CN112871198B - Catalyst for synthesizing formic acid by carbon dioxide hydrogenation, preparation method and application thereof - Google Patents
Catalyst for synthesizing formic acid by carbon dioxide hydrogenation, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a catalyst for synthesizing formic acid by carbon dioxide hydrogenation, a preparation method and application thereof, belonging to the technical field of catalyst synthesis and fine chemical engineering. The Pd-based metal material catalyst provided by the invention has the advantages of high active metal dispersion degree and adjustable structure and property on an atomic scale, can realize the process of preparing formic acid by hydrogenating carbon dioxide at normal temperature and normal pressure on the aspect of catalytic effect, is expected to solve the problem of low efficiency of catalytic conversion of carbon dioxide into formic acid by a heterogeneous catalyst under a mild condition, provides a successful example for capture and conversion of carbon dioxide at normal temperature and normal pressure, and has simple preparation method and low production cost, thereby having good value of practical application.
Description
Technical Field
The invention belongs to the technical field of catalyst synthesis and fine chemical engineering, and particularly relates to a catalyst for synthesizing formic acid by carbon dioxide hydrogenation, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the excessive exploitation and use of fossil energy, excessive emissions of carbon dioxide have become one of the most interesting environmental issues in the world today. In 2017, the concentration of carbon dioxide in the atmosphere exceeds 400ppm, which is the highest value in human history, and the method has great threat to the ecological system of the earth. How to capture and convert carbon dioxide to realize carbon emission reduction has important practical significance. CO 22As the most inexpensive and abundant carbon resource in the C1 family, its selective hydroconversion into useful liquid fuels is believed to control fossil energy overuse and achieve CO2The most effective of emission reductionThe effective way is. Wherein CO is2The hydrogenation of formic acid has received increasing attention in recent years. The reasons for this are mainly two: 1) formic acid can be used as a safe hydrogen energy carrier, and the formic acid has high volume hydrogen density (53 g of H per liter of HCOOH) along with the rapid development of formic acid dehydrogenation technology2) The hydrogen carrier has the advantages of good chemical stability, low toxicity and the like, and is expected to become an attractive hydrogen carrier in a fuel cell; 2) CO 22Conversion to formate is also recognized as CO2The first elementary step of the synthesis of methanol, methane and high value-added hydrocarbons. Thus investigating CO2The process of preparing the formic acid by hydrogenation has important practical application value and theoretical research significance. But CO2Is a completely symmetrical and weakly polar molecule with a high chemical inertness (. DELTA.G-396 kJ/mol), in general CO2Hydrogenation reaction is carried out under severe conditions such as high temperature and high pressure, which brings about further energy consumption. Therefore, the development of a high-efficiency catalytic system realizes CO under mild conditions2The conversion of hydrogen to formic acid will undoubtedly be towards CO2The resource utilization and the large-scale application of hydrogen energy have important influence.
For CO2The reaction for preparing formic acid by hydrogenation, the high-efficiency catalyst system widely studied at home and abroad at present, mainly focuses on a homogeneous catalysis system, an immobilized homogeneous catalysis-like system and a supported nano noble metal catalyst system. Of these, homogeneous catalytic systems exhibit the highest catalytic activity, and the use of homogeneous Ru phosphine complex catalysts for CO has been reported as early as 1976 by Inoue et al2Study of the hydro-synthesis of formic acid (chem. lett.,1976, (8), 863-864.). Fujita et al firstly realized CO at normal temperature and pressure by using deprotonated Ir-dipyridyl chelate2A process for the preparation of formic acid by hydrogenation (nat. chem.,2012,4(5), 383-. However, the homogeneous catalysis system generally has the problems of poor reaction continuity, easy loss of the catalyst, difficult product separation and the like, and does not have large-scale use potential. The immobilized homogeneous catalysis system is characterized in that the homogeneous coordination compound is immobilized on the surface of a carrier through the complexation of functional groups on the surface of the carrier, so that the catalyst is easy to recycle and separate. The immobilized homogeneous-phase-like catalytic system reported in the literature at present is mainly SiO2Organic porous material, etcImmobilized homogeneous complexes (Catal. Commun.,2004,5(10), 643-C646; ACS Catal.,2018,8(5), 4346-C4353.). Although the strategy of the immobilization of the homogeneous catalyst greatly improves the problem that the homogeneous catalyst is difficult to separate, the method still has the problems of easy loss of active components, poor cycle stability, remarkable reduction of activity and the like. The heterogeneous catalysis system has the advantages of good reaction continuity, easy catalyst recovery and the like, and is CO2The research of the catalytic system focuses on the noble metal nanoparticles modified by the auxiliary agent at present, and because the atom utilization rate of the nanoparticles is limited, the regulation and control of the structure and the electronic performance of the noble metal on the atomic scale are difficult to realize, and the catalytic effect of the catalytic system is lower than that of a homogeneous catalytic system.
