CN113735065B - Method for producing hydrogen peroxide by using modified amino functionalized zirconium-based metal-organic framework composite photocatalyst - Google Patents
Method for producing hydrogen peroxide by using modified amino functionalized zirconium-based metal-organic framework composite photocatalyst Download PDFInfo
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Abstract
The invention discloses a method for producing hydrogen peroxide by utilizing a modified amino functionalized zirconium-based metal-organic framework composite photocatalyst, which comprises the following steps: mixing the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst with an electron donor solution for photocatalytic reaction to obtain hydrogen peroxide, wherein the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst comprises an enol-ketone covalent organic framework and an amino-functionalized zirconium-based metal-organic framework which grows on the surface of the enol-ketone covalent organic framework in situ. The method has the advantages of high preparation efficiency, high yield and the like, can be used for preparing hydrogen peroxide on a large scale, is beneficial to industrial application, and has high use value and good application prospect; meanwhile, the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst has excellent stability, so that the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst can be used for producing hydrogen peroxide for multiple times, and the production cost is further reduced.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, relates to a method for producing hydrogen peroxide, and in particular relates to a method for producing hydrogen peroxide by utilizing a modified amino functionalized zirconium-based metal-organic framework composite photocatalyst.
Background
With the development of modern industry, the energy crisis and environmental pollution are increasingly serious, wherein the energy shortage and the environmental deterioration are important problems facing and urgently needed to be solved by human beings. Therefore, the new energy utilization and the environmental pollution control have important significance for the national sustainable development strategy. The photocatalysis technology has wide application prospect in the aspects of energy storage, conversion and environmental protection due to the advantages of low cost, no pollution, high efficiency and the like.
The metal organic framework Materials (MOFs) are porous crystal materials with periodic network structures, which are constructed by metal or metal clusters and organic ligands, and have the characteristics of regular and ordered pore channel structures, adjustable pore size, modifiable framework and the like. In recent years, MOFs have been attracting attention for use in the field of heterogeneous photocatalysis. The 2008 Norway scientists synthesized a zirconium-based metal-organic framework material UIO-66 for the first time, which is made of regular octahedron Zr 6 O 4 (OH) 4 The metal cluster is formed by complexing with organic ligand terephthalic acid, the structure of the metal cluster contains two pore cages of regular octahedron and tetrahedron, and the two pore cages are mutually communicated through triangular pore windows, so that the metal cluster has excellent thermal stability and chemical stability. Although the amino-functionalized UIO-66 has photocatalysis performance, the light absorption range is narrow, the photo-generated electron-hole separation efficiency is low, and the application of the amino-functionalized UIO-66 in the photocatalysis field is severely restricted.
In order to expand the light absorption capacity of the amino-functionalized UIO-66 and improve the photocatalysis performance of the amino-functionalized UIO-66, scientific researchers modify the amino-functionalized UIO-66 by adopting different methods, wherein the construction of a semiconductor heterojunction is a better modification method, mainly means that the amino-functionalized UIO-66 is compounded with one or more semiconductors with proper band gaps, and the light absorption advantages of the respective energy band structures can be combined to expand and increase the response of the amino-functionalized UIO-66 to a large positive spectrum; and simultaneously, a binary or multi-element heterostructure is constructed, so that the potential of a valence band and a conduction band can be further improved. However, the constructed amino-functionalized UIO-66 based semiconductor heterojunction still has the following problems: the problems of insufficient light absorption performance, easy recombination of photo-generated carriers, high electron-hole pair recombination rate, insufficient catalytic degradation performance and the like severely limit the wide application of the amino-functionalized zirconium-based metal-organic framework composite photocatalyst. In addition, during the actual research of the present inventors, it was also found that: because the enol-ketone covalent organic framework/graphene carbon nitride composite photocatalyst is formed by a traditional II-type heterojunction, the charge separation efficiency is relatively low, and the catalytic activity is relatively poor, the