CN113941354A - Nano composite carbon nitride catalytic material and preparation method and application thereof - Google Patents
Nano composite carbon nitride catalytic material and preparation method and application thereof Download PDFInfo
- Publication number
- CN113941354A CN113941354A CN202111177905.2A CN202111177905A CN113941354A CN 113941354 A CN113941354 A CN 113941354A CN 202111177905 A CN202111177905 A CN 202111177905A CN 113941354 A CN113941354 A CN 113941354A
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- catalytic material
- nano composite
- composite carbon
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title claims abstract description 52
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 42
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 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 claims abstract description 17
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000006731 degradation reaction Methods 0.000 claims description 19
- 230000015556 catabolic process Effects 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 16
- 230000004298 light response Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- -1 nitrogen-containing compound Chemical class 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000007547 defect Effects 0.000 description 9
- KOAWAWHSMVKCON-UHFFFAOYSA-N 6-[difluoro-(6-pyridin-4-yl-[1,2,4]triazolo[4,3-b]pyridazin-3-yl)methyl]quinoline Chemical class C=1C=C2N=CC=CC2=CC=1C(F)(F)C(N1N=2)=NN=C1C=CC=2C1=CC=NC=C1 KOAWAWHSMVKCON-UHFFFAOYSA-N 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001362 electron spin resonance spectrum Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SOWBFZRMHSNYGE-UHFFFAOYSA-N oxamic acid Chemical compound NC(=O)C(O)=O SOWBFZRMHSNYGE-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Images
Classifications
-
- 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
-
- B01J35/23—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a nano composite carbon nitride catalytic material, a preparation method and application thereof, wherein a small molecular nitrogen-containing compound is used as a raw material, and C60As an auxiliary agent, the carbon nitride catalyst with red light response is simply and conveniently prepared by adopting a high-temperature calcination-ball milling method. Firstly, weighing and putting a measured micromolecular nitrogen-containing compound into a crucible with a cover, putting the crucible into a muffle furnace for roasting, naturally cooling, and then mixing the obtained carbon nitride with a proper amount of C60After uniform mixing, a small amount of water or alcohol is dripped, and the mixture is put into a ball mill for ball milling and dried to obtain the required nano composite carbon nitride catalytic material. The composite carbon nitride catalytic material has obvious up-conversion capability, can effectively carry out photocatalytic degradation on rhodamine B under the irradiation of visible light and red light (with the wavelength of 420-660 nm), has high catalytic activity and good repeatability, and has potential utilization value in the aspect of sewage treatment. The preparation method is simple, convenient, easy to operate, low in cost and suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of preparation and application of catalytic materials, in particular to a nano composite carbon nitride catalytic material and a preparation method and application thereof.
Background
The photocatalytic reaction has great potential in the aspects of environmental purification and energy conversion, and in the solar spectrum, visible light and infrared light account for more than 95% of solar irradiation energy. Therefore, how to efficiently utilize visible light and infrared light has become a hot point of research. In addition, designing a high-efficiency sewage degradation photocatalyst is a challenging task in the field of photocatalysis, and a photocatalytic system needs to simultaneously meet the capabilities of high-efficiency supply and catalytic conversion of photo-generated charges so as to realize effective conversion of pollutants.
Graphite phase carbon nitride (g-C)3N4) The material has good chemical stability, low price, easy obtaining, environmental protection, proper band gap, unique physical and chemical properties and controllable electronic structure. Generally, carbon nitride has an absorption edge of about 460nm, and shows a narrow visible light response range, and thus, how to increase g-C3N4The light capturing capability of the LED light source improves the utilization rate of visible light and red light, and becomes a hotspot of research. For example, Zhang et al dramatically reduced g-C by co-condensing urea and oxalic amide, followed by calcination in molten salts3N4Band gap, extending the visible light utilization range (Angewandte Chemie International Edition,2017,56: 13445-. Yang et al successfully synthesized a carbon nitride sample with an absorption edge as high as 735nm by polymerizing melamine and cyanuric chloride under the guidance of ultraviolet light. (Angewandte Chemie International Edition,2018,57: 8674-.
