CN115007186A - Carbon nitride based site-specific double-monoatomic catalyst, preparation and application thereof - Google Patents
Carbon nitride based site-specific double-monoatomic catalyst, preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
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- 229920000877 Melamine resin Polymers 0.000 claims description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- HWDGVJUIHRPKFR-UHFFFAOYSA-I copper;trisodium;18-(2-carboxylatoethyl)-20-(carboxylatomethyl)-12-ethenyl-7-ethyl-3,8,13,17-tetramethyl-17,18-dihydroporphyrin-21,23-diide-2-carboxylate Chemical compound [Na+].[Na+].[Na+].[Cu+2].N1=C(C(CC([O-])=O)=C2C(C(C)C(C=C3C(=C(C=C)C(=C4)[N-]3)C)=N2)CCC([O-])=O)C(=C([O-])[O-])C(C)=C1C=C1C(CC)=C(C)C4=N1 HWDGVJUIHRPKFR-UHFFFAOYSA-I 0.000 claims description 11
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C01—INORGANIC CHEMISTRY
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- C01B32/40—Carbon monoxide
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Abstract
The invention provides a carbon nitride based site-specific double-monoatomic catalyst, a preparation method thereof and application thereof in the field of photocatalytic carbon dioxide reduction. Wherein the carbon nitride is a tubular phase-like structure composed of nano sheets, the length is from several micrometers to dozens of micrometers, and the diameter is mainly located at 0.5-3 μm. One metal single atom is a metal with amino or carboxyl complexing ability, and the other metal single atom is a molecular layered structure with a conjugated system. The monoatomic species are exemplified by palladium and copper, and site-specific palladium-copper double monoatomic species are successfully anchored on carbon nitride materials, i.e., palladium sites are located within the carbon nitride planes and copper sites are located between the carbon nitride layers. The synthesis method is simple and easy to operate, and provides possibility for future commercial application. In the photocatalytic carbon dioxide reduction, the site-specific double-monoatomic structure realizes the cascade of specific functions of the two, namely, a palladium site is mainly responsible for adsorption activation and conversion, and a copper site is mainly responsible for transmission of photo-generated electrons.
Description
Technical Field
The invention belongs to the technical field of monoatomic catalysts, and particularly relates to a carbon nitride based site-specific double-monoatomic catalyst, a preparation method thereof and application thereof in the field of photocatalytic carbon dioxide reduction.
Technical Field
Photocatalytic reduction of carbon dioxide (CO) 2 ) The technology is one of the green technologies which have the most application prospect in 'solving the environmental and energy problems simultaneously' and are internationally acknowledged at present. However, the strong chemical inertness of carbon dioxide molecules and the high energy required to dissociate C ═ O bonds, as well as its sluggish kinetic reaction processes, are all serious challenges facing the push of this technology to life and production. Furthermore, due to the nature of the reaction in which multiple electrons participate, the highly selective production of the desired product is still difficult to achieve.
Recently, the construction of highly coordinatively unsaturated, atomically dispersed catalytic materials has enabled the highest atomic utilization efficiency of catalysts, improved activation of substrate molecules and unique optoelectronic properties to be imparted to the materials, and thus, high performance and cost effective CO 2 Promising candidates for photoreduction. However, isolated single atoms have high surface energy and are easily agglomerated into clusters or nanoparticles during the catalytic process, which causes a decrease in catalytic efficiency, thereby affecting the stability of the catalyst material. In addition, most of the developed monatomic photocatalysts use the monometal sites as adsorption sites to regulate and control the material performance, and are lack of exploration and integration of different functional monatomic species, so that the overall efficiency of photocatalytic reduction of carbon dioxide is influenced.
Intensive research into developing a double monometallic site catalyst with a strong support and perfect adjacent coordinating atoms is a promising approach to solve the above problems. Besides, the double-monoatomic catalytic center is constructed, so that the electronic local structure of a catalytic site can be more deeply and accurately adjusted on an atomic/molecular level, a catalytic action mechanism in a multi-intermediate catalytic process can be understood, and a catalytic material with a cascade function can be constructed. However, it is only reported how to accurately construct a site-specific bi-monatomic catalyst to achieve its cascade function.
