CN117181265A - Preparation method of efficient catalyst for preparing DMF (dimethyl formamide) by carbon dioxide hydrogenation - Google Patents
Preparation method of efficient catalyst for preparing DMF (dimethyl formamide) by carbon dioxide hydrogenation Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 39
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 39
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 title claims description 86
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000013132 MOF-5 Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 239000012876 carrier material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 229910052741 iridium Inorganic materials 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- OYEVFSJZQTUDDN-UHFFFAOYSA-N methanol;n-methylmethanamine Chemical compound OC.CNC OYEVFSJZQTUDDN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- -1 iridium metal compounds Chemical class 0.000 claims description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 239000013110 organic ligand Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- PTSZYEWEQITNAC-UHFFFAOYSA-N zinc dinitrate dihydrate Chemical compound O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O PTSZYEWEQITNAC-UHFFFAOYSA-N 0.000 claims description 3
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004873 anchoring Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- ZHNNHZFCTWXJND-UHFFFAOYSA-L zinc;sulfate;dihydrate Chemical compound O.O.[Zn+2].[O-]S([O-])(=O)=O ZHNNHZFCTWXJND-UHFFFAOYSA-L 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 4
- 238000001704 evaporation Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 11
- 238000012360 testing method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000004913 activation Effects 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- NSFMUUDGMZOUHO-UHFFFAOYSA-N N1=CC=CC2=CC=C3C=CC=NC3=C12.[Ir] Chemical compound N1=CC=CC2=CC=C3C=CC=NC3=C12.[Ir] NSFMUUDGMZOUHO-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The application provides a preparation method of a carbon dioxide hydrogenation catalyst and a catalytic method for preparing DMF by using the same, wherein the preparation method at least comprises the following steps: grinding the MOF-5 material, and performing preliminary carbonization under nitrogen atmosphere to obtain a carbon carrier material; taking the carbon material in ethanol, and performing ultrasonic dispersion; adding a certain amount of 1, 10-phenanthroline and a metal solution into ethanol, mixing, and fully performing ultrasonic treatment to completely coordinate to obtain a complex of the metal and the 1, 10-phenanthroline; and uniformly mixing the two mixed solutions, evaporating to dryness, grinding the solid, and performing secondary carbonization under the nitrogen atmosphere to obtain the catalytic material. The application provides a catalyst with high efficiency, high activity and repeated utilization and a preparation process thereof, and the catalyst adopts a high-dispersion metal atom catalytic active center, can achieve the effects of wide use temperature, high DMF yield and reasonable industrial operation cost, can meet the requirements of future carbon dioxide resource utilization and mass chemicals DMF production industrialization, and has good application prospect.
Description
Technical Field
The application belongs to the technical field of DMF (dimethyl formamide) preparation by thermocatalytic carbon dioxide hydrogenation, and particularly relates to a catalyst for preparing DMF by thermocatalytic carbon dioxide hydrogenation and a preparation method thereof.
Background
With the development of society, traditional fossil fuels are rapidly consumed in form of CO 2 The emission of predominantly greenhouse gases is increasing. How to better realize the resource utilization of carbon dioxide is a hot topic which has become a global concern. However due to CO 2 Thermodynamically stable, fully oxidized and kinetically inert, so that activation and conversion thereof are not readily accomplished, but if high energy molecules (e.g., H) are provided in the process 2 ) And a high-activity catalyst is adopted, the problem can be solved greatly. Wherein, CO is utilized by a thermocatalytic mode 2 The hydrogenation synthesis of a high value added bulk chemical product N, N-dimethyl diamide (DMF for short) is a feasible route. DMF is a common organic reagent, is widely applied to industrial production, and has great application value. By CO 2 The DMF is synthesized by hydrogenation, so that CO can be effectively utilized 2 And the carbon reduction is realized, and meanwhile, certain economic benefits can be brought.
The supported heterogeneous catalyst is widely studied as a catalyst with high stability, high activity, high selectivity and relatively low price, wherein the single-atom catalyst is formed by single atoms and a carrier only in the active site, so that the catalytic performance and the active site utilization rate are greatly improved. Metal-organic frameworks (MOFs) materials are commonly used as carbon-based heterogeneous catalyst supports due to their high specific surface area, high porosity, ease of pore structure adjustment, and various metal coordination configurations. Therefore, how to construct a monoatomic catalytic material with high specific surface area, porous structure and high activity by loading metal on the surface of MOFs is important.
