CN115888831B - Preparation method and application of platinum-loaded tin-iron bimetallic organic frame material - Google Patents
Preparation method and application of platinum-loaded tin-iron bimetallic organic frame material Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 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
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 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 49
- 238000003756 stirring Methods 0.000 claims abstract description 37
- 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
- 238000005406 washing Methods 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000013384 organic framework Substances 0.000 claims abstract description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000227 grinding Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229940040102 levulinic acid Drugs 0.000 claims abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000002244 precipitate Substances 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
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 19
- 239000000725 suspension Substances 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 2
- 230000002776 aggregation Effects 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- 229910005382 FeSn Inorganic materials 0.000 description 15
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012456 homogeneous solution Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
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- 239000007789 gas Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
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- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
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- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
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- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- GLOBUAZSRIOKLN-UHFFFAOYSA-N pentane-1,4-diol Chemical compound CC(O)CCCO GLOBUAZSRIOKLN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a platinum-loaded tin-iron bimetallic organic frame material, and belongs to the technical field of metal organic frame materials. The preparation method comprises the following steps: dissolving terephthalic acid in DMF and stirring to form a uniform solution; snCl is added 2 ·2H 2 O and Fe (NO) 3 ) 3 ·9H 2 O is dissolved in the uniform solution; adding glacial acetic acid; transferring 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, collecting precipitate, drying and grinding to obtain a tin-iron bimetallic organic framework material carrier; adding chloroplatinic acid into water under the condition of avoiding light, 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 tin-iron bimetallic organic frame material loaded with platinum. The preparation method is simple, the material is easy to obtain, pt has no obvious agglomeration phenomenon, and the preparation method is used in the levulinic acid hydrogenation reaction, has no generation of other byproducts and can optimize the reaction conditions.
Description
Technical Field
The invention belongs to the technical field of metal-organic frame materials, and particularly relates to a preparation method and application of a platinum-loaded tin-iron bimetallic organic frame material.
Background
The large-scale utilization of fossil energy has greatly promoted the development of human society and economy, but at the same time, has also brought about unavoidable derivative problems such as global warming, air pollution, and energy shortage. In recent years, researchers have gradually sought to develop new green renewable resource utilization schemes in order to alleviate the increasingly serious environmental pollution and global energy crisis problems. The woody biomass resource is used as a natural clean renewable energy source with wide sources, abundant reserves and low price, and has the potential of being converted into various important liquid fuels and high-added-value chemicals and the potential of 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 converting 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, and also can be used as green solvent and nylon intermediate, and can be further converted into various derivatives such as methyltetrahydrofuran, alkane and 1, 4-pentanediol. At present, the focus of scientific research is on optimizing the production process of preparing gamma-valerolactone by catalytic hydrogenation of biomass platform molecules, namely levulinic acid.
Currently, 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 use in industrial catalysis. The 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 high, and the requirements on production equipment are strict. In contrast, liquid phase hydrogenation processes are simple and more economical and have attracted attention from researchers. But the industrial non-noble metal catalyst, such as Cu-based catalyst, has low catalyst activity, low target yield, generally higher than 200 ℃ working temperature and higher than 3 MPa working pressure, and the catalyst has poor repeated stability, active metal is easy to lose, and coke with high yield is easy to generate. For noble metal catalysts used industrially, such as Ru/C, the working temperature is above 150 ℃ and the working pressure is above 3 MPa, the active noble metal component is rapidly deactivated in the reaction process and the deactivation is irreversible, so that the production cost is greatly increased.
The Metal Organic Framework (MOF) material is formed by self-assembly of metal ions or metal clusters and organic ligands, has high specific surface area and porosity, good stability, adjustable pore channels and flexible structure, and has many potential applications in separation, gas storage, drug delivery and batteries, especially in the catalytic field. In the prior art, when preparing the metal organic frame material, the ligand and the metal can not react completely because the coordination reaction is reversible reaction, and simultaneously, the ligand such as terephthalic acid and the like is not easy to dissolve in water, so that the reaction is slow and takes a long time, therefore, the method needs to be improved when preparing the metal organic frame material. In addition, the efficiency of the common supported Pt catalyst is low, the hydrogen pressure of more than 4MPa is generally required, the danger coefficient is large, and the catalyst activity is sensitive to the particle size due to the specificity of Pt, so that the development of a catalyst carrier capable of making Pt highly dispersed is still a challenge.
