CN115888831A - Preparation method and application of platinum-loaded tin-iron bimetallic organic framework material - Google Patents
Preparation method and application of platinum-loaded tin-iron bimetallic organic framework material Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 51
- NNIPDXPTJYIMKW-UHFFFAOYSA-N iron tin Chemical compound [Fe].[Sn] NNIPDXPTJYIMKW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000013384 organic framework Substances 0.000 title claims abstract description 35
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 64
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 47
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 28
- 238000005406 washing Methods 0.000 claims abstract description 28
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 229940040102 levulinic acid Drugs 0.000 claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- 229960000583 acetic acid Drugs 0.000 claims abstract description 13
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000006228 supernatant Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
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- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 14
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- 230000001276 controlling effect Effects 0.000 description 8
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- 229910000831 Steel Inorganic materials 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a tin-iron bimetallic organic framework material loaded with platinum, and belongs to the technical field of metal organic framework materials. The preparation method comprises the following steps: dissolving terephthalic acid in DMF, and stirring to obtain a uniform solution; snCl 2 ·2H 2 O and Fe (NO) 3 ) 3 ·9H 2 Dissolving O in the uniform solution; adding glacial acetic acid; transferring the mixture into a polytetrafluoroethylene high-pressure reaction kettle; cooling after the reaction is finished, centrifuging, washing with N, N-dimethylformamide, washing with methanol until the supernatant is colorless, and collectingPrecipitating, drying and grinding to obtain a tin-iron bimetallic organic framework material carrier; adding chloroplatinic acid into water under the condition of keeping out of the sun, stirring uniformly, adding a carrier, and dropwise adding excessive NaBH 4 A solution; and carrying out suction filtration, washing, drying and grinding on the solution to obtain the platinum-loaded tin-iron bimetal organic framework material. The preparation method is simple, the materials are easy to obtain, pt does not have obvious agglomeration phenomenon, other byproducts are not generated when the Pt is used in the levulinic acid hydrogenation reaction, and the reaction conditions can be optimized.
Description
Technical Field
The invention belongs to the technical field of metal organic framework materials, and particularly relates to a preparation method and application of a tin-iron bimetallic organic framework material loaded with platinum.
Background
The large-scale utilization of fossil energy has greatly promoted the development of human society and economy, but also has brought about inevitable derived problems such as global warming, air pollution and energy shortage. In recent years, in order to alleviate the increasingly serious problems of environmental pollution and global energy crisis, researchers are gradually seeking to develop new green renewable resource utilization schemes. The wood biomass resource is a natural clean renewable energy source with wide source, abundant reserves and low price, and has the potential of being converted into various important liquid fuels and high value-added chemicals and the potential of being used for replacing the traditional fossil energy greatly. Among these, the synthesis of gamma valerolactone, which is considered to be the most promising biomass-derived platform molecule, is one of the key steps in the conversion of biomass resources into liquid fuels and high value-added chemicals. Gamma valerolactone has attractive physicochemical properties and potential fuel applications, is non-toxic and biodegradable; can be used as food additive and fuel additive, green solvent and nylon intermediate, and can be further upgraded and converted into various derivatives such as methyl tetrahydrofuran, alkane and 1, 4-pentanediol. At present, the key point of scientific research is the optimization of the production process for preparing gamma-valerolactone by catalytic hydrogenation of a biomass platform molecule, i.e. levulinic acid.
At present, the developed catalysts for catalyzing levulinic acid hydrogenation to produce gamma-valerolactone are mainly divided into: homogeneous catalysts and heterogeneous catalysts. Homogeneous catalysts require complex synthetic steps and are expensive, have poor durability and are difficult to recycle, which greatly limits their large scale application in industrial catalysis. The gas phase hydrogenation process with heterogeneous catalyst has energy sensitivity to the vaporization of levulinic acid (the boiling point of levulinic acid is 245-246 ℃), the required working temperature is very high, and the requirements on production equipment are very strict. In contrast, liquid phase hydrogenation processes are simple and more economical and have attracted the attention of researchers. However, the non-noble metal catalyst used in industry, such as Cu-based catalyst, has low catalyst activity, low target yield, working temperature generally above 200 ℃, working pressure above 3 MPa, poor catalyst repeatability stability, easy loss of active metal, and easy generation of high-yield coke. For noble metal catalyst used in industry, such as Ru/C, the working temperature is above 150 deg.C, the working pressure is above 3 MPa, the active noble metal component is quickly deactivated in the reaction process, and the deactivation is irreversible, thus the production cost is greatly increased.
