CN111185235B - Preparation of gold nanoparticle/metal organic framework compound and application of gold nanoparticle/metal organic framework compound in p-nitrophenol reduction - Google Patents
Preparation of gold nanoparticle/metal organic framework compound and application of gold nanoparticle/metal organic framework compound in p-nitrophenol reduction Download PDFInfo
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- CN111185235B CN111185235B CN202010047881.8A CN202010047881A CN111185235B CN 111185235 B CN111185235 B CN 111185235B CN 202010047881 A CN202010047881 A CN 202010047881A CN 111185235 B CN111185235 B CN 111185235B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
Abstract
Hair brushThe invention discloses a preparation method of a gold nanoparticle/metal organic framework (Au/FMOF) compound and an application of the Au/FMOF compound in p-nitrophenol reduction. The metal organic framework (FMOF) of the present invention is made of zirconium chloride (ZrCl)4) And 1, 1' -ferrocene dicarboxylic acid (FDC) is used as a metal node and a ligand, and is synthesized and prepared by a solvothermal method under the condition that acetic acid is used as a regulator; the gold nanoparticle/metal organic framework compound is prepared by reducing a metal organic framework and chloroauric acid in an aqueous solution by using sodium borohydride as a reducing agent. The Au/FMOF of is used as an efficient catalyst to be applied to the reduction of p-nitrophenol, and the reaction rate constant can reach 1.72min‑1And can maintain the reaction conversion rate close to 100 percent after repeating ten times of cycles, which shows that the catalyst has high catalytic performance.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysis, and particularly relates to preparation of a gold nanoparticle/metal organic framework (Au/FMOF) compound and application of the Au/FMOF compound in p-nitrophenol reduction.
Background
With the rapid development of the modern chemical industry, more and more organic compounds are developed and used by us. As the most common solvent on earth, waste water containing unreacted organic reagents or by-products is continuously generated, and proper treatment of the waste water has become an urgent problem. P-nitrophenol (4-NP) is an aromatic phenol compound widely used in the pharmaceutical, pesticide and dye industries, and even water containing a trace amount of 4-NP has neurotoxicity and carcinogenicity to humans. Chemical reduction of 4-NP to low-toxicity para-aminophenol (4-AP) in the presence of sodium borohydride and a catalyst is considered a versatile and effective method for removing such contaminants due to the high solubility of 4-NP in water. Gold nanoparticles have been shown to be an effective noble metal catalyst for the reduction of 4-NP with high conversion and selectivity. However, the current difficulty is that when the size of the metal particles is reduced to several nanometers or less, the gold nanoparticles always tend to agglomerate and form larger particles due to the high surface energy inherent to the nanoparticles, so that the reactivity thereof is reduced. In addition, for gold nanoparticles having a hydrophobic surface, it is also difficult for simple physical methods (such as mechanical stirring or ultrasonic treatment) to enable the gold nanoparticles to be uniformly dispersed in an aqueous solution for a long period of time.
To address these faced disadvantages, gold nanoparticles are typically supported on a suitable support that should be reasonably stable in water and have a strong affinity or binding effect to the gold nanoparticles, separating them to avoid aggregation. To date, several supports have been used to support gold nanoparticles, such as graphene, spherical polyelectrolytes, metal oxides, and the like. In the past decades, as a new class of porous materials, Metal Organic Frameworks (MOFs) have been extensively studied due to their highly regular structure, ultra-large surface area and a variety of functional organic ligands. With narrow channels and cavities inside, MOFs can be used as potential carriers for the formation of metal-MOF heterocomposites. However, MOFs used as supports are mainly 3D structures, and metal nanoparticles are difficult to enter the interior of MOFs by diffusion. Also, when these complexes are used as catalysts, in some cases the channels of the MOFs will be too narrow for large-sized substrate molecules to reach the active sites. These drawbacks may limit the application of MOFs as an ideal carrier. Recently, two-dimensional MOFs have received much attention due to their inherent ultrathin nanosheet structure, and thus have unique advantages in membrane separation, electrochemistry, chemical sensors, and catalysis. While the lack of internal cavities and channels may reduce the confinement effect on the nanoparticles, the larger exposed area of the two-dimensional MOF and oxygen-containing organic ligands will facilitate the loading of the metal nanoparticles and diffusion of the target molecule to the active site.