Based on the knowledge, on the basis of the heterogeneous catalyst, by using the active structure characteristics of the homogeneous catalyst for reference, the high-dispersion and even monoatomic-dispersion metal catalyst is prepared, and the modulation of the structure and the property of the catalyst on the atomic scale is hopeful to realize the process of preparing the formic acid by the hydrogenation of the carbon dioxide.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a catalyst for synthesizing formic acid by hydrogenating carbon dioxide and a preparation method and application thereof, the catalyst provided by the invention has the advantages of high dispersion degree of active metals and adjustable structure and property on atomic scale, the process of preparing formic acid by hydrogenating carbon dioxide at normal temperature and normal pressure can be realized on the aspect of catalytic effect, the problem of low efficiency of the heterogeneous catalyst in catalytic conversion of carbon dioxide into formic acid under mild conditions is hopefully solved, a successful example is provided for capturing and converting carbon dioxide at normal temperature and normal pressure, and the preparation method adopted by the invention is simple and low in production cost, so that the catalyst has good value of practical application.
Specifically, the invention relates to the following technical scheme:
in a first aspect of the present invention, there is provided a Pd-based metal material which is a Pd-based monometallic material or a Pd-based bimetallic material;
when the Pd-based metal material is a Pd-based bimetallic material, the second metal is any one of Fe, Co, Ni, Cu and Zn;
the Pd-based metal material is characterized in that the active metal Pd and the second metal of the Pd-based metal material are loaded on a carrier in a sub-nanometer or monoatomic dispersion state;
the content of Pd is 0.001-20 wt.%, and the content of the second metal (any one of Fe, Co, Ni, Cu, Zn) is 0-40wt.%, based on the total weight of the Pd-based metal material.
In a second aspect of the present invention, there is provided a method for producing the above-mentioned Pd-based metal material, comprising: soaking a carbon material or a nitrogen-doped carbon material in a Pd-containing precursor solution, stirring under an inert atmosphere, filtering, washing, and carrying out high-temperature vacuum drying treatment to obtain the catalyst.
When the prepared Pd-based metal material is a Pd-based bimetallic material, the Pd-containing precursor solution also contains a second metal, and the second metal is any one of Fe, Co, Ni, Cu and Zn.
In a third aspect of the present invention, there is provided the use of the Pd-based metal material described above as and/or for the preparation of a catalyst.
More specifically, the catalyst is a catalyst for catalyzing the reaction of preparing formic acid by hydrogenating carbon dioxide, and experiments prove that the catalyst realizes the capture of carbon dioxide to the maximum extent by utilizing a porous carbon material and a nitrogen-doped carbon material carrier, realizes the activation of hydrogen and carbon dioxide to the maximum extent by loading highly-dispersed Pd and a second metal, has excellent catalytic activity for the reaction of preparing formic acid by hydrogenating carbon dioxide, and can realize high-efficiency conversion at normal temperature and normal pressure.
In a fourth aspect of the invention, a catalyst is provided, wherein the catalyst comprises the Pd-based metal material, and the catalyst can be used for efficiently catalyzing carbon dioxide hydrogenation to synthesize formic acid at normal temperature and pressure.
In a fifth aspect of the present invention, a method for synthesizing formic acid by carbon dioxide hydrogenation is provided, wherein the method comprises adding the Pd-based metal material and/or the catalyst into a reaction system, thereby achieving efficient conversion at normal temperature and pressure.
The beneficial technical effects of one or more of the above technical solutions are as follows:
1. the catalyst disclosed by the technical scheme has the advantages of good metal dispersibility and high atom utilization rate. Wherein the active metal Pd and the second metal (one of Fe, Co, Ni, Cu and Zn) are in a sub-nanometer or even monoatomic dispersion state.
2. Compared with the existing preparation method of the high-dispersion and monoatomic catalyst, the preparation method of the catalyst provided by the invention has the advantages of fewer operation steps, easily controlled parameters and easy realization of industrial scale-up production.
3. The catalyst provided by the technical scheme realizes the capture of carbon dioxide to the maximum extent by utilizing the porous carbon material and the nitrogen-doped carbon material carrier, realizes the activation of hydrogen and carbon dioxide to the maximum extent by loading highly-dispersed Pd and the second metal, has excellent catalytic activity for the reaction of preparing formic acid by hydrogenating carbon dioxide, can realize high-efficiency conversion at normal temperature and normal pressure, and has good circulation stability, thereby having good practical application value.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a spherical aberration electron microscope image of Pd/[2,6-DCP-C ] samples prepared by examples 1-5 using the method of the present invention. Wherein (a) is 0.5Pd/[2,6-DCP-C ], (b) is 1Pd/[2,6-DCP-C ], (C) is 2Pd/[2,6-DCP-C ], (d) is 3Pd/[2,6-DCP-C ], and (e) is 4Pd/[2,6-DCP-C ].