The Metal Organic Framework (MOF) material is formed by self-assembling metal ions or metal clusters and organic ligands, has higher specific surface area and porosity, good stability, adjustable pore channels and flexible structure, and has a plurality of potential applications in separation, gas storage, drug delivery and batteries, in particular to the field of catalysis. In the prior art, when a metal organic framework material is prepared, because a coordination reaction is a reversible reaction, a phenomenon that a ligand and a metal can not completely react occurs, and meanwhile, because ligands such as terephthalic acid are not easy to dissolve in water, the reaction is slow and takes a long time, so that the method is necessary to be improved when the metal organic framework material is prepared. In addition, the common supported Pt catalyst has low efficiency, generally needs hydrogen pressure of more than 4MPa, has a large risk coefficient, and due to the particularity of Pt, the catalyst activity is sensitive to the particle size, so that the development of a catalyst carrier capable of highly dispersing Pt is still a challenge at present.
Disclosure of Invention
In order to overcome the technical problems in the background art, the invention provides a preparation method and application of a platinum-loaded tin-iron bimetallic organic framework material, the preparation method is simple, pt in the prepared platinum-loaded metal organic framework material has no obvious agglomeration phenomenon, and no surfactant is added for assistance in the preparation process, so that the problem of surfactant residue in the system is avoided; the product prepared by the invention is used as a catalyst, no other by-product is generated in the hydrogenation reaction of levulinic acid, the reaction condition is optimized, the reaction can be completed under the conditions of low temperature and low pressure, and the yield of gamma-valerolactone can reach 100% after 5 hours of reaction.
In order to realize the purpose, the invention is realized by the following technical scheme:
a preparation method of a tin-iron bimetallic organic framework material loaded with platinum comprises the following specific steps:
1) Mixing terephthalic acid (H) 2 BDC) is dissolved in N, N-Dimethylformamide (DMF) and is stirred into uniform solution;
2) SnCl 2 ·2H 2 O and Fe (NO) 3 ) 3 ·9H 2 Dissolving O in the uniform solution in the step 1);
3) Adding 5mL of glacial acetic acid into the solution obtained in the step 2), and stirring for 30 minutes;
4) Transferring the solution in the step 3) into a polytetrafluoroethylene high-pressure reaction kettle, and reacting for 24 hours;
5) After the reaction is finished, placing the reaction kettle in a cold water bath, cooling for 4 hours, taking out, centrifuging a suspension after the reaction, washing with N, N-dimethylformamide, washing with methanol until a supernatant is colorless, collecting a lower-layer precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain the tin-iron bimetallic organic framework material carrier;
6) Under the condition of keeping out of the sun, adding chloroplatinic acid into water, stirring uniformly, adding the carrier prepared in the step 5), stirring for 30 minutes, and dropwise adding excessive NaBH 4 Stirring the solution for more than 6 hours;
7) And (3) carrying out suction filtration on the solution in the step 6), washing the solid, drying at 80 ℃, taking out the solid, grinding the solid into powder, and storing under a drying condition to prepare the platinum-loaded tin-iron bimetallic organic frame material Pt/Sn-Fe-BDC.
Further, in step 2), snCl 2 ·2H 2 O and Fe (NO) 3 ) 3 ·9H 2 The sum of the amounts of the two metal precursor species is equal to the amount of the terephthalic acid species.
Further, in the step 4), the reaction temperature is controlled to be 110-120 ℃.
Further, in the step 5), the suspension is centrifuged for 10min at a rotation speed of 5000r.
Further, in the step 6), the mass of the carrier of the tin-iron bimetallic organic framework material is 200 times of that of platinum in chloroplatinic acid, and the loading amount is 0.5wt%.
