CN114984997B - Three-dimensional porous carbon nitride based Zn monatomic photocatalyst, preparation method and application - Google Patents
Three-dimensional porous carbon nitride based Zn monatomic photocatalyst, preparation method and application Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 67
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 26
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 25
- 239000011667 zinc carbonate Substances 0.000 claims description 25
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 25
- 235000004416 zinc carbonate Nutrition 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 239000011261 inert gas Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 229920000877 Melamine resin Polymers 0.000 claims description 19
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
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- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 abstract description 7
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 238000007146 photocatalysis Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 241001530209 Swertia Species 0.000 description 1
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
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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
-
- B01J35/39—
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- B01J35/615—
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a three-dimensional porous carbon nitride based Zn monatomic photocatalyst, a preparation method and application thereof 2+ In the liquid phase environment Zn 2+ Fully coordinating with pyridine nitrogen in melem to form a large amount of Zn-N bonds, then filtering and washing until the supernatant is neutral, calcining for 2-4 h under inert atmosphere at the calcining temperature of 500-600 ℃ after freeze drying, and releasing a large amount of CO in the whole preparation process 2 And NH 3 Meanwhile, znO can serve as a hard template, and the finally prepared three-dimensional porous carbon nitride based Zn monatomic photocatalyst has the advantages of large specific surface area, excellent photocatalytic decomposition water performance, good dispersibility and stable storage. The whole preparation process is simple to operate, strong in controllability, good in repeatability, low in raw material cost, wide in source, green, safe and environment-friendly, and suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of monoatomic materials, and particularly relates to a three-dimensional porous carbon nitride-based Zn monoatomic photocatalyst, and a preparation method and application thereof.
Background
The metal monatomic catalyst has excellent catalytic performance and nearly 100% atom utilization rate, and is continuously concerned about and widely researched in multiple catalytic fields (thermal catalysis, electrocatalysis, photocatalysis and the like). The single atoms have extremely small physical dimensions and thus their surface energy is extremely large. Therefore, a carrier material capable of chemically interacting with the metal monoatomic atoms to effectively disperse the metal monoatomic atoms is indispensable, which not only can ensure the stability of the metal monoatomic atoms, but also can suppress the agglomeration of the metal monoatomic atoms. The Polymer Carbon Nitride (PCN) has a rich pyridine nitrogen atom in its tris-s-triazine structural unit, which carries a large number of unpaired electrons, so that PCN can provide sufficient anchoring sites for metal atoms by forming strong N-metal bonds, and thus PCN is considered as an ideal metal monoatomic carrier material. Concomitantly, the physicochemical properties of PCN also change with the introduction of metal single atoms. Therefore, due to the electronic structure of good regulation and control of PCN and the excellent catalytic performance of the metal monatomic active site, charge transmission and surface reaction kinetics in the PCN-based metal monatomic catalyst are greatly accelerated, so that the PCN-based metal monatomic catalyst has great potential in the field of solar photocatalytic water decomposition. Until now, various PCN-based metal monatomic photocatalysts have been successfully developed, such as Pt/PCN (Angew. Chem. Int. Ed.2020,59, 6224-6229), pd/PCN (ACS Catal.2022,12, 5077-5093), ag/PCN (Angew. Chem. Int. Ed.2020,59, 23112-23116), co/PCN (Sci. Bull.2022,67, 520-528), and the like. All of these monatomic photocatalysts achieve a certain water decomposition capacity. The most studied noble metals of the genus swertia are monatomic, but the preparation cost is often high. Research on non-noble metal monatomic has focused mainly on Co, and relatively little has been done on other PCN-based metal monatomic photocatalysts used for photocatalytic water splitting. In order to realize efficient solar-hydrogen energy conversion early, more novel metal monatomic photocatalysts are urgently needed to be developed so as to provide more effective theoretical support for the design of photocatalysts.
Disclosure of Invention
The invention aims to provide a three-dimensional porous carbon nitride-based Zn monatomic photocatalyst, a preparation method and application thereof, so as to overcome the defects of the prior art.
A preparation method of a three-dimensional porous carbon nitride based Zn monatomic photocatalyst comprises the following steps:
s1, uniformly mixing zinc carbonate and melamine according to a mass ratio (0.5-2) to 1 to obtain a mixture A;
s2, calcining the mixture A in an inert gas atmosphere to obtain a solid B;
s3, placing the solid B in a hydrochloric acid aqueous solution, stirring for 6-12 h, and then sequentially filtering, washing, freezing and drying to obtain a solid C;
and S4, calcining the solid C in an inert gas atmosphere to obtain the target product three-dimensional porous carbon nitride based Zn monatomic photocatalyst.
