CN115805091B - Preparation method of copper-silver double single-atom photocatalyst - Google Patents
Preparation method of copper-silver double single-atom photocatalyst Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 46
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052802 copper Inorganic materials 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 29
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 6
- 230000002708 enhancing effect Effects 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- 229910052709 silver Inorganic materials 0.000 claims description 15
- 239000004332 silver Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- ALKZAGKDWUSJED-UHFFFAOYSA-N dinuclear copper ion Chemical compound [Cu].[Cu] ALKZAGKDWUSJED-UHFFFAOYSA-N 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention belongs to the technical field of preparation methods of photocatalysts, and discloses a preparation method of a copper-silver diatomic photocatalyst, which comprises the following steps of S1, adding C 3N4 photocatalyst powder loaded with copper diatomic atoms into absolute ethyl alcohol, and uniformly dispersing; s2, adding 100-500 mu L of silver nitrate solution into the dispersion system obtained in the step S1, performing ultrasonic reaction for 1-5 hours, fully dispersing solid powder by utilizing the mechanical effect of ultrasonic waves, and enhancing the reaction between C 3N4 base powder and silver nitrate by the cavitation effect of the ultrasonic waves in the liquid; s3, continuously stirring the dispersion system obtained in the step S2 for 2-10 hours, then centrifugally separating out precipitate at a high speed, and drying to obtain the copper-silver double single-atom photocatalyst; the method is used for preparing the copper-silver double-single-atom photocatalyst, has the advantages of simple operation steps, short time consumption, low raw material cost and the like, and the prepared photocatalyst has good electron selectivity and high catalytic activity, and has wide application prospects in the fields of industrial production, environmental engineering and the like.
Description
Technical Field
The invention relates to the technical field of preparation methods of photocatalysts, in particular to a preparation method of a copper-silver double-single-atom photocatalysts.
Background
The single-atom catalyst refers to a metal catalyst which is uniformly and dispersedly deposited on the surface of a carrier in a single-atom mode, and catalytic active sites are furthest exposed, so that the utilization efficiency of the catalyst is improved, and the cost of the catalyst is reduced. When the dispersity of the particles reaches the single-atom size, a plurality of new characteristics, such as sharply increased surface free energy, quantum size effect, unsaturated coordination environment, metal-carrier interaction and the like, are caused, and the characteristics are obviously different from those of nano or sub-nano particles, so that the single-atom catalyst is endowed with excellent activity and selectivity, the catalytic performance is further improved, and the manufacturing cost is reduced. Therefore, the monoatomic catalyst has great application potential in industrial catalysis.
C 3N4 is used as a novel photocatalytic base material, the material is simple to prepare, the single atom type capable of being loaded is rich, the catalytic performance is excellent, and the material becomes a research hot spot in the field of photocatalysis in recent years, but the active site of the single metal atom is difficult to realize the catalysis of a series of reactions such as reduction of CO 2, decomposition of H 2 O and the like, so that the yield of high-added-value products such as CH 4 and the like is low, and the further promotion and application of the C 3N4 material are limited.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-silver double single-atom photocatalyst, which utilizes electrostatic adsorption between an electropositive C 3N4 photocatalyst absolute ethyl alcohol dispersion system and an electronegative silver nitrate solution to form copper-silver double single-atom pairs, so that the effect of step catalysis on different metal atoms is realized. The method for preparing the copper-silver diatomic photocatalyst has the advantages of simple operation, low raw material cost, short time consumption, high production efficiency, good electron selectivity of the prepared photocatalyst, high catalytic activity and wide application prospect.
In order to achieve the above object, the present invention provides the following technical solutions:
The preparation method of the copper-silver double single-atom photocatalyst comprises the following steps:
S1, adding C 3N4 photocatalyst powder loaded with copper single atoms into absolute ethyl alcohol, and uniformly dispersing;
S2, adding 100-500 mu L of silver nitrate solution into the dispersion system obtained in the step S1, performing ultrasonic reaction for 1-5 hours, fully dispersing solid powder by utilizing the mechanical effect of ultrasonic waves, and enhancing the reaction between C 3N4 base powder and silver nitrate by the cavitation effect of the ultrasonic waves in the liquid;
and S3, continuously stirring the dispersion system obtained in the step S2 for 2-10 hours, then centrifugally separating out precipitate at a high speed, and drying to obtain the copper-silver double single-atom photocatalyst.
Further, in S1, the resulting C 3N4 absolute ethanol dispersion is electropositive, and in S2, the electropositive C 3N4 absolute ethanol dispersion and the electronegative silver nitrate solution charge silver monoatoms to the C 3N4 base material by electrostatic adsorption.