Disclosure of Invention
The application aims at: in order to solve the problems of high activation difficulty, low conversion rate and the like in the carbon dioxide recycling, the application provides the catalyst for preparing DMF by the carbon dioxide hydrogenation with high efficiency and high selectivity and the preparation process thereof.
In order to solve the technical problems, the application adopts the following technical scheme:
a preparation method of a single-atom catalyst for preparing DMF by carbon dioxide hydrogenation comprises the following steps:
step 1, preparing a carbon substrate material: the precursor MOF-5 is synthesized by using zinc nitrate dihydrate as a metal source, terephthalic acid as an organic ligand and triethylamine as a coordination regulator through a hot solvent method and carbonized, and specifically comprises the following steps:
step 1.1: weighing quantitative terephthalic acid: zinc sulfate dihydrate (mass ratio 1:3.5);
step 1.2: suspending the solid weighed in the step 1.1 in DMF, and adding triethylamine (3 ml) to obtain a suspension;
step 1.3: stirring the suspension in the step 1.2 at 125 ℃ for reaction for 24 hours, and cooling to room temperature after the reaction is finished to generate white solid;
step 1.4: centrifuging to collect the white solid generated in the step 1.3, washing with ethanol (100 ml x 3), and drying in a vacuum drying oven at 60 ℃ for 7-8h to obtain a pure white solid product MOF-5;
step 1.5: grinding the solid product obtained in the step 1.4 to obtain N 2 Carbonizing at 1100 deg.c in high temperature in atmosphere for 2 hr, and cooling to room temperature to obtain carbon carrier material MOF-5-C.
Step 2, using chloroiridium acid as an iridium metal source, carrying out coordination anchoring on the MOF-5-C material to obtain a catalytic material, wherein the catalytic material specifically comprises the following steps:
step 2.1: weighing 1, 10-phenanthroline, adding the phenanthroline into ethanol absolute ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol dispersion solution of the phenanthroline;
step 2.2: weighing the carbon carrier material (MOF-5-C) prepared in the step 1, adding the carbon carrier material into absolute ethyl alcohol, and performing ultrasonic dispersion for 30min to obtain an ethanol dispersion solution of the carbon material;
step 2.3: measuring a certain amount of H2 IrCl6.6H2O solution, adding the ethanol dispersion solution of the phenanthroline obtained in the step 2.1, and carrying out ultrasonic mixing to completely coordinate the solution to obtain a complex of metal and the phenanthroline;
step 2.4: mixing the ethanol dispersion solution of the carbon material in the step 2.2 with the metal in the step 2.3 and the phenanthroline complex, and carrying out ultrasonic reaction for 2 hours;
step 2.5: stirring the mixed solution obtained in the step 2.4 for 6 hours at room temperature;
2.6, rotationally distilling the product obtained after the reaction in the step 2.5 for 5-10min, and then drying at 60 ℃ for 7-8h to obtain a solid product;
step 2.7, grinding the solid obtained in step 2.6, and then adding N 2 And (3) carrying out secondary carbonization under the atmosphere, wherein the secondary carbonization temperature is 800 ℃, maintaining for 1h, then introducing ammonia gas for 15min, and cooling to obtain the designed catalytic material.
The method for preparing DMF catalyst by hydrogenation of carbon dioxide according to claim 1, wherein the mixing ratio of zinc nitrate dihydrate of the trimetallic source to terephthalic acid and triethylamine of the organic ligand in the mixed solution in step 1.2.
Further, the preparation method of the catalyst for preparing DMF through carbon dioxide hydrogenation according to claim 1, wherein after centrifugation in step 1.4, the reaction solid is washed 3-4 times with absolute ethanol to remove residual ligand of MOF-5 and DMF solvent.
Further, the preparation method of the DMF catalyst by hydrogenation of carbon dioxide according to claim 1, wherein in step 1.5, MOF-5 obtained in step 1.4 is ground into powder, then added into a porcelain boat, and then placed in a tube furnace. Firstly, vacuumizing at room temperature, then introducing nitrogen, heating, wherein the heating rate is 5 ℃/min, the heating end point is 1200 ℃, and the heat preservation time is 2h.
Further, the preparation method of the catalyst for preparing DMF by hydrogenating carbon dioxide according to claim 1, wherein in the step 2.3, the iridium chloride is replaced by one or a combination of several iridium metal compounds including potassium chloroiridate, iridium chloride, iridium trichloride and the like, and the iridium content of the iridium metal compound accounts for 1wt% of the catalyst.
