CN113372185A - Infrared-driven carbon dioxide catalytic conversion method - Google Patents
Infrared-driven carbon dioxide catalytic conversion method Download PDFInfo
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- CN113372185A CN113372185A CN202110378508.5A CN202110378508A CN113372185A CN 113372185 A CN113372185 A CN 113372185A CN 202110378508 A CN202110378508 A CN 202110378508A CN 113372185 A CN113372185 A CN 113372185A
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- carbon dioxide
- catalytic conversion
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- infrared
- plasmonic
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 113
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 88
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 88
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 57
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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Abstract
The invention provides a method for catalytic conversion of carbon dioxide, which comprises the following steps of carrying out catalytic conversion reaction on a raw material containing carbon dioxide under the action of a plasmon material composite material catalyst and under the drive of infrared rays to obtain a carbon-containing compound. The invention directly uses clean and abundant solar energy, is clean and economic, can utilize the infrared ray which is most abundant in energy storage in sunlight, and greatly improves the conversion efficiency of the solar energy to the chemical energy. In addition, the carbon dioxide is used as a main raw material to synthesize a series of necessary chemicals, so that the carbon dioxide in the atmosphere can be fixed, and the carbon dioxide can be directionally catalytically converted with high efficiency and high selectivity by using a reasonable composite catalyst based on the plasmon material.
Description
Technical Field
The invention belongs to the technical field of plasmon metal catalysts, relates to a carbon dioxide catalytic conversion method, and particularly relates to an infrared-driven carbon dioxide catalytic conversion method.
Background
Fossil fuels are indispensable energy sources for human beings, however, the combustion of a large amount of fossil fuels can cause the emission of a large amount of carbon dioxide gas, so that the concentration of carbon dioxide in the atmosphere is continuously increased, and the conditions of the climate, biosphere, food chain and other human beings depending on survival are further influenced. In view of the above, it is necessary to adopt a chemical synthesis method to utilize the fundamental principle of carbon cycle in nature to efficiently and rapidly convert carbon resources such as carbon dioxide in the air into fuel molecules by using energy forms such as light, heat, electricity and the like. The key technology to achieve this series of chemical transformations is catalysis. The most attractive approach in the technology of catalytic conversion of carbon dioxide is the photocatalytic system, which can directly convert solar radiation energy into chemical energy. The solar energy reserves are far larger than fossil fuels on earth, and as a clean energy source which covers the earth to the widest extent and can be used for the longest time, the energy reaching the earth per second is equivalent to burning 500 ten thousand tons of coal. Thus, the use of solar energy to convert carbon dioxide to useful chemicals through artificial photosynthesis has the efficacy of Shierjie in clean energy utilization and reduction of carbon dioxide emissions.
It is well known that in the solar spectrum, ultraviolet rays account for only up to about 4% of the solar energy at the earth's surface, while the energy distributed in the infrared region is up to 50%. And the infrared rays of long wavelength reach the earth's surface more easily than other light and are collected and converted. Obviously, from the practical point of view, the utilization of the infrared part of the sunlight is very critical. In order to more effectively utilize the clean energy of solar energy and realize the high-efficiency conversion of carbon dioxide, the development of the carbon dioxide catalytic conversion technology which can be driven by infrared rays has profound significance for the development of the human society.
Therefore, how to develop a novel catalyst for light-driven carbon dioxide catalytic conversion can solve the above problems, especially, the realization of the carbon dioxide catalytic conversion process under the infrared irradiation condition has a very important meaning, and is one of the focuses of the great attention of many prospective researchers in the field.
Disclosure of Invention
In view of the above, the present invention provides a method for catalytic conversion of carbon dioxide, particularly a method for catalytic conversion of carbon dioxide driven by infrared. The method provided by the invention utilizes renewable clean energy, namely solar energy, to directionally convert carbon dioxide in the atmosphere into chemical raw materials and fuels, simultaneously realizes the utilization of the clean energy and the negative emission of the carbon dioxide, and has important significance for promoting the strategic goal of realizing carbon neutralization.
The invention provides a method for catalytic conversion of carbon dioxide, which comprises the following steps:
under the action of a plasmon material composite material catalyst and under the drive of infrared rays, a raw material containing carbon dioxide is subjected to catalytic conversion reaction to obtain a carbon-containing compound.
