CN111569927A - Ag2CO3/g-C3N4Nano composite material and preparation method and application thereof - Google Patents
Ag2CO3/g-C3N4Nano composite material and preparation method and application thereof Download PDFInfo
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- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 title claims abstract description 48
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 title claims abstract description 47
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title description 5
- 239000002114 nanocomposite Substances 0.000 claims abstract description 74
- 239000000463 material Substances 0.000 claims abstract description 69
- 238000003756 stirring Methods 0.000 claims abstract description 55
- 239000006185 dispersion Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 11
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 9
- 239000012498 ultrapure water Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 11
- 238000007146 photocatalysis Methods 0.000 abstract description 9
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 30
- 229940012189 methyl orange Drugs 0.000 description 30
- 239000000975 dye Substances 0.000 description 27
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 230000000593 degrading effect Effects 0.000 description 9
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 239000002245 particle Substances 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 superoxide ion Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 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—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G5/00—Compounds of silver
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The application discloses an Ag2CO3/g‑C3N4A nano composite material and a preparation method and application thereof relate to the technical field of photocatalysis, and the preparation method comprises the following steps: (1) thin layer g-C3N4Ultrasonic dispersion is carried out in deionized water to obtain g-C3N4A dispersion liquid; (2) AgNO is added under stirring3Dropping the solution into g-C obtained in the step (1)3N4Continuing stirring in the dispersion liquid; (3) under the condition of stirring, adding K2CO3Dripping the solution into the dispersion liquid obtained in the step (2), and continuously stirring; (4) at the end of the stirringNaturally settling, taking out supernatant, washing the lower precipitate with ultrapure water, centrifuging, and freeze drying to obtain Ag2CO3/g‑C3N4A nanocomposite material. The application solves g-C3N4The material has low visible light catalytic activity, so that the catalytic activity of the material under visible light is improved, and the dosage of the catalyst is greatly reduced.
Description
Technical Field
The application relates to the technical field of photocatalysis, in particular to Ag2CO3/g-C3N4A nano composite material and a preparation method and application thereof.
Background
With the rapid development of human society, the consumption of fossil fuel resources is serious, the resource shortage is caused, and the environmental pollution is immeasurable, so how to treat the environmental problem by using renewable resources becomes an urgent task all over the world, and meanwhile, the attention of more researchers is also aroused, and the nano semiconductor photocatalysis technology comes along. Graphite-like phase g-C3N4Is a new covalent compound which is not found in the nature, and has excellent physicochemical properties, such as: can absorb visible light, has the characteristics of strong chemical stability and thermal stability, no toxicity, rich sources, simple preparation and forming process and the like, and becomes a new favorite for the research in the field of photocatalysis at present. But pure g-C3N4The energy band of the catalyst is about 2.7eV, the energy level of the conduction band is positioned at-1.3 eV, and the oxygen adsorbed on the surface of the catalyst can be oxidized into superoxide ion free radicals (O) by photo-generated electrons2 ·-) And the valence band energy level is 1.4eV, the generated photogenerated holes can not oxidize water into hydroxyl radical (. OH), and O2 ·-And OH is a key active species for degrading organic pollutants, so the reduction of active species greatly reduces the catalytic activity of the catalyst. At the same time, g-C3N4The separation efficiency of the self photoproduction electron and the hole is lower, and the visible light catalytic activity of the self photoproduction electron and the hole is limited to a certain extent.
To increase g-C3N4The researchers have adopted various modification methods for the catalytic activity of (2). Konglin Wu et al use soft chemistry to prepare rod-like Ag2CO3And g-C3N4The nano composite material degrades Methylene Blue (MB) and rhodamine B (Rh B) under visible light, and is mixed with pure Ag2CO3Comparative example g-C3N4/Ag2CO3Show a higher photocatalytic activity [ Konglin Wu, YanweiCui, et al, the hybridization of Ag2CO3rods with g-C3N4sheets with improvedphotocatalytic activity[J].Journal of Saudi Chemical Society,2015,19:465–470.]. Yunfeng Li et al convert Ag2CO3Nanoparticle loading to treated g-C3N4On the nano-sheet, a hetero-structure is formed, which has good degradation effect on Methyl Orange (MO) and Rh B under visible light [ Yunfeng Li, Lin Fang, Renxi Jin, et al3N4nanosheets loaded with Ag2CO3nanoparticles[J].Nanoscale,2015,7:758-764.]. Lei Shi et al by3N4Upper load of Ag2CO3Particle formation of composite materials to increase the visible light catalytic efficiency of Rh B [ Lei Shi, Lin Liang, Fangxiao Wang, et al3N4/Ag2CO3composites[J].Journalof Materials Science,2015,50:1718–1727.]. The composite materials are all prepared by increasing g-C3N4The catalytic activity is improved by the separation efficiency of photo-generated electrons and holes, but the dosage and degradation rate of the catalyst are still to be improved.