Further, the preparation method of the DMF catalyst by hydrogenation of carbon dioxide according to claim 1, wherein in step 2.7, MOF-5 obtained in step 2.6 is ground into powder, then added into a porcelain boat, and then placed in a tube furnace. Nitrogen is firstly introduced at room temperature for 1h, then the temperature is raised, the temperature raising rate is 5 ℃/min, the temperature raising end point is 800 ℃, the ammonia is introduced after the temperature is kept for 1h for 15min, and the stability of N sites in the catalyst is ensured.
Further, the application of the carbon-based N-coordinated monoatomic catalytic material in the catalytic reaction for preparing DMF by thermally catalyzing the hydrogenation of carbon dioxide comprises the carbon-based N-coordinated monoatomic catalytic material and is characterized in that: the carbon-based N coordination monoatomic catalytic material can efficiently catalyze carbon dioxide and hydrogen to prepare DMF under relatively mild conditions.
Further, the application of the carbon-based N-coordinated monoatomic catalytic material in the catalytic reaction for preparing DMF through carbon dioxide hydrogenation according to claim 7 is characterized by comprising the following steps: placing a catalytic material into a pressure reaction kettle, and adding a dimethylamine methanol solution and a carbon dioxide and hydrogen mixed gas, wherein the carbon dioxide is prepared by the following steps: the hydrogen ratio is 1:1, sealing reaction, wherein the reaction temperature is between 90 ℃ and 150 ℃, and the reaction pressure package is between 2MPa and 6 MPa.
Compared with the prior art, the application can obtain the following technical effects:
1) The preparation method provided by the application comprises the steps of firstly constructing a carbon material with a hierarchical pore by adopting a template method as a carrier material, strictly controlling the gas environment, the heating rate and the heating end point in carbonization synthesis of the carrier material, and ensuring that the material is regular in morphology and uniform in size;
2) The method is simple to operate, has high atom utilization rate, and has excellent material performance;
3) The active metal is carbonized and reduced for the second time, ammonia is introduced in the process to adjust the doping amount of N, and the evaporation of N in the carbon matrix can be effectively avoided, so that metal atoms are effectively anchored, and a high-efficiency single-atom catalytic center is constructed.
4) The heterogeneous single-atom catalytic material can realize efficient hydrogenation of carbon dioxide to prepare DMF in a pressure reaction kettle, has high product selectivity, simple device, recyclable catalyst, reduced energy consumption and cost and easy popularization;
drawings
FIG. 1 is a process flow diagram of a method for preparing a DMF catalyst by high efficiency carbon dioxide hydrogenation;
FIG. 2 is an XRD pattern of precursor MOF-5, carrier material MOF-5-C and catalyst prepared in the preparation method of DMF catalyst by high-efficiency carbon dioxide hydrogenation;
FIG. 3 is an SEM image of a single-atom catalyst MOF-5-C-Ir prepared in an example of a preparation method of a high-efficiency catalyst for preparing DMF by carbon dioxide hydrogenation;
FIG. 4 is a HRTEM diagram of a monoatomic catalyst MOF-5-C-Ir prepared in an example of a method for preparing DMF catalyst by high efficiency carbon dioxide hydrogenation according to the present application;
FIG. 5 is a STEM diagram of a single-atom catalyst MOF-5-C-Ir prepared in an example of a preparation method of a catalyst for preparing DMF by hydrogenation of carbon dioxide.
FIG. 6 is a graph showing TON of a single-atom catalyst prepared by the preparation method of the DMF catalyst by high-efficiency carbon dioxide hydrogenation according to the reaction pressure, the reaction temperature and the reaction time.
Detailed Description
The implementation of the application is described below with specific examples, from which other advantages and effects of the application will be readily apparent to those skilled in the art. The application is capable of other and different embodiments and its several details are capable of modifications and various obvious aspects, all from the various views and applications, without departing from the spirit of the application.
See the attached drawings. It should be noted that in this embodiment, the material structural design drawing is provided only for illustrating the basic concept of the present application, and in this drawing, only the structures and components related to the present application are shown, not drawn according to the number, distribution and size of the structures and components in actual implementation, and the distribution, number and ratio of the respective components may be arbitrarily changed in actual implementation.
Example 1
A preparation method of a DMF catalyst by carbon dioxide hydrogenation comprises the following steps:
1) 2g of terephthalic acid and 7g of zinc acetate dihydrate were dissolved in 80mL of DMF and 3mL of triethylamine was added. The resulting solution was reacted at 125℃with stirring for 24 hours. The MOF-5 product was collected by centrifugation and washed 3-4 times with ethanol, then dried under vacuum at 60℃overnight to give the white solid material MOF-5.