defect of low yield still exists when the enol-ketone covalent organic framework/graphene carbon nitride composite photocatalyst is used for preparing hydrogen peroxide, in addition, the existing enol-ketone covalent organic framework is prepared by adopting a solvothermal method, in the related preparation method, the adopted heating mode is difficult to effectively realize synchronous heating inside and outside a solution system during the heating process of the solution system, so that the reaction is uneven, the good structural stability of a product is difficult to ensure, and in addition, longer reaction time and more heat energy are required for promoting the interaction of precursor bonding, so that the method is unfavorable for large-scale preparation, and the energy-saving requirement in industrial production is difficult to be met; the preparation method of the existing enol-ketone covalent organic framework/graphene carbon nitride composite photocatalyst has the outstanding problem that in the preparation method of the existing enol-ketone covalent organic framework/graphene carbon nitride composite photocatalyst, a graphite-phase carbon nitride and an enol-ketone covalent organic framework are compounded together by means of physical mixing (such as ultrasonic, stirring and drying), so that the bonding strength between the graphite-phase carbon nitride and the enol-ketone covalent organic framework in the formed composite photocatalyst is poor, and therefore, the preparation of the composite photocatalyst with a stable structure is difficult. The existence of the defects makes the prior enol-ketone covalent organic framework/graphene carbon nitride composite photocatalyst difficult to be widely applied in the field of hydrogen peroxide production. Up to now, no report has been made on the use of a composite photocatalyst obtained by compositing an enol-ketone covalent organic framework as a template through an amino-supported functionalized zirconium-based metal organic framework for photocatalytic production of hydrogen peroxide. Therefore, how to effectively overcome the problems, the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst which has the advantages of high specific surface area, more reaction active sites, wide light absorption range, low electron-hole pair recombination rate, good photocatalysis performance and good stability, and the preparation method of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst which is matched with the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst, has the advantages of simple process, wide raw material source, low cost, high preparation efficiency and high yield, and has important significance for improving the preparation efficiency and yield of hydrogen peroxide.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a method for producing hydrogen peroxide by utilizing a modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst, which has high preparation efficiency and high yield.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for producing hydrogen peroxide by utilizing a modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst comprises the following steps: mixing a modified amino functionalized zirconium-based metal-organic framework composite photocatalyst with an electron donor solution to perform a photocatalytic reaction to obtain hydrogen peroxide; the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst comprises an enol-ketone covalent organic framework and an amino-functionalized zirconium-based metal-organic framework, wherein the amino-functionalized zirconium-based metal-organic framework grows on the surface of the enol-ketone covalent organic framework in situ.
The method is further improved, and the mass ratio of the amino-functionalized zirconium-based metal organic framework to the enol-ketone covalent organic framework is 1:0.01-0.35; the enol-ketone covalent organic framework photocatalyst is a porous framework material formed by taking melamine and 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde as organic network construction units and carrying out irreversible enol-ketone tautomeric connection.
The method is further improved, and the amino-functional zirconium-based metal organic framework is of a regular octahedral structure; the enol-ketone covalent organic framework is in a fiber stick shape; the mass ratio of the amino-functionalized zirconium-based metal organic framework to the enol-ketone covalent organic framework is 1:0.020-0.28. Further preferably, the mass ratio of the amino-functionalized zirconium-based metal organic framework to the enol-ketone covalent organic framework is 1:0.20-0.28.
The method is further improved, and the preparation method of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst comprises the following steps of:
s1, mixing 2-amino terephthalic acid, enol-ketone covalent organic framework and N, N-dimethylformamide, and performing ultrasonic dispersion to obtain a dispersion liquid;
s2, mixing the dispersion liquid obtained in the step S1 with zirconium tetrachloride for hydrothermal reaction, filtering, washing and drying to obtain the enol-ketone covalent organic framework/amino functional zirconium-based metal organic framework composite photocatalyst.