Disclosure of Invention
The embodiment of the application provides Ag2CO3/g-C3N4The nanometer composite material, the preparation method and the application thereof solve the problem of g-C3N4The nano composite material not only improves the catalytic activity of the material under visible light, but also greatly reduces the dosage of the catalyst.
In order to achieve the above purpose, the present application mainly provides the following technical solutions:
the embodiment of the application provides Ag2CO3/g-C3N4The preparation method of the nano composite material comprises the following steps:
(1) thin layer g-C3N4In the process of deionizationUltrasonic dispersion in water to obtain g-C3N4A dispersion liquid;
(2) AgNO is added under stirring3Dropping the solution into g-C obtained in the step (1)3N4Continuing stirring in the dispersion liquid;
(3) under the condition of stirring, adding K2CO3Dripping the solution into the dispersion liquid obtained in the step (2), and continuously stirring;
(4) naturally settling the reaction system in the step (3) after stirring, taking out supernatant, washing the lower precipitate with ultrapure water, centrifuging, and freeze-drying to obtain Ag2CO3/g-C3N4A nanocomposite material.
Preferably, the thin layer g-C3N4The preparation method comprises the following steps:
calcining urea to obtain primary calcined g-C3N4(ii) a Grinding the ground g-C3N4Then carrying out secondary calcination to obtain a thin layer g-C3N4。
Preferably, the conditions of the primary calcination and the secondary calcination are both: raising the temperature to 550 ℃ at the heating rate of 4 ℃/min, preserving the heat for 4 hours, and then reducing the temperature to the room temperature at the cooling rate of 4 ℃/min.
Preferably, the thin layer g-C3N4With AgNO3The mass ratio of the components is 9:1-2: 8.
Preferably, the thin layer g-C3N4With AgNO3The mass ratio of (A) to (B) is 2: 3.
Preferably, the thin layer g-C3N4And carrying out ultrasonic dispersion in deionized water for 6-18 h.
Preferably, the AgNO3Dropping the solution into g-C obtained in the step (1)3N4After dispersing in the liquid, continuing stirring for 30-60 min; k2CO3And (3) after the solution is dripped into the dispersion liquid obtained in the step (2), continuously stirring for 30-60 min.
Preferably, Ag2CO3/g-C3N4Ag in nano composite material2CO3The mass percentage of the component (A) is 10-80%.
The embodiment of the application also provides Ag prepared by the preparation method2CO3/g-C3N4A nanocomposite material.
The embodiment of the application also provides the Ag2CO3/g-C3N4Application of the nano composite material in visible light catalysis.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
the examples of the present application use thin layers g-C3N4With Ag2CO3The nanometer particles have synergistic effect, so that the separation of photon-generated carriers is effectively realized, the compounding efficiency is reduced, and the Ag is improved2CO3/g-C3N4Photocatalytic activity of the nanocomposite. The thin layer g-C is prepared by adopting single raw material urea and a two-step method3N4So that the nano composite material has larger specific surface area and more active sites, and the catalytic activity of the nano composite material is increased. Ag of the present application2CO3/g-C3N4The nano composite material has less catalyst consumption, and can obtain better catalytic degradation effect when the catalyst consumption is less.
