CN115646546A - Preparation method of carbon-based bimetallic site catalytic material for producing formic acid by carbon dioxide hydrogenation - Google Patents
Preparation method of carbon-based bimetallic site catalytic material for producing formic acid 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 66
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 38
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title claims abstract description 34
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 33
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000002195 synergetic effect Effects 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 22
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 22
- 239000003575 carbonaceous material Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- 229910000510 noble metal Inorganic materials 0.000 claims description 12
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- 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
- 238000002156 mixing Methods 0.000 claims description 8
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 5
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- 239000007787 solid Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
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- 238000001816 cooling Methods 0.000 claims 1
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- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical compound OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
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- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 abstract 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- 241000282414 Homo sapiens Species 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a carbon-based bimetallic site co-catalytic material for producing formic acid by carbon dioxide hydrogenation, wherein a cascade synthesis strategy for accurately constructing co-catalytic sites is adopted, and the preparation method belongs to the technical field of catalysts. The catalyst has a special bimetallic atom catalytic structure, namely a Zn-N4 coordinated and Ir-N coordinated bimetallic site structure and a synergistic catalytic structure, and has excellent CO 2 Catalytic activity of formate prepared by hydrogenation. The method is simple to operate, and the obtained material has controllable structure and catalytic selectionStrong (100% formic acid), active TOF>3000, has excellent stability, TON>25000; the precise synthesis strategy of the catalyst is simple and feasible, and the industrial production is easy to realize.
Description
Technical Field
The invention relates to the technical field of carbon dioxide resource utilization and catalyst synthesis, in particular to a preparation method and application of an N-coordination bimetallic atom site catalytic material for producing formic acid by carbon dioxide hydrogenation.
Background
With the rapid development of society, the demand of people for fossil fuels is increased sharply, however, the combustion of fossil fuels generates a large amount of carbon dioxide, which causes global warming and is not beneficial to the long-term survival and development of human beings, thus seriously threatening the ecological environment on the earth and the sustainable development of human beings. Therefore, how to promote energy safety and climate stabilization is currently a matter of great concern. At present, fossil fuels are being explored in decreasing quantities, while carbon dioxide emissions are increasing. The carbon dioxide is converted into renewable fuel by using the catalytic technology, so that the influence of greenhouse effect can be reduced, and useful chemicals can be generated, thereby relieving the problem of energy shortage.
At present, most of catalysts with higher performance are homogeneous catalysts, however, the subsequent processes of separating, enriching and recycling the catalysts in the catalytic reaction of the homogeneous catalysts are very complicated and energy-consuming. In addition, since the catalyst itself is rich in heavy metals, unrecoverable catalysts can have a deleterious effect on the ecological environment. This has hindered its further development, and the key to solving this problem is the preparation of heterogeneous catalysts that are easy to recycle.
Disclosure of Invention
Aiming at the problems, the invention provides preparation and application of an N-coordination bimetallic atomic site catalytic material for producing formic acid by carbon dioxide hydrogenation, and mainly provides a synergistic catalytic hydrogenation effect of a Zn-N4 single-site center. The preparation method is simple, the cost is low, the catalyst is easy to recycle, and the conversion rate is high.
In order to achieve the purpose, the invention adopts the technical scheme that:
a carbon-based N-coordinated bimetallic atom site catalytic material for a carbon dioxide hydrogenation reaction is prepared by carbonizing ZIF-8 at 800 ℃ for 2h in a nitrogen atmosphere to obtain an N-doped monodisperse Zn-N4-coordinated porous carbon material, and anchoring a noble metal Ir on the carbon material by a post-loading method to construct a catalytic site Ir-N.
The preparation method of the catalytic material for producing formic acid by hydrogenating carbon dioxide comprises the following steps:
s1: 2-methylimidazole and Zn (NO) 3 ·6H 2 And reacting the O in a methanol solution to obtain the ZIF-8.
S2: and (3) putting the ZIF-8 into a tube furnace for carbonization at the high temperature of 800 ℃ to obtain the Zn-N4 carbon material containing N-doped high-load Zn with single atomic site dispersion.
S3: and (3) utilizing a post-loading method to anchor noble metal Ir in a high-dispersion manner on the obtained Zn-N4 carbon material to construct an Ir-N coordination center, thereby obtaining the designed catalytic material.