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 frame material, the preparation method is simple, pt in the prepared platinum-loaded metal organic frame material has no obvious agglomeration phenomenon, no surfactant is added for assistance in the preparation process, and the problem of surfactant residue in a system is avoided; the product prepared by the method is used as a catalyst in the levulinic acid hydrogenation reaction, no other byproducts are generated, the reaction condition is optimized, the reaction can be completed under the low-temperature and low-pressure condition, and the yield of gamma-valerolactone can reach 100% after the reaction for 5 hours.
In order to achieve the above 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) Terephthalic acid (H) 2 BDC) is dissolved in N, N-Dimethylformamide (DMF) and stirred into a uniform solution;
2) SnCl is added 2 ·2H 2 O and Fe (NO) 3 ) 3 ·9H 2 O is dissolved in the uniform solution of step 1);
3) Adding 5mL of glacial acetic acid into the solution in the step 2), and stirring for 30 minutes;
4) Transferring the solution obtained in the step 3) into a polytetrafluoroethylene high-pressure reaction kettle for reaction 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 the suspension after the reaction, washing with N, N-dimethylformamide, washing with methanol until the supernatant is colorless, collecting the lower precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain a tin-iron bimetallic organic framework material carrier;
6) Adding chloroplatinic acid into water under the condition of avoiding light, 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 into powder, and preserving under the drying condition to obtain the Pt/Sn-Fe-BDC of the tin-iron bimetallic organic framework material loaded with platinum.
Further, in step 2), snCl 2 ·2H 2 O and Fe (NO) 3 ) 3 ·9H 2 The amount of the two metal precursor species added together is equal to the amount of the terephthalic acid species.
Further, in the step 4), the temperature of the reaction is controlled to be 110-120 ℃.
Further, in the step 5), the suspension is centrifuged for 10min at 5000r.
Further, in the step 6), the mass of the tin-iron bimetallic organic framework material carrier is 200 times of the mass of platinum in chloroplatinic acid, and the load is 0.5 weight percent.
The platinum-loaded tin-iron bimetallic organic framework material prepared by the preparation method is applied to the catalyst.
Further, the tin-iron bimetallic organic framework material loaded with platinum is applied to 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) According to the invention, sn and Fe are used 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 the carrier; the platinum-loaded metal organic frame material prepared by the method has no obvious agglomeration phenomenon of Pt, realizes high dispersion of Pt on a carrier, and maximally saves cost.
(2) The platinum-loaded metal organic framework material prepared by the method is used as a catalyst in levulinic acid hydrogenation reaction, can optimize the reaction environment, compress the reaction time, realize the optimal hydrogenation effect and generate no other byproducts.
Drawings
FIG. 1 is 0.5wt.% Pt/FeSn 0.2 -Scanning Electron Microscope (SEM) images of BDC catalysts;
FIG. 2 is 0.5wt.% Pt/FeSn 0.2 TEM element 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 above.
