CN113735065A - 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 using 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 growing 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 the 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 many 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 particularly relates to a method for producing hydrogen peroxide by using a modified amino functionalized zirconium-based metal organic framework composite photocatalyst.
Background
With the development of modern industry, the problems of energy crisis and environmental pollution become more serious, wherein the shortage of energy and the deterioration of environment are major problems facing and urgently waiting for solving. Therefore, the utilization of new energy and the control of environmental pollution have important significance for the national sustainable development strategy. The photocatalysis technology has the advantages of low cost, no pollution, high efficiency and the like, and has wide application prospect in the aspects of energy storage, conversion and environmental protection.
The metal organic framework Materials (MOFs) are porous crystal materials with periodic network structures constructed by metal or metal clusters and organic ligands, and have the characteristics of regular and ordered pore channel structures, adjustable pore sizes, modifiable frameworks and the like. In recent years, the application of MOFs in the field of heterogeneous photocatalysis has received much attention. Norwegian scientists synthesized for the first time in 2008 a zirconium-based metal-organic framework material UIO-66, which is composed of octahedral Zr6O4(OH)4The metal cluster and the organic ligand terephthalic acid are complexed, the structure contains two hole cages of an octahedron and a tetrahedron which are mutually communicated through a triangular hole window, and the metal cluster has excellent thermal stability and chemical stability. Although studies have reported that amino-functionalized UIO-66 has photocatalytic properties, it has a narrow light absorption range,The low efficiency of separating the photo-generated electron and the hole seriously restricts the application of the photo-generated electron and the hole in the field of photocatalysis.
In order to expand the light absorption capacity of the amino-functionalized UIO-66 and improve the photocatalytic performance of the amino-functionalized UIO-66, researchers modify the amino-functionalized UIO-66 by different methods, wherein the construction of a semiconductor heterojunction is a better modification method, mainly means that one or more semiconductors with proper band gaps are compounded by the amino-functionalized UIO-66, and the response of the amino-functionalized UIO-66 to a sunlight spectrum can be widened and increased by combining the advantages of light absorption of respective energy band structures; and meanwhile, 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 following problems still exist with the constructed amino-functionalized UIO-66-based semiconductor heterojunctions: the wide application of the amino-functionalized zirconium-based metal organic framework composite photocatalyst is severely limited by the existence of the problems of insufficient light absorption performance, easy recombination of photon-generated carriers, high recombination rate of electron-hole pairs, insufficient catalytic degradation performance and the like. In addition, during the practical research process of the inventor of the present application, it is also found that: in the related preparation method, when a solution system is heated, the adopted heating mode is difficult to effectively realize synchronous heating inside and outside the solution system, so that the reaction is uneven, the product is difficult to ensure to have better structural stability, and meanwhile, in order to promote the mutual effect of precursor bonding, longer reaction time and more heat energy consumption are needed, this is not conducive to large-scale preparation, and it is difficult to meet the energy-saving requirement in industrial production; more particularly, in the existing preparation method of the enol-ketone covalent organic framework/graphene carbon nitride composite photocatalyst, the graphite phase carbon nitride and the enol-ketone covalent organic framework are compounded together by utilizing a physical mixing mode (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 the composite photocatalyst with a stable structure is difficult to prepare. Due to the defects, the existing enol-ketone covalent organic framework/graphene carbon nitride composite photocatalyst is difficult to be widely applied to the field of hydrogen peroxide production. Until now, no report about the application of a composite photocatalyst prepared by compounding an enol-ketone covalent organic framework serving as a template and an amino-functionalized zirconium-based metal organic framework to photocatalytic production of hydrogen peroxide is found. Therefore, how to effectively overcome the problems is to obtain the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst with high specific surface area, multiple reactive active sites, wide light absorption range, low electron-hole pair recombination rate, good photocatalytic performance and good stability, and the preparation method of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst matched with the compound photocatalyst has the advantages of simple process, wide raw material sources, low cost, high preparation efficiency and high yield, and has important significance for improving the preparation efficiency and the yield of hydrogen peroxide.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for producing hydrogen peroxide by using a modified amino-functional zirconium-based metal organic framework composite photocatalyst, which has high preparation efficiency and high yield, aiming at the defects in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for producing hydrogen peroxide by using a modified amino functionalized zirconium-based metal organic framework composite photocatalyst 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; 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.
