CN115646546B - 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 62
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 39
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 31
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 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 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 18
- 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 abstract description 18
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000004873 anchoring Methods 0.000 claims abstract description 5
- 238000010000 carbonizing Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 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
- 239000007787 solid Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 229910052741 iridium Inorganic materials 0.000 abstract 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 abstract 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
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- 239000002253 acid Substances 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
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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
- YNJJJJLQPVLIEW-UHFFFAOYSA-M [Ir]Cl Chemical compound [Ir]Cl YNJJJJLQPVLIEW-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
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- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a carbon-based bi-metal site synergistic catalytic material for producing formic acid by carbon dioxide hydrogenation, which adopts a cascading synthesis strategy for accurately constructing synergistic catalytic sites, belongs to the technical field of catalysts, and comprises the steps of firstly carbonizing ZIF-8 to obtain a nitrogen (N) and zinc (Zn) -doped carbon material, and then anchoring noble metal iridium (Ir) sites on the doped carbon material, wherein the utilization rate of the noble metal Ir in the porous carbon-based bi-atom site catalytic material can reach 100%. The catalyst has a special bimetallic atom catalytic structure, namely a bimetallic site structure and a synergistic catalytic structure of Zn-N4 coordination and Ir-N coordination, and has excellent catalytic activity for preparing formate by CO 2 hydrogenation. The method is simple to operate, the obtained material has controllable structure and strong catalytic selectivity (100% formic acid), the activity TOF is more than 3000, the stability is excellent, and the TON is more than 25000; the accurate synthesis strategy of the catalyst is simple and feasible, and the catalyst is easy for industrial production.
Description
Technical Field
The invention relates to the technical field of carbon dioxide resource utilization and the technical field of 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 fossil fuels has increased dramatically, however, the burning of fossil fuels generates a large amount of carbon dioxide, which will cause global climate warming, and is unfavorable for the long-term survival and development of human beings, which seriously threatens the ecological environment on the earth and the sustainable development of human beings. Therefore, how to drive energy safety and climate stabilization is a current concern. Currently, fossil fuels are increasingly being identified with reduced reserves and increased carbon dioxide emissions. The catalytic technology is utilized to convert carbon dioxide into renewable fuel, so that the influence of greenhouse effect can be reduced, and meanwhile, 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 catalyst in the catalytic reaction of the homogeneous catalysts are very tedious and are high-energy-consumption processes. In addition, the catalyst is rich in heavy metals, so that the catalyst which cannot be recovered can have toxic action on the ecological environment. This hampers 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 atom site catalytic material for producing formic acid by carbon dioxide hydrogenation, and mainly provides a synergistic catalytic hydrogenation effect of Zn-N4 unit centers. 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 following technical scheme:
a carbon-based N coordination bimetallic atom site catalytic material for carbon dioxide hydrogenation reaction is prepared by carbonizing ZIF-8 at 800 ℃ for 2h in nitrogen atmosphere to obtain an N-doped monodisperse Zn-N4 coordination porous carbon material, and anchoring noble metal Ir on the carbon material by a post-loading method to construct a catalytic site Ir-N, so as to obtain the carbon-based bimetallic atom site catalytic material.
The preparation method of the catalytic material for producing formic acid by carbon dioxide hydrogenation comprises the following steps:
s1: and (3) reacting the 2-methylimidazole with Zn (NO) 3·6H2 O in a methanol solution to obtain the ZIF-8.
S2: and (3) putting the ZIF-8 into a tube furnace, and carbonizing at a high temperature of 800 ℃ to obtain the Zn-N4 carbon material containing N-doped high-load Zn monoatomic site dispersion.
S3: and (3) anchoring noble metal Ir on the obtained Zn-N4 carbon material in a highly dispersed manner by utilizing a post-loading method, and constructing an Ir-N coordination center to obtain the designed catalytic material.
In the step S1, 2-methylimidazole and Zn (NO) 3·6H2 O are respectively dissolved in methanol solution, dropwise added and mixed, stirred at room temperature, filtered to obtain solid, washed with methanol for 2 times, and placed in a vacuum oven for drying at 60 ℃ overnight to obtain ZIF-8 powder.
Preferably, the mixed solution is stirred at a rate of 600r/min for reaction for 24 hours in step S1.
In the step S2, ZIF-8 is placed in a quartz boat, then placed in a tube furnace, and the ZIF-8 is carbonized at a high temperature of 800 ℃ in a gas atmosphere of N 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, ultrasonically dispersing the single-atom dispersed Zn-N4 carbon material in deionized water, adding a noble metal solution into the dispersion liquid, stirring at a high speed overnight after ultrasonic treatment, filtering, washing with water, and drying in a vacuum oven.