Example 1
6mmol of terephthalic acid (H) 2 BDC) was dissolved in 30mLN, N-Dimethylformamide (DMF) and stirred to a homogeneous solution; 0.6mmol SnCl 2 ·2H 2 O and 5.4mmolFe (NO) 3 ) 3 ·9H 2 O is dissolved 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, and controlling the temperatureReacting for 24 hours at 110 ℃; 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 for 10 minutes at a rotation speed of 5000r, washing with N, N-dimethylformamide, washing with methanol to obtain a supernatant, collecting a lower precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain a tin-iron bimetallic organic framework material carrier; under the condition of avoiding light, adding 0.5ml of 4.76mgPt/ml chloroplatinic acid solution into water, stirring uniformly, adding carrier, stirring for 30 min, and dropwise adding excess NaBH 4 Stirring the solution for more than 6 hours; filtering the solution, washing the solid, drying at 80 ℃, taking out the solid, grinding the solid into powder, and preserving the powder 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) was dissolved in 30mL of N, N-Dimethylformamide (DMF) and stirred to a homogeneous solution; 1mmol SnCl 2 ·2H 2 O and 5mmolFe (NO) 3 ) 3 ·9H 2 O is dissolved 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 for 10 minutes at a rotation speed of 5000r, washing with N, N-dimethylformamide, washing with methanol to obtain a supernatant, collecting a lower precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain a tin-iron bimetallic organic framework material carrier; under the condition of avoiding light, adding 0.5ml of 4.76mgPt/ml chloroplatinic acid solution into water, stirring uniformly, adding carrier, stirring for 30 min, and dropwise adding excess NaBH 4 Stirring the solution for more than 6 hours; filtering the solution, washing the solid, drying at 80 ℃, taking out the solid, grinding the solid into powder, and preserving the powder under the drying condition to obtain the platinum-loaded tin-iron bimetallic organic framework material Pt/FeSn 0.2 -BDC。
As shown in fig. 1, from a scanning electron microscopeCharacterization of FeSn can be seen in the representation of (C) 0.2 The BDC support has a large number of pores, which allows Pt nanoparticles to be easily adsorbed in the pores of the MOF without any surfactant addition. Also, it can be seen from the image of fig. 2 that Pt is highly dispersed on the carrier and that no phenomenon of Pt nanoparticle aggregation is observed.
Example 3
6mmol of terephthalic acid (H) 2 BDC) was dissolved in 30mLN, N-Dimethylformamide (DMF) and stirred to a homogeneous solution; 1.5mmol SnCl 2 ·2H 2 O and 4.5mmol Fe (NO) 3 ) 3 ·9H 2 O is dissolved 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 to be 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 for 10 minutes at a rotation speed of 5000r, washing with N, N-dimethylformamide, washing with methanol to obtain a supernatant, collecting a lower precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain a tin-iron bimetallic organic framework material carrier; under the condition of avoiding light, adding 0.5ml of 4.76mgPt/ml chloroplatinic acid solution into water, stirring uniformly, adding carrier, stirring for 30 min, and dropwise adding excess NaBH 4 Stirring the solution for more than 6 hours; filtering the solution, washing the solid, drying at 80 ℃, taking out the solid, grinding the solid into powder, and preserving the powder under the drying condition to obtain the platinum-loaded tin-iron bimetallic organic framework material Pt/FeSn 0.33 -BDC。
Example 4
6mmol of terephthalic acid (H) 2 BDC) was dissolved in 30mL of N, N-Dimethylformamide (DMF) and stirred to a homogeneous solution; 3mmol of SnCl 2 ·2H 2 O and 3mmol Fe (NO) 3 ) 3 ·9H 2 O is dissolved 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, cooled for 4 hours, taken out and reversedCentrifuging the suspension after reaction for 10min at 5000r, washing with N, N-dimethylformamide, washing with methanol until the supernatant is colorless, collecting the lower precipitate, drying at 80deg.C for 6 hr, and grinding into powder to obtain tin-iron bimetallic organic frame material carrier; under the condition of avoiding light, adding 0.5ml of 4.76mgPt/ml chloroplatinic acid solution into water, stirring uniformly, adding carrier, stirring for 30 min, and dropwise adding excess NaBH 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 preserving the powder under the drying condition to obtain the platinum-loaded tin-iron bimetallic organic framework material Pt/FeSn-BDC.