In the method, 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 performing irreversible enol-ketone tautomeric connection.
In the method, the amino functionalized zirconium-based metal organic framework is in 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.
In a further improvement of the above method, 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, an 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 functionalized zirconium-based metal organic framework composite photocatalyst.
In a further improvement of the above method, in step S1, the method for preparing the enol-ketone covalent organic framework comprises the following steps:
(1) mixing melamine, 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde and a mixed solution of N, N-dimethylacetamide and dimethyl sulfoxide, performing ultrasonic dispersion, and adding a glacial acetic acid solution to obtain a precursor solution;
(2) and (2) heating the precursor solution obtained in the step (1) under the microwave condition, carrying out polycondensation reaction, filtering, washing and drying to obtain the enol-ketone covalent organic framework.
In the step (1), the molar ratio of the melamine to the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde 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 time of ultrasonic dispersion is 5-30 min.
In the step (2), the power of the microwave is controlled to be 20W-150W in the heating process; the polycondensation reaction is carried out in a nitrogen atmosphere; the polycondensation reaction is carried out at the temperature of 100-300 ℃; the time of the polycondensation reaction is 10min to 60 min; the washing is to wash the product of the polycondensation reaction by sequentially adopting N, N-dimethylacetamide, water and ethanol; the drying is carried out under vacuum conditions; the drying temperature is 60-100 ℃; the drying time is 6-12 h.
In a further improvement of the above method, in step S1, the temperature of ultrasonic dispersion is 25 ℃ to 45 ℃; the ultrasonic dispersion time is 0.5-3 h.
In a further improvement of the above method, in step S2, the temperature of the hydrothermal reaction is 100 ℃ to 150 ℃; the time of the hydrothermal reaction is 12-48 h; the washing is to wash the product of the hydrothermal reaction by water and ethanol for 3 to 5 times respectively; the drying is carried out under vacuum conditions; the drying temperature is 60-100 ℃; the drying time is 6-12 h.
In the method, the addition amount of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst is further improved, and 500 mg-1000 mg of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst is added into each liter of the electron donor solution.
In the method, the electron donor solution is isopropanol solution; the isopropanol solution is obtained 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 the method, the volume ratio of the isopropanol to the 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 using a modified amino-functional zirconium-based metal organic framework composite photocatalyst. 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, and has the advantages of high specific surface area, more reactive active sites, wide light absorption range, low electron-hole pair recombination rate, good photocatalytic performance, good stability and the like2 -) And further converted into hydrogen peroxide (H) under illumination2O2) Wherein the yield of hydrogen peroxide is 1.51X 104μM h-1g-1And after three times of recycling, the yield of the hydrogen peroxide is still as high as 1.13 multiplied by 104μM h-1g-1The highest yield of the existing conventional enol-ketone covalent organic framework graphite-phase carbon nitride composite photocatalyst is only 0.88 multiplied by 104μM h-1g-1. The method for producing hydrogen peroxide by using 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, 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 many 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 clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalysts (TUN-1, TUN-2, TUN-3 and TUN-4) and amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention2-UIO-66) in a liquid phase.
FIG. 2 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalysts (TUN-1, TUN-2, TUN-3 and TUN-4) and amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention2UIO-66).
FIG. 3 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalysts (TUN-1, TUN-2, TUN-3 and TUN-4) and amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention2UIO-66).
FIG. 4 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3), enol-ketone covalent organic framework (TpMa) and amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention2UIO-66) in which (a) is NH2-UIO-66, (b) is TpMa, (c) is TUN-3.