Preferably, the plasmonic material composite material comprises a plasmonic material and a material with carbon dioxide catalytic conversion performance;
the plasmonic material comprises a plasmonic material having light absorption properties in the infrared wavelength range;
the material with the carbon dioxide catalytic conversion performance comprises one or more of a metal material, an alloy material, a semiconductor and a metal organic framework material.
Preferably, the plasmonic material comprises a plasmonic metal material;
the morphology structure of the composite catalyst comprises one or more of a full-coating core-shell structure, a porous core-shell structure, a main body-satellite structure, a heterostructure and a layered stack;
the metal material comprises palladium, copper, platinum, rhodium, nickel, iron, cobalt or zinc;
the alloy material comprises two or more of palladium, copper, platinum, rhodium, nickel, iron, cobalt and zinc;
the semiconductor material comprises one or more of indium hydroxide, indium oxide and titanium dioxide;
the metal organic framework material comprises MIL-125(Ti), UiO-66(Zr), MIL-101(Fe) and MIL-125-NH2And PCN-222.
Preferably, the plasmonic material comprises one or more of gold, silver and copper;
the appearance of the plasmon material comprises one or more of nanospheres, nanocubes, nanosheets, nanocones and nanorods;
the composite catalyst comprises a physically mixed composite catalyst.
Preferably, the wavelength of the infrared ray is 750-2500 nm;
the infrared rays comprise near infrared rays;
the infrared ray includes 2 or more wavelengths of infrared rays.
Preferably, the plasmonic material composite catalyst may be supported on a catalyst support;
the catalyst carrier comprises one or more of a carbon carrier, a silicon dioxide carrier, an aluminum oxide carrier, a ceramic carrier, a molecular sieve, silicon carbide, kaolin, a fluorine polymer and quartz glass;
the catalyst support comprises a gel support;
the load capacity of the load is 1-50%.
Preferably, the generation source of the infrared ray includes one or more of a xenon lamp, an LED lamp, a tungsten lamp, and an infrared lamp;
the intensity of the infrared ray is 5-10000 mW/cm2。
Preferably, the raw material containing carbon dioxide comprises an aqueous solution of carbon dioxide and/or a mixed gas containing carbon dioxide;
the mixed gas also comprises one or more of water vapor, hydrogen, methane and ammonia gas;
the conditions for the catalytic conversion reaction further include one or more of heat, pressure, and applied voltage.
Preferably, the heating temperature is 0-800 ℃;
the pressurizing pressure is 0.1-10 Mpa;
the bias range of the applied voltage is 0.05 to 3V.
Preferably, the catalytic conversion comprises catalytic reduction;
the reaction vessel for catalytic conversion reaction comprises one or more of a light-permeable fixed bed reactor with a quartz or glass window, a light-permeable fluidized bed reaction vessel with a quartz or glass window, a fixed bed reactor integrated with an internal light source and a fluidized bed reaction vessel integrated with an internal light source.
The invention provides a method for catalytic conversion of carbon dioxide, which comprises the following steps of carrying out catalytic conversion reaction on a raw material containing carbon dioxide under the action of a plasmon material composite material catalyst and under the drive of infrared rays to obtain a carbon-containing compound. Compared with the prior art, the solar energy storage device directly uses clean and abundant solar energy, is clean and economic, can utilize the infrared rays with the most abundant energy storage in sunlight, and greatly improves the conversion efficiency of the solar energy to chemical energy; in addition, the carbon dioxide is used as a main raw material to synthesize a series of necessary chemicals, so that the carbon dioxide in the atmosphere can be fixed, and the carbon dioxide can be directionally catalytically converted with high efficiency and high selectivity by using a reasonable composite catalyst based on the plasmon material.
The invention creatively provides an infrared-driven carbon dioxide catalytic conversion method. The invention utilizes the plasmon effect of the metal nano material to effectively absorb infrared rays and generate electromagnetic near field enhancement and thermal electron effect to drive chemical reaction; the material with the carbon dioxide catalytic conversion performance is used as an active site to play a role in adsorbing and activating carbon dioxide molecules, so that the high-efficiency conversion from solar energy to chemical energy under the irradiation of infrared rays is realized.
Experimental results show that the method for driving carbon dioxide catalytic conversion by infrared adopts the plasmon material composite materialThe yield of methane can reach 14.4 mu mol g at most-1·h-1。
Drawings
FIG. 1 is a chromatogram of a gas phase of methane produced by catalytic conversion of carbon dioxide in example 1 of the present invention;
FIG. 2 is a graphical representation of the average methane yield versus the number of cycles for 10 carbon dioxide reductions of the catalyst in example 15 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs purity which is conventional in the field of analytical purification or preparation of metal catalysts.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
All the processes of the invention, the abbreviations thereof belong to the common abbreviations in the art, each abbreviation is clear and definite in the field of its associated use, and the ordinary process steps thereof can be understood by those skilled in the art from the abbreviations.