Disclosure of Invention
In order to solve the problems in the background art, the invention provides a preparation method of a gold nanoparticle/metal organic framework composite (Au/FMOF) and an application of the gold nanoparticle/metal organic framework composite in p-nitrophenol reduction.
The invention aims to select a metal organic framework (FMOF) from zirconium chloride (ZrCl)4) And 1, 1' -ferrocene dicarboxylic acid (FDC) is used as a metal node and a ligand, and is synthesized and prepared by a solvothermal method under the condition that acetic acid is used as a regulator. The Au/FMOF is prepared by reducing a metal organic framework and chloroauric acid in an aqueous solution by using sodium borohydride as a reducing agent. Au/FMOF of inventionThe catalyst is an efficient catalyst applied to the reduction of p-nitrophenol, has high reaction rate, can keep reaction conversion rate close to 100 percent after repeating ten times of circulation, and has high catalytic performance and practical application value.
The Au/FMOF can limit and disperse the gold nanoparticles, the loading capacity can be regulated and controlled by changing the feeding amount of the chloroformic acid, and the size of the gold nanoparticles can be controlled to a certain extent. When the Au/FMOF is used for reducing p-nitrophenol in a water body, the Au/FMOF can realize rapid catalytic conversion on p-nitrophenol solutions with different concentrations, and can still keep the reaction conversion rate close to 100% after being repeatedly used for ten times.
The technical scheme adopted by the invention is as follows:
gold nanoparticle/metal organic framework compound
The gold nanoparticle/metal organic framework compound is mainly obtained by loading gold nanoparticles on a metal organic framework; the metal organic framework is in a nano sheet shape, and the unit structural formula of the metal organic framework is [ Zr ]6O8(FDC)2]n。
The side length of the nano sheet is 500-1000nm, and the thickness is 10-15 nm.
Using zirconium chloride (ZrCl)4) And 1, 1' -ferrocene dicarboxylic acid (FDC) respectively serves as a metal node and a ligand of the metal-organic framework.
Each asymmetric unit in the metal-organic framework structure comprises one zirconium-oxygen metal cluster and two organic ligands FDC, wherein the organic ligands FDC are 1, 1' -ferrocene dicarboxylic acid.
The metal organic framework is a triclinic system, a P-1 space group and a volume of
Cell parameters
α＝90.00°、β＝90.00°、γ＝90.00°。
The gold nanoparticles are mainly obtained by reduction of chloroauric acid as a precursor.
In the gold nanoparticle/metal organic framework compound, the size of the gold nanoparticles is between 3 and 6 nanometers and is uniformly distributed on the surface of the metal organic framework.
Secondly, the preparation method of the gold nanoparticle/metal organic framework compound
The method comprises the following steps:
(1) dissolving zirconium chloride and organic ligand FDC in a solvent, adding a monobasic acid regulator, and carrying out ultrasonic treatment at the normal temperature of 20-25 ℃ for 30 minutes;
(2) placing the solution reacted in the step 1) at 120 ℃ for closed reaction for 12 hours, and after the reaction is finished, cooling, washing and drying to obtain a metal organic framework;
(3) dispersing the metal organic framework obtained in the step 2) in an aqueous solution, performing ultrasonic treatment at the normal temperature of 20-25 ℃ for 30 minutes, adding chloroauric acid, uniformly stirring and dispersing, adding a sodium borohydride reducing agent, continuously stirring and reacting for five minutes, centrifuging, washing and drying to obtain the gold nanoparticle/metal organic framework composite.
The monoacid regulator in the step 1) is acetic acid, and the solvent is N, N-dimethylformamide; the volume ratio of the monoacid to the solvent is 1: 5-15.
The molar ratio of the zirconium chloride to the organic ligand FDC to the monobasic acid in step 1) is 1:1: 50-100.