In step S1, 2-methylimidazole and Zn (NO) 3 ·6H 2 And dissolving O in a methanol solution respectively, dropwise mixing, stirring at room temperature, performing suction filtration to obtain a solid, washing with methanol for 2 times, and drying in a vacuum oven at 60 ℃ overnight to obtain ZIF-8 powder.
Preferably, the mixed solution is stirred and reacted for 24 hours at a speed of 600r/min in the step S1.
Step S2, the ZIF-8 is placed in a quartz boat and then placed in a tube furnace, and the quartz boat is heated in a furnace N 2 The ZIF-8 was carbonized at a high temperature of 800 ℃ in the gas atmosphere of (2).
Preferably, in the step S2, the heating rate is 5 ℃/min, the heating end point is 800 ℃, and the heat preservation time is 120min.
And S3, performing ultrasonic dispersion on the monoatomic Zn-N4 carbon material in deionized water, adding a noble metal solution into the dispersion liquid, performing ultrasonic stirring overnight at a high speed, performing suction filtration, washing with water, and drying in a vacuum oven.
Preferably, the dispersion liquid is added with the noble metal solution in step S3, and then is subjected to ultrasonic treatment for 120min, and then is stirred for 16 hours at the speed of 800 r/min.
Another object of the present invention is to provide the use of the above carbon-based N-coordinated bimetallic atom site catalytic material in the reduction of carbon dioxide to formic acid (salt).
In the application technical scheme, the carbon-based N-coordinated bimetallic atom site catalytic material is used for carrying out hydrogenation reduction reaction on carbon dioxide to obtain formic acid (salt) in a pressure reaction kettle.
In the above application technical scheme, the method comprises the following steps: placing the carbon-based bimetallic atomic site catalytic material in a pressure reaction kettle, and introducing hydrogen and carbon dioxide gas to ensure that the hydrogen: mixing carbon dioxide gas according to a volume ratio of 1; hydrogen is preferred: mixing carbon dioxide gas according to a volume ratio of 1.
In the application technical scheme, the pressure reaction kettle can bear the high temperature of 200-250 ℃ and the pressure of 12 MPa.
Compared with the prior art, the invention has the advantages and positive effects that:
1) According to the preparation method of the carbon-based bimetallic atom catalytic material, the gas environment, the heating rate and the heating end point are strictly controlled in the first step of carbonization synthesis, and the evaporation of N and Zn in a carbon matrix can be effectively avoided, so that the single-site center Zn-N4 with an important synergistic catalytic action in the carbon dioxide hydrogenation research is effectively constructed.
2) The method utilizes a multi-cascade synthesis strategy, prepares the carbon-based atomic site catalytic center Ir-N by a post-loading method on the basis of the existing cocatalyst center Zn-N4, constructs the bimetallic synergistic catalyst, and has the advantages of simple operation, high atom utilization rate and excellent performance of the obtained material.
3) The carbon-based bimetallic atom catalytic material can realize the efficient reduction reaction of carbon dioxide in a pressure reaction kettle, has high product selectivity, high activity stability and simple device, can recycle the catalyst, reduces energy consumption and cost, and is easy to popularize.
Drawings
FIG. 1 is an X-ray diffraction pattern of ZIF-8, ZIF-8-C and ZIF-8-C-Ir;
FIG. 2 is an SEM image of ZIF-8-C;
FIG. 3 is an XPS map of ZIF-8-C-Ir;
FIG. 4 is a graph showing the change in concentration of ZIF-8-C-Ir carboxylic acid with respect to reaction time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments of the present invention, belong to the protection scope of the present invention.
Unless otherwise specified, all goods or reagents of the present invention are purchased through market channels.
Example 1
A preparation method of a carbon-based bimetallic atom site catalytic material for producing formic acid by carbon dioxide hydrogenation comprises the following steps:
(1) 6.75g of 2-methylimidazole and 8.15g of Zn (NO) 3 ·6H 2 And dissolving O in 25ml of methanol respectively, dropwise adding the dissolved O into 400ml of methanol, uniformly mixing, stirring at the room temperature of 800r/min for 48 hours, performing suction filtration to obtain a solid, washing with 200ml of methanol for 2 times, and putting into a vacuum oven to dry at 60 ℃ overnight to obtain ZIF-8 powder.
(2) Taking 1.5g of ZIF-8 obtained in the step (1), putting the ZIF-8 into a quartz boat, then putting the quartz boat into a tube furnace, introducing nitrogen to replace air, and adding nitrogen into the tube furnace to replace nitrogen in the atmosphere 2 The temperature rise rate is 5 ℃/min, the temperature rise end point is 800 ℃, and the heat preservation time is 120min, so that the N-doped monodisperse Zn-N4 carbon material is obtained.