The invention provides a method for catalytic conversion of carbon dioxide, which comprises the following steps:
under the action of a plasmon material composite material catalyst and under the drive of infrared rays, a raw material containing carbon dioxide is subjected to catalytic conversion reaction to obtain a carbon-containing compound.
The composition of the plasmonic material composite material is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application condition, the product requirement and the specific application.
The selection of the plasmonic material is not particularly limited in principle by the present invention, and can be selected and adjusted by those skilled in the art according to the actual application, product requirements and specific application, and in order to ensure the high efficiency and continuity of the catalytic conversion method, the plasmonic material preferably comprises a plasmonic metal material, and more specifically, the plasmonic material preferably comprises a plasmonic material having light absorption properties in the infrared wavelength range.
The material of the plasmonic material is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application condition, the product requirements and the specific application.
The present invention is not particularly limited in principle to the morphology of the plasmonic material, and those skilled in the art can select and adjust the material according to the actual application, product requirements, and specific application, and in order to ensure the high efficiency and continuity of the catalytic conversion method, the morphology of the plasmonic material preferably includes one or more of nanospheres, nanocubes, nanosheets, nanocones, and nanorods, more preferably nanospheres, nanocubes, nanosheets, nanocones, or nanorods, and most preferably nanocones.
The selection of the material having the carbon dioxide catalytic conversion performance is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application, product requirements and specific application, and in order to ensure the high efficiency and continuity of the catalytic conversion method, the material having the carbon dioxide catalytic conversion performance preferably comprises one or more of a metal, an alloy material, a semiconductor and a metal-organic framework material, and more preferably a metal, an alloy material, a semiconductor or a metal-organic framework material.
The invention is in principle not particularly restricted to the specific choice of the metallic material, which can be selected and adapted by the person skilled in the art according to the actual application, the product requirements and the specific application, and which preferably comprises palladium, copper, platinum, rhodium, nickel, iron, cobalt or zinc in order to ensure the high efficiency and continuity of the catalytic conversion process.
The invention is in principle not particularly restricted to the specific choice of said alloy materials, which can be selected and adapted by the person skilled in the art according to the actual application, the product requirements and the specific application, and which preferably comprise two or more of palladium, copper, platinum, rhodium, nickel, iron, cobalt and zinc in order to ensure the high efficiency and continuity of the catalytic conversion process.
The invention is in principle not particularly restricted to the specific choice of said semiconductor material, which can be selected and adapted by the person skilled in the art according to the actual application, the product requirements and the specific application, and which preferably comprises one or more of indium hydroxide, indium oxide and titanium dioxide in order to ensure the high efficiency and continuity of the catalytic conversion process.
The specific selection of the metal organic framework material is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the practical application, product requirements and specific application, and the metal organic framework material comprises MIL-125(Ti), UiO-66(Zr), MIL-101(Fe) and MIL-125-NH (NH) in order to ensure the high efficiency and continuity of the catalytic conversion method2And PCN-222.
In order to ensure the high efficiency and the continuity of the catalytic conversion method, the morphological structure of the composite material catalyst preferably comprises one or more of a fully-coated core-shell structure, a porous core-shell structure, a main body-satellite structure, a heterostructure and a layered stack, and more preferably comprises the fully-coated core-shell structure, the porous core-shell structure, the main body-satellite structure, the heterostructure or the layered stack. In the present invention, the plasmonic material may be fully coated with a material having carbon dioxide catalytic conversion properties, whereas the material having carbon dioxide catalytic conversion properties cannot be fully coated with the plasmonic material.
The selection of the composite catalyst is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application, product requirements and specific application, and the composite catalyst preferably comprises a physically mixed composite catalyst in order to ensure the high efficiency and continuity of the catalytic conversion process.
The specific choice of the infrared ray is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application, the product requirements and the specific application, and the infrared ray preferably comprises near infrared ray in order to ensure the high efficiency and the continuity of the catalytic conversion method.