The closed reaction in the step 2) is specifically as follows: transferring the solution reacted in the step 1) into a polytetrafluoroethylene reaction tank, sealing the polytetrafluoroethylene reaction tank, placing the sealed polytetrafluoroethylene reaction tank into an electric heating forced air drying box, heating the solution to 120 ℃ at the speed of 5 ℃/min, and reacting for 12 hours;
the mass ratio of the chloroauric acid to the metal organic framework in the step 2) is 1:1-5, and the mass ratio of the sodium borohydride to the metal organic framework is 1: 10-50.
The preparation method of the gold nanoparticle/metal organic framework compound specifically comprises the following steps:
(a) dissolving zirconium chloride and FDC in N, N-dimethylformamide solution, adding acetic acid, and performing ultrasonic treatment at normal temperature for 30 minutes;
(b) transferring the solution into a polytetrafluoroethylene reaction tank, sealing, placing in an electric heating forced air drying oven, heating to 120 ℃ at the speed of 5 ℃/min, and reacting for 12 hours;
(c) and after the reaction is finished, cooling to room temperature, washing with N, N-dimethylformamide for three times, then washing with deionized water for two times, and freeze-drying to obtain the metal organic framework.
(d) Dispersing a metal organic framework in an aqueous solution, performing ultrasonic treatment at normal temperature for 30 minutes, adding chloroauric acid, stirring at 30 ℃ for 1 minute, adding sodium borohydride, continuously stirring for five minutes, centrifuging the dispersion, washing with deionized water for three times, and then performing freeze drying to obtain the gold nanoparticle/metal organic framework composite.
Application of gold nanoparticle/metal organic framework composite in catalytic reduction of p-nitrophenol
Dispersing the gold nanoparticle/metal organic framework composite in an aqueous solution, ultrasonically dispersing for 20 minutes, adding p-nitrophenol, stirring for 5 minutes at 30 ℃, adding sodium borohydride, and reducing the p-nitrophenol into p-aminophenol under the catalysis of the gold nanoparticle/metal organic framework composite.
After the gold nanoparticle/metal organic framework compound is dispersed in the aqueous solution, adding sodium borohydride, stirring for 5 minutes at 30 ℃, adding p-nitrophenol, and continuing stirring for reaction, wherein the p-nitrophenol can be quickly converted into p-aminophenol under the condition that gold is used as a catalyst and hydrogen is provided by the sodium borohydride. The mass ratio of the p-nitrophenol to the gold nanoparticle/metal organic framework composite is 1: 0.4-3. The mass ratio of the sodium borohydride to the gold nanoparticle/metal organic framework composite is 1: 3-50.
The invention has the beneficial effects that:
(1) the metal organic framework provided by the invention can be prepared by a simple dissolution thermal method, the loading of the gold nanoparticles is easy to regulate and control, the dispersity and the scale are good, a good choice is provided for removing organic matters in a water body by a chemical method, and the potential application of the metal organic framework as a noble metal nanoparticle carrier in the aspect of wastewater treatment is expanded.
(2) The invention is catalytic to p-nitrophenol in aqueous solutionHas better catalytic activity in the reduction, and the maximum reaction rate obtained after calculation is 1.72min-1Compared with most of the reported similar system catalysts, the catalyst has obvious advantages: the maximum reaction rate of the gold-oxidized graphene complex as reported in the literature is 0.19min-1The maximum reaction rate of the gold-silver nano-particle alloy is 1.18min-1And the maximum reaction rate of the gold-tetraoxide three-body compound is 0.225min-1And the like.
(3) The material of the invention has good thermal stability and chemical stability, the crystal structure is kept intact before and after catalysis, the gold nanoparticles do not have serious agglomeration phenomenon, the reaction activity is not influenced, and a good foundation is laid for the reutilization efficiency of the gold nanoparticles.
Drawings
FIG. 1 is a scanning electron microscope image of a metal organic framework prepared by the present invention.
FIG. 2 is a transmission electron microscope image of the Au/FMOF compound prepared by the invention after three repeated reactions.
FIG. 3 shows the conversion of Au/FMOF complex prepared according to the present invention in 10 cycles.
Detailed Description
The present invention is described in more detail by the following examples, but the present invention is not limited thereto, and those skilled in the art can make various modifications and improvements without departing from the principle of the present invention, and these modifications and improvements are also considered to be within the scope of the present invention. Those not described in detail in this specification are within the skill of the art.