(3) And (3) taking 100mg of monodisperse Zn-N4 carbon material in the step (2), adding 20ml of deionized water, performing ultrasonic dispersion for 30min, adding a noble metal solution (chloroiridic acid) containing 0.6mg of Ir into the dispersion, performing high-speed stirring for 20h after performing ultrasonic treatment for 120min, performing suction filtration, washing with water, and drying in a vacuum oven to obtain a catalyst product.
And (3) carrying out catalyst performance test in a high-temperature high-pressure reaction kettle.
Example 2
A preparation method of a carbon-based bimetallic atom site catalytic material for producing formic acid by carbon dioxide hydrogenation comprises the following steps:
(1) 2.4g 2-methylimidazole and 4g Zn (NO) 3 ·6H 2 And dissolving O in 25ml of methanol respectively, dropwise adding 200ml of methanol, uniformly mixing, stirring at the room temperature of 800r/min for 48 hours, performing suction filtration to obtain a solid, washing for 2 times by using 100ml of methanol, and putting into a vacuum oven for drying at 60 ℃ overnight to obtain ZIF-8 powder.
(2) Taking 1.5g of ZIF-8 obtained in the step (1), putting the ZIF-8 into a quartz boat, then putting the quartz boat into a tube furnace, introducing nitrogen to replace air, and adding N 2 The temperature rise rate is 5 ℃/min, the temperature rise end point is 800 ℃, and the heat preservation time is 60min, so that the monodisperse Zn-N4 carbon material is obtained.
(3) And (3) taking 100mg of monodisperse Zn-N4 carbon material in the step (2), adding 20ml deionized water, performing ultrasonic dispersion for 30min, adding a noble metal solution (chloroiridic acid) containing 1mg of Ir into the dispersion, performing ultrasonic stirring for 20h after 120min, performing suction filtration, washing with water, and drying in a vacuum oven to obtain a catalyst product.
And (3) carrying out catalyst performance test in a high-temperature high-pressure reaction kettle.
Test example
5mg of carbon-based bimetallic atom site catalytic material is placed in a high-temperature high-pressure reaction kettle, and 10ml1M KHCO is added 3 Sealing the reactor, and introducing hydrogen and carbon dioxide gas into the reactor to ensure that the hydrogen: mixing carbon dioxide gas at a volume ratio of 1:1, introducing the reactor gas at a total pressure of 6MPa, heating to 150 ℃, and reacting for 8h. The obtained reaction solution was filtered with an inorganic filter, acidified with a phosphoric acid solution, and analyzed by liquid chromatography.
TON and TOF of the catalyst were calculated according to the following formulas:
TON = (formic acid concentration in acidified reaction solution:volumeof reaction solution)/(mass of metal in catalyst/relative molecular mass of metal)
TOF = TON/reaction time
The test results are shown in Table I
As can be seen from Table 1, the catalyst prepared by the present invention can better realize the technical effect of preparing formic acid by hydrogenation of carbon dioxide, for example, in example 1, TOF is as high as 3166, TON is as high as 25366, which exceeds the performance of most of the currently reported heterogeneous catalysts.
The technical idea of the present invention is illustrated by the above embodiments, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must depend on the above embodiments to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitution of individual materials (Zn, ir, N) and addition of auxiliary components, selection of specific modes, etc., of the products of the present invention, fall within the scope and disclosure of the present invention.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention 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 (10)
1. The preparation method of the carbon-based bimetallic site catalytic material for producing formic acid by carbon dioxide hydrogenation is characterized by comprising the following steps: the preparation method comprises the steps of carbonizing ZIF-8 at 800 ℃ for 2h in a nitrogen atmosphere to obtain an N and Zn doped porous carbon material, and uniformly anchoring N coordinated noble metal Ir on the carbon material by utilizing a post-loading method to obtain the catalytic material, wherein the mass percentage of the Ir in the catalytic material is 0.3% -3%, and the optimal mass percentage is 0.6%.
2. A process for the preparation of a carbon-based bimetallic site catalytic material for the hydrogenation of carbon dioxide to formic acid as defined in claim 1, characterized by comprising the following steps:
s1: 2-methylimidazole and Zn (NO) 3 ·6H 2 And reacting the O in a methanol solution to obtain the ZIF-8.