Preferably, in S1, zinc carbonate and melamine are placed in a mortar at a mass ratio (0.5-2): 1, and are mixed by grinding and stirring for 10-30 min to obtain a uniform mixture A.
Preferably, the mixture A is heated from room temperature to the calcination temperature of 350-450 ℃ at the heating rate of 5-10 ℃/min under the inert gas atmosphere, then calcined at the calcination temperature of 350-450 ℃ for 2-4 h, and then naturally cooled to room temperature to obtain the solid B.
Preferably, the hydrochloric acid aqueous solution used in S3 has a concentration of 0.5 to 1.5mol/L, and H is added to the hydrochloric acid aqueous solution + The molar weight of the zinc carbonate is 2.1 to 3 times of the molar weight of the zinc carbonate used in S1.
Preferably, the stirring speed is 500-1000 r/min, the stirring time is 6-12 h, the filtering water is washed until the supernatant is neutral, and the freeze drying time is 12-24 h, so that the solid C can be obtained.
Preferably, the solid C is heated to the calcination temperature of 500-600 ℃ from the room temperature at the heating rate of 5-10 ℃/min under the inert gas atmosphere, then calcined at the calcination temperature of 500-600 ℃ for 2-4 h, and then naturally cooled to the room temperature, so that the target product three-dimensional porous carbon nitride based Zn monatomic photocatalyst can be obtained.
Preferably, the inert gas is nitrogen or argon.
The invention provides a three-dimensional porous carbon nitride based Zn monatomic photocatalyst obtained by a preparation method of the three-dimensional porous carbon nitride based Zn monatomic photocatalyst.
The invention provides an application of a three-dimensional porous carbon nitride based Zn monatomic photocatalyst in photocatalytic water decomposition, artificial photosynthesis, organic pollutant degradation or gas oxidation/reduction.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to aA preparation method of a three-dimensional porous carbon nitride based Zn monatomic photocatalyst comprises the steps of taking melamine as a precursor of carbon nitride, taking zinc carbonate as a Zn source and a template, uniformly mixing the zinc carbonate and the melamine according to a mass ratio of (0.5-2): 1, calcining for 2-4 hours at a calcining temperature of 350-450 ℃ in an inert gas atmosphere to obtain a mixture of zinc oxide and melem monomer, and then stirring in an excessive hydrochloric acid aqueous solution, wherein at the moment, all zinc oxide can be dissolved to generate Zn 2+ In the liquid phase environment Zn 2+ Fully coordinating with pyridine nitrogen in melem to form a large amount of Zn-N bonds, then filtering and washing until the supernatant is neutral, and calcining for 2-4 hours at the calcining temperature of 500-600 ℃ in an inert atmosphere after freeze drying to obtain the target product, namely the three-dimensional porous carbon nitride based Zn monatomic photocatalyst. It is worth mentioning that a large amount of CO is released during the preparation process 2 And NH 3 Meanwhile, znO can serve as a hard template, and the finally prepared three-dimensional porous carbon nitride based Zn monatomic photocatalyst has a large specific surface area, so that abundant surface active sites are provided for catalytic reaction, and higher reaction activity is facilitated. The whole preparation process is simple to operate, strong in controllability, good in repeatability, low in raw material cost, wide in source, green, safe and environment-friendly, and suitable for large-scale production.
Further, in the obtained three-dimensional porous polymer carbon nitride based Zn monoatomic photocatalyst, zn monoatomic is Zn-N 6 The coordination structure exists stably.
Furthermore, the mass percent of Zn in the three-dimensional porous carbon nitride based Zn monatomic photocatalyst obtained by the method is 2.09-4.79%, and the maximum specific surface area of the three-dimensional porous carbon nitride based Zn monatomic photocatalyst can reach 224.99m 2 g -1 The highest photocatalytic decomposition rate of hydrogen in water can reach 1172.9 mu mol h -1 g -1 。
The three-dimensional porous carbon nitride based Zn monoatomic photocatalyst is successfully prepared by utilizing a safe and easy-to-operate method of intermediate coordination and then polymerization, the obtained monoatomic photocatalyst is novel in structure, excellent in photocatalytic water decomposition performance and good in dispersibility, can be stably stored, does not contain organic solvent in the reaction process, can avoid environmental pollution to a certain extent, and can be widely applied to the fields of photocatalytic water decomposition, artificial photosynthesis, organic pollutant degradation, gas oxidation/reduction and the like due to the non-toxic characteristic of carbon nitride.