In the above method, further improved, in step S1, the preparation method of the enol-ketone covalent organic framework includes the following steps:
(1) Mixing melamine, 2,4, 6-trihydroxybenzene-1, 3, 5-trioxymethylene, N-dimethylacetamide and dimethyl sulfoxide, performing ultrasonic dispersion, and adding glacial acetic acid solution to obtain a precursor solution;
(2) And (3) heating the precursor solution obtained in the step (1) under the microwave condition, performing polycondensation reaction, filtering, washing and drying to obtain the enol-ketone covalent organic framework.
In the method, the mole ratio of the melamine to the 2,4, 6-trihydroxybenzene-1, 3, 5-trioxymethylene in the step (1) is 0.5-2:1-3; the concentration of the glacial acetic acid solution is 1M-4M; the volume ratio of the N, N-dimethylacetamide to the dimethyl sulfoxide in the mixed solution of the N, N-dimethylacetamide and the dimethyl sulfoxide is 1-3:0.5-2; the ultrasonic dispersion time is 5-30 min.
In the method, in the step (2), the power of the microwaves is controlled to be 20-150W in the heating process; the polycondensation reaction is carried out under nitrogen atmosphere; the polycondensation reaction is carried out at a temperature of 100-300 ℃; the polycondensation reaction time is 10 min-60 min; the washing is a product of a polycondensation reaction by adopting N, N-dimethylacetamide, water and ethanol in turn; the drying is performed under vacuum; the drying temperature is 60-100 ℃; the drying time is 6-12 h.
In the method, in a further improved step S1, the temperature of ultrasonic dispersion is 25-45 ℃; the ultrasonic dispersion time is 0.5-3 h.
In the method, in a further improved step S2, the temperature of the hydrothermal reaction is 100-150 ℃; the hydrothermal reaction time is 12-48 hours; the washing is the product of the water and ethanol washing water heat reaction, 3 to 5 times respectively; the drying is performed under vacuum; the drying temperature is 60-100 ℃; the drying time is 6-12 h.
According to the method, the addition amount of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst is 500-1000 mg/liter of the electron donor solution.
In the above method, further improved, the electron donor solution is an isopropanol solution; the isopropanol solution is prepared by mixing isopropanol and water; the volume ratio of the isopropanol to the ultrapure water is 1:5-1:9; the time of the photocatalytic reaction is 45-65 min.
In a further development of the above method, the volume ratio of isopropyl alcohol to ultrapure water is 1:9.
Compared with the prior art, the invention has the advantages that:
the invention provides a method for producing hydrogen peroxide by utilizing a modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst, which can be used for efficiently producing hydrogen peroxide by mixing the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst with an electron donor solution for photocatalytic reaction. In the invention, the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst comprises an enol-ketone covalent organic framework and an amino-functionalized zirconium-based metal-organic framework, wherein the amino-functionalized zirconium-based metal-organic framework grows on the surface of the enol-ketone covalent organic framework in situ, has the advantages of high specific surface area, multiple reaction active sites, wide light absorption range, low electron-hole pair recombination rate, good photocatalysis performance, good stability and the like, and when the amino-functionalized zirconium-based metal-organic framework composite photocatalyst is used as a photocatalyst for producing hydrogen peroxide, the photogenerated electrons are converted from the enol-ketone covalent organic framework to the amino-functionalized zirconium-based metal-organic framework and react with adsorbed oxygen to generate superoxide radicals(·O 2 - ) Further converted into hydrogen peroxide (H) 2 O 2 ) Wherein the yield of hydrogen peroxide is 1.51X10 4 μM h -1 g -1 And after three times of recycling, the yield of the hydrogen peroxide is still as high as 1.13 multiplied by 10 4 μM h -1 g -1 The highest yield of the existing conventional enol-ketone covalent organic framework graphite phase carbon nitride composite photocatalyst is only 0.88 multiplied by 10 4 μM h -1 g -1 . The method for producing hydrogen peroxide by utilizing the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst has the advantages of high preparation efficiency, high yield and the like, can be used for preparing hydrogen peroxide on a large scale, is beneficial to industrial application, has high use value and good application prospect; meanwhile, the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst has excellent stability, so that the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst can be used for producing hydrogen peroxide for multiple times, and the production cost is further reduced.