FIG. 5 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3), enol-ketone covalent organic framework (TpMa) and amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention2UIO-66) in which (a) is NH2-UIO-66, (b) is TpMa, (c) is TUN-3.
FIG. 6 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalysts (TUN-1, TUN-2, TUN-3 and TUN-4) and amino-functionalized zirconium-based metal-organic framework composite photocatalyst (NH) prepared in example 1 of the present invention2UIO-66) graph of the corresponding time-yield relationship in the photocatalytic production of hydrogen peroxide.
Fig. 7 is a diagram illustrating the effect of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst in the embodiment 3 of the present invention in the cyclic production of hydrogen peroxide.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the following examples of the present invention, unless otherwise specified, materials and instruments used are commercially available, processes used are conventional, apparatuses used are conventional, and the obtained data are average values of three or more repeated experiments.
Example 1:
a method for producing hydrogen peroxide by using 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)2UIO-66), 50mg of each, and adding the 50mg of the compounds into 100mL of 10 volume percent isopropanol aqueous solution respectively, magnetically stirring the mixture for one hour in a dark place (namely under dark conditions), turning on a light source after adsorption equilibrium is achieved, and carrying out photocatalytic reaction for 60min under visible light (lambda is more than or equal to 420nm) to produce hydrogen peroxide.
In this embodiment, the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1) used in the present embodiment includes an enol-ketone covalent organic framework and an amino-functionalized zirconium-based metal-organic framework, and the amino-functionalized zirconium-based metal-organic framework is grown in situ on the surface of the enol-ketone covalent organic framework. 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-triformal as organic network construction units and performing irreversible enol-ketone tautomeric connection, specifically irreversible-CH (N-and/or-CH)2N (OH) -is a connecting bond, and irreversible enol-ketone type tautomeric connection is generated among monomer molecules, so that a porous framework with a more stable structure and a periodic structure is formed. The amino functionalized zirconium-based metal organic framework is in a regular octahedral structure; enol-keto covalent bondThe organic framework is in a fiber stick shape.
In this embodiment, the preparation method of the modified amino-functionalized zirconium-based metal organic framework composite photocatalyst (TUN-1) includes the following steps:
s1, ultrasonically dispersing melamine (57mg) and 2,4, 6-trihydroxybenzene-1, 3, 5-triformal (95mg) into a mixed solution of N, N-dimethylacetamide and dimethyl sulfoxide according to the molar ratio of 1: 1 of melamine and 2,4, 6-trihydroxybenzene-1, 3, 5-triformal, wherein the ultrasonic dispersion time is 20min, and adding 0.3mL of 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 the 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 of single-mode microwave, keeping for 20 minutes, filtering after the reaction is finished, sequentially cleaning a precipitation product of the polycondensation reaction by using N, N-dimethylacetamide, water and ethanol, placing the obtained cleaned precipitation product under a vacuum condition, and drying at 80 ℃ for 12 hours to obtain the enol-ketone covalent organic framework photocatalyst named TpMa.
S3, mixing 0.2418g 2-amino terephthalic acid (1.5mmol), 28.8mg enol-ketone type covalent organic framework (TpMa) obtained in the step S1 and 60mL N, N-Dimethylformamide (DMF), ultrasonically dispersing for 30min, adding 0.3498g ZrCl4(1.5mmol), ultrasonically treating until the dispersion is uniform, putting the mixture into a reaction kettle, reacting in an 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 product into a vacuum drying oven to dry for 12 hours at 80 ℃ to obtain the modified amino functionalized zirconium-based metal organic framework composite photocatalyst, which is named as TUN-1.
In this embodiment, the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-2) and the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1) are basically the same, and the differences are only: the mass ratio of the amino functional zirconium-based metal organic framework to the enol-ketone covalent organic framework in the modified amino functional 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) is basically the same as that of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1), and the differences are only 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 36 mg.