The wavelength of the infrared ray is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application situation, the product requirements and the specific application, and in order to ensure the high efficiency and the continuity of the catalytic conversion method, the wavelength of the infrared ray is preferably 750-2500 nm, more preferably 850-1900 nm, and more preferably 950-1300 nm.
The specific choice of the infrared ray is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application, product requirements and specific application, and the invention is to ensure the high efficiency and continuity of the catalytic conversion method, wherein the infrared ray preferably comprises multiple wavelengths, particularly preferably comprises 2 or more than 2 wavelengths, and can also be near infrared rays of a full waveband or infrared rays of a full waveband in a wavelength range.
In the invention, in order to ensure the high efficiency and the continuity of the catalytic conversion method, the generation source of the infrared ray preferably comprises one or more of a xenon lamp, an LED lamp, a tungsten lamp and an infrared lamp, more preferably a xenon lamp, an LED lamp, a tungsten lamp or an infrared lamp, more preferably a xenon lamp or an LED lamp, and the illumination intensity is 400-1000 mW/cm2。
In the invention, the intensity of the infrared ray is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to actual application conditions, product requirements and specific application, and in order to ensure the high efficiency and continuity of the catalytic conversion method, the intensity of the infrared ray is preferably 5-10000 mW/cm2More preferably 100 to 4000mW/cm2More preferably 200-3000 mW/cm2More preferably 400-2500 mW/cm2。
The invention is a complete and refined integral preparation process, ensures the high efficiency and the continuity of a catalytic conversion method, and preferably the plasmon material composite catalyst can be loaded on a catalyst carrier.
In the present invention, in order to ensure the high efficiency and continuity of the catalytic conversion process, the catalyst carrier preferably includes one or more of a carbon carrier, a silica carrier, an alumina carrier, a ceramic carrier, a molecular sieve, silicon carbide, kaolin, a fluoropolymer and quartz glass, and more preferably includes one or more of a carbon carrier, a silica carrier, an alumina carrier, a ceramic carrier, a molecular sieve, silicon carbide, kaolin, a fluoropolymer or quartz glass. Alternatively, the catalyst support preferably comprises a gel support.
The loading of the load is not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application, product requirements and specific application, and the loading of the load is preferably 1% to 50%, more preferably 20% to 45%, and more preferably 30% to 40% in order to ensure the high efficiency and continuity of the catalytic conversion method.
The selection of the carbon dioxide-containing feedstock is not particularly limited in principle and can be selected and adjusted by the skilled person according to the actual application, the product requirements and the specific application, and in order to ensure the high efficiency and continuity of the catalytic conversion process, the carbon dioxide-containing feedstock preferably comprises an aqueous solution of carbon dioxide and/or a mixed gas containing carbon dioxide, more preferably an aqueous solution of carbon dioxide or a mixed gas containing carbon dioxide. The aqueous solution containing carbon dioxide is preferably an aqueous solution saturated with carbon dioxide.
The specific choice of the gas mixture is not particularly limited in the present invention, and can be selected and adjusted by those skilled in the art according to the actual application, the product requirements and the specific application, and in order to ensure the high efficiency and the continuity of the catalytic conversion method, the gas mixture preferably comprises one or more of water vapor, hydrogen, methane and ammonia, and more preferably water vapor, hydrogen, methane or ammonia. The proportion of different gases can be any proportion of gases containing carbon dioxide; the preferred ratio of the carbon dioxide to the water vapor, the hydrogen gas or the ammonia gas is 1 (0.3-1) (1 (0.4-0.9) or 1 (0.5-0.8)) by volume, and the more preferred ratio of the carbon dioxide to the water vapor or the hydrogen gas is 1 (0.3-0.7) (1 (0.4-0.8) or 1 (0.5-0.7)).
The conditions of the catalytic conversion reaction are not particularly limited in principle, and can be selected and adjusted by those skilled in the art according to the actual application, the product requirements and the specific application, and in order to ensure the high efficiency and the continuity of the catalytic conversion method, the conditions of the catalytic conversion reaction preferably include one or more of heating, pressurization and voltage application, and more preferably, heating, pressurization or voltage application.
In the invention, the heating temperature is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application situation, the product requirements and the specific application, and in order to ensure the high efficiency and the continuity of the catalytic conversion method, the heating temperature is preferably 0-800 ℃, more preferably 20-400 ℃, and more preferably 25-200 ℃.