FIG. 2 is an electron microscope picture of Pd-Co/[2,6-DCP-C ] bimetallic catalysts prepared by examples 6-8 according to the method of the present invention. Wherein (a) is 3Pd-3Co/[2,6-DCP-C ], (b) is 5Pd-5Co/[2,6-DCP-C ], (C) is 7Pd-7Co/[2,6-DCP-C ], and (d) is the spherical aberration electron microscope picture of the 5Pd-5Co/[2,6-DCP-C ] sample.
FIG. 3 is a graph showing the results of the reactions obtained in examples 14 to 18 and comparative examples 20 and 21, which were conducted by the method of the present invention.
FIG. 4 shows the results of the stability of the reaction cycles of example 22 using the method of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The present invention is further illustrated by reference to specific examples, which are intended to be illustrative only and not limiting. If the experimental specific conditions not noted in the examples, they are generally according to the conventional conditions, or according to the conditions recommended by the sales companies; materials, reagents and the like used in examples were commercially available unless otherwise specified.
As previously mentioned, the CO is currently based on heterogeneous catalytic systems2The research of the reaction for preparing formic acid by hydrogenation mostly focuses on the noble metal nano-particles modified by the auxiliary agent, and because the atom utilization rate of the nano-particles is limited, the regulation and control of the structure and the electronic performance of the noble metal on the atomic scale are difficult to realize, the catalytic effect of the reaction is lower than that of a homogeneous catalytic system.
In view of this, on the basis of the heterogeneous catalyst, the invention prepares the highly-dispersed and even monoatomic metal catalyst by using the active structure characteristics of the homogeneous catalyst for reference, and realizes the modulation of the structure and properties of the catalyst on the atomic scale, thereby realizing the process of preparing the formic acid by the hydrogenation of the carbon dioxide with high efficiency.
In one embodiment of the present invention, a Pd-based metal material is provided, wherein the Pd-based metal material is a Pd-based monometallic material or a Pd-based bimetallic material;
when the Pd-based metal material is a Pd-based bimetallic material, the second metal is any one of Fe, Co, Ni, Cu and Zn;
the Pd-based metal material is characterized in that the active metal Pd and the second metal of the Pd-based metal material are loaded on a carrier in a sub-nanometer or monoatomic dispersion state;
the content of Pd is 0.001-20 wt.%, and the content of the second metal (any one of Fe, Co, Ni, Cu, Zn) is 0-40wt.%, based on the total weight of the Pd-based metal material;
in yet another embodiment of the present invention, the carrier has a specific surface area of 100-2A porous carbon material or nitrogen-doped carbon material having a nitrogen content of 0 to 60 wt.%.
In still another embodiment of the present invention, there is provided a method for preparing the Pd-based metal material described above, the method comprising: soaking a carbon material or a nitrogen-doped carbon material in a Pd-containing precursor solution, stirring under an inert atmosphere, filtering, washing, and carrying out high-temperature vacuum drying treatment to obtain the catalyst.
When the prepared Pd-based metal material is a Pd-based bimetallic material, the Pd-containing precursor solution also contains a second metal, and the second metal is any one of Fe, Co, Ni, Cu and Zn.
In another embodiment of the present invention, the precursor of Pd is an acid or salt containing Pd, including but not limited to any one or more of palladium chloride, potassium chloropalladate, palladium nitrate, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, and palladium triphenylphosphine acetate; the second metal precursor is any one or more of chlorides, nitrates, sulfates and corresponding metal organic complexes containing Fe, Co, Ni, Cu and Zn.
The inert atmosphere can be nitrogen, the stirring treatment temperature can be room temperature (such as 25 ℃) or high temperature (such as 50 ℃), the treatment time is controlled to be 1-24 hours, and the specific high-temperature vacuum drying treatment condition is vacuum drying at 60-150 ℃ for 6-24 hours.
In another embodiment of the present invention, the nitrogen-doped carbon material can be prepared by using 2, 6-pyridinedicarbonitrile (2,6-DCP) or 7,7,8, 8-Tetracyanoterephthalquinodimethane (TCNQ) as a precursor, and specifically, the method for preparing the nitrogen-doped carbon material comprises:
2, 6-pyridinedicarbonitrile or 7,7,8, 8-tetracyanoterephthalquinodimethane and ZnCl2And crushing and mixing the solids, uniformly crushing and mixing, then carrying out vacuum roasting treatment, cooling to room temperature, adding into acid liquor, stirring, filtering, washing, and then carrying out high-temperature vacuum drying treatment to obtain the catalyst.
In another embodiment of the present invention, the vacuum baking treatment conditions are as follows: roasting at 350-450 ℃ for 16-24 hours (preferably 400 ℃ for 20 hours), then heating to 550-650 ℃ for 16-24 hours (preferably 600 ℃ for 20 hours), and roasting at different temperatures, which is beneficial to improving the specific surface area of the prepared carrier.
