CN115805091A - Preparation method of copper-silver double-monoatomic photocatalyst - Google Patents
Preparation method of copper-silver double-monoatomic 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 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 claims abstract description 27
- 239000010949 copper Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 23
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 23
- 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
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000000694 effects Effects 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- 230000002708 enhancing effect Effects 0.000 claims abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 22
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 230000002776 aggregation Effects 0.000 claims description 4
- 238000005054 agglomeration Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 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
- 150000002500 ions Chemical class 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 10
- 238000012512 characterization method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 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
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005381 potential energy Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 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
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- 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
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 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
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- OGFYIDCVDSATDC-UHFFFAOYSA-N silver silver Chemical compound [Ag].[Ag] OGFYIDCVDSATDC-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing 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
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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
Abstract
The invention belongs to the technical field of preparation methods of photocatalysts, and discloses a preparation method of a copper-silver double-monoatomic photocatalyst, which comprises S1, C for loading copper monoatomic ions 3 N 4 Adding photocatalyst powder into absolute ethyl alcohol to be uniformly dispersed; s2, adding 100-500 mu L of silver nitrate solution into the dispersion system obtained in the step S1, carrying out ultrasonic reaction for 1-5 h, fully dispersing solid powder by utilizing the mechanical effect of ultrasonic waves, and simultaneously enhancing the cavitation effect of the ultrasonic waves in the liquidC 3 N 4 Reaction between the base powder and silver nitrate; s3, continuously stirring the dispersion system obtained in the step S2 for 2-10 hours, then centrifuging at a high speed to separate out precipitate, and drying to obtain the copper-silver double-monoatomic photocatalyst; the method is used for preparing the copper-silver double-monoatomic photocatalyst, has the advantages of simple operation steps, short time consumption, low raw material cost and the like, and the prepared photocatalyst has good electronic 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-monoatomic photocatalyst.
Background
The monatomic catalyst means that the metal catalyst is uniformly dispersed and deposited on the surface of the carrier in a monatomic form, so that the catalytic active sites are exposed to the maximum extent, the utilization efficiency of the catalyst is improved, and the cost of the catalyst is reduced. When the dispersion degree of the particles reaches the monoatomic size, many new characteristics such as sharply increased surface free energy, quantum size effect, unsaturated coordination environment, metal-carrier interaction and the like can be caused, and the characteristics are remarkably different from those of nano or sub-nano particles, so that the monoatomic catalyst is endowed with excellent activity and selectivity, the catalytic performance can be further improved, and the manufacturing cost can be reduced. Therefore, the monatomic catalyst has huge application potential in industrial catalysis.
C 3 N 4 As a novel photocatalytic substrate material, the material is simple to prepare, can be loaded with a large variety of single atoms, has excellent catalytic performance and becomes a research hotspot in the field of photocatalysis in recent years, but the active site of a single metal atom at present is difficult to realize on CO 2 Reduction of (2) and H 2 The decomposition of O and the like to generate CH 4 The yield of products with equal high added value is not high, and C is limited 3 N 4 Further promotion and application of the material.
Disclosure of Invention
The invention aims to provide a preparation method of a copper-silver double-monoatomic photocatalyst by utilizing electropositive C 3 N 4 The electrostatic adsorption between the photocatalyst absolute ethyl alcohol dispersion system and silver nitrate solution with electronegativity forms copper-silver double monoatomic atomsIn pair, the effect of step-by-step catalysis on different metal atoms is realized. The method for preparing the copper-silver double-monoatomic photocatalyst is simple to operate, low in raw material cost, short in time consumption and high in production efficiency, and the prepared photocatalyst is good in electronic selectivity, high in catalytic activity and wide in application prospect.
In order to achieve the above purpose, the invention provides the following technical scheme:
a preparation method of a copper-silver double-monoatomic photocatalyst comprises the following steps:
s1, C to be loaded with copper monoatomic 3 N 4 Adding photocatalyst powder into absolute ethyl alcohol to be uniformly dispersed;
s2, adding 100-500 mu L of silver nitrate solution into the dispersion system obtained in the step S1, carrying out ultrasonic reaction for 1-5 h, fully dispersing solid powder by utilizing the mechanical effect of ultrasonic waves, and simultaneously enhancing the cavitation effect of the ultrasonic waves in liquid to obtain C 3 N 4 Reaction between the base powder and silver nitrate;
and S3, continuously stirring the dispersion system obtained in the step S2 for 2-10 hours, then performing high-speed centrifugal separation to obtain a precipitate, and drying to obtain the copper-silver double-monoatomic photocatalyst.