In the invention, the pressurizing pressure is not particularly limited in principle, and can be selected and adjusted by a person skilled in the art according to the actual application condition, the product requirement and the specific application, and in order to ensure the high efficiency and the continuity of the catalytic conversion method, the pressurizing pressure is preferably 0.1-10 Mpa, more preferably 0.1-3 Mpa, and more preferably 0.1-1 Mpa.
In the invention, in order to ensure the high efficiency and the continuity of the catalytic conversion method, the bias range of the applied voltage is preferably 0.05 to 3V, more preferably 0.1 to 1.5V, and even more preferably 0.4 to 0.7V.
The requirements of the catalytic conversion are not particularly limited in principle, and can be selected and adjusted by the person skilled in the art according to the actual application, the product requirements and the specific application.
The reaction vessel for the catalytic conversion reaction is not particularly limited in principle, and may be selected and adjusted by those skilled in the art according to the actual application, product requirements and specific application, and in order to ensure the high efficiency and continuity of the catalytic conversion process, the reaction vessel for catalytic conversion reaction preferably comprises one or more of a light-permeable fixed bed reactor with a quartz or glass window, a light-permeable fluidized bed reaction vessel with a quartz or glass window, a fixed bed reactor integrated with an internal light source and a fluidized bed reaction vessel integrated with an internal light source, more preferably a light-permeable fixed bed reactor with a quartz or glass window, a light-permeable fluidized bed reaction vessel with a quartz or glass window, a fixed bed reactor integrated with an internal light source or a fluidized bed reaction vessel integrated with an internal light source, and more preferably a light-permeable fixed bed reactor or a fluidized bed reaction vessel with a quartz window.
The invention is in principle not particularly limited as to the specific type of carbon-containing compound, preferably comprising one or more of methane, ethane and ethylene, which can be selected and adapted by the person skilled in the art according to the actual application, the product requirements and the specific application, in order to ensure the high efficiency and continuity of the catalytic conversion process. In the present invention the carbon-containing compound product is predominantly methane.
The invention is a complete and detailed integral technical scheme, and the method for catalytic conversion of carbon dioxide specifically comprises the following steps:
in the reaction vessel, a composite catalyst based on a plasmon material is used, the conversion of raw materials containing carbon dioxide into valuable carbon-containing chemicals is efficiently catalyzed under infrared irradiation, and the efficiency and selectivity of the method for converting carbon dioxide molecules can be further improved by heating, pressurizing, applying voltage and the like.
Further, the invention provides a preparation method of the composite catalyst of the plasmon material, which is a complete and refined integral technical scheme, and specifically comprises the following steps:
preparation of the catalyst
The composite catalyst (gold nanopyramid coated by copper palladium alloy) based on the plasmon material is specifically prepared as follows:
the hexadecyl trimethyl ammonium chloride solution and the citric acid solution are taken, and the chloroauric acid tetrahydrate solution is added to be stirred vigorously. Then sodium borohydride solution in ice water is added rapidly and stirring is continued vigorously, the solution turns brown rapidly from light yellow. And then the prepared seed crystal solution is aged for later use.
In the synthesis of the gold nanocone, firstly, a hexadecyl trimethyl ammonium bromide solution is taken and stirred, and then a chloroauric acid tetrahydrate solution and a silver nitrate solution are added. The ascorbic acid solution was then added and the previously prepared seed solution was added immediately.
After 1 hour of reaction, potassium chloropalladite, copper chloride and ascorbic acid solution were added in this order, and the reaction was continued for 2 hours. The catalyst is washed clean with water and redispersed in deionized water or supported on a silica support. Thus, the gold nanocone coated with the copper-palladium alloy is obtained, and is detected by an inductively coupled plasma atomic emission spectrometer, wherein the mass ratio of copper to palladium is about 0.3: 1.
based on the same process, only the amount of potassium chloropalladite and copper chloride used is changed correspondingly, so that the mass ratio of copper to palladium is (0.04-0.3): 1 of gold nanocones coated with a copper-palladium alloy.
The steps of the invention provide an infrared-driven carbon dioxide catalytic conversion method. The method provided by the invention can utilize infrared rays with most abundant energy storage in sunlight, has cheap and easily-obtained raw materials, mild reaction conditions and high product selectivity, and can further improve the efficiency and selectivity of converting carbon dioxide molecules by heating, pressurizing, applying voltage and other methods. The invention directly uses clean and abundant solar energy, is clean and economic, can utilize the infrared ray which is most abundant in energy storage in sunlight, and greatly improves the conversion efficiency of the solar energy to the chemical energy; in addition, the carbon dioxide is used as a main raw material to synthesize a series of necessary chemicals, so that the carbon dioxide in the atmosphere can be fixed, and the carbon dioxide can be directionally catalytically converted with high efficiency and high selectivity by using a reasonable composite catalyst based on the plasmon material.