In still another embodiment of the present invention, there is provided the use of the Pd-based metal material described above as a catalyst and/or for preparing a catalyst.
In another embodiment of the present invention, the catalyst is a catalyst for catalyzing a reaction of preparing formic acid by carbon dioxide hydrogenation, and experiments prove that the catalyst maximally captures carbon dioxide by using a porous carbon material and a nitrogen-doped carbon material carrier, maximally activates hydrogen and carbon dioxide by loading highly dispersed Pd and a second metal, has excellent catalytic activity for the reaction of preparing formic acid by carbon dioxide hydrogenation, and can realize efficient conversion at normal temperature and normal pressure.
In another embodiment of the present invention, a catalyst is provided, which comprises the Pd-based metal material described above, and which can be used for efficiently catalyzing the synthesis of formic acid by hydrogenation of carbon dioxide at normal temperature and pressure.
In another embodiment of the present invention, a method for synthesizing formic acid by hydrogenating carbon dioxide is provided, which includes adding the Pd-based metal material and/or the catalyst to a reaction system, thereby achieving efficient conversion at normal temperature and pressure.
More specifically, the method comprises: and putting the Pd-based metal material and/or the catalyst into a reaction medium containing alkali, then introducing carbon dioxide and hydrogen, and stirring for reaction at 20-200 ℃ and 0.1-6MPa to obtain a formate product.
Wherein the base can be inorganic base or organic base, such as carbonate, bicarbonate, organic amine, etc., and further comprises sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, C1-C6Corresponding primary, secondary and tertiary amines.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Examples 1 to 5
Examples 1 to 5 are carbon materials loaded with Pd, doped with nitrogen, prepared using 2, 6-pyridinedicarbonitrile (2,6-DCP) as a precursor using the method provided by the present invention. The preparation method comprises the following steps: 1. preparation of nitrogen-doped carbon material: 3.0 g of 2, 6-pyridinedicarbonitrile and 15.9 g of ZnCl are weighed out2And grinding and mixing the solid in a glove box, uniformly grinding, putting the mixture into an ampoule tube, vacuumizing and sealing the ampoule tube, roasting the mixture in a muffle furnace at 400 ℃ for 20 hours, raising the roasting temperature to 600 ℃ for further roasting for 20 hours, cooling the mixture to room temperature, grinding and roasting the sample, adding 1L of 2mol/L hydrochloric acid solution, stirring and washing the mixture for 12 hours, filtering the mixture, washing the mixture with deionized water, washing the mixture with tetrahydrofuran, and performing vacuum drying at 150 ℃ for 12 hours to obtain a nitrogen-doped carbon material sample (2, 6-DCP-C). 2. 1.0g of the 2,6-DCP-C sample prepared as described above was weighed and immersed in a predetermined amount of palladium trifluoroacetate solution at room temperature of 25 ℃ under N2Stirring for 12 hours under atmosphere, then filtering, washing, and drying in vacuum at 80 ℃ for 12 hours to obtain five catalysts with theoretical loading of 0.5, 1, 2, 3, and 4 wt.% respectively, and respectively named as 0.5Pd/[2,6-DCP-C]、1Pd/[2,6-DCP-C]、2Pd/[2,6-DCP-C]、3Pd/[2,6-DCP-C]And 4Pd/[2,6-DCP-C]. The Pd in the sample is observed by a spherical aberration electron microscope to show atomic-scale dispersion (figure 1).