Disclosure of Invention
In order to solve the above technical problems, a first object of the present invention is to provide a carbon nitride based site-specific double-monatomic catalyst, wherein carbon nitride is used as a carrier, metal monatomic is different atomic species, one is a metal having an amino group or carboxyl group complexing ability, and the other is a molecular layered structure having a conjugated system.
The metal double monoatomic compound is exemplified by palladium (Pd) and copper (Cu), wherein the Pd content is 0-0.6 wt% based on the total weight of the catalyst, and the Cu content is 0-0.4 wt% based on the total weight of the catalyst.
Preferably, the carbon nitride carrier is a tubular bulk phase structure composed of nano sheets, the length of the carbon nitride carrier is different from several micrometers to dozens of micrometers, and the diameter of the carbon nitride carrier is mostly 0.5-3 μm.
Preferably, in the carbon nitride based site-specific double-monatomic catalyst, the Pd monatomic content is 0.4-0.5 wt%, and the Pd monatomic content is 0.2-0.3 wt%.
When the content of Pd is zero, the obtained catalyst is a carbon nitride-based Cu single-atom single-site catalyst; similarly, when the content of Cu is zero, a carbon nitride-based Pd single-atom single-site catalyst is obtained; when the content of the two is zero, the obtained carbon nitride catalytic material is obtained.
The second objective of the present invention is to provide a preparation method of the carbon nitride based site-specific bimetallic catalyst, which is an example of synthesis of a carbon nitride based Pd and Cu bimetallic catalyst, and comprises the following steps:
step S1, preparation of a palladium-complexed carbon nitride precursor (Pd-CN-P):
the melamine, cyanuric acid and sodium tetrachloropalladate are used as raw materials, and the melamine, cyanuric acid and sodium tetrachloropalladate are prepared by a hydrothermal method; the method specifically comprises the following steps: dispersing melamine (with the mass of 0.5g) and a certain amount of sodium tetrachloropalladate (with the mass of 0-1.69 mg) into 35mL of deionized water, dispersing cyanuric acid (with the mass of 0.5g) into another 35mL of deionized water, stirring the melamine and the cyanuric acid at 80 ℃ until the cyanuric acid is dissolved, fully stirring, mixing, stirring at the temperature for 30 minutes, transferring the mixture into a stainless steel autoclave with a polytetrafluoroethylene lining, and reacting at 180 ℃ for 10 hours; and after the reaction is finished, cooling, separating and washing the solid sample, and drying to obtain the Pd-CN-P.
Step S2, Pd-CN-P intercalation sodium copper chlorophyllin:
dispersing 1g of the Pd-CN-P precursor prepared in the step S1 in 100mL of deionized water, adding a certain amount of sodium copper chlorophyllin with the mass of 0.3-1.2 mg, stirring at room temperature for 8-15 hours, then separating, washing, and drying for later use.
Step S3, preparing the carbon nitride based double-monatomic catalyst by thermal calcination:
placing 1g of the precursor material obtained in the step S2 in a porcelain boat, heating to 600 ℃ at a heating rate of 2.5 ℃/min in an inert gas atmosphere, maintaining for 2-4 hours, and then naturally cooling; and after the reaction is finished, collecting a sample, namely the carbon nitride based double-monoatomic catalyst. Inert gases are well known in the art, such as nitrogen, argon, helium.
In the step S1, the palladium salt precursor is not limited to sodium tetrachloropalladate, the introduction of the complexing monoatomic group is not limited to Pd, and other metal salts with complexing ability such as Ru, Ni, and the like are similarly applicable to the method.
In step S2, the copper salt precursor is not limited to sodium copper chlorophyllin, the insertion layer type monoatomic group is not limited to Cu, and other metal coordination compounds having a layered structure are also suitable for use in the method.