The invention utilizes the plasmon effect of the metal nano material to effectively absorb infrared rays and generate electromagnetic near field enhancement and thermal electron effect to drive chemical reaction; the material with the carbon dioxide catalytic conversion performance is used as an active site to play a role in adsorbing and activating carbon dioxide molecules, so that the high-efficiency conversion from solar energy to chemical energy under the irradiation of infrared rays is realized, and furthermore, the invention realizes higher conversion efficiency (methane yield) and better cycle stability particularly under the drive of multi-band infrared rays. The method provided by the invention utilizes renewable clean energy, namely solar energy, to directionally convert carbon dioxide in the atmosphere into chemical raw materials and fuels, simultaneously realizes the utilization of the clean energy and the fixation of the carbon dioxide in the atmosphere, and has important significance for promoting the strategic target of realizing carbon neutralization in China.
Experimental results show that the yield of methane can reach 14.4 mu mol g at most by adopting the plasmon material composite material catalyst in the method for driving carbon dioxide catalytic conversion by infrared rays-1·h-1。
For further illustration of the present invention, the method for catalytic conversion of carbon dioxide provided by the present invention is described in detail with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific operation procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Catalyst preparation
The composite catalyst (gold nanopyramid coated by copper palladium alloy) based on the plasmon material used in the invention is prepared as follows:
a20 mL glass vial was charged with 5mL of a 0.1mol/L cetyltrimethylammonium chloride solution and 5mL of a 0.01mol/L citric acid solution, and was stirred vigorously by adding 250. mu.L of a chloroauric acid tetrahydrate solution (0.01 mol/L). Then 300. mu.L of sodium borohydride solution (0.1mol/L) in ice water was added rapidly using a pipette and stirring vigorously is continued for 2min, the solution quickly turning brown from light yellow. The seed solution was then aged at 80 ℃ for 60min for later use. In the synthesis of gold nanopyramids, 95mL of 0.1mol/L cetyltrimethylammonium bromide was first taken in a 200mL Erlenmeyer flask and stirred at room temperature. Next, 5mL of chloroauric acid tetrahydrate solution (0.01mol/L) and 1mL of silver nitrate solution (0.01mol/L) were added. Subsequently, 800. mu.L of 0.1mol/L ascorbic acid solution was added, and 200. mu.L of the previously prepared seed solution was immediately added. After 1 hour of the reaction, 1mL of potassium chloropalladite (0.01mol/L), 1mL of copper chloride (0.01mmol/L) and 2.4mL of an ascorbic acid solution (0.1mol/L) were added in this order, and the reaction was continued for 2 hours. The catalyst is cleaned with deionized water and redispersed in deionized water or supported on a silica support. Thus, the gold nanocone coated with the copper-palladium alloy is obtained, and is detected by an inductively coupled plasma atomic emission spectrometer, wherein the mass ratio of copper to palladium is about 0.3: 1.
based on the same procedure as described above, except that the amounts of potassium chloropalladite and copper chloride used were varied accordingly, a copper-to-palladium mass ratio of 0.04 to 0.3: 1 of gold nanocones coated with a copper-palladium alloy.
Based on the same procedures, the gold nanocones coated by the copper-platinum alloy or the copper-rhodium alloy can be obtained by correspondingly changing the used potassium chloropalladite into chloroplatinic acid or rhodium chloride.
Based on the same procedure, the obtained gold nanopyramid coated by the copper-palladium alloy is re-dispersed into 10mL of N, N-dimethylformamide, and 7mg of zirconium chloride and 6mg of 2, 5-dimethyl terephthalic acid are added into a hydrothermal reaction kettle, and the temperature is kept for 12h at 120 ℃, so that the UiO-66(Zr) and the gold nanopyramid coated by the copper-palladium alloy can be obtained.
Example 1
In a quartz tube reaction vessel, 1mg of a copper-palladium alloy-coated gold nanocone (copper-palladium mass ratio of about 0.3: 1) catalyst was dispersed in a carbon dioxide-saturated aqueous solution at 400mW/cm2The reaction was stirred for 3 hours under full spectrum illumination from a xenon lamp.
