ℃ for about 6 days, slowly cooling to room temperature to obtain a green blocky crystalline material, and washing and drying to obtain the three-dimensional POMOF material.
2-2) reaction of K4[PW11VVO40]·xH2O is dissolved in water, and then a copper (II) salt and trz, where K is added4[PW11VVO40]·xH2The mass ratio of O, copper (II) salt and 1,2, 4-triazole is 1.2: 7-7.5: 11.5; after stirring for 0.5h, adjusting the pH value to 1.4-1.6 by using dilute hydrochloric acid, continuing stirring for 0.5h, then transferring the mixture into a polytetrafluoroethylene reaction kettle, heating the mixture in an oven at 180 ℃ for about 5 days, slowly cooling the mixture to room temperature to obtain a brownish black blocky crystalline material, and washing and drying the material to obtain a three-dimensional POMOF material;
k in the step 2-2)4[PW11VVO40]·xH2O is formed by H3PW12O42·xH2O and ammonium metavanadate.
The catalytic application of polyacid-based metal organic framework crystal materials in selective oxidation of alkylphenol, alkoxybenzene and 2-methylnaphthalene to corresponding hydroquinone compounds is as follows:
adding the catalyst, the substrate and the internal standard substance naphthalene into a mixed solvent of acetonitrile and water with the same volume, heating to 60 ℃ under stirring, and adding aqueous hydrogen peroxide. 0.2. mu.L of the supernatant was aspirated by a micro gas injection needle and analyzed by a gas chromatograph. Wherein, the catalyst, the substrate, the internal standard substance and H2O2In a molar ratio of 0.005 to 0.03: 1: 1: 1-5, the substrate concentration is 0.5M.
The invention has the beneficial effects that:
(1) the POMOF material can be used as a heterogeneous catalyst to catalyze the high-efficiency synthesis of hydroquinone compounds, and particularly can realize the complete conversion of TMP and the high-yield production of TMBQ (96% -99%) in the reaction of catalyzing 2,3, 6-Trimethylphenol (TMP) to synthesize 2,3, 5-Trimethylphenol (TMBQ) within 10-20 min.
(2) The POMOF material has the conversion frequency of 300-600h in the reaction of catalyzing TMP to synthesize TMBQ-1This is also the highest conversion frequency in the reactions currently known for the synthesis of TMBQ by catalysis of TMP with heterogeneous catalytic systems based on polyacids.
(3) The POMOF material can still maintain the original state and level of structure and catalytic activity after ten cycles. And in a kinetic region (at a conversion rate of less than 20%), the catalyst still maintains excellent catalytic activity after 5 cycles.
(4) The POMOF material disclosed by the invention shows excellent catalytic performance, and the catalytic performance is derived from the synergistic effect between Keggin ions and a Cu-organic framework.
(5) The POMOF material is determined to have a novel structure through single crystal X-ray diffraction, and is a POMOF crystal material for catalyzing TMP to synthesize TMBQ.
Drawings
FIG. 1(a) shows an asymmetric unit of the crystalline material 1 of the invention, (b) a dinuclear subunit { Cu ] in the crystalline material 12(ttb)2} (c) Tetranuclear subunits in crystalline Material 1 { Cu4(ttb)4} (d) dinuclear subunit-based { Cu in crystalline material 12(ttb)2A one-dimensional chain structure of (e) a two-dimensional layer in the crystalline material 1, and (f) a three-dimensional polyacid-based metal-organic framework structure in the crystalline material 1.
FIG. 2(a) is an asymmetric unit of the crystalline material 2 of the present invention, (b) a tetranuclear subunit { Cu in the crystalline material 24(trz)4}, (c) eight-core subunits in crystalline material 2 { Cu }8(trz)8} (d) two-dimensional Metal Complex in crystalline Material 2Layers, (e) and (f) Keggin ions in the crystal material 2 occupy one-dimensional channels to construct a three-dimensional polyacid-based metal-organic framework structure, and (g) the coordination mode of polyacid anions in the crystal material 2.
FIG. 3(a) is an infrared spectrum of the crystalline material 1 of the present invention, and (b) an infrared spectrum of the crystalline material 2 of the present invention.