Preferably, in step S3, the dispersion is added with the noble metal solution and then sonicated for 120min, followed by stirring for 16 hours at 800 r/min.
Another object of the present invention is to provide the use of the above carbon-based N-coordinated bimetallic atomic site catalytic material for 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.
The application technical scheme comprises the following steps: placing a carbon-based bimetallic atomic site catalytic material into a pressure reaction kettle, and introducing hydrogen and carbon dioxide gas to enable the hydrogen to be: mixing carbon dioxide gas according to a volume ratio of 1:1-3:1, adding a catalytic material into a reaction kettle, performing a sealing reaction, wherein the total pressure of the gas is 4-6 MPa, and heating to 100-150 ℃; hydrogen is preferred: carbon dioxide gas is mixed according to the volume ratio of 1:1, the total pressure of the reaction gas is 6MPa, and the reaction temperature is 150 ℃.
In the application technical scheme, the pressure reaction kettle can bear high temperature of 200-250 ℃ and 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 atomic catalytic material, in the first carbonization synthesis step, the gas environment, the heating rate and the heating end point are strictly controlled, so that the evaporation of N, zn in a carbon matrix can be effectively avoided, and the single-point center Zn-N4 with important synergistic catalysis in the carbon dioxide hydrogenation research is effectively constructed.
2) The invention utilizes a multi-cascade synthesis strategy, prepares the carbon-based atomic site catalytic center Ir-N on the basis of the existing catalytic center Zn-N4, and constructs the bimetallic synergistic catalyst.
3) The carbon-based bimetallic atomic catalytic material can realize efficient reduction reaction of carbon dioxide in a pressure reaction kettle, has high product selectivity and activity stability, is simple in device, can recycle a 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 diagram of ZIF-8-C-Ir;
FIG. 4 is a graph showing the change in ZIF-8-C-Ircarboxylic acid concentration with time.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
All commercial products or reagents of the invention are purchased through market channels unless otherwise specified.
Example 1
A preparation method of a carbon-based bimetallic atomic 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) 3·6H2 O are respectively dissolved in 25ml of methanol, dropwise added into 400ml of methanol and uniformly mixed, stirred at room temperature for 48 hours at 800r/min, filtered to obtain a solid, washed with 200ml of methanol for 2 times, and dried overnight in a vacuum oven at 60 ℃ to obtain ZIF-8 powder.
(2) Putting 1.5g of ZIF-8 obtained in the step (1) into a quartz boat, then putting the quartz boat into a tube furnace, introducing nitrogen to replace air, and obtaining the N-doped monodisperse Zn-N4 carbon material in the gas atmosphere of N 2, wherein the heating rate is 5 ℃/min, the heating end point is 800 ℃, and the heat preservation time is 120 min.
(3) Taking 100mg of the monodisperse Zn-N4 carbon material in the step (2), adding 20ml of deionized water, performing ultrasonic dispersion for 30min, adding a noble metal solution (chloroiridium acid) containing 0.6mg of Ir into the dispersion, performing ultrasonic stirring for 120min, stirring at a high speed for 20h, performing suction filtration, washing with water, and then placing into a vacuum oven for drying to obtain a catalyst product.
The catalyst performance test was performed in a high temperature high pressure autoclave.
Example 2
A preparation method of a carbon-based bimetallic atomic site catalytic material for producing formic acid by carbon dioxide hydrogenation comprises the following steps:
(1) 2.4g of 2-methylimidazole and 4g of Zn (NO) 3·6H2 O are respectively dissolved in 25ml of methanol, dropwise added into 200ml of methanol and uniformly mixed, stirred at room temperature for 48 hours at 800r/min, filtered to obtain a solid, washed with 100ml of methanol for 2 times, and placed in a vacuum oven for drying at 60 ℃ overnight to obtain ZIF-8 powder.
(2) Putting 1.5g of ZIF-8 obtained in the step (1) into a quartz boat, then putting the quartz boat into a tube furnace, introducing nitrogen to replace air, and obtaining the monodisperse Zn-N4 carbon material in the gas atmosphere of N 2 at a heating rate of 5 ℃/min, at a heating end point of 800 ℃ and for 60 min.