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In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 shows a modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1, TUN-2, TUN-3, TUN-4) prepared in example 1 of the present invention, an amino-functionalized zirconium-based metal-organic framework (NH) 2 -UIO-66).
FIG. 2 shows the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1, TUN-2, TUN-3, TUN-4) prepared in example 1 of the present invention, amino-functionalized zirconium-based metal-organic framework (NH) 2 -UIO-66).
FIG. 3 shows the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1, TUN-2, TUN-3, TUN-4) prepared in example 1 of the present invention, amino-functionalized zirconium-based metal-organic framework (NH) 2 -UIO-66).
FIG. 4 is a schematic illustration of a modified amino functionalized zirconium-based metal organic framework complex prepared in example 1 of the present inventionPhoto-catalyst (TUN-3), enol-ketone covalent organic framework (TpMa), amino functional zirconium-based metal organic framework (NH) 2 -a TEM image of UIO-66), where (a) is NH 2 -UIO-66, (b) TpMa, (c) TUN-3.
FIG. 5 shows a modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3), an enol-ketone covalent organic framework (TpMa), an amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention 2 -UIO-66), wherein (a) is NH 2 -UIO-66, (b) TpMa, (c) TUN-3.
FIG. 6 shows the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1, TUN-2, TUN-3, TUN-4) and the amino-functionalized zirconium-based metal-organic framework composite photocatalyst (NH) prepared in example 1 of the present invention 2 -UIO-66) a corresponding time-yield plot for the photocatalytic production of hydrogen peroxide.
FIG. 7 is a graph showing the effect of the modified amino functionalized zirconium-based metal organic framework composite photocatalyst in example 3 of the present invention in cyclic production of hydrogen peroxide.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
In the following examples of the present invention, unless otherwise specified, materials and instruments used were commercially available, processes used were conventional, equipment used was conventional, and the data obtained were average of three or more repeated experiments.
Example 1:
a method for producing hydrogen peroxide by utilizing a modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst comprises the following steps:
taking modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1, TUN-2, TUN-3 and TUN-4) and amino-functionalized zirconium-based metal-organic framework (NH) 2 UIO-66), 50mg each, and adding them to 100mL of 10% strength by volume aqueous isopropanol solution, magnetically stirring in the dark (i.e. under dark conditions) for one hour,after reaching adsorption equilibrium, turning on a light source, and carrying out photocatalytic reaction under visible light (lambda is more than or equal to 420 nm) for 60min to produce hydrogen peroxide.
In this example, a modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1) is used, which comprises an enol-ketone covalent organic framework and an amino-functionalized zirconium-based metal-organic framework, wherein the amino-functionalized zirconium-based metal-organic framework grows on the surface of the enol-ketone covalent organic framework in situ. The mass ratio of the amino-functionalized zirconium-based metal organic framework to the enol-ketone covalent organic framework is 1:0.12. The enol-ketone covalent organic bone is a porous skeleton formed by taking melamine and 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde as organic network building units and carrying out irreversible enol-ketone tautomeric connection, in particular to irreversible-CH=N-and/or-CH 2 N (OH) -is a connecting bond, so that irreversible enol-ketone tautomeric connection occurs among all monomer molecules, and a porous framework with a periodic structure and a more stable structure is formed. The amino functional zirconium-based metal organic framework is of a regular octahedral structure; the enol-ketone covalent organic framework is in a fiber stick shape.
In the embodiment, the preparation method of the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1) comprises the following steps:
s1, ultrasonically dispersing melamine (57 mg) and 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde (95 mg) in a mixed solution of N, N-dimethylacetamide and dimethyl sulfoxide according to the mole ratio of the melamine to the 2,4, 6-trihydroxybenzene-1, 3, 5-trioxymethylene to be 1:1, wherein the ultrasonic dispersion time is 20min, and adding 0.3mL glacial acetic acid solution with the concentration of 3M as a catalyst to obtain a precursor solution.