Example 1:
139.6mg of zirconium chloride and 164.4mg of 1,1 '-ferrocene dicarboxylic acid are weighed into a polytetrafluoroethylene tank, 20 ml of N, N-dimethylformamide solution and 1.7 ml of acetic acid solution are added, and ultrasonic dispersion is carried out for 30 minutes to ensure that the zirconium chloride and the 1, 1' -ferrocene dicarboxylic acid are completely dissolved. Then, the polytetrafluoroethylene tank containing the solution is sealed in a stainless steel reaction kettle, placed in an electric heating air blowing drying oven, heated to 120 ℃, and then kept warm for 12 hours. And after the reaction is finished, cooling to room temperature, centrifuging the obtained solution at 3000r.p.m for 30 minutes, taking the centrifuged dark brown precipitate, continuously washing the precipitate for three times by using an N, N-dimethylformamide solution, then washing the precipitate for two times by using deionized water, and freeze-drying the precipitate for 5 days to obtain the dry powder of the metal organic framework.
The prepared metal organic framework is in a nanometer sheet shape as can be seen from the attached figure 1. Firstly, compared with most of the existing granular or blocky metal organic framework materials, the nano-flaky metal organic framework has larger surface exposed area, and is beneficial to fully combining the metal organic framework with gold nanoparticle precursors and pollutants in a solution in subsequent reaction; secondly, potential interaction exists among metal nodes in the metal organic framework, the ferrocene ligand and the gold nanoparticles, and the metal nodes and the ferrocene ligand can limit the gold nanoparticles and are uniformly distributed on the surface of the metal organic framework without falling off; finally, the interaction between the metal organic framework and the gold nanoparticles also ensures that the gold nanoparticles can not cause the reduction of reaction activity due to the generation of obvious agglomeration after long-time reaction, thereby improving the stability and the reutilization property of the composite material.
Example 2:
10 mg of the dried metal organic framework powder was weighed, dispersed in 50 ml of deionized water and sonicated for 30 minutes to obtain a uniform dispersion. And (3) placing the dispersion into a flask, adding 4 ml of chloroauric acid solution with the concentration of 4 mg/ml, stirring at 30 ℃ for 5 minutes, then adding 20 mg of sodium borohydride, continuing stirring for 5 minutes, taking out the dispersion, centrifuging, washing the precipitate twice by using deionized water, and freeze-drying for 5 days to obtain the gold nanoparticle/metal organic framework compound. The loading capacity of the gold nanoparticles is improved along with the increase of the amount of chloroauric acid and sodium borohydride added in the reaction formula, and the loading capacity can be adjusted between 3 and 20 weight percent.
Example 3:
weighing 1.5 mg of gold nanoparticle/metal organic framework composite with 7 wt% gold loading in a flask, adding 10 ml of deionized water, and performing ultrasonic treatment for 20 minutes to obtain a uniform dispersion liquid. To the above dispersion, 20 mg of sodium borohydride was added and the mixture was stirred at 30 ℃ for 5 minutes, followed by 1 ml of a 1 mg/ml p-nitrophenol solution and further stirring at 30 ℃ for 10 minutes, during which a yellow solution was observed to gradually lighten in color and finally turn colorless. After the reaction is finished, the reaction solution is centrifuged at 3000r.p.m for 30 minutes, the supernatant is sampled and subjected to ultraviolet test, the absorbance of the supernatant at 400nm is measured, and the concentration of the residual p-nitrophenol in the supernatant can be calculated according to a standard curve, so that the conversion rate of the reaction is calculated. In the experimental example, p-nitrophenol can be completely reduced into p-aminophenol within 4 minutes, and the reaction conversion rate is more than 99 percent by calculation.
As can be seen from the attached figure 2, the crystal structure of the compound is kept intact before and after catalysis, and the gold nanoparticles do not have serious agglomeration phenomenon.