The tin-iron bimetallic organic framework material loaded with platinum prepared by the preparation method is applied as a catalyst.
Further, the tin-iron bimetallic organic framework material loaded with platinum is applied to the levulinic acid hydrogenation reaction.
Further, the reaction temperature of the levulinic acid hydrogenation reaction is 120 ℃, the reaction time is 3-6h, and the reaction pressure is controlled to be 2MPa.
The invention has the beneficial effects that:
(1) The invention takes Sn and Fe as raw materials, the materials are easy to obtain, the cost is low, and the coordination degree is improved by adding glacial acetic acid; sodium borohydride is used for pre-reduction, and other surfactants are not required to be added for assistance in the adsorption process of Pt and a carrier; in the platinum-loaded metal organic framework material prepared by the invention, pt does not have obvious agglomeration phenomenon, so that Pt is highly dispersed on a carrier, and the cost is saved to the maximum extent.
(2) The platinum-loaded metal organic framework material prepared by the invention is used as a catalyst to be applied to levulinic acid hydrogenation reaction, can optimize reaction environment, shorten reaction time, realize optimal hydrogenation effect, and does not generate any other by-product.
Drawings
FIG. 1 is 0.5wt.% Pt/FeSn 0.2 -Scanning Electron Microscope (SEM) images of BDC catalyst;
FIG. 2 is 0.5wt.% Pt/FeSn 0.2 TEM elemental mapping images of four elements in BDC catalyst.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited to the examples.
Example 1
6mmol of terephthalic acid (H) 2 BDC) is dissolved in 30mLN, N-Dimethylformamide (DMF) and stirred to be evenly dissolvedLiquid; 0.6mmol of SnCl 2 ·2H 2 O and 5.4 mmole Fe (NO) 3 ) 3 ·9H 2 Dissolving O in the uniform solution; then adding 5mL of glacial acetic acid, and stirring for 30 minutes; transferring the solution into a polytetrafluoroethylene high-pressure reaction kettle, controlling the temperature at 110 ℃, and reacting for 24 hours; after the reaction is finished, placing the reaction kettle in a cold water bath, cooling for 4 hours, taking out, centrifuging the suspension after the reaction, wherein the centrifuging time is 10min, the rotating speed is 5000r, washing the suspension by using N, N-dimethylformamide, washing the suspension by using methanol until the supernatant is colorless, collecting the lower-layer precipitate, drying the precipitate at the temperature of 80 ℃ for 6 hours, and grinding the precipitate into powder to obtain the tin-iron bimetal organic framework material carrier; under the condition of keeping out of the sun, 0.5ml of 4.76mgPt/ml chloroplatinic acid solution is added into water, after being evenly stirred, the carrier is added, the stirring is carried out for 30 minutes, and excessive NaBH is dropwise added 4 Stirring the solution for more than 6 hours; filtering the solution, washing the solid, drying at 80 ℃, taking out the solid, grinding into powder, and storing under the drying condition to obtain the platinum-loaded tin-iron bimetallic organic framework material Pt/FeSn 0.11 -BDC。
Example 2
6mmol of terephthalic acid (H) 2 BDC) is dissolved in 30mL of N, N-Dimethylformamide (DMF) and stirred into a uniform solution; 1mmol of SnCl 2 ·2H 2 O and 5mmol Fe (NO) 3 ) 3 ·9H 2 Dissolving O in the uniform solution; then adding 5mL of glacial acetic acid, and stirring for 30 minutes; transferring the solution into a polytetrafluoroethylene high-pressure reaction kettle, controlling the temperature at 110 ℃, and reacting for 24 hours; after the reaction is finished, placing the reaction kettle in a cold water bath, cooling for 4 hours, taking out, centrifuging the suspension after the reaction, wherein the centrifuging time is 10min, the rotating speed is 5000r, washing with N, N-dimethylformamide, washing with methanol until the supernatant is colorless, collecting the lower-layer precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain the tin-iron bimetallic organic framework material carrier; under the condition of keeping out of the sun, 0.5ml of 4.76mgPt/ml chloroplatinic acid solution is added into water, after being evenly stirred, the carrier is added, the stirring is carried out for 30 minutes, and excessive NaBH is dropwise added 4 Stirring the solution for more than 6 hours; the solution is filtered by suction and the solid is washed inDrying at 80 ℃, taking out the solid, grinding the solid into powder, and storing the powder under the drying condition to prepare the platinum-loaded tin-iron bimetallic organic framework material Pt/FeSn 0.2 -BDC。
As shown in FIG. 1, feSn can be seen from the characterization by scanning electron microscope 0.2 BDC supports have a large number of channels, which allows Pt nanoparticles to be easily adsorbed in the channels of MOFs without adding any surfactant. Also, from the image of fig. 2, it can be seen that Pt is highly dispersed on the support and no phenomenon that Pt nanoparticles are aggregated is observed.