After the reaction was complete, a gas sample was taken and the product distribution was determined by gas chromatography. The gas chromatography model is Agilent 7890B, argon carrier gas, a flame ionization detector, a capillary column, and the column temperature is 60 ℃. The product was methane as determined by gas chromatography, with the methane being produced at a rate of about 14.0. mu. mol g-1·h-1The selectivity was about 100%.
Referring to fig. 1, fig. 1 is a gas chromatogram of methane generated by catalytic conversion of carbon dioxide in example 1 of the present invention.
As can be seen from fig. 1, under the conditions of example 1, a high efficiency directional catalytic conversion of carbon dioxide can be achieved.
Example 2
The specific reaction process andthe detection method was the same as in example 1 except that 100mW/cm was used2The LED monochromatic light source with the wavelength of 850nm replaces a xenon lamp light source. It was found that the methane generation rate was about 7.4. mu. mol. g-1·h-1The selectivity approaches 100%.
Example 3
The specific reaction process and detection method are the same as those in example 1, except that a cut-off filter of 810nm is used in combination with a xenon lamp, so that the wavelength of the emergent light is larger than 810 nm. It was found that the methane generation rate was about 7.5. mu. mol. g-1·h-1The selectivity approaches 100%.
Example 4
The specific reaction process and detection method are the same as those in example 3, except that 100mW/cm is used simultaneously based on the specific reaction process and detection method2The LED monochromatic light source with the wavelength of 850nm irradiates the catalytic reaction system. It was found that the methane production rate was about 11.8. mu. mol. g-1·h-1The selectivity approaches 100%.
Example 5
The specific reaction process and detection method are the same as those in example 1, except that the reaction time is prolonged to 24 hours. It was found that the methane formation rate was about 12. mu. mol. g-1·h-1The selectivity was 98%, and the other products were mainly ethane and ethylene.
Example 6
The specific reaction process and detection method are the same as those of example 1, except that the copper-palladium mass ratio is about 0.16: 1 gold nanometer cone coated by copper palladium alloy is used as a catalyst. The methane formation rate was determined to be about 8. mu. mol g-1·h-1The selectivity approaches 100%.
Example 7
The specific reaction process and detection method were the same as in example 3, except that the copper-platinum alloy-coated gold nanocones were used as the catalyst instead of the copper-palladium alloy-coated gold nanocones. It was found that the methane generation rate was about 1.4. mu. mol. g-1·h-1The selectivity approaches 100%.
Example 8
Specific reaction procedure and detection method and example 3The same is true except that copper rhodium alloy coated gold nanopyramids are used as catalysts instead of copper palladium alloy coated gold nanopyramids. It was found that the methane production rate was about 1.6. mu. mol. g-1·h-1The selectivity approaches 100%.
Example 9
The specific reaction process and detection method are the same as in example 3, except that the copper-palladium mass ratio is about 0.04: 1 gold nanometer cone coated by copper palladium alloy is used as a catalyst. It was found that the methane generation rate was about 2.0. mu. mol. g-1·h-1The selectivity approaches 100%.
Example 10
The specific reaction process and detection method were the same as in example 3, except that the copper-palladium alloy-coated gold nanopyramids were replaced with the UiO-66(Zr) and copper-palladium alloy-coated gold nanopyramids as catalysts. It was found that the methane generation rate was about 8.0. mu. mol. g-1·h-1The selectivity approaches 100%.
Example 11
The specific reaction process and detection method were the same as in example 1, except that a copper-palladium alloy-coated gold nanocone (copper-palladium mass ratio of about 0.3: 1) catalyst was supported on a silica carrier. It was found that the methane formation rate was about 4. mu. mol. g-1·h-1The selectivity approaches 100%.
Example 12
The specific reaction process and detection method are the same as those in example 1, except that carbon dioxide and water vapor are used as raw material gases. The methane formation rate was determined to be about 6. mu. mol g-1·h-1The selectivity approaches 100%.
Example 13
The specific reaction process and detection method are the same as in example 1, except that carbon dioxide and hydrogen are used as raw materials. The methane formation rate was determined to be about 6. mu. mol g-1·h-1The selectivity approaches 100%.
Example 14
The specific reaction process and detection method are the same as those in example 1, except that the copper-palladium alloy-coated gold nanocone (copper-palladium mass ratio) is usedAbout 0.3: 1) the catalyst was coated on a glassy carbon electrode and a bias of 0.6V was applied. It was found that the methane production rate was about 5000. mu. mol. g-1·h-1The selectivity approaches 60%.