| Preparation formula and conditions | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| 2,6-DCP-C(g) | 1 | 1 | 1 | 1 | 1 |
| Palladium trifluoroacetate (g) | 0.0157 | 0.0313 | 0.0626 | 0.0940 | 0.1253 |
| H2O(mL) | 30 | 30 | 30 | 30 | 30 |
| Reaction temperature (. degree.C.) | 25 | 25 | 25 | 25 | 25 |
| Reaction time (h) | 12 | 12 | 12 | 12 | 12 |
| Drying temperature (. degree.C.) | 80 | 80 | 80 | 80 | 80 |
| Drying time (h) | 12 | 12 | 12 | 12 | 12 |
Examples 6 to 8
Examples 6-8 were prepared using the methods provided by the present invention to prepare Pd-based bimetallic catalysts using bimetallic Pd and Co supported on nitrogen-doped carbon materials prepared using 2, 6-pyridinedicarbonitrile (2,6-DCP) as a precursor. The preparation method comprises the following steps: 1. preparation of nitrogen-doped carbon material: 3.0 g of 2, 6-pyridinedicarbonitrile and 15.9 g of ZnCl are weighed out2Grinding and mixing the solid in a glove box, uniformly grinding, putting the mixture into an ampoule tube, vacuumizing and sealing the ampoule tube, roasting the mixture in a muffle furnace at 400 ℃ for 20 hours, raising the roasting temperature to 600 ℃ for further roasting for 20 hours, cooling the roasted mixture to room temperature, grinding the roasted sample, and adding 1L of the ground sampleThe mixture was washed with 2mol/L hydrochloric acid solution for 12 hours under stirring, and then filtered, washed with deionized water, washed with tetrahydrofuran, and vacuum-dried at 150 ℃ for 12 hours to obtain a nitrogen-doped carbon material sample (2, 6-DCP-C). 2. 1.0g of the 2,6-DCP-C sample prepared by the above method was weighed and immersed in a certain amount of a methanol solution of palladium acetylacetonate and cobalt acetylacetonate as shown in the following table, and the temperature was 50 ℃ and N was measured2Stirring for 12 hours under the atmosphere, then filtering, washing, and drying in vacuum at 80 ℃ for 12 hours to obtain three bimetallic catalysts with theoretical load of Pd and Co of 3, 5 and 7 wt.% respectively, which are named as 3Pd-3Co/[2,6-DCP-C respectively]、5Pd-5Co/[2,6-DCP-C]And 7Pd-7Co/[2,6-DCP-C]。
| Preparation formula and conditions | Example 6 | Example 7 | Example 8 |
| 2,6-DCP-C(g) | 1 | 1 | 1 |
| Palladium acetylacetonate (g) | 0.0863 | 0.1439 | 0.2014 |
| Acetylacetonatocobalt (g) | 0.1810 | 0.3017 | 0.4224 |
| CH3OH(mL) | 30 | 30 | 30 |
| Reaction temperature (. degree.C.) | 50 | 50 | 50 |
| Reaction time (h) | 12 | 12 | 12 |
| Drying temperature (. degree.C.) | 80 | 80 | 80 |
| Drying time (h) | 12 | 12 | 12 |
Example 9
Example 9 a Pd-based bimetallic catalyst was prepared using the method of the present invention, using bimetallic Pd and Fe supported on nitrogen-doped carbon material prepared using 2, 6-pyridinedicarbonitrile (2,6-DCP) as a precursor. The preparation method comprises the following steps: 1. preparation of nitrogen-doped carbon material: 3.0 g of 2, 6-pyridinedicarbonitrile and 15.9 g of ZnCl are weighed out2Grinding and mixing the solid in a glove box, uniformly grinding, putting into an ampoule tube, vacuumizing, sealing, and putting into a 400 ℃ horseRoasting for 20 hours in a muffle furnace, raising the roasting temperature to 600 ℃ for further roasting for 20 hours, after the temperature is reduced to room temperature, grinding the roasted sample, adding the ground sample into 1L of 2mol/L hydrochloric acid solution, stirring and washing for 12 hours, then filtering, washing with deionized water and washing with tetrahydrofuran, and performing vacuum drying for 12 hours at 150 ℃ to obtain a nitrogen-doped carbon material sample (2, 6-DCP-C). 2. Weighing 1.0g of the 2,6-DCP-C sample prepared by the method, adding into 30 ml of methanol solution containing 0.1439g of palladium acetylacetonate and 0.3152g of iron acetylacetonate, and heating at 50 ℃ under N2Stirring for 12 hours under atmosphere, filtering, washing and drying in vacuum at 80 ℃ for 12 hours to obtain a bimetallic catalyst with theoretical Pd and Fe loading of 5 wt.%, which is named as 5Pd-5Fe/[2,6-DCP-C]。
Example 10
Example 10 a Pd-based bimetallic catalyst was prepared by loading bimetallic Pd and Ni on a nitrogen-doped carbon material prepared using 2, 6-pyridinedicarbonitrile (2,6-DCP) as a precursor using the method provided by the present invention. The preparation method comprises the following steps: 1. preparation of nitrogen-doped carbon material: 3.0 g of 2, 6-pyridinedicarbonitrile and 15.9 g of ZnCl are weighed out2And grinding and mixing the solid in a glove box, uniformly grinding, putting the mixture into an ampoule tube, vacuumizing and sealing the ampoule tube, roasting the mixture in a muffle furnace at 400 ℃ for 20 hours, raising the roasting temperature to 600 ℃ for further roasting for 20 hours, cooling the mixture to room temperature, grinding and roasting the sample, adding 1L of 2mol/L hydrochloric acid solution, stirring and washing the mixture for 12 hours, filtering the mixture, washing the mixture with deionized water, washing the mixture with tetrahydrofuran, and performing vacuum drying at 150 ℃ for 12 hours to obtain a nitrogen-doped carbon material sample (2, 6-DCP-C). 2. Weighing 1.0g of the 2,6-DCP-C sample prepared by the method, adding into 30 ml of methanol solution containing 0.1439g of palladium acetylacetonate and 0.2178g of nickel acetylacetonate, and reacting at 50 ℃ with N2Stirring for 12 hours under atmosphere, then filtering, washing and drying in vacuum at 80 ℃ for 12 hours to obtain a bimetallic catalyst with theoretical Pd and Ni loading of 5 wt.%, which is named as 5Pd-5Ni/[2,6-DCP-C]。