Example 3
6mmol of terephthalic acid (H) 2 BDC) is dissolved in 30mLN, N-Dimethylformamide (DMF) and stirred into a uniform solution; 1.5mmol of SnCl 2 ·2H 2 O and 4.5mmol Fe (NO) 3 ) 3 ·9H 2 Dissolving O in the uniform solution; then adding 5mL of glacial acetic acid, and stirring for 30 minutes; transferring the solution into a polytetrafluoroethylene high-pressure reaction kettle, controlling the temperature at 120 ℃, and reacting for 24 hours; after the reaction is finished, placing the reaction kettle in a cold water bath, cooling for 4 hours, taking out, centrifuging the suspension after the reaction, wherein the centrifuging time is 10min, the rotating speed is 5000r, washing the suspension by using N, N-dimethylformamide, washing the suspension by using methanol until the supernatant is colorless, collecting the lower-layer precipitate, drying the precipitate at the temperature of 80 ℃ for 6 hours, and grinding the precipitate into powder to obtain the tin-iron bimetal organic framework material carrier; under the condition of keeping out of the sun, 0.5ml of 4.76mgPt/ml chloroplatinic acid solution is added into water, after being evenly stirred, the carrier is added, the stirring is carried out for 30 minutes, and excessive NaBH is dropwise added 4 Stirring the solution for more than 6 hours; filtering the solution, washing the solid, drying at 80 ℃, taking out the solid, grinding into powder, and storing under the drying condition to obtain the platinum-loaded tin-iron bimetal organic framework material Pt/FeSn 0.33 -BDC。
Example 4
6mmol of terephthalic acid (H) 2 BDC) is dissolved in 30mL of N, N-Dimethylformamide (DMF) and is stirred into a uniform solution; 3mmol of SnCl 2 ·2H 2 O and 3mmol Fe (NO) 3 ) 3 ·9H 2 Dissolving O in the homogeneous solutionPerforming the following steps; then 5mL of glacial acetic acid is added, and the mixture is stirred for 30 minutes; transferring the solution into a polytetrafluoroethylene high-pressure reaction kettle, controlling the temperature at 110 ℃, and reacting for 24 hours; after the reaction is finished, placing the reaction kettle in a cold water bath, cooling for 4 hours, taking out, centrifuging the suspension after the reaction, wherein the centrifuging time is 10min, the rotating speed is 5000r, washing with N, N-dimethylformamide, washing with methanol until the supernatant is colorless, collecting the lower-layer precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain the tin-iron bimetallic organic framework material carrier; under the condition of keeping out of the sun, 0.5ml of 4.76mgPt/ml chloroplatinic acid solution is added into water, after being evenly stirred, the carrier is added, the stirring is carried out for 30 minutes, and excessive NaBH is dropwise added 4 Stirring the solution for more than 6 hours; and (3) carrying out suction filtration on the solution, washing the solid, drying at 80 ℃, taking out the solid, grinding the solid into powder, and storing under a drying condition to prepare the platinum-loaded tin-iron bimetallic organic frame material Pt/FeSn-BDC.