Drawings
FIG. 1 shows Ag prepared according to an embodiment of the present application2CO3/g-C3N4Mechanism diagram of nano composite material photocatalysis;
FIG. 2 shows a thin layer g-C prepared according to another embodiment of the present application3N4XRD diffraction pattern of (1);
FIG. 3 shows a thin layer g-C prepared according to another embodiment of the present application3N4Scanning and transmission electron micrographs of;
FIG. 4 shows Ag prepared in another embodiment of the present application2CO3/g-C3N4Transmission electron microscopy of the nanocomposite;
FIG. 5 shows Ag prepared in another embodiment of the present application2CO3/g-C3N4XRD diffraction pattern of the nano composite material;
FIG. 6 shows Ag prepared in another embodiment of the present application2CO3/g-C3N4A quasi-first order reaction kinetic curve diagram of the nano composite material for catalyzing and degrading Methyl Orange (MO) dye under visible light;
FIG. 7 shows Ag prepared in another embodiment of the present application2CO3/g-C3N4A quasi-first order reaction kinetic curve diagram of the catalytic degradation of Methylene Blue (MB) dye by the nano composite material under visible light.
Detailed Description
In order to facilitate the understanding of the scheme of the present application by those skilled in the art, the following further description is provided with specific examples, and it should be understood that the examples are illustrative of the scheme of the present application and are not intended to limit the scope of the present application.
The embodiment of the application solves the problem of g-C by providing the carbon nitride/silver carbonate nanocomposite material and the preparation method and the application thereof3N4The nano composite material not only improves the catalytic activity of the material under visible light, but also greatly reduces the dosage of the catalyst.
In order to solve the above problems, the technical solution in the embodiment of the present application has the following general idea:
the embodiment of the application provides Ag2CO3/g-C3N4The preparation method of the nano composite material comprises the following steps:
(1) thin layer g-C3N4Ultrasonic dispersion is carried out in deionized water to obtain g-C3N4A dispersion liquid;
(2) AgNO is added under stirring3Dropwise adding the solution into g-C obtained in the step (1)3N4Continuing stirring in the dispersion liquid;
(3) under the condition of stirring, adding K2CO3Dropwise adding the solution into the dispersion liquid obtained in the step (2), and continuously stirring;
(4) step by stepNaturally settling the reaction system in the step (3) after stirring, taking out supernatant, washing the lower precipitate with ultrapure water, centrifuging, and freeze-drying to obtain Ag2CO3/g-C3N4A nanocomposite material.
Ag prepared in the examples of the application2CO3/g-C3N4The nano composite material as a catalyst has excellent photocatalytic performance in the aspect of degrading dye by visible light, which is mainly attributed to Ag2CO3Nanoparticles and thin layer g-C3N4Under the synergistic effect, the separation of photon-generated carriers can be effectively realized, the recombination efficiency is reduced, and meanwhile, the photon-generated electrons can reduce oxygen adsorbed on the surface of the catalyst to react to form O2 ·-And O is2 ·-The dye can be further oxidized, and the catalytic activity is further improved, and the mechanism is shown in figure 1.
The examples of this application use thin layers g-C3N4To prepare Ag2CO3/g-C3N4Nanocomposite material due to a thin layer g-C3N4Is in a thin sheet shape, has larger specific surface area and more active sites, and can increase the catalytic activity of the nano composite material.
Thin layer g-C used in the examples of this application3N4The preparation method comprises the following steps:
calcining urea to obtain primary calcined g-C3N4(ii) a Grinding the ground g-C3N4Then carrying out secondary calcination to obtain a thin layer g-C3N4。
The preferable conditions of the primary calcination and the secondary calcination in the embodiment of the application are as follows: raising the temperature to 550 ℃ at the heating rate of 4 ℃/min, preserving the heat for 4 hours, and then reducing the temperature to the room temperature at the cooling rate of 4 ℃/min.
The embodiment of the application preferably carries out the primary calcination in a covered dry pot, and the secondary calcination is carried out in a magnetic boat.
The thin layer g-C is prepared by adopting single raw material urea and a two-step method in the embodiment of the application3N4Wherein g-C after the first calcination step3N4The film has thinner sheet shape, and after the second step of oxidation etching, the transparency of the sheet layer is higher, and simultaneously the g-C3N4The size of the sheet layer is reduced, and the specific surface area and the active sites are increased. And Ag2CO3/g-C3N4Supported Ag in nanocomposite2CO3The particle size is smaller, the average particle size is 8.9nm, and the dispersion is uniform, so that the catalytic activity sites can be increased, and the catalytic activity of the nano composite material can be increased.
Preferred layers g-C in the examples of the present application3N4With AgNO3The mass ratio of the components is 9:1-2: 8. More preferably a thin layer g-C3N4With AgNO3The mass ratio of (A) to (B) is 2: 3.