S2, sealing the precursor solution obtained in the step S1 in a microwave tube under a nitrogen atmosphere, and heating by using a CEM Explorer microwave synthesizer to perform polycondensation reaction, wherein the method specifically comprises the following steps: heating to 300 ℃ under 100W single-mode microwave, maintaining for 20 minutes, filtering after the reaction is finished, cleaning a precipitation product of the polycondensation reaction by adopting N, N-dimethylacetamide, water and ethanol in sequence, and drying the obtained cleaned precipitation product for 12 hours at 80 ℃ under a vacuum condition to obtain the enol-ketone covalent organic framework photocatalyst named TpMa.
S3, mixing 0.2418g of 2-amino terephthalic acid (1.5 mmol) and 28.8mg of enol-ketone covalent organic framework (TpMa) obtained in the step S1 with 60mL of N, N-Dimethylformamide (DMF), performing ultrasonic dispersion for 30min, and adding 0.3498g of ZrCl 4 (1.5 mmol) and carrying out ultrasonic treatment until the mixture is uniformly dispersed, putting the mixture into a reaction kettle, carrying out reaction in a baking oven at 120 ℃ for 24 hours, taking out the mixture, washing the obtained product with water and ethanol for three times, and then putting the obtained product into a vacuum drying oven and drying the dried product at 80 ℃ for 12 hours to obtain the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst named TUN-1.
In this example, the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-2) used was substantially the same as the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1), except that: the mass ratio of the amino-functionalized zirconium-based metal-organic framework to the enol-ketone covalent organic framework in the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-2) is 1:0.15.
In this embodiment, the preparation method of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-2) adopted is basically the same as that of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1), and the difference is that: in the preparation method of the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-2), the dosage of the enol-ketone covalent organic framework (TpMa) is 36mg.
In this example, the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3) used was substantially the same as the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1), except that: the mass ratio of the amino-functionalized zirconium-based metal-organic framework to the enol-ketone covalent organic framework in the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3) is 1:0.25.
In this embodiment, the preparation method of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3) is basically the same as that of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1), and the difference is that: in the preparation method of the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3), the dosage of the enol-ketone covalent organic framework (TpMa) is 60.2mg.
In this example, the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-4) used was substantially the same as the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1), except that: the mass ratio of the amino-functionalized zirconium-based metal-organic framework to the enol-ketone covalent organic framework in the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-4) is 1:0.30.
In this embodiment, the preparation method of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-4) is basically the same as that of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1), and the difference is that: in the preparation method of the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-4), the dosage of the enol-ketone covalent organic framework (TpMa) is 72mg.
In this example, an amino-functionalized zirconium-based metal organic framework (NH) 2 -UIO-66), comprising the steps of:
0.2418g of 2-amino terephthalic acid (1.5 mmol) was dispersed in 60mL of DMF and 0.3498g of ZrCl was added to the solution 4 (1.5 mmol) and ultrasonic treating to obtain a mixture, placing into a reaction kettle, reacting in an oven at 120deg.C for 24 hr, taking out, washing the obtained product with water and ethanol three times, placing into 80deg.C, and vacuum drying in a vacuum drying oven for 12 hr to obtain amino-functionalized zirconium-based metal organic skeleton named NH 2 -UIO-66。
FIG. 1 shows a modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1, TUN-2, TUN-3, TUN-4) prepared in example 1 of the present invention, an amino-functionalized zirconium-based metal-organic framework (NH) 2 -UIO-66). As can be seen from FIG. 1, the peak of enol-ketone covalent organic framework (TpMa) in XRD of the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst is not obvious, partly because of the amino functionalized zirconium-based metal-organic framework (NH) 2 -UIO-66) asThe main body has a smaller compound amount of enol-ketone covalent organic frameworks (TpMa), and on the other hand, the crystallinity of the enol-ketone covalent organic frameworks (TpMa) is higher than that of amino-functionalized zirconium-based metal organic frameworks (NH) 2 -UIO-66) weak; meanwhile, as can be seen from the XRD pattern of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst, as the enol-ketone covalent organic framework (TpMa) composite amount increases, the amino-functionalized zirconium-based metal-organic framework (NH 2 -UIO-66), indicating that the amino-functionalized zirconium-based metal-organic framework (NH) 2 -UIO-66) is modified, laterally demonstrating the presence of an enol-ketone covalent organic framework (TpMa).