Example 5
6mmol of terephthalic acid (H) 2 BDC) is dissolved in 30mLN and N-Dimethylformamide (DMF), and is stirred into a uniform solution; adding 4.5mmol SnCl 2 ·2H 2 O and 1.5 mmoleFe (NO) 3 ) 3 ·9H 2 Dissolving O in the uniform solution; then 5mL of glacial acetic acid is added, and the mixture is stirred for 30 minutes; transferring the solution into a polytetrafluoroethylene high-pressure reaction kettle, controlling the temperature at 110 ℃, and reacting for 24 hours; after the reaction is finished, placing the reaction kettle in a cold water bath, cooling for 4 hours, taking out, centrifuging the suspension after the reaction, wherein the centrifuging time is 10min, the rotating speed is 5000r, washing the suspension by using N, N-dimethylformamide, washing the suspension by using methanol until the supernatant is colorless, collecting the lower-layer precipitate, drying the precipitate at the temperature of 80 ℃ for 6 hours, and grinding the precipitate into powder to obtain the tin-iron bimetal organic framework material carrier; under the condition of keeping out of the sun, 0.5ml of 4.76mgPt/ml chloroplatinic acid solution is added into water, after being evenly stirred, the carrier is added, the stirring is carried out for 30 minutes, and excessive NaBH is dropwise added 4 Stirring the solution for more than 6 hours; filtering the solution, washing the solid, drying at 80 ℃, taking out the solid, grinding into powder, and storing under the drying condition to obtain the platinum-loaded tin-iron bimetallic organic framework material Pt/FeSn 3 -BDC。
Comparative example 1
6mmol of terephthalic acid (H) 2 BDC) is dissolved in 30mLN, N-Dimethylformamide (DMF) and stirred into a uniform solution; 1mmol of SnCl 2 ·2H 2 O and 5 mmoleFe (NO) 3 ) 3 ·9H 2 Dissolving O in the uniform solution; then adding 5mL of glacial acetic acid, and stirring for 30 minutes; transferring the solution into a polytetrafluoroethylene high-pressure reaction kettle, controlling the temperature at 110 ℃, and reacting for 24 hours; after the reaction is finished, the reaction kettle is placed in a cold water bath, the reaction kettle is taken out after being cooled for 4 hours, suspension liquid after the reaction is centrifuged for 10 minutes at the rotating speed of 5000r, the suspension liquid is washed by N, N-dimethylformamide and methanol until the supernatant liquid is colorless, lower-layer precipitate is collected, the lower-layer precipitate is dried for 6 hours at the temperature of 80 ℃, the lower-layer precipitate is ground into powder, and the FeSn carrier serving as the tin-iron bimetal organic framework material is obtained 0.2 -BDC。
Comparative example 2
6mmol of terephthalic acid (H) 2 BDC) is dissolved in 30mL of N, N-Dimethylformamide (DMF) and stirred into a uniform solution; 1mmol of SnCl 2 ·2H 2 O and 5 mmoleFe (NO) 3 ) 3 ·9H 2 Dissolving O in the uniform solution; then adding 5mL of glacial acetic acid, and stirring for 30 minutes; transferring the solution into a polytetrafluoroethylene high-pressure reaction kettle, controlling the temperature at 110 ℃, and reacting for 24 hours; after the reaction is finished, placing the reaction kettle in a cold water bath, cooling for 4 hours, taking out, centrifuging a suspension after the reaction, washing with N, N-dimethylformamide, washing with methanol until a supernatant is colorless, collecting a lower-layer precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain the tin-iron bimetallic organic framework material carrier; putting a certain amount of carrier powder into a small beaker, dropwise adding 0.5ml of 4.76mgPt/ml chloroplatinic acid solution, adding one drop at a time, adding the next drop after the liquid is completely immersed into the powder, and putting the solid powder into a vacuum drying oven for drying at 80 ℃. Placing the dried solid in a tube furnace, introducing hydrogen (flow rate of 20 ml/min), reducing at 300 deg.C for 0.5h (temperature rise rate of 5 deg.C/min), taking out solid powder when the tube furnace is cooled to room temperature, and drying and storing under dark condition to obtain the final productPlatinum-loaded tin-iron bimetal organic framework material Pt/FeSn 0.2 -BDC（300H）。
Comparative example 3