Further, in S1, C is obtained 3 N 4 The absolute ethyl alcohol dispersion system is electrically positive, in S2, the silver nitrate solution is electrically negative, and C is electrically positive 3 N 4 The anhydrous ethanol dispersion system and the silver nitrate solution with electronegativity are used for loading silver monoatomic atoms to C through electrostatic adsorption 3 N 4 On a base material.
Further, in S2, the concentration of silver nitrate solution is 2mg/mL, so that aggregation can be avoided while silver atoms are effectively loaded, and the optimal catalytic effect is realized.
Further, during the continuous stirring of S3, the copper monoatomic atoms and the silver monoatomic atoms are in C 3 N 4 The double monoatomic pairs are formed on the substrate material through copper-silver metal bonds to prepare the copper-silver double monoatomic photocatalyst.
The principle and the beneficial effects of the technical scheme are as follows:
copper, silver metal atomThe loading amount of the catalyst 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 in C 3 N 4 A base material; and too much addition amount can easily cause the agglomeration of metal single atoms to form nanoclusters, and the catalytic effect of the copper-silver double single atom pair cannot be realized. The invention utilizes C which is electropositive 3 N 4 The electrostatic adsorption between the photocatalyst absolute ethyl alcohol dispersion system and the silver nitrate solution with electronegativity forms a copper-silver double-monoatomic pair, which can ensure that metal monoatomic ions are effectively loaded on C 3 N 4 On the substrate material, the agglomeration of metal atoms can be effectively avoided. The method breaks through the traditional C 3 N 4 Base photocatalyst CH 4 The yield is low, the preparation process is simple to operate, the raw material cost is low, the time consumption is short, the production efficiency is high, and the prepared photocatalyst has good electronic selectivity and high catalytic activity, and has wide application prospects in the fields of industrial production, environmental engineering and the like.
Drawings
FIG. 1 shows the use of a copper-loaded monoatomic compound C according to the present invention 3 N 4 A synthetic schematic diagram of a photocatalyst synthetic copper-silver double monoatomic photocatalyst;
FIG. 2 shows a schematic view of a copper monoatomic support of C according to the present invention 3 N 4 Zeta potential diagram of catalyst powder absolute ethyl alcohol dispersion and silver nitrate water solution;
FIG. 3 is a spherical aberration correction electron micrograph of a copper-silver bimonoatom photocatalyst prepared by a method for preparing a copper-silver bimonoatom photocatalyst according to the present invention;
FIG. 4 is an X-ray diffraction spectrum of a copper-silver bimonoatom photocatalyst prepared by the method of the present invention;
FIG. 5 is an expanded X-ray absorption fine structure spectrum of a copper-silver double-monoatomic photocatalyst prepared by the method for preparing the copper-silver double-monoatomic photocatalyst in copper K-edge;
FIG. 6 is an expanded X-ray absorption fine structure spectrum of a copper-silver bimonoatom photocatalyst prepared by the method for preparing a copper-silver bimonoatom photocatalyst of the present invention at silver K-edge;
FIG. 7 shows the CO catalytic reduction of a copper-silver double-monatomic photocatalyst prepared by the method for preparing the copper-silver double-monatomic photocatalyst 2 And (5) performance test results.
Detailed Description
The invention is described in further detail below with reference to the following figures and embodiments:
as shown in fig. 1, a method for preparing a copper-silver bi-monoatomic photocatalyst comprises the following steps:
s1, loading C of copper monoatomic 3 N 4 Adding photocatalyst powder into anhydrous ethanol, and dispersing to obtain C 3 N 4 The absolute ethyl alcohol dispersion system is electropositive; wherein C carrying copper monoatomic is prepared 3 N 4 A method of photocatalyst powder comprising the steps of:
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 continuously heating and stirring for 10min;
a3, standing the solution obtained in the step A2, cooling to room temperature, removing supernate, and drying the precipitate in a drying oven;
a4, putting the dried precursor in the step A3 into a covered alumina porcelain boat, calcining for 1-5 hours under the condition of introducing Ar into a tubular furnace, and naturally cooling to room temperature;
a5, performing ball milling treatment on the product obtained by calcining in the step A4 to obtain C loaded with copper monoatomic atoms 3 N 4 A photocatalyst powder;
s2, adding 100-500 mu L of silver nitrate solution into the dispersion system obtained in the step S1, carrying out ultrasonic reaction for 1-5 h, fully dispersing solid powder by utilizing the mechanical effect of ultrasonic waves, and simultaneously enhancing the cavitation effect of the ultrasonic waves in liquid to obtain C 3 N 4 Reaction between the base powder and silver nitrate; wherein, sodium nitrate is addedThe silver acid solution is as follows: 0.1g of silver nitrate solid is weighed and dissolved in 50mL of pure water to prepare a silver nitrate solution with the concentration of 2mg/mL, wherein the silver nitrate solution is electronegative, and C with electropositivity is in S1 3 N 4 The absolute ethyl alcohol dispersion system and silver nitrate solution with electronegativity make silver monoatomic atom be loaded to C by means of electrostatic adsorption action 3 N 4 A base material;
s3, continuously stirring the dispersion system obtained in the step S2 for 2-10 hours, then centrifuging at a high speed to separate out precipitates, and drying to obtain the copper-silver double-monoatomic photocatalyst, wherein in the continuous stirring process, copper monoatomic and silver monoatomic are in C 3 N 4 The double monoatomic pair is formed on the substrate material through a copper-silver metal bond to prepare the copper-silver double monoatomic photocatalyst.