In this embodiment, the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3) and the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1) are basically the same, and the differences are only that: the mass ratio of the amino functional zirconium-based metal organic framework to the enol-ketone covalent organic framework in the modified amino functional 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 differences are only 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 60.2 mg.
In this embodiment, the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-4) and the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-1) are basically the same, and the differences are only that: the mass ratio of the amino functional zirconium-based metal organic framework to the enol-ketone covalent organic framework in the modified amino functional 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 differences are only 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 72 mg.
In this example, an amino-functionalized zirconium-based metal organic framework (NH) was used2-UIO-66) comprising the steps of:
0.2418g of 2-aminoterephthalic acid (1.5mmol) were dispersed in 60mL of DMF, and 0.3498g of ZrCl was added to the solution4(1.5mmol), ultrasonically treating until the dispersion is uniform, putting the mixture into a reaction kettle, reacting in a 120 ℃ oven for 24 hours, taking out the mixture, washing the obtained product with water and ethanol for three times, then putting the product into a 80 ℃ vacuum drying oven for drying for 12 hours to obtain an amino functionalized zirconium-based metal organic framework, which is named as NH2-UIO-66。
FIG. 1 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalysts (TUN-1, TUN-2, TUN-3 and TUN-4) and amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention2-UIO-66) in a liquid phase. From FIG. 1, it can be seen that the peak of enol-ketone covalent organic skeleton (TpMa) in XRD of the modified amino-functionalized zirconium-based metal-organic skeleton composite photocatalyst is not obvious, and is partly due to the amino-functionalized zirconium-based metal-organic skeleton (NH)2UIO-66) as a main component, the enol-ketone covalent organic skeleton (TpMa) being incorporated in a smaller amount, and the enol-ketone covalent organic skeleton (TpMa) being more crystalline than the amino-functionalized zirconium-based metal organic skeleton (NH)2-UIO-66) weak; meanwhile, from the XRD pattern of the modified amino-functionalized zirconium-based metal organic framework composite photocatalyst, it can be seen that the amino-functionalized zirconium-based metal organic framework (NH) increases along with the increase of the compounding amount of the enol-ketone covalent organic framework (TpMa)2UIO-66) was reduced, indicating an amino-functionalized zirconium-based metal organic framework (NH)2UIO-66) flanking the presence of an enol-keto covalent organic skeleton (TpMa).
FIG. 2 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalysts (TUN-1, TUN-2, TUN-3 and TUN-4) and amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention2UIO-66). As can be seen from FIG. 2, the amino-functionalized zirconium-based metal organic framework (NH)2UIO-66) as a main material and simultaneously modifying amino-functionalized zirconium-based metal organic framework composite photocatalystMiddle 806cm-2The peak appeared here is from the triazine ring in the enol-keto covalent organic backbone (TpMa), indicating successful material complexation.
FIG. 3 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalysts (TUN-1, TUN-2, TUN-3 and TUN-4) and amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention2UIO-66). As can be seen in FIG. 3, the amino-functionalized zirconium-based metal organic framework (NH)2UIO-66) is about 450nm, the absorption wavelength band 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 shifts red with the increase of the content of the enol-ketone covalent organic framework, the absorption wavelength is widened to more than 600nm, the absorption range of light is increased, and the utilization rate of light is improved. Furthermore, an amino-functionalized zirconium-based metal-organic framework (NH)2UIO-66) having a specific surface area of 753.6m2The specific surface area of the modified amino-functionalized zirconium-based metal organic framework composite photocatalyst (TUN-3) is 759.1m2/g。
FIG. 4 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3), enol-ketone covalent organic framework (TpMa) and amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention2UIO-66) in which (a) is NH2-UIO-66, (b) is TpMa, (c) is TUN-3. FIG. 5 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst (TUN-3), enol-ketone covalent organic framework (TpMa) and amino-functionalized zirconium-based metal-organic framework (NH) prepared in example 1 of the present invention2UIO-66) in which (a) is NH2-UIO-66, (b) is TpMa, (c) is TUN-3. As can be seen from FIGS. 4 and 5, the amino-functionalized zirconium-based metal organic framework (NH)2UIO-66) which presents a regular octahedral aggregation structure, the enol-ketone covalent organic framework (TpMa) is a fiber stick-shaped structure, and the modified amino-functionalized zirconium-based metal organic framework composite photocatalyst (TUN-3) can be seen to uniformly wrap the amino-functionalized zirconium-based metal organic framework outside the enol-ketone covalent organic framework, which shows that the amino-functionalized zirconium-based metal organic framework isThe scaffold was successfully loaded on an enol-keto covalent organic backbone.