The third purpose of the invention is to provide a double-monoatomic catalyst with specific carbon nitride-based sites for photocatalysis of CO 2 Application in the field of reduction; specifically, under the irradiation of visible light (300W xenon lamp), the CO generation rate of the carbon-based palladium-copper nitride double-monatomic catalyst is as high as 9.98 mu mol g -1 h -1 And has a CO selectivity of 93.8%.
Compared with the existing composite functional photocatalytic material, the invention has the following beneficial effects:
(1) the carbon nitride based site-specific double-monoatomic catalyst material realizes the anchoring of double-monoatomic sites of specific sites on a carbon nitride material, and double-monoatomic species can be screened and combined in a large number according to the specific characteristics of the double-monoatomic species. Taking palladium-copper double monatomic catalyst as an example, the site specificity characteristics are as follows: the Pd sites are located in the carbon nitride planes and the Cu sites are located between the carbon nitride layers; in the photocatalysis of carbon dioxide reduction, the site-specific double monoatomic structure realizesThe specific functional cascade of the two, namely the Pd site is mainly responsible for the adsorption, activation and CO conversion 2 The Cu sites are mainly responsible for the transmission of photo-generated electrons between the bulk-phase carbon nitride layers.
(2) In the synthesis method of the carbon nitride based site-specific double-monoatomic catalyst, Pd type monoatomic atoms are anchored by complexing of precursor materials, Cu type monoatomic atoms are obtained by an intercalation method, the improved monoatomic introduction method minimizes the interference of the two types of monoatomic atoms to each other, and finally the heterogeneous double-monoatomic site-specific anchoring is realized by simple thermal calcination treatment. The whole synthesis process has clear thought and clear steps, and the method is simple and easy to operate, is convenient for large-scale production, and provides possibility for future commercial application.
(3) The carbon nitride based site-specific double-monatomic catalyst material disclosed by the invention does not need to add any sacrificial agent or cocatalyst in the carbon dioxide reduction process, so that the economic cost is greatly saved and no pollution is caused in the aspect of environment.
Drawings
Fig. 1 shows an X-ray diffraction pattern (a) and a partially enlarged view (b) of a carbon nitride-based site-specific double monatomic catalyst according to the present invention.
FIG. 2 is a transmission electron microscope image of the carbon nitride based site-specific bi-monatomic catalyst and the precursor thereof of the present invention, wherein a and b correspond to the precursor, and c and d correspond to the synthesized bi-monatomic catalyst (scale for a and c is 2 μm, and scale for b and d is 0.5 μm).
FIG. 3 is a spherical aberration electron micrograph (5 nm on a scale) of the carbon nitride based site-specific double monatomic catalyst of the present invention.
FIG. 4 is a graph comparing the rate of formation of the photocatalytic reduction product of carbon dioxide with a carbon nitride based site-specific bis-monatomic catalyst of the present invention.
FIG. 5 is a graph showing the selectivity of the carbon dioxide photocatalytic reduction product of the carbon nitride based site-specific double monatomic catalyst of the present invention.
FIG. 6 is a carbon dioxide isotope tracing experiment of the carbon nitride based site-specific double monatomic catalyst of the present invention.
The specific description is as follows:
the carbon nitride based site specific double monatomic catalyst of the present invention will be described in detail with reference to the accompanying drawings. Embodiments of the present invention will be described in detail below with reference to the drawings, but the scope of the present invention is not limited to these embodiments.
Example 1:
step S1, preparation of a palladium-complexed carbon nitride precursor (Pd-CN-P):
the melamine, cyanuric acid and sodium tetrachloropalladate are used as raw materials, and the melamine, cyanuric acid and sodium tetrachloropalladate are prepared by a hydrothermal method; the method specifically comprises the following steps: dispersing melamine (with the mass of 0.5g) and a certain amount of sodium tetrachloropalladate (1.69mg) into 35mL of deionized water, dispersing cyanuric acid (with the mass of 0.5g) into another 35mL of deionized water, stirring the melamine and the cyanuric acid at 80 ℃ until the cyanuric acid is dissolved, mixing the melamine and the cyanuric acid after sufficient stirring, stirring the mixture at the temperature for 30 minutes, transferring the mixture into a stainless steel autoclave with a polytetrafluoroethylene lining, and reacting the mixture for 10 hours at 180 ℃; and after the reaction is finished, cooling, separating and washing the solid sample, and drying to obtain the Pd-CN-P.