Drawings
Fig. 1 is a data diagram of a three-dimensional porous carbon nitride based Zn monatomic photocatalyst prepared in example 1 of the present invention, wherein fig. 1a is a spherical aberration electron micrograph; FIG. 1b is synchrotron radiation R spatial data; FIG. 1c is R-space fit data; FIG. 1d is a scanning electron micrograph; figure 1e shows nitrogen adsorption-desorption data; FIG. 1f shows data of hydrogen production by visible light photocatalytic decomposition.
Fig. 2 is a data diagram of a three-dimensional porous carbon nitride-based Zn monatomic photocatalyst prepared in example 2 of the present invention, in which fig. 2a is nitrogen adsorption-desorption data; FIG. 2b shows data of hydrogen production by visible light photocatalytic decomposition.
Fig. 3 is a data diagram of a three-dimensional porous carbon nitride based Zn monatomic photocatalyst prepared in example 3 of the present invention, wherein fig. 3a is nitrogen adsorption-desorption data; FIG. 3b shows data of hydrogen production by visible light photocatalytic decomposition.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a preparation method of a three-dimensional porous carbon nitride based Zn monatomic photocatalyst, which comprises the following steps:
step 1), uniformly mixing zinc carbonate and melamine according to a mass ratio (0.5-2) to 1 to obtain a mixture A;
specifically, a mortar is used as a carrier of zinc carbonate and melamine, the zinc carbonate and the melamine are placed in the mortar according to the mass ratio (0.5-2): 1, and a uniform mixture A is obtained by grinding, stirring and mixing for 10-30 min;
step 2), calcining the mixture A in an inert gas atmosphere to obtain a solid B;
specifically, the mixture A is placed into a tubular furnace along with a crucible, inert gas is introduced into the tubular furnace to serve as protective gas, the tubular furnace is heated from room temperature to the calcination temperature of 350-450 ℃ at the heating rate of 5-10 ℃/min, then the mixture is calcined at the calcination temperature of 350-450 ℃ for 2-4 hours, and then the mixture is naturally cooled to the room temperature to obtain a solid B; the inert gas is nitrogen or argon.
Step 3), placing the solid B in a hydrochloric acid aqueous solution, stirring for 6-12 h, and then sequentially carrying out filtration, washing, freezing and drying to obtain a solid C;
adopting hydrochloric acid aqueous solution with the concentration of 0.5-1.5 mol/L and H + The molar weight is 2.1 to 3 times of the molar weight of the zinc carbonate used in the step 1), the stirring speed is 500 to 1000r/min, the stirring time is 6 to 12 hours, the filtering water is washed until the supernatant is neutral, and the freeze drying time is 12 to 24 hours;
and 4) calcining the solid C in an inert gas atmosphere to obtain the target product three-dimensional porous carbon nitride based Zn monatomic photocatalyst.
And putting the solid C into a crucible, putting the solid C into a tubular furnace, introducing inert gas into the tubular furnace as protective gas, heating the tubular furnace from room temperature to the calcination temperature of 500-600 ℃ at the heating rate of 5-10 ℃/min, calcining for 2-4 h at the calcination temperature of 500-600 ℃, and naturally cooling to room temperature to obtain the target product, namely the three-dimensional porous carbon nitride-based Zn monatomic photocatalyst.
The preparation method of the three-dimensional porous carbon nitride based Zn monatomic photocatalyst provided by the invention is characterized in that the three-dimensional porous carbon nitride based Zn monatomic photocatalyst is prepared by a safe and easy-to-operate method of intermediate coordination and then polymerization, the obtained monatomic catalyst has a novel structure, excellent photocatalytic water decomposition performance, good dispersibility, stable storage, short reaction time in the whole preparation process, low reaction temperature, simple operation, strong controllability, good repeatability, cheap and wide raw materials, greenness, safety and environmental friendliness, and is beneficial to large-scale preparation and practical application. The invention enriches the research field of the monatomic photocatalyst and accumulates valuable experience for the development of the high-efficiency photocatalyst.