In order to verify that the target catalyst product can be obtained in this embodiment, various characterizations are performed on the obtained product, and the following is a description of each characterization result.
Characterization experiment 1:
as shown in FIG. 2, C loaded with copper monoatomic 3 N 4 Zeta potential of the catalyst powder absolute ethyl alcohol dispersion system and silver nitrate aqueous solution shows that the C of the loaded copper monoatomic atom 3 N 4 The catalyst powder is dispersed with absolute ethyl alcohol to form positive charge, the silver nitrate water solution is negatively charged, and due to the electrostatic effect, silver atoms can be effectively loaded to C 3 N 4 On a substrate.
Characterization experiment 2:
the catalyst sample powder is subjected to transmission imaging by adopting a U.S. FEI Titan Themis type spherical aberration correction electron microscope, and the test voltage is 300kV. As shown in FIG. 3, the distances between the copper atoms and the silver atoms in the four regions tested were
On the left and right, it is shown that copper and silver are supported on C in the form of a double monoatomic pair 3 N 4 On a substrate.
Characterization experiment 3:
the present application employs a PANalytical b.v.x' Pert model X-ray diffractometer (Cu K alpha,λ =0.154nm, operating voltage and operating current 40kV and 40mA, respectively) were subjected to XRD characterization tests on the catalyst sample powder. As shown in fig. 4, the XRD results showed that the catalyst sample powder showed two peaks at around 13 ° and 27 °, typical of C 3 N 4 Diffraction peaks of the material, wherein the 13 ° peak corresponds to the inter-plane C 3 N 4 Stacking (100) between cells, with 27 ° peak corresponding to C 3 N 4 Stacking between crystal faces (002); in addition, no other distinct characteristic peaks were observed. This demonstrates that the undoped, loaded monoatomic pairs of such embodiments do not affect C 3 N 4 And (4) synthesizing materials.
Characterization experiment 4:
the catalyst sample powder was tested in the extended X-ray absorption fine structure of copper and silver K-edge, respectively, as shown in FIGS. 5 and 6, and the fitting results show that C loaded with copper monoatomic atoms 3 N 4 Sample and C loaded with copper-silver double monoatomic pair 3 N 4 No copper-copper or silver-silver metallic bond appears in the sample, which indicates that the copper atom is loaded on C in the form of single atom 3 N 4 A substrate; in addition, C carrying copper monoatomic 3 N 4 The copper in the sample has three coordination with nitrogen and carries C of copper-silver double monoatomic pair 3 N 4 The copper and the nitrogen in the sample have two coordination, and the addition of the silver monoatomic atom leads to the unsaturated coordination environment of the copper atom, thereby proving that the copper and the silver are loaded on the C in the form of a double monoatomic atom pair 3 N 4 On the substrate, the extended X-ray absorption fine structure fitting parameters for the samples at copper K-edge and silver K-edge are shown in tables 1 and 2:
TABLE 1 extended X-ray absorption Fine Structure fitting parameters of samples at copper K-edge
Wherein CN is the coordination number and R is between the absorber and the backscatter atomDistance, σ 2 Delta E to account for Debye-Waller factor of thermal and structural disorder 0 For internal potential energy correction, the R factor indicates the degree of fit. Fitting spectrum of X-ray absorption fine structure of copper element obtained by fixing CN as known crystal value in experiment, S 0 2 Is fixed at 0.892. The fitting range is:
and
and
a reasonable range for the X-ray absorption fine structure fitting parameter is 0.700<S 0 2 <1.000；CN>0；
|ΔE 0 |<10eV; r factor<0.02。
TABLE 2 extended X-ray absorption Fine Structure fitting parameters of samples at silver K-edge
Where CN is the coordination number, R is the distance between the absorber and the backscattering atom, σ 2 Delta E to account for Debye-Waller factors of thermal and structural disorder 0 For internal potential energy correction, the R factor indicates the degree of fit. Fitting spectrum of X-ray absorption fine structure of silver element obtained by fixing CN as known crystal value in experiment, S 0 2 Is fixed at 0.8. A reasonable range for the X-ray absorption fine structure fitting parameter is 0.700<S 0 2 <1.000；CN>0；