Example 4:
the reusability of the gold nanoparticle/metal organic framework composite in the invention was examined as follows, the reaction was performed under the same conditions as in example 3, after the reaction was completed, the reaction solution was transferred to a 40 ml volumetric centrifuge tube, centrifuged at 3000 rpm at room temperature (25 ℃) for 30 minutes, the supernatant was sampled to detect the residual p-nitrophenol concentration and calculate the reaction conversion rate, and the remaining supernatant was discarded. The precipitate at the bottom of the tube was re-dispersed in 10 ml of deionized water, and the reaction was again carried out under the same conditions as in example 3. The same batch of gold nanoparticle/metal organic framework composite was repeated 10 times according to this procedure, and the results showed that in 10 recycles, a conversion of more than 99% of p-nitrophenol could be achieved in 10 minutes. The conversion rate for each cycle is shown in figure 3.
Claims (6)
1. A gold nanoparticle/metal organic framework composite characterized by: the gold nanoparticle/metal organic framework compound is mainly obtained by loading gold nanoparticles on a metal organic framework; the metal organic framework is in a nano sheet shape, and the unit structural formula of the metal organic framework is [ Zr ]6O8(FDC)2]n；
The gold nanoparticle/metal organic framework compound is prepared by reducing a metal organic framework and chloroauric acid in an aqueous solution by using sodium borohydride as a reducing agent;
each asymmetric unit in the metal-organic framework structure comprises a zirconium-oxygen metal cluster and two organic ligands FDC, wherein the organic ligands FDC are 1, 1' -ferrocenedicarboxylic acid;
the metal organic framework is a triclinic system, a P-1 space group and has a volume of 2812.83A3(ii) a Unit cell parameters a =14.1161 a, b =14.1161 a, c =14.1161 a, α =90.00 °, β =90.00 °, γ =90.00 °.
2. The gold nanoparticle/metal-organic framework composite according to claim 1, wherein: the gold nanoparticles are obtained by reduction of chloroauric acid as a precursor.
3. The method for preparing a gold nanoparticle/metal-organic framework composite according to any one of claims 1 to 2, comprising the following steps:
(1) dissolving zirconium chloride and organic ligand FDC in a solvent, adding a monobasic acid regulator, and carrying out ultrasonic treatment at normal temperature for 30 minutes;
(2) placing the solution reacted in the step 1) at 120 ℃ for closed reaction for 12 hours, and after the reaction is finished, cooling, washing and drying to obtain a metal organic framework;
(3) dispersing the metal organic framework obtained in the step 2) in an aqueous solution, performing ultrasonic treatment at normal temperature for 30 minutes, adding chloroauric acid, uniformly stirring and dispersing, adding a sodium borohydride reducing agent, continuously stirring and reacting for five minutes, and then centrifuging, washing and drying to obtain a gold nanoparticle/metal organic framework compound;
the molar ratio of the zirconium chloride to the organic ligand FDC to the monobasic acid in the step 1) is 1:1: 50-100;
the mass ratio of the chloroauric acid to the metal organic framework in the step 2) is 1:1-5, and the mass ratio of the sodium borohydride to the metal organic framework is 1: 10-50.
4. The method for preparing gold nanoparticle/metal organic framework composite according to claim 3, wherein the monobasic acid regulator in step 1) is acetic acid, and the solvent is N, N-dimethylformamide; the volume ratio of the monoacid to the solvent is 1: 5-15.
5. The method for preparing a gold nanoparticle/metal organic framework composite according to claim 3, wherein the sealing reaction in the step 2) is specifically as follows: transferring the solution reacted in the step 1) into a polytetrafluoroethylene reaction tank, sealing the polytetrafluoroethylene reaction tank, placing the polytetrafluoroethylene reaction tank into an electric heating air blowing drying oven, heating the solution to 120 ℃ at the speed of 5 ℃/min, and reacting for 12 hours.
6. The application of the gold nanoparticle/metal organic framework composite in catalytic reduction of p-nitrophenol according to any one of claims 1 to 2, wherein the gold nanoparticle/metal organic framework composite is dispersed in an aqueous solution, the p-nitrophenol is added after ultrasonic dispersion is carried out for 20 minutes, the mixture is stirred for 5 minutes at 30 ℃, then sodium borohydride is added, and the p-nitrophenol is reduced into the p-aminophenol under the catalysis of the gold nanoparticle/metal organic framework composite.
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