S2: and (3) putting the ZIF-8 into a tube furnace for carbonization at the high temperature of 800 ℃ to obtain the Zn-N4 carbon material containing N-doped high-load Zn with single atomic site dispersion.
S3: and (3) utilizing a post-loading method to anchor the noble metal Ir on the obtained Zn-N4 carbon material in a high dispersion way, and constructing an Ir-N coordination center to obtain the designed catalytic material.
S4: the non-noble metal is not limited to Zn, but also comprises Mg and Ca metals, and the noble metal is not limited to Ir and also comprises other hydrogenation metal catalytic centers Pd, pt, ru, au and the like.
3. The method of claim 2, wherein: 2-methylimidazole and Zn (NO) in step S1 3 ·6H 2 Dissolving O in methanol solution, dripping, mixing, stirring at room temperature for 24 hr, vacuum filtering to obtain solid, washing with methanol for 2 times, and drying in vacuum oven at 60 deg.c overnight.
4. The method for preparing a carbon-based bimetallic site catalytic material for the production of formic acid by the hydrogenation of carbon dioxide according to claim 2, characterized in that: step S2, ZIF-8 is placed in a tube furnace in N 2 Heating ZIF-8 to 800 ℃ from room temperature at the heating rate of 5 ℃/min in the gas atmosphere, keeping for 2h, and then naturally cooling to room temperature to obtain the monoatomic Zn-N4 carbon material.
5. The method of claim 2, wherein the catalyst material comprises at least one of the following components: and S3, ultrasonically dispersing the Zn-N4 carbon material in deionized water, adding a noble metal solution into the dispersion, stirring at a high speed overnight, performing suction filtration to obtain a solid, washing with water, and drying in a vacuum oven at 60 ℃ overnight.
6. The method of claim 1, wherein the catalyst material comprises at least one of the following components: the ZIF-8 is carbonized at 800 ℃, and N and Zn elements in the ZIF-8 can be reserved, so that a monodisperse Zn-N4 coordinated monoatomic Zn carbon material is obtained.
7. The method of claim 1, wherein the catalyst material comprises at least one of the following components: placing ZIF-8 at N 2 The method has the advantages that the carbonization is carried out at 800 ℃ in the gas atmosphere, the load of the ZIF-8 morphology can be reserved, so that the porous (mesoporous) carbon material with a regular morphology is obtained, the monodispersed single-site Zn-N4 coordinated catalytic sites are reserved, and the noble metal Ir can be anchored in the porous carbon material through rapid stirring.
8. The application of the carbon-based bimetallic atom catalytic material in reducing carbon dioxide into formic acid (formate) comprises the carbon-based bimetallic atom catalytic material and is characterized in that: the Zn-N4 sites have synergistic catalytic action in the diatomic site catalyst.
9. Use of a carbon-based bimetallic atom catalytic material as in claim 8 for the reduction of carbon dioxide to formic acid (salt), characterized in that: the carbon-based bimetallic atom catalytic material is used for carrying out hydrogenation reduction reaction on carbon dioxide to obtain formic acid (salt) under relatively mild reaction conditions.
10. Use of a carbon-based bimetallic atom catalytic material as in claim 9 for the reduction of carbon dioxide to formic acid (salt), characterized in that it comprises the following steps: placing the carbon-based bimetallic atomic site catalytic material in a pressure reaction kettle, and introducing hydrogen and carbon dioxide gas to ensure that the hydrogen: mixing carbon dioxide gas according to a volume ratio of 1; hydrogen is preferred: the carbon dioxide gas is mixed according to the volume ratio of 1.
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| CN112853379A (en) * | 2021-02-08 | 2021-05-28 | 北京航空航天大学 | Preparation method and application of supported metal monatomic catalyst |
| CN112871198A (en) * | 2021-02-20 | 2021-06-01 | 山东大学 | Catalyst for synthesizing formic acid by carbon dioxide hydrogenation, preparation method and application thereof |
| CN114618550A (en) * | 2022-03-01 | 2022-06-14 | 西北工业大学 | Noble metal monoatomic catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116808949A (en) * | 2023-08-29 | 2023-09-29 | 昆明贵金属研究所 | Continuous reaction device for preparing formic acid by carbon dioxide hydrogenation |
| CN116808949B (en) * | 2023-08-29 | 2023-11-03 | 昆明贵金属研究所 | Continuous reaction device for preparing formic acid by carbon dioxide hydrogenation |
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