The thin layers g to C in step (1) above are preferred in the examples of this application3N4Performing ultrasonic dispersion in deionized water for 6-18 h; preferably AgNO3Dropping the solution into g-C obtained in the step (1)3N4After dispersing in the liquid, continuing stirring for 30-60 min; preferably K2CO3And (3) after the solution is dripped into the dispersion liquid obtained in the step (2), continuously stirring for 30-60 min.
Ag prepared in the examples of the present application2CO3/g-C3N4Ag in nano composite material2CO3The mass percentage of the component (A) is 10-80%. Ag is more preferable in the examples of the present application2CO3/g-C3N4Ag in nano composite material2CO3The mass percentage of (B) is 60%.
The embodiment of the application also provides Ag prepared by the preparation method2CO3/g-C3N4A nanocomposite material.
The embodiment of the application also provides the Ag2CO3/g-C3N4Application of the nano composite material in visible light catalysis.
For better understanding of the above technical solutions, the following detailed descriptions will be provided with reference to the drawings and specific embodiments of the specification, but the present invention is not limited thereto.
Example 1
Preparation of thin layer g-C3N4：
Weighing 10g of urea solid, placing the urea solid in a covered crucible, placing the crucible in a muffle furnace, raising the temperature to 550 ℃ at the temperature rise rate of 4 ℃/min, preserving the heat for 4h, and then reducing the temperature to room temperature at the temperature drop rate of 4 ℃/min to obtain the once-calcined g-C3N4Then grinding, and grinding the ground g-C3N4Transferring to a magnetic boat, placing in a muffle furnace for secondary calcination, heating to 550 deg.C at 4 deg.C/min, maintaining for 4 hr, and cooling to room temperature at 4 deg.C/min to obtain thin layer g-C3N4。
Preparation of Ag2CO3/g-C3N4Nano composite material:
(1) 80mg of the above-prepared thin layer g-C was added3N4Ultrasonic dispersion is carried out in deionized water for 18 hours to obtain g-C3N4A dispersion liquid;
(2) AgNO with Ag content of 94mg is added under stirring3Dropwise adding the solution into g-C obtained in the step (1)3N4Stirring the dispersion for 60 min;
(3) under the condition of stirring, 10mL of K with the mass concentration of 1mg/mL2CO3Dropwise adding the solution into the dispersion liquid obtained in the step (2), and continuously stirring for 60 min;
(4) naturally settling the reaction system in the step (3) after stirring, taking out supernatant, washing the lower precipitate with ultrapure water, centrifuging, and freeze-drying to obtain Ag2CO3/g-C3N4-6 nanocomposite.
Ag2CO3/g-C3N4The nano composite material is used for photocatalytic degradation of dyes:
weighing 20mg of the Ag prepared above2CO3/g-C3N4And (4) putting the-6 nano composite material into a photocatalysis tube, adding 25mL of dye (the mass concentration is 20mg/L), stirring in a dark room for 30min, and reacting under visible light.
Thin layers g-C prepared in this example3N4The XRD diffraction pattern of the compound is shown in figure 2, the scanning and transmission electron micrographs are shown in figure 3, and the g-C can be seen from the transmission electron micrographs3N4The film has thinner sheet shape, and after secondary oxidation etching, the transparency of the sheet layer is higher, and simultaneously the g-C3N4The size of the lamella is reduced, which is beneficial to increasing the specific surface area and the active site; the g-C after the secondary roasting can be clearly seen from the scanning electron microscope picture3N4Exhibit a porous structure, illustrating the thin layer g-C3N4The material has large specific surface area, and on a macroscopic scale, thin layers g-C3N4The material showed a great loft.
Ag prepared in this example2CO3/g-C3N4The transmission electron micrograph and XRD diffraction pattern of the-6 nanocomposite are shown in figures 4 and 5, respectively. As can be seen from FIGS. 4 and 5, Ag2CO3/g-C3N4-6 Supports Ag in nanocomposites2CO3The particle size is smaller, the average particle size is 8.9nm, and the dispersion is uniform, so that the catalytic activity sites can be increased, and the catalytic activity of the nano composite material can be increased.