The technical scheme of the invention comprises anchoring Zn monoatomic atoms on three-dimensional porous carbon nitride in situ, and soaking Zn by using hydrochloric acid aqueous solution in the polymerization intermediate stage of the carbon nitride 2+ Fully coordinating with pyridine nitrogen, simultaneously realizing a three-dimensional porous structure, and combining with filtration, washing, freeze drying and calcining to obtain the three-dimensional porous carbon nitride based Zn monatomic photocatalyst.
The preferable specific technical scheme of the invention specifically comprises the following reaction steps:
step 1), uniformly mixing zinc carbonate and melamine according to a mass ratio (0.5-2) to 1 to obtain a mixture A;
specifically, zinc carbonate and melamine are placed in a mortar according to the mass ratio (0.5-2) of 1, and are ground, stirred and mixed for 10-30 min to obtain a uniform mixture A.
Step 2), calcining the mixture A in an inert gas atmosphere to obtain a solid B;
specifically, the mixture A is placed into a crucible and then is placed into a tubular furnace, nitrogen or argon is introduced into the tubular furnace as protective gas, the tubular furnace is heated from room temperature to the calcination temperature of 350-450 ℃ at the heating rate of 5-10 ℃/min, then is calcined at the calcination temperature of 350-450 ℃ for 2-4 h, and then is naturally cooled to room temperature, so that the solid B is obtained.
Step 3), placing the solid B into a hydrochloric acid aqueous solution, stirring for 6-12 h, and then sequentially carrying out filtration, washing and freeze drying to obtain a solid C;
specifically, the concentration of the hydrochloric acid aqueous solution used is 0.5 to 1.5mol/L and H + The molar weight is 2.1 to 3 times of the molar weight of the zinc carbonate used in the step 1), the stirring speed is 500 to 1000r/min, the stirring time is 6 to 12 hours, the filtering water is washed until the supernatant is neutral, and the freeze drying time is 12 to 24 hours.
And 4) calcining the solid C in an inert gas atmosphere to obtain the target product three-dimensional porous carbon nitride based Zn monatomic photocatalyst.
Specifically, the solid C is placed into a crucible and then is placed into a tubular furnace, nitrogen or argon is introduced into the tubular furnace to serve as protective gas, the tubular furnace is heated from room temperature to the calcination temperature of 500-600 ℃ at the heating rate of 5-10 ℃/min, then is calcined at the calcination temperature of 500-600 ℃ for 2-4 hours, and then is naturally cooled to the room temperature, so that the target product three-dimensional porous carbon nitride based Zn monatomic photocatalyst is obtained. The mass percent of Zn in the obtained three-dimensional porous carbon nitride based Zn monatomic photocatalyst is 2.09-4.79%, and the maximum specific surface area can reach 224.99m 2 g -1 The highest photocatalytic decomposition rate of hydrogen in water can reach 1172.9 mu mol h -1 g -1 。
The zinc carbonate and the melamine are uniformly mixed according to the mass ratio of (0.5-2) 1, then are calcined for 2-4 h at the calcining temperature of 350-450 ℃ in the inert gas atmosphere to obtain the mixture of the zinc oxide and the melem monomer, and then are placed in an excessive hydrochloric acid aqueous solution to be stirred, at the moment, all the zinc oxide is dissolved to generate Zn 2+ In the liquid phase environment Zn 2+ Will fully coordinate with pyridine nitrogen in melem to form a large amount of Zn-N bonds, then is filtered and washed until the supernatant is neutral, is calcined for 2 to 4 hours under inert atmosphere at the calcination temperature of 500 to 600 ℃ after being frozen and dried, and releases a large amount of CO in the whole preparation process 2 And NH 3 Meanwhile, znO can serve as a hard template, and the finally prepared three-dimensional porous carbon nitride based Zn monatomic photocatalyst has the advantages of large specific surface area, excellent photocatalytic decomposition water performance, good dispersibility and stable storage. The whole preparation process is simple to operate, strong in controllability, good in repeatability, low in raw material price, wide in source, green, safe and environment-friendly, and suitable for large-scale production.