Example 11
Example 11 to utilize the process provided by the present invention,the Pd-based bimetallic catalyst is prepared by adopting a nitrogen-doped carbon material prepared by taking 2, 6-pyridinedicarbonitrile (2,6-DCP) as a precursor to load bimetallic Pd and Cu. The preparation method comprises the following steps: 1. preparation of nitrogen-doped carbon material: 3.0 g of 2, 6-pyridinedicarbonitrile and 15.9 g of ZnCl are weighed out2And grinding and mixing the solid in a glove box, uniformly grinding, putting the mixture into an ampoule tube, vacuumizing and sealing the ampoule tube, roasting the mixture in a muffle furnace at 400 ℃ for 20 hours, raising the roasting temperature to 600 ℃ for further roasting for 20 hours, cooling the mixture to room temperature, grinding and roasting the sample, adding 1L of 2mol/L hydrochloric acid solution, stirring and washing the mixture for 12 hours, filtering the mixture, washing the mixture with deionized water, washing the mixture with tetrahydrofuran, and performing vacuum drying at 150 ℃ for 12 hours to obtain a nitrogen-doped carbon material sample (2, 6-DCP-C). 2. Weighing 1.0g of the 2,6-DCP-C sample prepared by the method, adding into 30 ml of methanol solution containing 0.1439g of palladium acetylacetonate and 0.2045g of copper acetylacetonate, and heating at 50 ℃ under N2Stirring for 12 hours under atmosphere, then filtering, washing and drying in vacuum at 80 ℃ for 12 hours to obtain a bimetallic catalyst with theoretical Pd and Cu loadings of 5 wt.%, which is named as 5Pd-5Cu/[2,6-DCP-C]。
Example 12
Example 13
Examples 14 to 18
Examples 14-18 illustrate the use of Pd-based monometallics and bimetallic catalysts prepared by the methods provided herein to catalyze the hydrogenation of carbon dioxide to formic acid. Example 5(4Pd/[2, 6-DCP-C)]) Example 7(5Pd-5Co/[2, 6-DCP-C)]) Example 10(5Pd-5Ni/[2, 6-DCP-C)]) Example 11(5Pd-5Cu/[2, 6-DCP-C)]) And example 13(Pd/[ TCNQ-C)]) The prepared catalyst is used for the reaction of preparing formic acid by carbon dioxide hydrogenation. The specific operation steps are that firstly 20mg of the catalyst is weighed and put into 5mL of 1M sodium bicarbonate solution, and then the solution is introduced into the reactor according to the volume ratio of 1:1Carbon dioxide and hydrogen, stirring and reacting for 12 hours at 30 ℃ and 1bar pressure, and detecting the concentration of formic acid in the product by using high performance liquid chromatography. As shown in FIG. 3, the TOF values of the catalysts were 8.64h respectively-1、12.92h-1、10.12h-1、8.77h-1And 3.14h-1. The Pd-based catalyst disclosed by the invention can catalyze the reaction of preparing formic acid by carbon dioxide hydrogenation at normal temperature and normal pressure, and the addition of the second metal can obviously improve the catalytic activity of the catalyst.
Comparative example 19
Comparative example 19 illustrates the preparation of a comparative catalyst having low metal dispersion by high temperature reduction using the catalyst disclosed herein. The specific implementation process is that the 3Pd/[2,6-DCP-C ] catalyst prepared in example 4 is heated to 300 ℃ at the speed of 5 ℃/min in hydrogen atmosphere and is kept for 2 hours, so that a 3Pd/[2,6-DCP-C ] -300R sample is obtained, and the sample has lower dispersion degree and metal utilization rate compared with the 3Pd/[2,6-DCP-C ].
Comparative example 20
Comparative example 20 illustrates the reaction of commercial Pd/C catalyst to prepare formic acid by hydrogenation of carbon dioxide at ambient temperature and pressure. The mass fraction of Pd of the purchased commercial Pd/C catalyst is 9.70-10.30 wt.%, and the specific surface area is 800-2000m2(ii) in terms of/g. The catalyst is used for carrying out the reaction of preparing formic acid by carbon dioxide hydrogenation at normal temperature and normal pressure, and the specific operation steps are that firstly 20mg of a commercial Pd/C catalyst is weighed and put into 1M sodium bicarbonate solution, then carbon dioxide and hydrogen with the volume ratio of 1:1 are introduced, the stirring reaction is carried out for 12 hours at the temperature of 30 ℃ and the pressure of 1bar, and the concentration of formic acid in the product is detected by utilizing high performance liquid chromatography. As shown in FIG. 3, the TOF values of the catalysts are respectively only 0.84h-1This shows that the catalyst disclosed by the invention has obviously excellent catalytic activity for the reaction of preparing formic acid by hydrogenating carbon dioxide compared with the existing commercial Pd/C catalyst.