Ag of the example2CO3/g-C3N4FIG. 6 shows the quasi-first order reaction kinetics curve of-6 nano composite material for catalytic degradation of Methyl Orange (MO) dye under visible light, in this example, Ag2CO3/g-C3N4The quasi-first order reaction kinetic curve of the-6 nano composite material for catalyzing and degrading Methylene Blue (MB) dye under visible light is shown in figure 7, wherein Ag2CO3/g-C3N4The degradation rate of the-6 nano composite material in the process of degrading Methyl Orange (MO) dye under visible light reaches 0.0151min-1；Ag2CO3/g-C3N4-6 degradation rate of the nanocomposite for degrading Methylene Blue (MB) dye under visible light is 0.0040min-1. The dye and Ag in this example2CO3/g-C3N4The mass ratio of the nanocomposite material is 0.025:1, compared with the conventional g-C3N4The material and the catalyst are used less. And in Ag2CO3/g-C3N4After the-6 nano composite material is used for 3 times, the catalytic activity of the nano composite material is hardly changed, which shows that the nano composite material has good stability under the irradiation of visible light.
Example 2
Preparation of thin layer g-C3N4：
Weighing 10g of urea solid, placing the urea solid in a covered crucible, placing the crucible in a muffle furnace, raising the temperature to 550 ℃ at the temperature rise rate of 4 ℃/min, preserving the heat for 4h, and then reducing the temperature to room temperature at the temperature drop rate of 4 ℃/min to obtain the once-calcined g-C3N4Then grinding, and grinding the ground g-C3N4Transferring to a magnetic boat, placing in a muffle furnace for secondary calcination, heating to 550 deg.C at 4 deg.C/min, maintaining for 4 hr, and cooling to room temperature at 4 deg.C/min to obtain thin layer g-C3N4。
Preparation of Ag2CO3/g-C3N4Nano composite material:
(1) 80mg of the above-prepared thin layer g-C was added3N4Ultrasonic dispersion is carried out in deionized water for 6 hours to obtain g-C3N4A dispersion liquid;
(2) AgNO with Ag content of 31.4mg is added under stirring3Dropwise adding the solution into g-C obtained in the step (1)3N4Stirring the dispersion for 60 min;
(3) under the condition of stirring, 10mL of K with the mass concentration of 2mg/mL2CO3Dropwise adding the solution into the dispersion liquid obtained in the step (2), and continuously stirring for 30 min;
(4) naturally settling the reaction system in the step (3) after stirring, taking out supernatant, washing the lower precipitate with ultrapure water, centrifuging, and freeze-drying to obtain Ag2CO3/g-C3N4-2 nanocomposite.
Ag2CO3/g-C3N4The nano composite material is used for photocatalytic degradation of dyes:
weighing 20mg of the above preparedAg2CO3/g-C3N4And (3) putting the-2 nano composite material into a photocatalysis tube, adding 25mL of Methyl Orange (MO) dye (the mass concentration is 20mg/L), stirring for 30min in a dark room, and reacting under visible light.
Ag prepared in this example2CO3/g-C3N4The quasi-first order reaction kinetic curve of-2 nano composite material for catalyzing and degrading Methyl Orange (MO) dye under visible light is shown in figure 6, from which it can be seen that Ag2CO3/g-C3N42 when the nano composite material degrades Methyl Orange (MO) dye under visible light, the degradation rate reaches 0.0086min-1。
Example 3
Preparation of thin layer g-C3N4：
Weighing 10g of urea solid, placing the urea solid in a covered crucible, placing the crucible in a muffle furnace, raising the temperature to 550 ℃ at the temperature rise rate of 4 ℃/min, preserving the heat for 4h, and then reducing the temperature to room temperature at the temperature drop rate of 4 ℃/min to obtain the once-calcined g-C3N4Then grinding, and grinding the ground g-C3N4Transferring to a magnetic boat, placing in a muffle furnace for secondary calcination, heating to 550 deg.C at 4 deg.C/min, maintaining for 4 hr, and cooling to room temperature at 4 deg.C/min to obtain thin layer g-C3N4。
Preparation of Ag2CO3/g-C3N4Nano composite material:
(1) 80mg of the above-prepared thin layer g-C was added3N4Ultrasonic dispersion is carried out in deionized water for 12 hours to obtain g-C3N4A dispersion liquid;
(2) AgNO with Ag content of 62.8mg is added under stirring3Dropwise adding the solution into g-C obtained in the step (1)3N4Stirring the dispersion for 60 min;
(3) under the condition of stirring, 10mL of K with the mass concentration of 4mg/mL2CO3Dropwise adding the solution into the dispersion liquid obtained in the step (2), and continuously stirring for 60 min;
(4) the reaction system in the step (3) is naturally performed after the stirring is finishedSettling, taking out supernatant, washing the lower precipitate with ultrapure water, centrifuging, and freeze drying to obtain Ag2CO3/g-C3N4-4 nanocomposite.