Further, in S2, the concentration of the silver nitrate solution is 2mg/mL, so that the agglomeration can be avoided while silver atoms are effectively loaded, and the optimal catalytic effect is realized.
Further, in the process of continuously stirring in S3, copper monoatoms and silver monoatoms form double monoatoms pairs on the C 3N4 substrate material through copper-silver metal bonds, so that the copper-silver double monoatoms photocatalyst is prepared.
The technical proposal has the following principle and beneficial effects:
The loading of copper and silver metal atoms is a key factor influencing the catalytic activity of the catalyst, and if the addition amount of copper and silver elements is too small in the preparation process, copper and silver atoms cannot be effectively loaded on a C 3N4 substrate material; and excessive addition amount can easily cause agglomeration of metal monoatoms to form nanoclusters, so that the catalysis effect of copper-silver double monoatoms can not be realized. The invention forms copper-silver diatomic pairs by utilizing the electrostatic adsorption effect between the electropositive C 3N4 photocatalyst absolute ethyl alcohol dispersion system and the electronegative silver nitrate solution, which not only can ensure that metal diatomic is effectively loaded on a C 3N4 substrate material, but also can effectively avoid agglomeration of metal atoms. The method breaks through the limitation of low yield of the traditional C 3N4 -based photocatalyst CH 4, and has the advantages of simple operation in the preparation process, low raw material cost, short time consumption, high production efficiency, good electron selectivity of the prepared photocatalyst, high catalytic activity and wide application prospect in the fields of industrial production, environmental engineering and the like.
Drawings
FIG. 1 is a schematic diagram of the synthesis of a copper-silver double monoatomic photocatalyst using a supported copper monoatomic C 3N4 photocatalyst according to the present invention;
FIG. 2 is a Zeta potential diagram of an anhydrous ethanol dispersion of copper monatomic loaded C 3N4 catalyst powder, and an aqueous silver nitrate solution according to the present invention;
FIG. 3 is a copper-silver double single-atom photocatalyst spherical aberration correction electron micrograph obtained by a preparation method of a copper-silver double-single-atom photocatalyst according to the present invention;
FIG. 4 is an X-ray diffraction chart of a copper-silver double single-atom photocatalyst prepared by the preparation method of the copper-silver double single-atom photocatalyst;
FIG. 5 is an expanded X-ray absorption fine structure pattern of a copper-silver double single atom photocatalyst in copper K-edge prepared by a preparation method of the copper-silver double single atom photocatalyst according to the present invention;
FIG. 6 is an expanded X-ray absorption fine structure pattern of a copper-silver double single atom photocatalyst in silver K-edge prepared by a preparation method of the copper-silver double single atom photocatalyst according to the present invention;
fig. 7 is a test result of performance of the copper-silver double single atom photocatalyst prepared by the preparation method of the copper-silver double single atom photocatalyst for catalytic reduction of CO 2.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and embodiments:
As shown in fig. 1, a preparation method of a copper-silver double single-atom photocatalyst comprises the following steps:
S1, adding C 3N4 photocatalyst powder loaded with copper single atoms into absolute ethyl alcohol to uniformly disperse, wherein the obtained C 3N4 absolute ethyl alcohol dispersion system is electropositive; wherein, the method for preparing the C 3N4 photocatalyst powder loaded with copper single atoms comprises the following steps:
A1, weighing 30g of thiourea, adding the thiourea into 120mL of pure water, heating at 60 ℃ and magnetically stirring for 10min until the solution is clear and transparent;
A2, weighing 0.4g of copper chloride dihydrate, adding the copper chloride dihydrate into the transparent solution obtained in the step A1, and continuing heating and stirring for 10min;
a3, standing and cooling the solution obtained in the step A2 to room temperature, discarding supernatant, and putting the precipitate into a drying oven for drying;
a4, placing the dried precursor in the step A3 into a capped alumina porcelain boat, calcining for 1-5 h under the condition of introducing Ar into a tube furnace, and naturally cooling to room temperature;
A5, ball milling is carried out on the product obtained by calcining in the step A4, and C 3N4 photocatalyst powder carrying copper single atoms is obtained;
S2, adding 100-500 mu L of silver nitrate solution into the dispersion system obtained in the step S1, performing ultrasonic reaction for 1-5 hours, fully dispersing solid powder by utilizing the mechanical effect of ultrasonic waves, and enhancing the reaction between C 3N4 base powder and silver nitrate by the cavitation effect of the ultrasonic waves in the liquid; wherein, the added silver nitrate solution is as follows: weighing 0.1g of silver nitrate solid, dissolving the silver nitrate solid in 50mL of pure water, preparing a silver nitrate solution with the concentration of 2mg/mL, wherein the silver nitrate solution is electronegative, and carrying out electrostatic adsorption on a C 3N4 absolute ethyl alcohol dispersion system which is electropositive in S1 and the silver nitrate solution which is electronegative to enable silver monoatoms to be loaded on a C 3N4 base material;
And S3, continuously stirring the dispersion system obtained in the step S2 for 2-10 hours, then centrifugally separating out precipitate at a high speed, and drying to obtain the copper-silver diatomic photocatalyst, wherein in the continuous stirring process, the copper diatomic and silver diatomic form a diatomic pair on a C 3N4 substrate material through a copper-silver metal bond, so that the copper-silver diatomic photocatalyst is prepared.