(3) Taking 100mg of the monodisperse Zn-N4 carbon material in the step (2), adding 20ml of deionized water, performing ultrasonic dispersion for 30min, adding a noble metal solution (chloroiridium acid) containing 1mg of Ir into the dispersion, performing ultrasonic stirring for 120min, performing high-speed stirring for 20h, performing suction filtration, washing with water, and then putting into a vacuum oven for drying to obtain a catalyst product.
The catalyst performance test was performed in a high temperature high pressure autoclave.
Test case
5Mg of carbon-based bimetallic atomic site catalytic material is placed in a high-temperature high-pressure reaction kettle, 10ml of 1M KHCO 3 is added, the reactor is sealed, and hydrogen and carbon dioxide gas are introduced into the reactor to enable the hydrogen to be: mixing carbon dioxide gas according to the volume ratio of 1:1, introducing the total pressure of the reactor gas to be 6MPa, heating to 150 ℃, and reacting for 8 hours. The obtained reaction solution was filtered by an inorganic filter, and then, the reaction solution was 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 reaction solution after acidification x dilution x volume of 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 invention can better realize the technical effect of preparing formic acid by hydrogenating carbon dioxide, and by taking example 1 as an example, TOF is as high as 3166, TON is as high as 25366, and the performance of most of the currently reported heterogeneous catalysts is exceeded.
The technical idea of the present invention is described 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 be implemented depending on the above embodiments. It should be clear to those skilled in the art that any modification of the present invention, equivalent substitution of individual raw materials (Zn, ir, N) of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., fall within the scope of the present invention and the scope of disclosure.
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 characteristics 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 (5)
1. An application of a carbon-based bimetallic site catalytic material in reducing carbon dioxide to formic acid, which is characterized in that: carbonizing ZIF-8 at 800 ℃ for 2 hours in a nitrogen atmosphere to obtain N, zn-doped porous carbon material, uniformly anchoring N-coordinated noble metal Ir on the carbon material by using a post-loading method to obtain the catalytic material, wherein the mass percentage of the Ir in the catalytic material is 0.3% -3%;
The preparation method of the carbon-based bimetallic site catalytic material for producing formic acid by hydrogenation of carbon dioxide comprises the following steps:
s1: reacting 2-methylimidazole with Zn (NO) 3·6H2 O in methanol solution to obtain ZIF-8;
S2: placing ZIF-8 into a tubular furnace, carbonizing at a high temperature of 800 ℃ to obtain a Zn-N 4 carbon material containing N-doped high-load Zn monoatomic site dispersion;
S3: and (3) anchoring noble metal Ir on the obtained Zn-N 4 carbon material in a highly dispersed manner by utilizing a post-loading method, and constructing an Ir-N coordination center to obtain the catalytic material.
2. Use of a carbon-based bimetallic site catalytic material in the reduction of carbon dioxide to formic acid according to claim 1, wherein: in the step S1, 2-methylimidazole and Zn (NO) 3·6H2 O are respectively dissolved in methanol solution, dropwise added and mixed, stirred for 24 hours at room temperature, filtered to obtain solid, washed with methanol for 2 times, and dried overnight at 60 ℃ in a vacuum oven.
3. Use of a carbon-based bimetallic site catalytic material in the reduction of carbon dioxide to formic acid according to claim 1, wherein: and in the step S2, the ZIF-8 is placed in a tube furnace, the ZIF-8 is heated to 800 ℃ from room temperature at a heating rate of 5 ℃/min in the gas atmosphere of N 2, and is kept for 2 hours, and then the ZIF-8 is naturally cooled to the room temperature, so that the single-atom dispersed Zn-N 4 carbon material is obtained.
4. Use of a carbon-based bimetallic site catalytic material in the reduction of carbon dioxide to formic acid according to claim 1, wherein: in the step S3, the Zn-N 4 carbon material is dispersed in deionized water by ultrasonic, a noble metal solution is added into the dispersion liquid, the mixture is stirred at a high speed overnight, the solid is obtained by suction filtration, and the solid is dried overnight at 60 ℃ in a vacuum oven after being washed by water.
5. Use of a carbon-based bimetallic site catalytic material in the reduction of carbon dioxide to formic acid according to claim 1, wherein: the method comprises the following steps: placing a carbon-based bimetallic site catalytic material in a pressure reaction kettle, and introducing hydrogen and carbon dioxide gas to enable the hydrogen to be: mixing carbon dioxide gas according to the volume ratio of 1:1-3:1, adding a catalytic material into a reaction kettle, performing a sealing reaction, and heating to 100-150 ℃.
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| 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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