In this example, 100mL of 10% strength by volume isopropanol solution without any added material was used as a blank for comparison.
Determination of hydrogen peroxide production: absorbing the photocatalytic reaction solution in a reaction container of 3mL every 10min, and filtering by using an organic phase filter head of 0.22 mu m to obtain a transparent colorless solution to be detected. 1mL of a 0.1mol/L potassium hydrogen phthalate solution and 1mL of a 0.4mol/L potassium iodide solution were sequentially added dropwise to the solution to be measured, and the mixture was kept for 30 minutes for color development. And detecting the developed liquid to be detected on an ultraviolet-visible spectrophotometer instrument.
FIG. 6 shows modified amino-functionalized zirconium-based metal-organic framework composite photocatalysts (TUN-1, TUN-2, TUN-3 and TUN-4) and amino-functionalized zirconium-based metal-organic framework composite photocatalyst (NH) prepared in example 1 of the present invention2UIO-66) graph of the corresponding time-yield relationship in the photocatalytic production of hydrogen peroxide. As shown in FIG. 6, after 1 hour of light irradiation, the amino-functionalized zirconium-based metal-organic framework composite photocatalyst (NH)2UIO-66) produced almost no hydrogen peroxide, while the modified amino-functionalized zirconium-based metal-organic framework composite photocatalysts (TUN-1, TUN-2, TUN-3 and TUN-4) produced 155.635. mu.M, 202.030. mu.M, 575.878. mu.M and 259.669. mu.M, respectively. The results show that: the yield of the modified amino-functionalized zirconium-based metal organic framework composite photocatalyst (TUN-3) to hydrogen peroxide is the highest and is 575.878 mu M h-1Corresponding to a maximum yield of 1.51X 104μM h-1g-1The main reason for causing the phenomenon is that the amino-functionalized zirconium-based metal organic framework grows in situ by taking the enol-ketone covalent organic framework as a template, and the interaction between the interfaces of the enol-ketone covalent organic framework and the amino-functionalized zirconium-based metal organic framework and the synergistic effect of the enol-ketone covalent organic framework and the amino-functionalized zirconium-based metal organic framework are utilized, so that the separation efficiency of electron-hole and the light absorption efficiency in the modified amino-functionalized zirconium-based metal organic framework composite photocatalyst are effectively improved, the light absorption range is expanded, and the modified amino-functionalized zirconium-based metal organic framework is enhancedThe photocatalytic activity of the framework composite photocatalyst is realized, and the efficient production of hydrogen peroxide is finally realized.
Example 2:
the method for investigating the reusability of the modified amino-functionalized zirconium-based metal organic framework composite photocatalyst in the process of producing hydrogen peroxide by photocatalysis 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 a 10% volume concentration aqueous isopropanol solution to obtain a reaction system.
(2) And (2) placing the reaction system (the isopropanol solution added with TUN-3) obtained in the step (1) on a magnetic stirrer, stirring for 1h in a dark place to achieve adsorption balance, taking 3mL of solution out to represent initial solution to be reacted, namely the solution with the reaction time of 0min, filtering and 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 remaining in the step (2) under visible light, taking 3mL of solution out of a reaction system (isopropanol solution added with TUN-3) when the reaction time is 60min, filtering and developing color, measuring the concentration of hydrogen peroxide generated in the solution to be measured by using an ultraviolet-visible spectrophotometer, and converting the concentration into the yield.