FIG. 2 shows the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1, TUN-2, TUN-3, TUN-4) prepared in example 1 of the present invention, amino-functionalized zirconium-based metal-organic framework (NH) 2 -UIO-66). As can be seen from fig. 2, the amino-functionalized zirconium-based metal organic framework (NH 2 -UIO-66) as a main material, and modifying 806cm in the amino-functionalized zirconium-based metal-organic framework composite photocatalyst -2 The peak appearing here is the triazine ring from the enol-ketone covalent organic framework (TpMa), indicating successful material compounding.
FIG. 3 shows the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1, TUN-2, TUN-3, TUN-4) prepared in example 1 of the present invention, amino-functionalized zirconium-based metal-organic framework (NH) 2 -UIO-66). As can be seen from fig. 3, the amino-functionalized zirconium-based metal organic framework (NH 2 -UIO-66) is about 450nm, the absorption wavelength bands of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1, TUN-2, TUN-3 and TUN-4) prepared in example 1 gradually red shift with the increase of the enol-ketone covalent organic framework content, the absorption wavelength is widened to above 600nm, the light absorption range is increased, and the light utilization rate is improved. Furthermore, an amino-functionalized zirconium-based metal-organic framework (NH 2 -UIO-66) of 753.6m 2 Per g, and the specific surface area of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3) is 759.1m 2 /g。
FIG. 4 shows a modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3), an enol-ketone covalent organic framework (TpMa), an amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention 2 -a TEM image of UIO-66), where (a) is NH 2 -UIO-66, (b) TpMa, (c) TUN-3. FIG. 5 shows a modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3), an enol-ketone covalent organic framework (TpMa), an amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention 2 -UIO-66), wherein (a) is NH 2 -UIO-66, (b) TpMa, (c) TUN-3. As can be seen from fig. 4 and 5, the amino-functionalized zirconium-based metal organic framework (NH 2 -UIO-66) presents a regular octahedral aggregation structure, the enol-ketone type covalent organic framework (TpMa) is a fiber rod-shaped structure, the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3) can see that the amino-functionalized zirconium-based metal-organic framework is uniformly wrapped outside the enol-ketone type covalent organic framework, which illustrates that the amino-functionalized zirconium-based metal-organic framework is successfully loaded on the enol-ketone type covalent organic framework.
In this example, 100mL of 10% strength by volume isopropyl alcohol solution without any material was used as a blank for comparison.
Measurement of hydrogen peroxide production: sucking the photocatalytic reaction liquid in the 3mL reaction vessel every 10min, and filtering with a 0.22 μm organic phase filter head to obtain transparent colorless liquid to be measured. 1mL of potassium hydrogen phthalate solution with the concentration of 0.1mol/L and 1mL of potassium iodide solution with the concentration of 0.4mol/L are sequentially added into the liquid to be detected in a dropwise manner, and the liquid to be detected is kept for 30 minutes to develop color. And detecting the liquid to be detected after color development on an ultraviolet-visible spectrophotometer instrument.