Example 5
6mmol of terephthalic acid (H) 2 BDC) was dissolved in 30mLN, N-Dimethylformamide (DMF) and stirred to a homogeneous solution; 4.5mmolSnCl 2 ·2H 2 O and 1.5mmolFe (NO) 3 ) 3 ·9H 2 O is dissolved 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 for 10 minutes at a rotation speed of 5000r, washing with N, N-dimethylformamide, washing with methanol to obtain a supernatant, collecting a lower precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain a tin-iron bimetallic organic framework material carrier; under the condition of avoiding light, adding 0.5ml of 4.76mgPt/ml chloroplatinic acid solution into water, stirring uniformly, adding carrier, stirring for 30 min, and dropwise adding excess NaBH 4 Stirring the solution for more than 6 hours; filtering the solution, washing the solid, drying at 80 ℃, taking out the solid, grinding the solid into powder, and preserving the powder 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) was dissolved in 30mLN, N-Dimethylformamide (DMF) and stirred to a homogeneous solution; will be 1mmol SnCl 2 ·2H 2 O and 5mmolFe (NO) 3 ) 3 ·9H 2 O is dissolved 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 for 10 minutes at a rotation speed of 5000r, washing with N, N-dimethylformamide, washing with methanol to obtain a supernatant, collecting a lower precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain a tin-iron bimetallic organic frame material carrier FeSn 0.2 -BDC。
Comparative example 2
6mmol of terephthalic acid (H) 2 BDC) was dissolved in 30mL of N, N-Dimethylformamide (DMF) and stirred to a homogeneous solution; 1mmol SnCl 2 ·2H 2 O and 5mmolFe (NO) 3 ) 3 ·9H 2 O is dissolved 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, washing with N, N-dimethylformamide, washing with methanol until the supernatant is colorless, collecting the lower precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain a tin-iron bimetallic organic framework material carrier; a certain amount of carrier powder was placed in a small beaker, 0.5ml of a solution of 4.76mg pt/ml chloroplatinic acid was added dropwise, one drop at a time, the next drop was added after the liquid was completely immersed in the powder, and the solid powder was placed in a vacuum drying oven and dried at 80 ℃. Placing the dried solid in a tube furnace, introducing hydrogen (flow speed is 20 ml/min), reducing for 0.5h at 300 ℃ (heating rate is 5 ℃/min), taking out solid powder after the tube furnace is cooled to room temperature, drying and storing under the condition of light shielding to obtain the platinum-loaded tin-iron bimetallic organic frame material Pt/FeSn 0.2 -BDC（300H）。
Comparative example 3
6mmol of terephthalic acid (H) 2 BDC）Dissolving in 30mLN, N-Dimethylformamide (DMF), and stirring to obtain a uniform solution; 1mmol SnCl 2 ·2H 2 O and 5mmol Fe (NO) 3 ) 3 ·9H 2 O is dissolved in the uniform solution and 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, washing with N, N-dimethylformamide, washing with methanol until the supernatant is colorless, collecting the lower precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain a tin-iron bimetallic organic framework material carrier; under the condition of avoiding light, adding 0.5ml of 4.76mgPt/ml chloroplatinic acid solution into water, stirring uniformly, adding carrier, stirring for 30 min, and dropwise adding excess NaBH 4 Stirring the solution for more than 6 hours; filtering the solution, washing the solid, drying at 80 ℃, taking out the solid, grinding the solid into powder, and preserving the powder under the drying condition to obtain the platinum-loaded tin-iron bimetallic 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, and the specific steps are as follows:
step one, sequentially adding 100 mg Pt/Fe into a polytetrafluoroethylene lining of a batch-type high-pressure reaction kettle x Sn y BDC catalyst, magnon, 5mmol levulinic acid and 10ml dioxane were added again;
step two, after the reaction kettle is installed, argon is used for purging three times, vacuum is extracted, the reaction kettle is connected with a hydrogen steel cylinder, hydrogen with the pressure of 0.5 MPa is introduced for purging three times, and then the pressure of the hydrogen is increased 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 stabilized at 120 ℃, and simultaneously starting magnetic stirring, wherein the rotating speed is 900 rpm;
and fourthly, starting timing when the temperature in the kettle reaches 120 ℃, taking out the reaction kettle after the reaction lasts for 5h, cooling for 10min by using an ice water bath, releasing gas in the kettle, sucking the reaction liquid in the kettle by using a syringe, filtering by using a 0.45-micrometer filter head, diluting the filtrate, and quantitatively analyzing by using a Siemens flight 1310 type gas chromatograph. Wherein the Siemens flight ce 1310 type gas chromatograph is equipped with a TR-5 capillary chromatographic column and a FID detector. The test results are shown in Table 1.