2) Grinding the MOF-5 material obtained in the step (1) into powder. And (3) carbonizing the powder at a high temperature under a nitrogen atmosphere, wherein the carbonization temperature is 1100 ℃, the time is 2 hours, the heating rate is 5 ℃/min, and cooling to obtain the carbon carrier material.
3) Adding 50mg of the carbon material obtained in the step (2) into 10mL of absolute ethyl alcohol, and performing ultrasonic dispersion to obtain an ethanol dispersion solution of the carbon carrier; and adding 5ml of absolute ethyl alcohol into 50mg of 1, 10-phenanthroline, and performing ultrasonic dispersion to obtain an ethanol dispersion solution of the phenanthroline. Adding a certain amount of chloroiridium acid solution (the mass ratio of iridium to phenanthroline is 1:10) into 600mml of ethanol dispersion solution of phenanthroline, and carrying out ultrasonic mixing to completely coordinate to obtain iridium-phenanthroline complex. Mixing ethanol dispersion solution of carbon carrier with complex of iridium and phenanthroline, ultrasonic treating for 2 hr, stirring at high speed for 6 hr, and vacuum drying at 60deg.C for 7-8 hr.
4) Grinding the solid dried in the step (3) into powder. And (3) carrying out secondary carbonization on the powder in a nitrogen atmosphere, wherein the carbonization temperature is 800 ℃, the heating rate is 5 ℃/min, the temperature is kept for 1h, then ammonia gas is introduced for 15min, and the catalytic material is obtained after cooling.
Step 1.4: the Pyrex tube of the step 1.3 is heated at a temperature of 5 ℃ for min in the range of 200 ℃ to 300 DEG C -1 Calcining for 24 hours at the heating rate, and then cooling to room temperature;
test example 1
10mg of the catalyst material was placed in an autoclave, 20ml of 2mol/L of dimethylamine methanol solution was added, and 1:1, controlling the reaction pressure to be 2MPa/4MPa/6MPa, maintaining the reaction temperature at 150 ℃ and reacting for 6 hours. After the reaction, the liquid product was collected, and the gas component was analyzed and collected by a gas chromatograph.
Test 2
10mg of the catalyst material was placed in an autoclave, 20ml of 2mol/L of dimethylamine methanol solution was added, and 1:1, the carbon dioxide and hydrogen mixed gas react, the reaction temperature is controlled to be 90 ℃/120 ℃/150 ℃ respectively, the reaction pressure is kept to be 150MPa, and the reaction time is 6 hours. After the reaction, the liquid product was collected, and the gas component was analyzed and collected by a gas chromatograph.
Test 3;
10mg of the catalyst material was placed in an autoclave, and 2mol/L of dimethylamine methanol solution (20 ml) was added thereto, followed by introducing 1: the reaction pressure of the 1 carbon dioxide and hydrogen mixed gas reaches 6MPa, the reaction time is controlled to be 6h/12h/24h respectively, the reaction pressure is kept to be 150MPa, and the reaction temperature is 150 ℃. After the reaction, the liquid product was collected, and the gas component was analyzed and collected by a gas chromatograph.
The test results are shown in Table I
The technical concept of the present application has been described by way of the above embodiments, but the present application is not limited to the above embodiments, that is, the present application is not necessarily implemented by means of the above embodiments. It will be apparent to those of ordinary skill in the art that any modification to the present application, equivalent substitution of the individual starting materials (Ir, C, N) for the present application, and the addition of auxiliary components, as well as the selection of the particular metal coordination scheme, are within the scope of the present application.