Comparative example 21
Comparative example 21 illustrates the low metal dispersion of the catalyst disclosed by the invention after high temperature reduction treatmentThe catalyst has the catalytic performance of the catalyst for preparing formic acid by hydrogenating carbon dioxide. The specific operation steps are as follows: weighing 3Pd/[2,6-DCP-C]The catalyst 20mg (300R) is put into a sodium bicarbonate solution of 1M, then carbon dioxide and hydrogen are introduced in a volume ratio of 1:1, the reaction is stirred for 12 hours at 30 ℃ and under the pressure of 1bar, and the concentration of formic acid in the product is detected by high performance liquid chromatography. As shown in FIG. 3, the TOF values of the catalysts were only 0.27h respectively-1. This demonstrates that the high metal dispersion characteristics of the disclosed catalysts are responsible for the high catalytic activity.
Example 22
Example 22 illustrates the stability of the reaction cycle for the preparation of formic acid by hydrogenation of carbon dioxide using a Pd-based catalyst prepared by the method of the present invention. The specific operation steps are as follows: weighing 20mg of the 5Pd-5Co/[2,6-DCP-C ] catalyst prepared in example 7, adding the weighed catalyst into 5mL of 1M sodium bicarbonate solution, introducing carbon dioxide and hydrogen in a volume ratio of 1:1, and stirring the mixture at 30 ℃ under the pressure of 1bar for reaction for 12 hours; after the reaction is finished, the reaction solution is filtered, the catalyst after the reaction is separated out and washed by deionized water, after the catalyst is dried in vacuum at 80 ℃ for 12 hours, the reaction is carried out again according to the procedure, the process is repeated for 4 times, and the concentration of formic acid in the product after each cycle is detected by using high performance liquid chromatography, and the result is shown in figure 4, and the catalyst still keeps high catalytic activity after four cycles, namely the sample has good cycle stability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A Pd-based metal material, wherein the Pd-based metal material is a Pd-based monometallic material or a Pd-based bimetallic material;
when the Pd-based metal material is a Pd-based bimetallic material, the second metal is any one of Fe, Co, Ni, Cu and Zn;
the Pd-based metal material is characterized in that the active metal Pd and the second metal of the Pd-based metal material are loaded on a carrier in a sub-nanometer or monoatomic dispersion state; the carrier is a nitrogen-doped porous carbon material with the specific surface area of 100-5000m2(iv)/g, nitrogen content greater than 0 but not more than 60 wt.%;
the content of Pd is 0.001-20 wt.% and the content of the second metal is 0-40wt.%, based on the total weight of the Pd-based metal material;
the nitrogen-doped porous carbon material is prepared by taking 2, 6-pyridinedicarbonitrile (2,6-DCP) or 7,7,8, 8-Tetracyanoterephthalquinodimethane (TCNQ) as a precursor; the preparation method of the nitrogen-doped porous carbon material comprises the following steps: 2, 6-pyridinedicarbonitrile or 7,7,8, 8-tetracyanoterephthalquinodimethane and ZnCl2And crushing and mixing the solids, uniformly crushing and mixing, then carrying out vacuum roasting treatment, cooling to room temperature, adding into acid liquor, stirring, filtering, washing, and then carrying out high-temperature vacuum drying treatment to obtain the catalyst.
2. The method for producing a Pd-based metal material according to claim 1, wherein the production method comprises: soaking a nitrogen-doped porous carbon material in a Pd-containing precursor solution, stirring under an inert atmosphere, filtering, washing, and carrying out high-temperature vacuum drying treatment to obtain the product;
when the prepared Pd-based metal material is a Pd-based bimetallic material, the Pd-containing precursor solution also contains a second metal, and the second metal is any one of Fe, Co, Ni, Cu and Zn.
3. The preparation method according to claim 2, wherein the precursor of Pd is an acid or salt containing Pd, and comprises any one or more of palladium chloride, potassium chloropalladate, palladium nitrate, palladium acetate, palladium trifluoroacetate, palladium acetylacetonate, and palladium triphenylphosphine acetate; the second metal precursor is any one of chloride, nitrate and sulfate containing Fe, Co, Ni, Cu and Zn and a corresponding metal organic complex.
4. The method according to claim 2, wherein the inert atmosphere is nitrogen, the stirring treatment temperature is room temperature or high temperature, the treatment time is controlled to be 1-24 hours, and the specific conditions of the high temperature vacuum drying treatment are 60-150 ℃ vacuum drying for 6-24 hours.