Example 15
The specific reaction process and the detection method were the same as in example 4, except that in example 15, the catalyst after the catalytic reaction was collected again and subjected to the carbon dioxide reduction reaction, and the reaction was repeated 10 times.
The present invention calculates the average methane yield of the catalyst in example 15 for 10 reuses of the catalyst for carbon dioxide reduction.
Referring to fig. 2, fig. 2 is a graph showing the average methane yield of carbon dioxide reduction reaction performed in 10 times of repeated use of the catalyst in example 15 of the present invention as a function of the number of cycles.
As can be seen from fig. 2, the yield of methane was stable when the carbon dioxide reduction reaction was performed 10 times with the catalyst repeatedly used. The stability of the gold nanocone catalyst coated by the copper-palladium alloy in the actual reaction is good.
While the present invention has been described in detail with respect to a method for catalytic conversion of carbon dioxide by infrared light, the principles and embodiments of the present invention are described herein using specific examples, which are included to assist in understanding the method and its core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A method for catalytic conversion of carbon dioxide, comprising the steps of:
under the action of a plasmon material composite material catalyst and under the drive of infrared rays, a raw material containing carbon dioxide is subjected to catalytic conversion reaction to obtain a carbon-containing compound.
2. The method according to claim 1, wherein the plasmonic material composite comprises a plasmonic material and a material having carbon dioxide catalytic conversion properties;
the plasmonic material comprises a plasmonic material having light absorption properties in the infrared wavelength range;
the material with the carbon dioxide catalytic conversion performance comprises one or more of a metal material, an alloy material, a semiconductor and a metal organic framework material.
3. The method of claim 2, wherein the plasmonic material comprises a plasmonic metallic material;
the morphology structure of the composite catalyst comprises one or more of a full-coating core-shell structure, a porous core-shell structure, a main body-satellite structure, a heterostructure and a layered stack;
the metal material comprises palladium, copper, platinum, rhodium, nickel, iron, cobalt or zinc;
the alloy material comprises two or more of palladium, copper, platinum, rhodium, nickel, iron, cobalt and zinc;
the semiconductor material comprises one or more of indium hydroxide, indium oxide and titanium dioxide;
the metal organic framework material comprises MIL-125(Ti), UiO-66(Zr), MIL-101(Fe) and MIL-125-NH2And PCN-222.
4. The method of claim 1, wherein the plasmonic material comprises one or more of gold, silver and copper;
the appearance of the plasmon material comprises one or more of nanospheres, nanocubes, nanosheets, nanocones and nanorods;
the composite catalyst comprises a physically mixed composite catalyst.
5. The method according to claim 1, wherein the infrared ray has a wavelength of 750 to 2500 nm;
the infrared rays comprise near infrared rays;
the infrared ray includes 2 or more wavelengths of infrared rays.
6. The method according to claim 1, wherein the plasmonic material composite catalyst may be supported on a catalyst support;
the catalyst carrier comprises one or more of a carbon carrier, a silicon dioxide carrier, an aluminum oxide carrier, a ceramic carrier, a molecular sieve, silicon carbide, kaolin, a fluorine polymer and quartz glass;
the catalyst support comprises a gel support;
the load capacity of the load is 1-50%.
7. The method according to claim 1, wherein the generation source of the infrared ray includes one or more of a xenon lamp, an LED lamp, a tungsten lamp, and an infrared lamp;
the intensity of the infrared ray is 5-10000 mW/cm2。
8. The method according to claim 1, wherein the carbon dioxide-containing feedstock comprises an aqueous solution of carbon dioxide and/or a mixed gas containing carbon dioxide;
the mixed gas also comprises one or more of water vapor, hydrogen, methane and ammonia gas;
the conditions for the catalytic conversion reaction further include one or more of heat, pressure, and applied voltage.
9. The method according to claim 8, wherein the heating temperature is 0 to 800%οC；
The pressurizing pressure is 0.1-10 Mpa;
the bias range of the applied voltage is 0.05 to 3V.
10. The method of claim 1, wherein the catalytic conversion comprises catalytic reduction;
the reaction vessel for catalytic conversion reaction comprises one or more of a light-permeable fixed bed reactor with a quartz or glass window, a light-permeable fluidized bed reaction vessel with a quartz or glass window, a fixed bed reactor integrated with an internal light source and a fluidized bed reaction vessel integrated with an internal light source.
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