As shown in FIG. 1, FIG. 1a is a spherical aberration electron micrograph of the material, FIG. 1b is synchrotron radiation R space data, FIG. 1c is R space fitting data, and it can be seen from FIGS. 1a-c that Zn monoatomic atoms are successfully anchored to carbon nitride and Zn-N is used 6 The coordination structure exists stably; FIG. 1d is a scanning electron micrograph, FIG. 1e is nitrogen adsorption-desorption data, and it can be known from FIG. 1d, e that the obtained carbon nitride based Zn monatomic material has a three-dimensional porous structure; FIG. 1f shows visible light photocatalytic decomposition of waterAnd hydrogen production data show that the obtained three-dimensional porous carbon nitride-based Zn monatomic material has excellent hydrogen production performance through visible light photocatalytic water decomposition, as can be known from FIG. 1 f.
The technical solutions of the present invention will be further described in detail below with reference to the accompanying drawings and several preferred embodiments of the present invention.
Example 1
1) 4g of zinc carbonate and 2g of melamine were ground, stirred and mixed for 30min to obtain a homogeneous mixture A.
2) Putting the mixture A into a crucible, putting the mixture A into a tubular furnace, introducing argon gas into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 400 ℃ at the heating rate of 5 ℃/min, calcining the mixture at the temperature of 400 ℃ for 2 hours, and naturally cooling the mixture to the room temperature to obtain a solid B.
3) And putting the solid B into a 1.0mol/L hydrochloric acid aqueous solution (80 mL), stirring at the rotating speed of 600r/min for 12 hours, then filtering and washing until the supernatant is neutral, and freeze-drying for 24 hours to obtain a solid C.
4) Putting the solid C into a crucible, putting the solid C into a tubular furnace, introducing argon gas into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 520 ℃ at the heating rate of 5 ℃/min, calcining at 520 ℃ for 4h, and naturally cooling to room temperature to obtain the target product, namely the three-dimensional porous carbon nitride-based Zn monatomic photocatalyst. The mass percent of Zn in the obtained three-dimensional porous carbon nitride based Zn monatomic photocatalyst is 4.79%, and the property parameters are shown in figure 1.
Example 2
1) 2g of zinc carbonate and 2g of melamine are ground, stirred and mixed for 30min to obtain a uniform mixture A.
2) Putting the mixture A into a crucible, putting the mixture A into a tubular furnace, introducing argon gas into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 400 ℃ at the heating rate of 5 ℃/min, calcining the mixture at the temperature of 400 ℃ for 2 hours, and naturally cooling the mixture to the room temperature to obtain a solid B.
3) And putting the solid B into 1.0mol/L hydrochloric acid aqueous solution (40 mL), stirring for 12h at the rotating speed of 600r/min, then filtering and washing until the supernatant is neutral, and freeze-drying for 24h to obtain the solid C.
4) Putting the solid C into a crucible, putting the solid C into a tubular furnace, introducing argon gas into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 520 ℃ at the heating rate of 5 ℃/min, calcining at 520 ℃ for 4h, and naturally cooling to room temperature to obtain the target product, namely the three-dimensional porous carbon nitride-based Zn monatomic photocatalyst. The mass percent of Zn in the obtained three-dimensional porous carbon nitride based Zn monatomic photocatalyst is 3.63%, and the property parameters are shown in figure 2.
Example 3
1) 1g of zinc carbonate and 2g of melamine were ground, stirred and mixed for 30min to obtain a homogeneous mixture A.
2) Putting the mixture A into a crucible, putting the mixture A into a tubular furnace, introducing argon gas into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 400 ℃ at the heating rate of 5 ℃/min, calcining the mixture at the temperature of 400 ℃ for 2 hours, and naturally cooling the mixture to the room temperature to obtain a solid B.
3) And putting the solid B into a 1.0mol/L hydrochloric acid aqueous solution (20 mL), stirring at the rotating speed of 600r/min for 12 hours, then filtering and washing until the supernatant is neutral, and freeze-drying for 24 hours to obtain a solid C.
4) Putting the solid C into a crucible, putting the solid C into a tubular furnace, introducing argon gas into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 520 ℃ at the heating rate of 5 ℃/min, calcining at 520 ℃ for 4h, and naturally cooling to room temperature to obtain the target product, namely the three-dimensional porous carbon nitride-based Zn monatomic photocatalyst. The mass percent of Zn in the obtained three-dimensional porous carbon nitride based Zn monatomic photocatalyst is 2.09%, and the property parameters are shown in figure 3.
Example 4
1) 4g of zinc carbonate and 2g of melamine were ground, stirred and mixed for 15min to obtain a homogeneous mixture A.
2) And putting the mixture A into a crucible, putting the crucible and the mixture A into a tubular furnace, introducing nitrogen into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 400 ℃ at the heating rate of 10 ℃/min, calcining at 400 ℃ for 3 hours, and naturally cooling to room temperature to obtain a solid B.