|ΔE 0 |<10eV; r factor<0.02。
Characterization experiment 5:
as shown in FIG. 7, photocatalytic reduction of CO was also performed in this experiment 2 The experimental method of the performance detection experiment is as follows:
weighing 5mg of catalyst powder into a glass culture dish, adding a proper amount of pure water, uniformly performing ultrasonic treatment, and drying to uniformly distribute the catalyst powder on the bottom of the culture dish;
then placing the culture dish filled with the catalyst into 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, the air in the reactor is discharged, and CO with the purity of 99.99 percent is introduced into the reactor 2 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 placed above the reactor and is aligned with the culture dish to irradiate for 2 hours, and cooling liquid is continuously introduced outside the reactor during the period, so that the temperature of the reactor is controlled to be about 15 ℃;
after the light irradiation is finished, 2mL of gas sample is extracted from the reactor and injected into a phase chromatograph (Japan Shimadzu GC-2014C) to detect CO 2 The concentration of the reduction product.
From the test results, CH in this experiment 4 The output performance reaches 13.14 mu mol g -1 ·h -1 The output performance of CO reaches 5.33 mu mol g -1 ·h -1 The electron selectivity is over 90%. In addition, five times of cycle tests are carried out on the catalyst sample according to the steps, and the results show that the photocatalytic performance of the catalyst sample is not reduced, and CH is not detected in the control group experiments carried out at the same time 4 And CO, indicating that both CH4 and CO detected in the experiment are products of catalyzing the reaction of carbon dioxide, and not the catalyst itself. Thus, the chemical property of the copper-silver double-monoatomic photocatalyst prepared by the embodiment is proved to be stable.
The above description is only an example of the present invention, and the common general knowledge of the technical solutions or characteristics known in the solutions is not described herein too much. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be defined by the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (4)
1. A preparation method of a copper-silver double-monoatomic photocatalyst is characterized by comprising the following steps:
s1, C to be loaded with copper monoatomic 3 N 4 Adding photocatalyst powder into absolute ethyl alcohol to be uniformly dispersed;
s2, adding 100-500 mu L of silver nitrate solution into the dispersion system obtained in the step S1, carrying out ultrasonic reaction for 1-5 h, fully dispersing solid powder by utilizing the mechanical effect of ultrasonic waves, and simultaneously enhancing the cavitation effect of the ultrasonic waves in liquid to obtain C 3 N 4 Reaction between the base powder and silver nitrate;
and S3, continuously stirring the dispersion system obtained in the step S2 for 2-10 hours, then centrifugally separating out precipitates at a high speed, and drying to obtain the copper-silver double-monoatomic photocatalyst.
2. The method for preparing a copper-silver double monatomic photocatalyst according to claim 1, wherein: in S1, C is obtained 3 N 4 The absolute ethyl alcohol dispersion system is electrically positive, in S2, the silver nitrate solution is electrically negative, and C is electrically positive 3 N 4 The anhydrous ethanol dispersion system and the silver nitrate solution with electronegativity are used for loading silver monoatomic atoms to C through electrostatic adsorption 3 N 4 On the base material.
3. The method for preparing a copper-silver double monatomic photocatalyst according to claim 2, wherein: in S2, the silver nitrate solution is added at a concentration of 2mg/mL, so that silver atoms can be effectively loaded, agglomeration is avoided, and the optimal catalytic effect is realized.
4. A method for preparing a copper-silver double monatomic photocatalyst according to claim 3, characterized in that: during the continuous stirring process of S3, copper monoatomic atoms and silver monoatomic atoms are in C 3 N 4 The double monoatomic pairs are formed on the substrate material through copper-silver metal bonds to prepare the copper-silver double monoatomic photocatalyst.
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