Step S2, Pd-CN-P intercalation sodium copper chlorophyllin:
dispersing 1g of the Pd-CN-P precursor prepared in the step S1 in 100mL of deionized water, adding a certain amount of sodium copper chlorophyllin with the mass of 1.2mg, stirring at room temperature for 10 hours, then separating, washing and drying for later use.
Step S3, preparing the carbon nitride based double-monatomic catalyst by thermal calcination:
1g of the precursor material obtained in the step S2 is placed in a porcelain boat at N 2 Heating to 600 ℃ at the heating rate of 2.5 ℃/min in the atmosphere, maintaining for 4 hours, and then naturally cooling; and after the reaction is finished, collecting a sample, namely the carbon nitride based double-monoatomic catalyst.
Fig. 1 is an X-ray diffraction pattern and a partial enlarged view thereof of the carbon nitride based site-specific bi-monatomic catalyst of the present invention, and it can be seen that there is no characteristic peak of nanoclusters or nanoparticles of Pd and Cu in the pattern, indicating that the existing form of the metal may be a monatomic form. In addition, the enlarged partial view shows that (002) of the carbon nitride shifts to the left after intercalation, indicating an increase in the interlayer spacing of the carbon nitride material.
FIG. 2 is a transmission electron microscope image of the carbon nitride based site-specific double-monatomic catalyst and the precursor thereof of the present invention, and it can be clearly seen that the precursor material has a tubular structure, the diameter is about 0.6 μm, and the length is greater than 4 μm. After calcination treatment, the structure evolves into a tubular phase-like structure composed of nano-sheets.
FIG. 3 is a spherical aberration electron micrograph of a carbon nitride based site specific bi-monatomic catalyst of the present invention, wherein the bright spots are isolated and dispersed, corresponding to the metallic Pd or Cu monatomic sites, indicating that the atomic scale metals Pd and Cu are successfully anchored to the carbon nitride material.
FIG. 4 is a graph comparing the rate of formation of carbon dioxide photocatalytic reduction products of carbon nitride based site-specific bi-monoatomic catalysts of the present invention. Wherein, CO is the main product, and the generation rate is as high as 9.98 mu mol g -1 h -1 The performance is 3.1,2.0 and 2.3 times of carbon nitride, Pd-CN and Cu-CN respectively.
Fig. 5 is a graph showing the selectivity of the carbon dioxide photocatalytic reduction product of the carbon nitride based site-specific double monatomic catalyst of the present invention, and the CO product selectivity of the synthesized composite material reaches 93.8%.
FIG. 6 is a carbon dioxide isotope tracing experiment of the carbon nitride based site-specific double monatomic catalyst of the present invention. In photocatalytic reduction of CO 2 In the process, corresponding reduction products CO and methane can be detected, which shows that the synthesized carbon nitride based site-specific double-monoatomic catalyst reduces CO in photocatalysis 2 Effective application of (1).
Example 2:
example 2 is different from example 1 in that: the amount of sodium tetrachloropalladate introduced in step S1 was adjusted to 0.85 mg. The remaining procedure was the same as in example 1.
Example 3:
example 3 is different from example 1 in that: the mass of the sodium copper chlorophyllin in step S2 was 0.4mg, and the mixture was stirred at room temperature for 8 hours. The rest of the procedure was the same as in example 1.
Example 4:
example 4 is different from example 1 in that: the mass of the sodium copper chlorophyllin in step S2 was 0.8 mg. The rest of the procedure was the same as in example 1.