3) And putting the solid B into a 0.5mol/L hydrochloric acid aqueous solution (160 mL), stirring at the rotating speed of 800r/min for 10 hours, then filtering and washing until the supernatant is neutral, and freeze-drying for 21 hours to obtain a solid C.
4) Putting the solid C into a crucible, putting the solid C into a tubular furnace, introducing nitrogen into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 550 ℃ at the heating rate of 10 ℃/min, calcining at 550 ℃ for 3h, and naturally cooling to room temperature to obtain the target product, namely the three-dimensional porous carbon nitride-based Zn monatomic photocatalyst.
Example 5
1) 2g of zinc carbonate and 2g of melamine were ground, stirred and mixed for 15min to obtain a homogeneous mixture A.
2) And putting the mixture A into a crucible, putting the crucible and the mixture A into a tubular furnace, introducing nitrogen into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 400 ℃ at the heating rate of 10 ℃/min, calcining at 400 ℃ for 3 hours, and naturally cooling to room temperature to obtain a solid B.
3) And placing the solid B into a 0.5mol/L hydrochloric acid aqueous solution (80 mL), stirring at the rotating speed of 800r/min for 10 hours, then filtering and washing until the supernatant is neutral, and freeze-drying for 21 hours to obtain a solid C.
4) Putting the solid C into a crucible, putting the solid C into a tubular furnace, introducing nitrogen into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 550 ℃ at the heating rate of 10 ℃/min, calcining at 550 ℃ for 3h, and naturally cooling to room temperature to obtain the target product, namely the three-dimensional porous carbon nitride based Zn monatomic photocatalyst.
Example 6
1) 1g of zinc carbonate and 2g of melamine are ground, stirred and mixed for 15min to obtain a uniform mixture A.
2) Putting the mixture A into a crucible, putting the mixture A into a tubular furnace, introducing nitrogen into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 400 ℃ at the heating rate of 10 ℃/min, calcining at 400 ℃ for 3h, and naturally cooling to room temperature to obtain a solid B.
3) And putting the solid B into a 0.5mol/L hydrochloric acid aqueous solution (40 mL), stirring at the rotating speed of 800r/min for 10 hours, then filtering and washing until the supernatant is neutral, and freeze-drying for 21 hours to obtain a solid C.
4) Putting the solid C into a crucible, putting the solid C into a tubular furnace, introducing nitrogen into the tubular furnace as protective gas, heating the tubular furnace from room temperature to 550 ℃ at the heating rate of 10 ℃/min, calcining at 550 ℃ for 3h, and naturally cooling to room temperature to obtain the target product, namely the three-dimensional porous carbon nitride based Zn monatomic photocatalyst.
The preparation method comprises the steps of firstly uniformly mixing zinc carbonate and melamine according to the mass ratio of (0.5-2) 1, then calcining the mixture for 2-4 hours at the calcining temperature of 350-450 ℃ in the inert gas atmosphere to obtain a mixture of zinc oxide and melem monomer, and then placing the mixture into an excessive hydrochloric acid aqueous solution for stirring, wherein at the moment, all the zinc oxide is dissolved to generate Zn 2+ In the liquid phase environment Zn 2+ Fully coordinating with pyridine nitrogen in melem to form a large amount of Zn-N bonds, then filtering and washing until the supernatant is neutral, and calcining for 2-4 hours at the calcining temperature of 500-600 ℃ in an inert atmosphere after freeze drying to obtain the target product, namely the three-dimensional porous carbon nitride based Zn monatomic photocatalyst. It is worth mentioning that a large amount of CO is released during this preparation process 2 And NH 3 Meanwhile, znO can serve as a hard template, and the finally prepared three-dimensional porous carbon nitride based Zn monatomic photocatalyst has a large specific surface area, so that abundant surface active sites are provided for catalytic reaction, and higher reaction activity is facilitated. The whole preparation process is simple to operate, strong in controllability, good in repeatability, low in raw material cost, wide in source, green, safe and environment-friendly, and suitable for large-scale production. The three-dimensional porous carbon nitride based Zn monoatomic photocatalyst is successfully prepared by utilizing a safe and easy-to-operate method of intermediate coordination and then polymerization, the obtained monoatomic photocatalyst is novel in structure, excellent in photocatalytic water decomposition performance and good in dispersibility, can be stably stored, does not contain organic solvent in the reaction process, can avoid environmental pollution to a certain extent, and can be widely applied to the fields of photocatalytic water decomposition, artificial photosynthesis, organic pollutant degradation, gas oxidation/reduction and the like due to the non-toxic characteristic of carbon nitride.