(4) And (3) centrifugally separating the solution reacted in the step (3), pouring off the supernatant, collecting the reacted TUN-3, desorbing isopropanol and hydrogen peroxide by using ethanol, centrifugally drying, weighing, and adding into 100mL of 10% volume concentration isopropanol water solution again.
(5) And (4) continuously repeating the steps (2) to (4) twice.
Fig. 7 is a diagram illustrating the effect of the modified amino-functionalized zirconium-based metal-organic framework composite photocatalyst in the embodiment 3 of the present invention in the cyclic production of hydrogen peroxide. Figure 7 shows the photocatalytic hydrogen peroxide cycle-yield results. As can be seen from FIG. 7, TUN-3 still exhibits high photocatalytic performance after three cycles, and the yield of hydrogen peroxide still reaches 565.180 μ M h after three cycles-1This shows that the modified amino-functionalized zirconium-based metal organic framework composite photocatalyst of the inventionThe novel visible light composite photocatalyst has the advantages of stable photocatalytic performance, stable structure and excellent catalytic performance, can efficiently produce hydrogen peroxide, has high preparation efficiency and high yield, can repeatedly produce the hydrogen peroxide, shows excellent reusability, and is favorable for further reducing the production cost.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A method for producing hydrogen peroxide by using a modified amino functionalized zirconium-based metal organic framework composite photocatalyst is characterized by comprising 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; 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.
2. The method according to claim 1, wherein the mass ratio of the amino-functionalized zirconium-based metal-organic framework to the enol-ketone covalent organic framework is 1: 0.01 to 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 performing irreversible enol-ketone tautomeric connection.
3. The method of claim 2, wherein the amino-functionalized zirconium-based metal-organic framework is 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.
4. The method as claimed in claim 3, 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, an 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 functionalized zirconium-based metal organic framework composite photocatalyst.
5. The method according to claim 4, wherein in step S1, the method for preparing the enol-ketone covalent organic framework comprises the following steps:
(1) mixing melamine, 2,4, 6-trihydroxybenzene-1, 3, 5-trimethyl aldehyde and a mixed solution of N, N-dimethylacetamide and dimethyl sulfoxide, performing ultrasonic dispersion, and adding a glacial acetic acid solution to obtain a precursor solution;
(2) and (2) heating the precursor solution obtained in the step (1) under the microwave condition, carrying out polycondensation reaction, filtering, washing and drying to obtain the enol-ketone covalent organic framework.
6. The method according to claim 5, wherein in the step (1), the molar ratio of the melamine to the 2,4, 6-trihydroxybenzene-1, 3, 5-trimethylaldehyde 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 5min to 30 min;
in the step (2), the power of the microwave is controlled to be 20-150W in the heating process; the polycondensation reaction is carried out in a nitrogen atmosphere; the polycondensation reaction is carried out at the temperature of 100-300 ℃; the time of the polycondensation reaction is 10min to 60 min; the washing is to wash the product of the polycondensation reaction by sequentially adopting N, N-dimethylacetamide, water and ethanol; the drying is carried out under vacuum conditions; the drying temperature is 60-100 ℃; the drying time is 6-12 h.
7. The method according to claim 4, wherein in step S1, the temperature of ultrasonic dispersion is 25-45 ℃; the ultrasonic dispersion time is 0.5-3 h;
in step S2, the temperature of the hydrothermal reaction is 100-150 ℃; the time of the hydrothermal reaction is 12-48 h; the washing is to wash the product of the hydrothermal reaction by water and ethanol for 3 to 5 times respectively; the drying is carried out under vacuum conditions; the drying temperature is 60-100 ℃; the drying time is 6-12 h.
8. The method according to any one of claims 1 to 7, 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.
9. The method of claim 8, wherein the electron donor solution is an isopropanol solution; the isopropanol solution is obtained 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.
10. The method of claim 9, wherein the volume ratio of isopropanol to ultrapure water is 1: 9.
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