FIG. 6 shows the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1, TUN-2, TUN-3, TUN-4) and the amino-functionalized zirconium-based metal-organic framework composite photocatalyst (NH) prepared in example 1 of the present invention 2 -UIO-66) a corresponding time-yield plot for the photocatalytic production of hydrogen peroxide. As shown in FIG. 6, after 1 hour of illumination, the amino-functionalized zirconium-based metal organic boneRack composite photocatalyst (NH) 2 UIO-66) produced almost no hydrogen peroxide, whereas the modified amino-functionalized zirconium-based metal-organic framework composite photocatalysts (TUN-1, TUN-2, TUN-3 and TUN-4) produced hydrogen peroxide at 155.635 μm, 202.030 μm, 575.878 μm and 259.669 μm, respectively. The results show that: the highest yield of the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3) to hydrogen peroxide is 575.878 mu M h -1 The corresponding highest yield was 1.51X10 4 μM h -1 g -1 The main reason for the phenomenon is that the enol-ketone covalent organic framework is used as a template to grow the amino-functionalized zirconium-based metal organic framework in situ, and the separation efficiency and the light absorption efficiency of electrons and holes in the modified amino-functionalized zirconium-based metal organic framework composite photocatalyst are effectively improved, the light absorption range is expanded, the photocatalytic activity of the modified amino-functionalized zirconium-based metal organic framework composite photocatalyst is enhanced, and finally the efficient production of hydrogen peroxide is realized by utilizing the interaction between the enol-ketone covalent organic framework and the amino-functionalized zirconium-based metal organic framework interface and the synergistic effect of the enol-ketone covalent organic framework and the amino-functionalized zirconium-based metal organic framework.
Example 2:
the recycling property of the modified amino functionalized zirconium-based metal-organic framework composite photocatalyst in the process of producing hydrogen peroxide by photocatalysis is examined, and the method comprises the following steps:
(1) 50mg of the alkene-modified amino-functionalized zirconium-based metal organic framework composite photocatalyst (TUN-3) prepared in example 1 was weighed and added to 100mL of an aqueous isopropanol solution with a volume concentration of 10% to obtain a reaction system.
(2) Placing the reaction system (isopropanol solution added with TUN-3) obtained in the step (1) on a magnetic stirrer, stirring for 1h away from light to reach adsorption balance, taking out 3mL of the solution to represent initial solution to be reacted, namely, the solution when the reaction time is 0min, filtering, developing color, measuring the concentration of the solution by using an ultraviolet-visible spectrophotometer, and converting the concentration into yield.
(3) And (3) carrying out photocatalytic reaction on the solution left in the step (2) under visible light, taking out 3mL of the solution from a reaction system (isopropanol solution added with TUN-3) when the reaction time reaches 60min, filtering, developing, measuring the concentration of hydrogen peroxide generated in the solution to be measured by an ultraviolet-visible spectrophotometer, and converting the concentration into yield.
(4) Centrifuging the solution reacted in the step (3), pouring out supernatant, collecting TUN-3 after the reaction, desorbing isopropanol and hydrogen peroxide by using ethanol, centrifuging, drying, weighing and re-adding into 100mL of 10% isopropanol water solution by volume concentration.
(5) And (5) repeating the steps (2) - (4) twice.
FIG. 7 is a graph showing the effect of the modified amino functionalized zirconium-based metal organic framework composite photocatalyst in example 3 of the present invention in cyclic production of hydrogen peroxide. FIG. 7 shows the cycle-yield results for photocatalytic hydrogen peroxide production. As can be seen from FIG. 7, TUN-3 still exhibits high photocatalytic performance after three cycles, and the hydrogen peroxide yield after three cycles still reaches 565.180 mu M h -1 The modified amino functionalized zirconium-based organic framework composite photocatalyst has the advantage of stable photocatalytic performance, is a novel visible light composite photocatalyst with stable structure and excellent catalytic performance, can efficiently produce hydrogen peroxide, has high preparation efficiency and high yield, can repeatedly produce hydrogen peroxide, shows excellent reusability, and is beneficial to further reducing production cost.