FIG. 4(a) is an X-ray powder diffraction pattern of the crystalline material 1 of the present invention, and (b) is an X-ray powder diffraction pattern of the crystalline material 2 of the present invention.
Figure 5(a) is the effect of the volume ratio of acetonitrile and water on the catalytic TMP oxidation of crystalline material 1 and (b) the effect of the volume ratio of acetonitrile and water on the catalytic TMP oxidation of crystalline material 2.
Figure 6 is a plot of the effect of ten times the amount of crystalline materials 1 and 2 on the oxidative performance of catalytic TMP.
FIGS. 7(a) and (b) are the results of cyclic experiments in which crystalline materials 1 and 2 catalyze the oxidation of TMP, respectively.
FIGS. 8(a) and (b) are X-ray powder diffraction patterns before and after the catalytic reaction of the crystalline materials 1 and 2, respectively, and (c) and (d) infrared patterns before and after the catalytic reaction of the crystalline materials 1 and 2, respectively.
Figure 9 is a graph of the effect of a radical scavenger on the catalytic TMP oxidation of crystalline materials 1 and 2.
Fig. 10 is a graph of the uv-vis spectrum of the crystalline material 1 before and after addition of hydrogen peroxide.
Fig. 11 is a raman spectrum of the crystalline material 1 before and after addition of hydrogen peroxide.
FIG. 12 is a reaction mechanism of TMBQ synthesis by oxidation of TMP catalyzed by crystalline material.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are provided herein for purposes of illustration and are not intended to be limiting.
Example 1:
polyacid-based metal-organic framework crystal material H [ Cu ]II(ttb)(H2O)3]2[CuII(ttb)Cl]2[PW12O40]·4H2The preparation method of O comprises the following specific steps:
1) synthesis of precursor K by conventional method4[PW11VVO40]·xH2O(Domaille,P.J.,Inorg. Synth.,John Wiley&Sons.:1990；Vol.27,96-104)；
2)K4[PW11VVO40]·xH2O (0.3g, 0.1mmol) was dissolved in 10mL of water, followed by the addition of CuCl2·2H2O (0.0682g,0.40mmol) and Httb (0.0491g,0.23mmol), stirring for 0.5h, adjusting pH to 2.0-2.8 with dilute hydrochloric acid, stirring for 0.5h, transferring to a polytetrafluoroethylene reaction kettle, heating in an oven at 180 deg.C for about 6 days, and slowly cooling to room temperature to obtain green block crystalline material with yield of about 52% (based on K)4[PW11VVO40]·xH2O)。
0.0682g of CuCl2·2H2O can be replaced by 0.0767g of CuCl2·2H2O or 0.0998-0.1124 g CuSO4·5H2O or 0.0966-0.1087 g CuNO3·3H2And replacing by O.
Example 2:
polyacid-based metal-organic framework crystalline material [ ClCu6 I(trz)4][ClCu5 I(trz)4]2[CuII(H2O)][PW12O40]The preparation method comprises the following specific steps:
1) synthesis of precursor K by conventional method4[PW11VVO40]·xH2O(Domaille,P.J.,Inorg. Synth.,John Wiley&Sons.:1990；Vol.27,96-104)；
2)K4[PW11VVO40]·xH2O (0.35g, 0.12mmol) was dissolved in 10mL water, then Cu (OAc) was added2·H2O (0.1497g,0.75mmol) and trz (0.0794g,1.15mmol), stirring for 0.5h, adjusting pH to 1.4-1.6 with dilute hydrochloric acid, stirring for 0.5h, transferring to a polytetrafluoroethylene reaction kettle, heating in an oven at 180 deg.C for about 5 days, and cooling slowly to room temperature to obtain brown-black crystalline material with yield of about 61% (based on K)4[PW11VVO40]·xH2O)。
0.1497g of Cu (OAc)2·H2O can be comprised of 0.1398g Cu (OAc)2·H2O or 0.1194-0.1279 g CuCl2·2H2And replacing by O.