It will be apparent to those skilled in the art that the application is not limited to the details of the exemplary embodiments described above and that the application may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (6)
1. The preparation method of the DMF catalyst by carbon dioxide hydrogenation is characterized by comprising the following steps:
step 1, preparing a carbon substrate material: the precursor MOF-5 is synthesized by using zinc nitrate dihydrate as a metal source, terephthalic acid as an organic ligand and triethylamine as a coordination regulator through a hot solvent method and carbonized, and specifically comprises the following steps:
step 1.1: weighing a certain amount of terephthalic acid and zinc sulfate dihydrate (the mass ratio is 1:3.5);
step 1.2: suspending the solid weighed in the step 1.1 in DMF, and adding triethylamine (3 ml) to obtain a suspension;
step 1.3: stirring the suspension in the step 1.2 at 125 ℃ for reaction for 24 hours, and cooling to room temperature after the reaction is finished to generate white solid;
step 1.4: centrifuging to collect the white solid generated in the step 1.3, washing with ethanol (100 ml x 3), and drying in a vacuum drying oven at 60 ℃ for 7-8h to obtain a pure white solid product MOF-5;
step 1.5: grinding the solid product obtained in step 1.4, then in N 2 Carbonizing at 1100 deg.c in high temperature for 2 hr, and cooling to room temperature to obtain carbon carrier MOF-5-C。
Step 2, using chloroiridium acid as an iridium metal source, carrying out coordination anchoring on the MOF-5-C material to obtain a catalytic material, wherein the catalytic material specifically comprises the following steps:
step 2.1: weighing 1, 10-phenanthroline, adding the 1, 10-phenanthroline into ethanol, and performing ultrasonic dispersion for 30min to obtain an ethanol dispersion solution of the phenanthroline;
step 2.2: weighing the carbon carrier material (MOF-5-C) prepared in the step 1, adding the carbon carrier material into ethanol, and performing ultrasonic dispersion for 30min to obtain carbon material ethanol dispersion solution;
step 2.3: measuring a certain amount of H2 IrCl6.6H2O solution, adding the ethanol dispersion solution of the 1, 10-phenanthroline obtained in the step 2.1, and carrying out ultrasonic mixing to completely coordinate the solution to obtain a complex of metal and the 1, 10-phenanthroline;
step 2.4: mixing the ethanol dispersion solution of the carbon material in the step 2.2 with the metal in the step 2.3 and the 1, 10-phenanthroline complex, and carrying out ultrasonic treatment for 2 hours;
step 2.5: stirring the mixed solution obtained in the step 2.4 for 6 hours at room temperature;
step 2.6: performing rotary distillation on the product obtained after the reaction in the step 2.5 for 5-10min, and then drying at 60 ℃ for 7-8h to obtain a solid product;
step 2.7: grinding the solid obtained in the step 2.6, and then adding the ground solid into N 2 And (3) carrying out secondary carbonization under the atmosphere, wherein the secondary carbonization temperature is 800 ℃, maintaining for 1h, then introducing ammonia gas for 15min, and cooling to obtain the designed catalytic material.
2. The method for preparing DMF catalyst by hydrogenation of carbon dioxide according to claim 1, wherein in step 1.5, MOF-5 obtained in step 1.4 is ground into powder, then added into a porcelain boat, and then placed in a tube furnace. Firstly, vacuumizing at room temperature, then introducing nitrogen, heating, wherein the heating rate is 5 ℃/min, the heating end point is 1200 ℃, and the heat preservation time is 2h.
3. The method for preparing the DMF catalyst by hydrogenating carbon dioxide according to claim 1, wherein in the step 2.3, iridium chloride is replaced by one or a combination of several iridium metal compounds including potassium chloroiridate, iridium trichloride and the like, and the iridium content of the iridium metal compounds accounts for 1wt% of the catalyst.
4. The method for preparing DMF catalyst by hydrogenation of carbon dioxide according to claim 1, wherein in step 2.7, MOF-5 obtained in step 2.6 is ground into powder, then added into a porcelain boat, and then placed in a tube furnace. Nitrogen is firstly introduced at room temperature for 1h, then the temperature is raised, the temperature raising rate is 5 ℃/min, the temperature raising end point is 800 ℃, the ammonia is introduced after the temperature is kept for 1h for 15min, and the stability of N sites in the catalyst is ensured.
5. The application of the carbon-based N-coordinated monoatomic catalytic material in the catalytic reaction for preparing DMF by carbon dioxide hydrogenation comprises the carbon-based N-coordinated monoatomic catalytic material and is characterized in that: the carbon-based N coordination monoatomic catalytic material can efficiently catalyze carbon dioxide and hydrogen to prepare DMF under relatively mild conditions.
6. The use of a carbon-based N-coordinated monoatomic catalytic material according to claim 7, in a catalytic reaction for preparing DMF by hydrogenation of carbon dioxide, comprising the steps of: placing a catalytic material into a pressure reaction kettle, and adding a dimethylamine methanol solution and a carbon dioxide and hydrogen mixed gas, wherein the carbon dioxide is prepared by the following steps: hydrogen is 1:1, sealing reaction, wherein the reaction temperature is between 90 ℃ and 150 ℃, and the reaction pressure package is between 2MPa and 6 MPa.
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