Ag2CO3/g-C3N4The nano composite material is used for photocatalytic degradation of dyes:
weighing 20mg of the Ag prepared above2CO3/g-C3N44-nanometer composite material is put into a photocatalysis tube, 25mL Methyl Orange (MO) dye (the mass concentration is 20mg/L) is added, stirring is carried out for 30min in a dark room, and then reaction is carried out under visible light.
Ag prepared in this example2CO3/g-C3N4The quasi-first order reaction kinetic curve of-4 nano composite material for catalyzing and degrading Methyl Orange (MO) dye under visible light is shown in FIG. 6, from which it can be seen that Ag2CO3/g-C3N44 when the nano composite material degrades Methyl Orange (MO) dye under visible light, the degradation rate reaches 0.0137min-1。
Example 4
Preparation of thin layer g-C3N4：
Weighing 10g of urea solid, placing the urea solid in a covered crucible, placing the crucible in a muffle furnace, raising the temperature to 550 ℃ at the temperature rise rate of 4 ℃/min, preserving the heat for 4h, and then reducing the temperature to room temperature at the temperature drop rate of 4 ℃/min to obtain the once-calcined g-C3N4Then grinding, and grinding the ground g-C3N4Transferring to a magnetic boat, placing in a muffle furnace for secondary calcination, heating to 550 deg.C at 4 deg.C/min, maintaining for 4 hr, and cooling to room temperature at 4 deg.C/min to obtain thin layer g-C3N4。
Preparation of Ag2CO3/g-C3N4Nano composite material:
(1) 80mg of the above-prepared thin layer g-C was added3N4Ultrasonic dispersion is carried out in deionized water for 6 hours to obtain g-C3N4A dispersion liquid;
(2) AgNO with Ag content of 15.7mg is added under stirring3Dropwise adding the solution into g-C obtained in the step (1)3N4Stirring the dispersion for 30 min;
(3) under the condition of stirring, 10mL of K with the mass concentration of 1mg/mL2CO3Dropwise adding the solution into the dispersion liquid obtained in the step (2), and continuously stirring for 30 min;
(4) naturally settling the reaction system in the step (3) after stirring, taking out supernatant, washing the lower precipitate with ultrapure water, centrifuging, and freeze-drying to obtain Ag2CO3/g-C3N4-1 nanocomposite.
Ag2CO3/g-C3N4The nano composite material is used for photocatalytic degradation of dyes:
weighing 20mg of the Ag prepared above2CO3/g-C3N4-1 nanometer composite material is put into a photocatalysis tube, 25mL Methyl Orange (MO) dye (the mass concentration is 20mg/L) is added, stirring is carried out for 30min in a dark room, and then reaction is carried out under visible light.
Ag prepared in this example2CO3/g-C3N4FIG. 6 shows the quasi-first order reaction kinetics curve of-1 nano composite material for catalytic degradation of Methyl Orange (MO) dye under visible light, from which it can be seen that Ag2CO3/g-C3N4-1 when the nano composite material degrades Methyl Orange (MO) dye under visible light, the degradation rate reaches 0.0024min-1。
Example 5
Preparation of thin layer g-C3N4：
Weighing 10g of urea solid, placing the urea solid in a covered crucible, placing the crucible in a muffle furnace, raising the temperature to 550 ℃ at the temperature rise rate of 4 ℃/min, preserving the heat for 4h, and then reducing the temperature to room temperature at the temperature drop rate of 4 ℃/min to obtain the once-calcined g-C3N4Then grinding, and grinding the ground g-C3N4Transferring to a magnetic boat, placing in a muffle furnace for secondary calcination, heating to 550 deg.C at 4 deg.C/min, maintaining for 4 hr, and cooling to room temperature at 4 deg.C/min to obtain thin layer g-C3N4。
Preparation of Ag2CO3/g-C3N4Nano composite material:
(1) 80mg of the above-prepared thin layer g-C was added3N4Ultrasonic dispersion is carried out in deionized water for 18 hours to obtain g-C3N4A dispersion liquid;
(2) AgNO with Ag content of 125.3mg is added under stirring3Dropwise adding the solution into g-C obtained in the step (1)3N4Stirring the dispersion for 60 min;
(3) under the condition of stirring, 10mL of K with the mass concentration of 8mg/mL2CO3Dropwise adding the solution into the dispersion liquid obtained in the step (2), and continuously stirring for 60 min;
(4) naturally settling the reaction system in the step (3) after stirring, taking out supernatant, washing the lower precipitate with ultrapure water, centrifuging, and freeze-drying to obtain Ag2CO3/g-C3N4-8 nanocomposite.