Example 3:
polyacid-based metal-organic framework crystalline material [ ClCu6 I(trz)4][ClCu5 I(trz)4]2[CuII(H2O)][PW12O40]The preparation method comprises the following specific steps:
1) synthesis of precursor H by conventional method3PW12O42·xH2O(John,C.B.J.,Inorg.Synth., John Wiley&Sons.:1939；Vol.1,132-133)；
2)H3PW12O42·xH2O (0.32g, 0.12mmol) was dissolved in 10mL of water, followed by addition of Cu (OAc)2·H2O (0.1497g,0.75mmol) and trz (0.0794g,1.15mmol), stirring for 0.5h, adjusting pH to 1.4-1.6 with dilute hydrochloric acid, stirring for 0.5h, transferring to a polytetrafluoroethylene reaction kettle, heating in an oven at 180 deg.C for about 5 days, cooling slowly to room temperature to obtain a brown-black block crystalline material with a yield of about 31% (based on K)4[PW12O40]·xH2O)。
0.1497g of Cu (OAc)2·H2O can be comprised of 0.1398g Cu (OAc)2·H2O or 0.1194-0.1279 g CuCl2·2H2And replacing by O.
The products obtained in the above examples were tested to obtain POMOF materials with the chemical formula of H [ Cu ]II(ttb)(H2O)3]2[CuII(ttb)Cl]2[PW12O40]·4H2O and [ ClCu6 I(trz)4][ClCu5 I(trz)4]2[CuII(H2O)][PW12O40]. Wherein, Httb is 1- (tetrazole-5-yl) -4- (triazole-1-yl) benzene, and trz is 1,2, 4-triazole. The crystal structures of the POMOF material provided by the invention are shown in figures 1 and 2.
The products obtained in the above examples were detected by infrared spectroscopy, and FIG. 3 is an infrared spectrum of two POMOF materials of the present invention, showing W-O of polyacid anionst、W-Ob、W-Oc、W-OaAnd P-OaAnd characteristic absorption peaks of ligand molecules and water molecules.
The products in the above examples were detected by X-ray powder diffraction, and fig. 4 is an X-ray powder diffraction spectrum of two POMOF materials of the present invention, in which the experimental spectrum is substantially consistent with the theoretical spectrum fitted based on single crystal diffraction, which proves that the sample used for property testing is pure.
The activity of the crystalline material prepared in the above examples as a heterogeneous catalyst was first evaluated using the selective oxidation of 2,3, 6-Trimethylphenol (TMP) as a model reaction, and the catalytic oxidation route is as follows:
the catalytic results of the crystalline materials prepared in examples 1 and 2 were detected by gas chromatography, and table 1 summarizes the corresponding catalytic results, wherein hydrogen peroxide is an oxidant, and can achieve complete conversion of TMP within 10-20min, the selectivity of corresponding 2,3, 5-trimethyl hydroquinone (TMBQ) reaches 96% -99%, and the conversion frequency (TOF) is 300h–1And 600h–1。
The optimal reaction conditions for catalyzing the oxidation of TMP by the crystal materials prepared in examples 1 and 2 are detected by using gas chromatography, the influence of different solvents on the oxidation of TMP by the POMOF materials is summarized in Table 2, and the result shows that acetonitrile is the optimal solvent; FIG. 5 shows the effect of the volume ratio of acetonitrile and water on the POMOF material catalyzing the oxidation of TMP, and the result shows that when the acetonitrile and water are equal in volume, the POMOF material has the best catalytic effect; table 3 summarizes the effect of the amount of hydrogen peroxide used on the catalytic TMP oxidation of the POMOF material, showing that the optimal amount is 1.0 mmol; table 4 summarizes the effect of reaction temperature on the catalytic TMP oxidation of the POMOF material, and shows that the optimal temperature is 60 ℃.
The application prospects of the crystal materials prepared in examples 1 and 2 as heterogeneous catalysts are detected by using gas chromatography, fig. 6 is a result of the POMOF material catalyzing TMP oxidation after the usage of all materials in the catalytic system is increased by 10 times, and the result shows that the POMOF material can still catalyze more than 90% of TMP conversion within 25min, and the selectivity of TMBQ also reaches more than 90%.
The cycle results of the crystalline materials prepared in examples 1 and 2 for catalyzing the oxidation of TMP were measured by gas chromatography, and fig. 7 is the catalytic results after 10 cycles, which shows that the catalytic activity of the catalyst is still maintained at a high level after 10 cycles.