5. The method according to claim 2, wherein the nitrogen-doped porous carbon material is prepared from 2, 6-pyridinedicarbonitrile or 7,7,8, 8-tetracyanoterephthalquinodimethane as a precursor.
6. A method for synthesizing formic acid by hydrogenating carbon dioxide, which comprises adding the Pd-based metal material as defined in claim 1 to a reaction system.
7. The method of claim 6, wherein the method comprises: the Pd-based metal material as defined in claim 1 is added to a reaction medium containing alkali, and then carbon dioxide and hydrogen are introduced to react under stirring at 20-200 ℃ and 0.1-6MPa to obtain a formate product.
8. The method of claim 7, wherein the base is an inorganic base or an organic base.
9. The method of claim 8, wherein the inorganic base comprises a carbonate or bicarbonate and the organic base comprises an organic amine.
10. The method of claim 8, wherein the inorganic base comprises sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, and the organic base comprises C1-C6Corresponding primary, secondary and tertiary amines.
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| CN113620798A (en) * | 2021-09-10 | 2021-11-09 | 中国华能集团清洁能源技术研究院有限公司 | System and method for synthesizing formic acid by hydrogenation of carbon dioxide driven by renewable energy |
| CN113877573A (en) * | 2021-10-21 | 2022-01-04 | 中国林业科学研究院林产化学工业研究所 | Bio-based mesoporous carbon material for catalyzing CO2Method for preparing liquid fuel by hydrogenation |
| CN114225668B (en) * | 2021-11-26 | 2023-01-13 | 山东大学 | Reaction device, method and application for preparing formic acid by capturing carbon dioxide and hydrogenating |
| CN114471626B (en) * | 2022-01-24 | 2024-04-09 | 深圳市德尼环境技术有限公司 | Preparation method and application of oxyfluoride supported noble metal catalyst |
| CN114436808B (en) * | 2022-01-28 | 2023-02-28 | 南京大学 | CO based on cyclic conversion of imidazolecarboxylate and imidazolecarbonate 2 Method for preparing formic acid by hydrogenation |
| CN114653366A (en) * | 2022-04-19 | 2022-06-24 | 苏州金宏气体股份有限公司 | Catalyst for preparing formic acid from carbon dioxide and preparation process thereof |
| CN115646546B (en) * | 2022-09-13 | 2024-04-16 | 中国石油大学(华东) | Preparation method of carbon-based bimetallic site catalytic material for producing formic acid by carbon dioxide hydrogenation |
| WO2024078279A1 (en) * | 2022-10-14 | 2024-04-18 | 中国石油化工股份有限公司 | Supported palladium catalyst, and preparation and use thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106861737A (en) * | 2015-12-10 | 2017-06-20 | 中国科学院大连化学物理研究所 | One kind synthesis Catalyzed by Formic Acid agent and its preparation and application |
| JP2018103158A (en) * | 2016-12-28 | 2018-07-05 | 国立研究開発法人科学技術振興機構 | Hydrogenation catalyst, manufacturing method of hydrogenation catalyst and manufacturing method of hydrogen carrier material |
| CN110639548A (en) * | 2019-09-19 | 2020-01-03 | 北京工业大学 | Monoatomic palladium-cobalt bimetallic nano-catalyst for efficiently catalyzing benzene oxidation |
| CN111530458A (en) * | 2020-05-15 | 2020-08-14 | 江南大学 | Monoatomic catalyst and application thereof in carbon dioxide hydrogenation reaction |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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-
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- 2021-02-20 CN CN202110192434.6A patent/CN112871198B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106861737A (en) * | 2015-12-10 | 2017-06-20 | 中国科学院大连化学物理研究所 | One kind synthesis Catalyzed by Formic Acid agent and its preparation and application |
| JP2018103158A (en) * | 2016-12-28 | 2018-07-05 | 国立研究開発法人科学技術振興機構 | Hydrogenation catalyst, manufacturing method of hydrogenation catalyst and manufacturing method of hydrogen carrier material |
| CN110639548A (en) * | 2019-09-19 | 2020-01-03 | 北京工业大学 | Monoatomic palladium-cobalt bimetallic nano-catalyst for efficiently catalyzing benzene oxidation |
| CN111530458A (en) * | 2020-05-15 | 2020-08-14 | 江南大学 | Monoatomic catalyst and application thereof in carbon dioxide hydrogenation reaction |
Non-Patent Citations (2)
| Title |
|---|
| Hydrogen and CO2 storage in high surface area covalent triazineebased frameworks;Deng Q.-W. et al.;《Materials Today Energy》;20200829;第18卷;摘要，1背景介绍部分第2-3段，2.1部分，图3 * |
| Pd基双金属催化剂的制备及其应用于CO2加氢合成甲酸反应的性能研究;祝芷晴;《中国优秀硕士论文库 工程科技I辑》;20200715;第1部分，第2部分，第4部分 * |
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