6mmol of terephthalic acid (H) 2 BDC) is dissolved in 30mLN, N-Dimethylformamide (DMF) and stirred into a uniform solution; 1mmol of SnCl 2 ·2H 2 O and 5mmol Fe (NO) 3 ) 3 ·9H 2 Dissolving O in the uniform solution, and stirring for 30 minutes; transferring the solution into a polytetrafluoroethylene high-pressure reaction kettle, controlling the temperature at 110 ℃, and reacting for 24 hours; after the reaction is finished, placing the reaction kettle in a cold water bath, cooling for 4 hours, taking out, centrifuging a suspension after the reaction, washing with N, N-dimethylformamide, washing with methanol until a supernatant is colorless, collecting a lower-layer precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain the tin-iron bimetallic organic framework material carrier; under the condition of keeping out of the sun, 0.5ml of 4.76mgPt/ml chloroplatinic acid solution is added into water, after being evenly stirred, the carrier is added, the stirring is carried out for 30 minutes, and excessive NaBH is dropwise added 4 Stirring the solution for more than 6 hours; filtering the solution, washing the solid, drying at 80 ℃, taking out the solid, grinding into powder, and storing under the drying condition to obtain the platinum-loaded tin-iron bimetal organic framework material Pt/FeSn 0.2 -BDC（No HAc）。
Application example
The Pt/FexSny-BDC prepared in examples 1-5 is used as a catalyst, and Pt/Fe-BDC and Pt/Sn-BDC are prepared and applied to levulinic acid hydrogenation reaction, and the specific steps are as follows:
step one, sequentially adding 100 mg of Pt/Fe into a polytetrafluoroethylene lining of an intermittent high-pressure reaction kettle x Sn y -BDC catalyst, magnetons, further 5mmol levulinic acid and 10ml dioxane;
step two, after the reaction kettle is installed, purging with argon for three times, extracting vacuum, connecting the reaction kettle with a hydrogen steel cylinder, introducing 0.5 MPa hydrogen for purging for three times, and raising the pressure of the hydrogen to keep the pressure in the kettle at 2.0 MPa;
step three, placing the reaction kettle into a preset oil bath kettle which is stable at 120 ℃, and simultaneously starting magnetic stirring at the rotation speed of 900 rpm;
and step four, starting timing when the temperature in the kettle reaches 120 ℃, taking out the reaction kettle after the reaction lasts for 5 hours, cooling the reaction kettle for 10 minutes by using an ice water bath, releasing gas in the kettle, sucking the reaction liquid in the kettle by using an injector, filtering the reaction liquid by using a 0.45 micrometer filter head, diluting the filtrate, and quantitatively analyzing the diluted filtrate by using a Sammer FeITRACE 1310 type gas chromatograph. Among them, the Sammerfue TRACE 1310 type gas chromatograph is equipped with a TR-5 capillary chromatographic column and an FID detector. The results are shown in Table 1.
TABLE 1 catalytic Performance test Table for different tin-iron center molar ratios with a loading of 0.5wt% Pt
As can be seen from Table 1, pt/Fe prepared according to the invention x Sn y BDC catalyst, iron centre mainly regulating conversion of levulinic acid and tin centre mainly regulating selectivity of gamma valerolactone. When the tin-iron ratio is 5 0.2 BDC as the preferred optimal ratio catalyst.
Pt/Fe prepared in example 2 and comparative examples 2 and 3 x Sn y -BDC and FeSn prepared in comparative example 1 0.2 BDC as catalyst, applied in the hydrogenation of levulinic acid, the results of the performance tests of the catalysts prepared by the different processes are given in table 2.
TABLE 2 test chart for catalytic performance of different treatment modes
As can be seen from Table 2, pt/FeSn prepared by hydrogen pre-reduction method 0.2 BDC and Pt/FeSn prepared according to the invention 0.2 Compared with a BDC catalyst, the levulinic acid has lower conversion rate and poorer catalytic performance; the catalyst prepared without glacial acetic acid addition during the preparation (comparative example 3) has a significantly lower catalytic performance than the process according to the inventionPrepared Pt/FeSn 0.2 -a BDC catalyst; feSn without supported Pt 0.2 BDC catalyst (comparative example 1), no catalytic effect in the levulinic acid hydrogenation reaction.