XRD and infrared spectrum are utilized to detect the stability of the crystal materials prepared in the examples 1 and 2 before and after catalytic reaction, and figure 8 is an X-ray powder diffraction contrast diagram and an infrared contrast diagram before and after the POMOF material catalytic reaction, and the contrast result shows that the structure of the POMOF material is not changed before and after the catalysis.
The results of the experiment for capturing free radicals of the crystal material prepared in example 1 to catalyze the oxidation of TMP were measured by gas chromatography, and fig. 9 is the reaction result of adding different free radical capturing agents, and the results show that oxygen radicals and carbon radicals may be generated in the process of oxidizing TMP to synthesize TMBQ by the pommof material, that is, TMP is oxidized by a free radical mechanism.
Preparation of crystalline Material in example 1 by UV-Vis Spectroscopy and Raman Spectroscopy in H2O2The peroxypolyacid compound formed under the condition is detected, fig. 10 is an ultraviolet-visible spectrum before and after adding trace hydrogen peroxide, fig. 11 is a raman spectrum before and after adding trace hydrogen peroxide, and the result shows that the POMOF material can be oxidized into peroxypolyacid species through hydrogen peroxide to catalyze TMP oxidation.
FIG. 12 shows the mechanism by which the crystalline material of the present invention catalyzes the oxidation of TMP to TMBQ, including both a free radical mechanism and an oxygen transfer mechanism that generates peroxygen species.
The results of the crystalline materials prepared in examples 1 and 2, which are used for catalyzing other substrates to be oxidized and synthesized into hydroquinone, are detected by gas chromatography, and table 5 summarizes the catalytic results of different alkylphenols, alkoxybenzenes and 2-methylnaphthalenes, and the results show that the POMOF material can show good catalytic activity on different alkylphenols, and can also show a certain catalytic activity on the alkoxybenzenes and the 2-methylnaphthalenes.
TABLE 1 POMOF materials catalysis of TMP oxidative Synthesis of TMBQ
TABLE 2 Effect of different solvents on the catalytic synthesis of TMBQ from TMP by POMOF materials
TABLE 3 Effect of the amount of Hydrogen peroxide used on the catalytic Synthesis of TMBQ by oxidation of TMP with POMOF materials
TABLE 4 Effect of reaction temperature on the Synthesis of TMBQ by oxidation of TMP catalyzed by POMOF Material
TABLE 5 POMOF materials catalyze the oxidation of different substrates to synthesize corresponding hydroquinone
TABLE 6 comparison of catalytic Activity of various heterogeneous catalysts for TMP oxidation in recent years
Claims (4)
1. The catalytic application of polyacid-based metal-organic framework crystal material in selective oxidation of alkylphenol, alkoxybenzene and 2-methylnaphthalene to corresponding hydroquinone compounds is characterized in that the polyacid-based metal-organic framework crystal material has the chemical formula of H [ Cu [II(ttb)(H2O)3]2[CuII(ttb)Cl]2[PW12O40]·4H2O and [ ClCu6 I(trz)4][ClCu5 I(trz)4]2[CuII(H2O)][PW12O40](ii) a Wherein, Httb is 1- (tetrazole-5-yl) -4- (triazole-1-yl) benzene, trz is 1,2, 4-triazole;
the polyacid-based metal organic framework crystal materials all belong to a monoclinic system;
when the ligand is Httb, the space group of the crystal material 1 is P21N, unit cell parameter of
β＝99.2120(10)°，
When the ligand is trz, the space group of the crystalline material 2 is C2/C, and the unit cell parameter is
β＝113.765(3)°，