Ag2CO3/g-C3N4The nano composite material is used for photocatalytic degradation of dyes:
weighing 20mg of the Ag prepared above2CO3/g-C3N4Adding 25mL of Methyl Orange (MO) dye (with the mass concentration of 20mg/L) into a photocatalytic tube, stirring for 30min in a dark room, and reacting under visible light.
Ag prepared in this example2CO3/g-C3N4The quasi-first order reaction kinetic curve of the-8 nano composite material for catalyzing and degrading Methyl Orange (MO) dye under visible light is shown in FIG. 6, and from the graph, Ag can be seen2CO3/g-C3N4When the-8 nano composite material degrades Methyl Orange (MO) dye under visible light, the degradation rate reaches 0.0123min-1。
Finally, the above embodiments are only used for illustrating the technical solutions of the present application and not for limiting, although the present application is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present application without departing from the spirit and scope of the technical solutions of the present application, and all the technical solutions of the present application should be covered by the claims of the present application.
Claims (10)
1. Ag2CO3/g-C3N4The preparation method of the nano composite material is characterized by comprising the following steps:
(1) thin layer g-C3N4Ultrasonic dispersion is carried out in deionized water to obtain g-C3N4A dispersion liquid;
(2) AgNO is added under stirring3Dropping the solution into g-C obtained in the step (1)3N4Continuing stirring in the dispersion liquid;
(3) under the condition of stirring, adding K2CO3Dripping the solution into the dispersion liquid obtained in the step (2), and continuously stirring;
(4) naturally settling the reaction system in the step (3) after stirring, taking out supernatant, washing the lower precipitate with ultrapure water, centrifuging, and freeze-drying to obtain Ag2CO3/g-C3N4A nanocomposite material.
2. The method of claim 1, wherein the thin layer g-C is3N4The preparation method comprises the following steps:
calcining urea to obtain primary calcined g-C3N4(ii) a Grinding the ground g-C3N4Then carrying out secondary calcination to obtain a thin layer g-C3N4。
3. The method according to claim 2, wherein the conditions of the primary calcination and the secondary calcination are both: raising the temperature to 550 ℃ at the heating rate of 4 ℃/min, preserving the heat for 4 hours, and then reducing the temperature to the room temperature at the cooling rate of 4 ℃/min.
4. The method of claim 1, wherein the thin layer g-C is3N4With AgNO3The mass ratio of the components is 9:1-2: 8.
5. The method of claim 4, wherein the thin layer g-C3N4With AgNO3The mass ratio of (A) to (B) is 2: 3.
6. The method of claim 1, wherein the thin layer g-C is3N4And carrying out ultrasonic dispersion in deionized water for 6-18 h.
7. The method of claim 1, wherein the AgNO3Dropping the solution into g-C obtained in the step (1)3N4After dispersing in the liquid, continuing stirring for 30-60 min; k2CO3And (3) after the solution is dripped into the dispersion liquid obtained in the step (2), continuously stirring for 30-60 min.
8. The method according to claim 1, wherein Ag is added2CO3/g-C3N4Ag in nano composite material2CO3The mass percentage of the component (A) is 10-80%.
9. Ag2CO3/g-C3N4Nanocomposite material, characterized in that Ag is2CO3/g-C3N4The nanocomposite is prepared by the preparation method of any one of claims 1 to 8.
10. Ag according to any one of claims 1 to 82CO3/g-C3N4Application of the nano composite material in visible light catalysis.
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Application publication date: 20200825 |