The invention takes Sn and Fe as raw materials, the materials are easy to obtain, the cost is low, and the coordination degree is improved by adding glacial acetic acid; sodium borohydride is used for pre-reduction, and other surfactants are not needed to be added for assistance in the adsorption process of Pt and a carrier; in the metal organic framework material loaded with platinum prepared by the invention, pt does not have obvious agglomeration phenomenon, so that high dispersion of Pt on a carrier is realized, and the cost is saved to the maximum extent.
The platinum-loaded metal organic framework material prepared by the invention is used as a catalyst to be applied to levulinic acid hydrogenation reaction, the reaction environment can be optimized, the reaction time is shortened, the yield of gamma-valerolactone can reach 100% after reaction for 5 hours at 120 ℃ under the condition of 2MPa hydrogen pressure, the optimal hydrogenation effect is realized, and no other by-product is generated.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a tin-iron bimetallic organic framework material loaded with platinum is characterized by comprising the following steps: the preparation method comprises the following specific steps:
1) Dissolving terephthalic acid in N, N-dimethylformamide, and stirring to obtain a uniform solution;
2) SnCl 2 ·2H 2 O and Fe (NO) 3 ) 3 ·9H 2 Dissolving O in the uniform solution in the step 1);
3) Adding 5-10 ml of glacial acetic acid into the solution obtained in the step 2), and stirring for 30 minutes;
4) Transferring the solution in the step 3) into a polytetrafluoroethylene high-pressure reaction kettle, and reacting for 24 hours;
5) After the reaction is finished, placing the reaction kettle in a cold water bath, cooling for 4 hours, taking out, centrifuging a suspension after the reaction, washing with N, N-dimethylformamide, washing with methanol until a supernatant is colorless, collecting a lower-layer precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain a tin-iron bimetal organic framework material carrier;
6) Under the condition of keeping out of the sun, adding chloroplatinic acid into water, stirring uniformly, adding the carrier prepared in the step 5), stirring for 30 minutes, and dropwise adding excessive NaBH 4 Stirring the solution for more than 6 hours;
7) And (3) carrying out suction filtration on the solution in the step 6), washing the solid, drying at 80 ℃, taking out the solid, grinding the solid into powder, and storing under a drying condition to prepare the platinum-loaded tin-iron bimetallic organic frame material Pt/Sn-Fe-BDC.
2. The method for preparing a platinum-loaded tin-iron bimetallic organic framework material as claimed in claim 1, characterized in that: in step 2), snCl 2 ·2H 2 O and Fe (NO) 3 ) 3 ·9H 2 The sum of the amounts of the two metal precursor species is equal to the amount of the terephthalic acid species.
3. The method for preparing a platinum-loaded tin-iron bimetallic organic framework material as claimed in claim 1, characterized in that: in the step 4), the reaction temperature is controlled to be 110-120 ℃.
4. The preparation method of the platinum-loaded tin-iron bimetallic organic framework material as described in claim 1, wherein the preparation method comprises the following steps: and 5), centrifuging the suspension for 10min at the rotating speed of 5000r.
5. The method for preparing a platinum-loaded tin-iron bimetallic organic framework material as claimed in claim 1, characterized in that: in the step 6), the mass of the carrier of the tin-iron bimetallic organic framework material is 200 times of that of platinum in chloroplatinic acid, and the load is 0.5wt%.
6. Use of the platinum-loaded tin-iron bimetallic organic framework material prepared by any one of the preparation methods according to claims 1-5 as a catalyst.
7. Use according to claim 6, characterized in that: the tin-iron bimetallic organic framework material loaded with platinum is applied to the levulinic acid hydrogenation reaction.
8. Use according to claim 7, characterized in that: the reaction temperature of the levulinic acid hydrogenation reaction is 120 ℃, the reaction time is 3-6h, and the reaction pressure is controlled to be 2MPa.
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