To verify that the present embodiment can produce the desired catalyst product, the produced product was subjected to various characterizations, and the results of each characterization are described below.
Characterization experiment 1:
As shown in fig. 2, the Zeta potential of the anhydrous ethanol dispersion of C 3N4 catalyst powder loaded with copper single atoms and the silver nitrate aqueous solution were tested, and the test results showed that the anhydrous ethanol dispersion of C 3N4 catalyst powder loaded with copper single atoms was positively charged, and the silver nitrate aqueous solution was negatively charged, and the silver atoms could be effectively loaded onto the C 3N4 substrate due to electrostatic effect.
Characterization experiment 2:
The application adopts a spherical aberration correction electron microscope of the model FEI TITAN THEMIS in the United states to carry out transmission imaging on the catalyst sample powder, and the test voltage is 300kV. As shown in FIG. 3, the distances between copper atoms and silver atoms in the four regions tested were About, copper and silver are illustrated as being supported on a C 3N4 substrate in the form of a double monoatomic pair.
Characterization experiment 3:
The application adopts a Holland PANalytical B.V.X' Pert X-ray diffractometer (Cu K alpha, lambda=0.154 nm, and working voltage and working current are 40kV and 40mA respectively) to carry out XRD characterization test on the catalyst sample powder. As shown in fig. 4, XRD results show that the catalyst sample powder exhibits two peaks at about 13 ° and 27 °, which are typical diffraction peaks of C 3N4 material, wherein 13 ° peak corresponds to the stack (100) between the inter-plane C 3N4 units, and 27 ° peak corresponds to the stack (002) between the C 3N4 crystal planes; in addition, no other distinct characteristic peaks were observed. This embodiment is thus demonstrated to be undoped, with the single atom pair being supported so as not to affect the synthesis of the C 3N4 material.
Characterization experiment 4:
According to the application, the catalyst sample powder is tested in the expanded X-ray absorption fine structures of copper and silver K-edge respectively, as shown in fig. 5 and 6, the fitting result shows that copper-copper and silver metal bonds do not appear in a C 3N4 sample loaded with copper single atoms and a C 3N4 sample loaded with copper-silver double single atom pairs, and the copper atoms are supported on a C 3N4 substrate in a single atom form; in addition, copper and nitrogen in the C 3N4 sample loaded with copper monoatoms have three coordination, copper and nitrogen in the C 3N4 sample loaded with copper-silver diatomic pairs have only two coordination, and the addition of silver monoatoms leads to unsaturated coordination environment of copper atoms, thereby proving that copper and silver are loaded on the C 3N4 substrate in the form of the diatomic pairs, and fitting parameters of the extended X-ray absorption fine structures of the samples at copper K-edge and silver K-edge are shown in the table 1 and the table 2:
TABLE 1 extended X-ray absorption fine structure fitting parameters for samples at copper K-edge
Where CN is coordination number, R is the distance between absorber and back-scattered atoms, σ 2 is the Debye-Waller factor of heat of solution and structural disorder, ΔE 0 is internal potential energy correction, and R factor indicates the degree of fit. S 0 2 was fixed at 0.892 based on the X-ray absorption fine structure fit spectrum of copper element obtained in the experiment by fixing CN as a known crystal value. The fitting range is as follows: And/> AndA reasonable range of X-ray absorbing fine structure fitting parameters is 0.700< s 0 2 <1.000; CN >0; /(I)Delta E 0 <10eV; the R factor is <0.02.
TABLE 2 extended X-ray absorption fine Structure fitting parameters for samples at silver K-edge
Where CN is coordination number, R is the distance between absorber and back-scattered atoms, σ 2 is the Debye-Waller factor of heat of solution and structural disorder, ΔE 0 is internal potential energy correction, and R factor indicates the degree of fit. S 0 2 was fixed at 0.8 based on an X-ray absorption fine structure fit spectrum of elemental silver obtained in the experiment by fixing CN as a known crystal value. A reasonable range of X-ray absorbing fine structure fitting parameters is 0.700< s 0 2 <1.000; CN >0; Delta E 0 <10eV; the R factor is <0.02.