Example 5:
example 5 differs from example 1 in that: after the calcination was carried out at 600 ℃ in step S3, the holding time was adjusted to 2 hours. The rest of the procedure was the same as in example 1.
Claims (5)
1. A carbon nitride based site specific bi-monatomic catalyst, characterized in that: carbon nitride is used as a carrier, metal single atoms are different atom types, one metal is a metal with amino or carboxyl complexing ability, and the other metal is a molecular layered structure with a conjugated system, specifically, single atom palladium (Pd) and copper (Cu) are taken as examples, wherein the content of Pd is 0-0.6 wt% based on the total weight of the catalyst, and the content of Cu is 0-0.4 wt% based on the total weight of the catalyst.
2. The bimonoatomic catalyst of claim 1, wherein: the carbon nitride carrier is a tubular bulk phase structure composed of nano sheets, the length of the carbon nitride carrier is different from several micrometers to dozens of micrometers, and the diameter of the carbon nitride carrier is mostly 0.5-3 micrometers.
3. The bimonoatomic catalyst of claim 1, wherein: in the carbon nitride based site-specific double-monatomic catalyst, the Pd monatomic content is preferably 0.4-0.5 wt%, and the Pd monatomic content is preferably 0.2-0.3 wt%.
4. The method for preparing the carbon nitride based site-specific double monatomic catalyst according to claims 1 to 3, which is a synthetic example of the carbon nitride based Pd and Cu double monatomic catalyst, and comprises the following steps:
step S1, preparation of a palladium-complexed carbon nitride precursor (Pd-CN-P):
the melamine, cyanuric acid and sodium tetrachloropalladate are used as raw materials, and the melamine, cyanuric acid and sodium tetrachloropalladate are prepared by a hydrothermal method; the method specifically comprises the following steps: dispersing melamine (with the mass of 0.5g) and a certain amount of sodium tetrachloropalladate (with the mass of 0-1.69 mg) into 35mL of deionized water, dispersing cyanuric acid (with the mass of 0.5g) into another 35mL of deionized water, stirring the melamine and the cyanuric acid at 80 ℃ until the cyanuric acid is dissolved, mixing the melamine and the cyanuric acid after fully stirring, stirring the mixture at the temperature for 30 minutes, transferring the mixture into a stainless steel autoclave with a polytetrafluoroethylene lining, and reacting the mixture at 180 ℃ for 10 hours; and after the reaction is finished, cooling, separating and washing the solid sample, and drying to obtain the Pd-CN-P.
Step S2, Pd-CN-P intercalation sodium copper chlorophyllin:
dispersing 1g of the Pd-CN-P precursor prepared in the step S1 in 100mL of deionized water, adding a certain amount of sodium copper chlorophyllin, wherein the mass of the sodium copper chlorophyllin is 0.3-1.2 mg, stirring at room temperature for 8-15 hours, then separating, washing, and drying for later use.
Step S3, preparing the carbon nitride based double-monatomic catalyst by thermal calcination:
placing 1g of the precursor material obtained in the step S2 in a porcelain boat, heating to 600 ℃ at a heating rate of 2.5 ℃/min in an inert gas atmosphere, maintaining for 2-4 hours, and then naturally cooling; after the reaction is finished, collecting the sample, namely the carbon nitride based double monatomic catalyst, wherein the inert gas is a gas well known in the art, such as nitrogen, argon and helium.
In the step S1, the palladium salt precursor is not limited to sodium tetrachloropalladate, the introduction of the complexing monoatomic group is not limited to Pd, and other metal salts with complexing ability such as Ru, Ni, and the like are similarly applicable to the method.
In step S2, the copper salt precursor is not limited to sodium copper chlorophyllin, the insertion layer type monoatomic group is not limited to Cu, and other metal coordination compounds having a layered structure are also suitable for use in the method.
5. The use of the carbon nitride based site specific bis-monatomic catalyst of claim 1 for the photocatalytic CO 2 Application in the field of reduction.
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