TABLE 1 catalytic Performance test Table for different tin-iron center molar ratios with 0.5wt% Pt loading
As can be seen from Table 1, the Pt/Fe alloy prepared according to the present invention x Sn y BDC catalyst, iron center mainly regulates the conversion of levulinic acid, and tin center mainly regulates the selectivity of gamma valerolactone. When the tin-iron ratio is 5:1, the catalyst realizes the optimal catalytic effect under mild conditions, so Pt/FeSn is obtained 0.2 BDC as the preferred optimum proportion of catalyst.
Pt/Fe prepared in example 2, comparative examples 2, 3 x Sn y BDC and FeSn prepared in comparative example 1 0.2 BDC is used as a catalyst and is applied to levulinic acid hydrogenation, and the performance test results of the catalysts prepared by different methods are shown in table 2.
Table 2 catalytic performance test table for different treatment modes
As can be seen from Table 2, pt/FeSn prepared by the hydrogen pre-reduction method 0.2 BDC and Pt/FeSn prepared according to the invention 0.2 Lower levulinic acid conversion and poorer catalytic performance compared to BDC catalysts; during the preparation process, the catalyst prepared by treatment without adding glacial acetic acid (comparative example 3) has the catalytic performance which is obviously lower than that of Pt/FeSn prepared by the method of the invention 0.2 -a BDC catalyst; feSn without Pt loading 0.2 BDC catalyst (comparative example 1), no catalytic effect in levulinic acid hydrogenation reactions.
According to the invention, sn and Fe are used 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 the carrier; the platinum-loaded metal organic frame material prepared by the method has no obvious agglomeration phenomenon of Pt, realizes high dispersion of Pt on a carrier, and maximally saves cost.
The platinum-loaded metal organic framework material prepared by the method is applied to levulinic acid hydrogenation reaction as a catalyst, can optimize the reaction environment, compress the reaction time, and can enable the yield of gamma-valerolactone to reach 100% after the reaction for 5 hours under the conditions of 120 ℃ and 2MPa hydrogen pressure, thereby realizing the optimal hydrogenation effect and avoiding any other byproducts.
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 details may be made therein without departing from the spirit and 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 is added 2 ·2H 2 O and Fe (NO) 3 ) 3 ·9H 2 O is dissolved in the uniform solution of step 1);
3) Adding 5-10 ml of glacial acetic acid into the solution in the step 2), and stirring for 30 minutes;
4) Transferring the solution obtained in the step 3) into a polytetrafluoroethylene high-pressure reaction kettle for reaction 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 the suspension after the reaction, washing with N, N-dimethylformamide, washing with methanol until the supernatant is colorless, collecting the lower precipitate, drying at 80 ℃ for 6 hours, and grinding into powder to obtain a tin-iron bimetallic organic framework material carrier;
6) Adding chloroplatinic acid into water under the condition of avoiding light, 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 into powder, and preserving under the drying condition to obtain the Pt/Sn-Fe-BDC of the tin-iron bimetallic organic framework material loaded with platinum.
2. The method for preparing the platinum-loaded tin-iron bimetallic organic framework material as claimed in claim 1, wherein the method comprises the following steps: in step 2), snCl 2 ·2H 2 O and Fe (NO) 3 ) 3 ·9H 2 The amount of the two metal precursor species added together is equal to the amount of the terephthalic acid species.
3. The method for preparing the platinum-loaded tin-iron bimetallic organic framework material as claimed in claim 1, wherein the method comprises the following steps: in step 4), the temperature of the reaction is controlled to be 110-120 ℃.
4. The method for preparing the platinum-loaded tin-iron bimetallic organic framework material as claimed in claim 1, wherein the method comprises the following steps: in the step 5), the suspension is centrifuged for 10min at 5000r.
5. The method for preparing the platinum-loaded tin-iron bimetallic organic framework material as claimed in claim 1, wherein the method comprises the following steps: in the step 6), the mass of the tin-iron bimetallic organic framework material carrier is 200 times of the mass of platinum in chloroplatinic acid, and the load is 0.5 weight percent.
6. Use of a platinum-loaded tin-iron bimetallic organic framework material prepared according to any one of the preparation methods of claims 1-5 as a catalyst.
7. The use according to claim 6, characterized in that: the tin-iron bimetallic organic framework material loaded with platinum is applied to levulinic acid hydrogenation reaction.
8. The 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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