Characterization experiment 5:
As shown in fig. 7, the performance test of the photocatalytic reduction CO 2 was also performed in this experiment, and the experimental method is as follows:
Firstly, weighing 5mg of catalyst powder into a glass culture dish, adding a proper amount of pure water, uniformly carrying out ultrasonic treatment, and then drying to uniformly distribute the catalyst powder at the bottom of the culture dish;
then placing the culture dish filled with the catalyst in a transparent quartz reactor with the volume of 150mL, adding 200 mu L of ultrapure water into the reactor, and sealing;
then a vacuum pump is connected into the reactor, air in the reactor is discharged, and CO 2 with the purity of 99.99 percent is introduced into the reactor until the air pressure in the reactor is balanced with the atmospheric pressure;
Then a 300W xenon lamp (PLS-SXE 300/300 UV) is turned on, the current is set to be 15A, a light source is arranged above the reactor, the reactor is aligned to a culture dish for irradiation for 2 hours, and cooling liquid is continuously introduced from the outside of the reactor during the irradiation, so that the temperature of the reactor is controlled to be about 15 ℃;
After the light irradiation was completed, 2mL of a gas sample was extracted from the reactor and injected into a phase chromatograph (Shimadzu GC-2014C) to detect the concentration of the CO 2 reduction product.
As shown by test results, in the experiment, CH 4 output performance reaches 13.14 mu mol g -1·h-1, CO output performance reaches 5.33 mu mol g -1·h-1, and electron selectivity exceeds 90%. In addition, five cycle tests are carried out on the catalyst sample according to the steps, and the results show that the photocatalytic performance of the catalyst is not reduced, and CH 4 and CO are not detected in a control group experiment carried out synchronously, which indicates that CH4 and CO detected in the experiment are products for catalyzing carbon dioxide reaction, but not the decomposition of the catalyst. This demonstrates that the copper-silver diatomic double monoatoms produced by this embodiment are chemically stable to the photocatalyst.
The foregoing is merely exemplary embodiments of the present application, and detailed technical solutions or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present application, and these should also be regarded as the protection scope of the present application, which does not affect the effect of the implementation of the present application and the practical applicability of the patent. The protection scope of the present application is subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (1)
1. The preparation method of the copper-silver double single-atom photocatalyst is characterized by comprising the following steps of:
S1, adding C 3N4 photocatalyst powder loaded with copper single atoms into absolute ethyl alcohol to uniformly disperse, wherein the obtained C 3N4 absolute ethyl alcohol dispersion system is electropositive; wherein, the method for preparing the C 3N4 photocatalyst powder loaded with copper single atoms comprises the following steps:
A1, weighing 30g of thiourea, adding the thiourea into 120mL of pure water, heating at 60 ℃ and magnetically stirring for 10min until the solution is clear and transparent;
A2, weighing 0.4g of copper chloride dihydrate, adding the copper chloride dihydrate into the transparent solution obtained in the step A1, and continuing heating and stirring for 10min;
a3, standing and cooling the solution obtained in the step A2 to room temperature, discarding supernatant, and putting the precipitate into a drying oven for drying;
a4, placing the dried precursor in the step A3 into a capped alumina porcelain boat, calcining for 1-5 h under the condition of introducing Ar into a tube furnace, and naturally cooling to room temperature;
A5, ball milling is carried out on the product obtained by calcining in the step A4, and C 3N4 photocatalyst powder carrying copper single atoms is obtained;
S2, adding 100-500 mu L of silver nitrate solution into the dispersion system obtained in the step S1, performing ultrasonic reaction for 1-5 hours, fully dispersing solid powder by utilizing the mechanical effect of ultrasonic waves, and enhancing the reaction between C 3N4 base powder and silver nitrate by the cavitation effect of the ultrasonic waves in the liquid; wherein, the added silver nitrate solution is as follows: weighing 0.1g of silver nitrate solid, dissolving in 50mL of pure water, preparing a silver nitrate solution with the concentration of 2mg/mL, wherein the silver nitrate solution is electronegative, and the C 3N4 absolute ethyl alcohol dispersion system which is electropositive in S1 and the silver nitrate solution which is electronegative enable silver monoatoms to be loaded on a C 3N4 substrate material through electrostatic adsorption;
And S3, continuously stirring the dispersion system obtained in the step S2 for 2-10 hours, then centrifugally separating out precipitate at a high speed, and drying to obtain the copper-silver diatomic photocatalyst, wherein in the continuous stirring process, the copper diatomic and silver diatomic form a diatomic pair on a C 3N4 substrate material through a copper-silver metal bond, so that the copper-silver diatomic photocatalyst is prepared.
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