FIGS. 1 to 3 are examples of the present inventionThe performance parameter data of the three-dimensional porous carbon nitride based Zn monatomic photocatalyst obtained in examples 1 to 3 show that, in the three-dimensional porous polymer carbon nitride based Zn monatomic photocatalyst obtained by the present invention, zn monatomic is Zn — N 6 The coordination structure exists stably, the mass percentage of Zn is 2.09-4.79%, and the maximum specific surface area can reach 224.99m 2 g -1 The highest rate of hydrogen decomposition of water by photocatalysis can reach 1172.9 mu mol h -1 g -1 。
It should be noted that the above description and the preferred embodiments are not to be construed as limiting the design concept of the present invention. Those skilled in the art can modify the technical idea of the present invention in various forms, and such modifications and changes are understood to fall within the scope of the present invention.
Claims (10)
1. A preparation method of a three-dimensional porous carbon nitride based Zn monatomic photocatalyst is characterized by comprising the following steps:
s1, uniformly mixing zinc carbonate and melamine according to a mass ratio of (0.5-2) to 1 to obtain a mixture A;
s2, calcining the mixture A in an inert gas atmosphere to obtain a solid B;
s3, placing the solid B in a hydrochloric acid aqueous solution, stirring for 6-12 h, and then sequentially carrying out filtration, washing, freezing and drying to obtain a solid C;
and S4, calcining the solid C in an inert gas atmosphere to obtain the target product three-dimensional porous carbon nitride based Zn monatomic photocatalyst.
2. The preparation method of the three-dimensional porous carbon nitride based Zn monatomic photocatalyst according to claim 1, wherein in S1, zinc carbonate and melamine are placed in a mortar according to the mass ratio (0.5-2) to 1, and are mixed by grinding and stirring for 10-30 min to obtain a uniform mixture A.
3. The preparation method of the three-dimensional porous carbon nitride based Zn monatomic photocatalyst according to claim 1, wherein the mixture A is heated from room temperature to the calcination temperature of 350-450 ℃ at the heating rate of 5-10 ℃/min under the inert gas atmosphere, then calcined at the calcination temperature of 350-450 ℃ for 2-4 h, and then naturally cooled to room temperature to obtain the solid B.
4. The method for preparing the three-dimensional porous carbon nitride-based Zn monatomic photocatalyst according to claim 3, wherein the inert gas is nitrogen or argon.
5. The method for preparing a three-dimensional porous carbon nitride based Zn monatomic photocatalyst according to claim 1, wherein the concentration of the hydrochloric acid aqueous solution used in S3 is 0.5 to 1.5mol/L, and H is added to the hydrochloric acid aqueous solution + The molar weight of the zinc carbonate is 2.1 to 3 times of the molar weight of the zinc carbonate used in S1.
6. The preparation method of the three-dimensional porous carbon nitride based Zn monatomic photocatalyst according to claim 5, wherein the stirring speed is 500-1000 r/min, the stirring time is 6-12 h, the filtering water washing is performed until the supernatant is neutral, and the freeze-drying time is 12-24 h, so that the solid C can be obtained.
7. The preparation method of the three-dimensional porous carbon nitride based Zn monatomic photocatalyst according to claim 1, characterized in that the solid C is heated from room temperature to the calcination temperature of 500-600 ℃ at the heating rate of 5-10 ℃/min under the inert gas atmosphere, then calcined at the calcination temperature of 500-600 ℃ for 2-4 hours, and then naturally cooled to room temperature, thus obtaining the target product, namely the three-dimensional porous carbon nitride based Zn monatomic photocatalyst.
8. The method for preparing the three-dimensional porous carbon nitride based Zn monatomic photocatalyst according to claim 7, wherein the inert gas is nitrogen or argon.
9. The three-dimensional porous carbon nitride based Zn monatomic photocatalyst produced according to the method of any one of claims 1 to 8.
10. The use of the three-dimensional porous carbon nitride based Zn monatomic photocatalyst according to claim 9 in photocatalytic water splitting, artificial photosynthesis, organic pollutant degradation, or gas oxidation/reduction.
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