The above description is merely a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (9)
1. A method for producing hydrogen peroxide by using a modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst, which is characterized by comprising the following steps: mixing a modified amino functionalized zirconium-based metal-organic framework composite photocatalyst with an electron donor solution to perform a photocatalytic reaction to obtain hydrogen peroxide; the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst comprises an enol-ketone covalent organic framework and an amino-functionalized zirconium-based metal-organic framework, wherein the amino-functionalized zirconium-based metal-organic framework grows on the surface of the enol-ketone covalent organic framework in situ; the mass ratio of the amino-functionalized zirconium-based metal organic framework to the enol-ketone covalent organic framework is 1:0.01-0.35; the enol-ketone covalent organic framework photocatalyst is a porous framework material formed by taking melamine and 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde as organic network construction units and carrying out irreversible enol-ketone tautomeric connection.
2. The method of claim 1, wherein the amino-functionalized zirconium-based metal organic framework is an octahedral structure; the enol-ketone covalent organic framework is in a fiber stick shape; the mass ratio of the amino-functionalized zirconium-based metal organic framework to the enol-ketone covalent organic framework is 1:0.020-0.28.
3. The method according to claim 2, wherein the preparation method of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst comprises the following steps:
s1, mixing 2-amino terephthalic acid, enol-ketone covalent organic framework and N, N-dimethylformamide, and performing ultrasonic dispersion to obtain a dispersion liquid;
s2, mixing the dispersion liquid obtained in the step S1 with zirconium tetrachloride for hydrothermal reaction, filtering, washing and drying to obtain the enol-ketone covalent organic framework/amino functional zirconium-based metal organic framework composite photocatalyst.
4. A method according to claim 3, wherein in step S1, the method for preparing the enol-ketone covalent organic framework comprises the steps of:
(1) Mixing melamine, 2,4, 6-trihydroxybenzene-1, 3, 5-trioxymethylene, N-dimethylacetamide and dimethyl sulfoxide, performing ultrasonic dispersion, and adding glacial acetic acid solution to obtain a precursor solution;
(2) And (3) heating the precursor solution obtained in the step (1) under the microwave condition, performing polycondensation reaction, filtering, washing and drying to obtain the enol-ketone covalent organic framework.
5. The process according to claim 4, wherein in step (1), the molar ratio of melamine to 2,4, 6-trihydroxybenzene-1, 3, 5-trioxymethylene is 0.5-2:1-3; the concentration of the glacial acetic acid solution is 1M-4M; the volume ratio of the N, N-dimethylacetamide to the dimethyl sulfoxide in the mixed solution of the N, N-dimethylacetamide and the dimethyl sulfoxide is 1-3:0.5-2; the ultrasonic dispersion time is 5-30 min;
in the step (2), controlling the power of microwaves to be 20-150W in the heating process; the polycondensation reaction is carried out under nitrogen atmosphere; the polycondensation reaction is carried out at a temperature of 100-300 ℃; the polycondensation reaction time is 10 min-60 min; the washing is a product of a polycondensation reaction by adopting N, N-dimethylacetamide, water and ethanol in turn; the drying is performed under vacuum; the drying temperature is 60-100 ℃; the drying time is 6-12 h.
6. A method according to claim 3, wherein in step S1, the temperature of the ultrasonic dispersion is 25 ℃ to 45 ℃; the ultrasonic dispersion time is 0.5-3 h;
in the step S2, the temperature of the hydrothermal reaction is 100-150 ℃; the hydrothermal reaction time is 12-48 hours; the washing is the product of the water and ethanol washing water heat reaction, 3 to 5 times respectively; the drying is performed under vacuum; the drying temperature is 60-100 ℃; the drying time is 6-12 h.
7. The method according to any one of claims 1 to 6, wherein the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst is added in an amount of 500mg to 1000mg per liter of the electron donor solution.
8. The method of claim 7, wherein the electron donor solution is an isopropanol solution; the isopropanol solution is prepared by mixing isopropanol and water; the volume ratio of the isopropanol to the ultrapure water is 1:5-1:9; the time of the photocatalytic reaction is 45-65 min.
9. The method of claim 8, wherein the volume ratio of isopropyl alcohol to ultrapure water is 1:9.
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