The asymmetric unit in the crystalline material 1 contains half of the crystallographically independent [ PW12O40]3–Ions, two divalent copper ions, two deprotonated 1- (tetrazol-5-yl) -4- (triazol-1-yl) benzene ligands (ttb), one chloride ion and two crystalline water molecules; the two copper ions have different configurations, one is a six-coordination octahedron configuration, and the other is a five-coordination quadrate cone configuration; copper ions are connected through ttb ligand to form two structural units, namely, binuclear { Cu2(ttb)2And tetranuclear { Cu }4(ttb)4}; first a binuclear subunit { Cu2(ttb)2Interconnect by common copper ions to produce a one-dimensional structure, with adjacent one-dimensional chains passing through a four-core subunit { Cu }4(ttb)4Mutually connecting, generating two-dimensional wavy metal complex layers along the c-axis direction, and enabling wave crests and wave troughs of adjacent wavy two-dimensional layers to meet to form one-dimensional pore channels, [ PW12O40]3–Anions are filled in the one-dimensional pore canal as bidentate ligands to form a three-dimensional polyacid-based metal organic framework;
half of the [ PW ] exists in an asymmetric unit of crystalline material 212O40]3-The material comprises ions, eight points of five copper ions, six 1,2, 4-triazole ligands (trz), one point of five chloride ions and half coordination water molecules; the eight-point five copper ions have three different coordination configurations, namely a three-coordination planar triangular configuration, a four-coordination planar square configuration and a five-coordination triangular bipyramid configuration; copper ions are connected through a trz ligand to form a tetranuclear subunit and an octanuclear subunit; each four-core subunit { Cu4(trz)4Cl } with four eight-core subunits Cu8(trz)8Are connected, and each eight-core subunit { Cu }8(trz)8And four-core subunits { Cu }4(trz)4Cl and four eight-core subunits Cu8(trz)8Connecting to form two-dimensional latticed metal complex layers, stacking adjacent two-dimensional layers in parallel to form a three-dimensional porous frame with one-dimensional zigzag channels, [ PW12O40]3–The anion being tenThe dentate ligand is filled in the one-dimensional pore channels through Cu-O interaction to form a three-dimensional polyacid-based metal organic framework;
the catalytic application steps are as follows:
adding a catalyst, a substrate and an internal standard substance naphthalene into a mixed solvent of acetonitrile and water with the same volume, heating to 60 ℃ under stirring, and adding a hydrogen peroxide aqueous solution; sucking the supernatant with a trace gas phase sampling needle, and analyzing with a gas chromatograph; wherein, the catalyst, the substrate, the internal standard substance and H2O2In a molar ratio of 0.005 to 0.03: 1: 1: 1-5, the substrate concentration is 0.5M.
2. The method for preparing a polyacid-based metal-organic framework crystalline material for catalytic application as in claim 1, wherein the polyacid-based metal-organic framework crystalline material is synthesized by a hydrothermal method, and comprises the following steps:
1) synthesis of precursor K by conventional method4[PW11VVO40]·xH2O and H3PW12O42·xH2O；
2-1) adding K4[PW11VVO40]·xH2O is dissolved in water, and then copper (II) salt and Httb, where K is added4[PW11VVO40]·xH2The ratio of the amounts of O, copper (II) salt and Httb is 1: 4-4.5: 2.3; after stirring for 0.5h, adjusting the pH to 2.0-2.8 by using dilute hydrochloric acid, continuing stirring for 0.5h, then transferring to a polytetrafluoroethylene reaction kettle, heating in an oven at 180 ℃ for about 6 days, slowly cooling to room temperature to obtain a green blocky crystalline material, and washing and drying to obtain a three-dimensional POMOF material;
2-2) reaction of K4[PW11VVO40]·xH2O is dissolved in water, and then a copper (II) salt and trz, where K is added4[PW11VVO40]·xH2The mass ratio of O, copper (II) salt and 1,2, 4-triazole is 1.2: 7-7.5: 11.5; stirring for 0.5h, adjusting pH to 1.4-1.6 with dilute hydrochloric acid, stirring for 0.5h, transferring to polytetrafluoroethylene reaction kettle, and adding at 180 deg.C in ovenAnd after the heating for about 5 days, slowly cooling to room temperature to obtain a brownish black blocky crystalline material, and washing and drying to obtain the three-dimensional POMOF material.
3. The method according to claim 2, wherein K in the step 2-2)4[PW11VVO40]·xH2O is formed by H3PW12O42·xH2O and ammonium metavanadate.
4. A method according to claim 2 or 3, wherein the copper (II) salt is copper acetate or copper chloride.
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