In addition to light trapping capability, charge separation is another key factor in determining the catalytic efficiency of semiconductor photocatalysts. C60As a novel carbon material, C has excellent electron transfer ability and can effectively inhibit the recombination of photogenerated electron-hole pairs on carbon nitride60And g-C3N4The photocatalysis performance of the carbon nitride can be effectively improved by compounding. In recent years, defects/vacancies that are ubiquitous in semiconductor materials have received great attention, and surface defects can serve as trapping sites to trap electrons or holes, thereby achieving separation of photogenerated carriers. In addition, the formation of surface defects can also lead to changes in the local coordination environment and electronic structure around the defects, which can act as active sites for redox Catalysis, thereby accelerating the reaction rate (Applied Catalysis B: Environmental,2018,238: 465-470.). Thus the obtained carbon nitride and C are baked at high temperature60The composite material is compounded in a ball milling mode, so that a large number of defect sites can be constructed, and the catalytic reaction of the catalytic material under visible light and red light is facilitated.
The preparation of the composite material with red light response by adopting a simple method is an innovative challenge. Therefore, the method for preparing the nano composite carbon nitride material, which is environment-friendly, low in cost and simple in process, has very important practical significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a nano composite carbon nitride catalytic material, a preparation method and application thereof, wherein a micromolecule nitrogen-containing compound is calcined and then reacts with C60The nano catalytic material with rich defect sites is obtained by ball milling and compounding, the prepared nano composite carbon nitride material has obvious up-conversion capacity, the method is simple and convenient, the operation is easy, the cost is low, and the problems mentioned in the background technology are solved.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing a nano composite carbon nitride catalytic material comprises the following steps:
s1, putting the measured small molecular nitrogen-containing compound into a container, putting the container into a muffle furnace for roasting, preserving heat for a period of time, and cooling to room temperature to obtain carbon nitride;
s2, mixing carbon nitride with C60After uniform mixing, a small amount of deionized water or alcohol is dripped, the mixture is placed in a ball mill for ball milling for a period of time, and the nano composite carbon nitride catalytic material is obtained after drying.
Preferably, the small molecular nitrogen-containing compound is one or more of melamine, urea, dicyandiamide and thiourea.
Preferably, in step S1, the temperature of the roasting is raised to 550-900 ℃ at a rate of 2-10 ℃/min, and the temperature is maintained for 3-6 h.
Preferably, in step S1, the temperature of the calcination is raised to 700 ℃ at a rate of 2 ℃/min, and the temperature is maintained for a period of 4 hours.
Preferably, in step S2, the carbon nitride, C60And the mass ratio of the alcohol to the deionized water is 5: 0.1-0.25: 8; the ball milling speed is 300-600 r/m, and the ball milling time is 2-12 h.
Preferably, said C60The doping amount of the catalyst is 0.1 to 10 percent.
The nano composite carbon nitride catalytic material is prepared by the preparation method.
Preferably, the morphology of the nano composite carbon nitride catalytic material is uniform lamellar, C60High dispersion on the flaky carbon nitride.
An application of a nano composite carbon nitride catalytic material in catalytic degradation of rhodamine B under red light irradiation.
Preferably, the wavelength of the red light is 660 nm.
The invention has the beneficial effects that: the invention takes cheap and easily obtained micromolecule nitrogen-containing compounds as main raw materials and adopts a high-temperature roasting-ball milling method to prepare the red light response nano composite carbon nitride material. In the preparation process, the small molecular nitrogen-containing compound is gradually polymerized to generate carbon nitride along with the continuous rise of the temperature. The calcination process does not exclude air, and the yield of the obtained carbon nitride is reduced along with the increase of the calcination temperature. During ball milling, adding small amount of alcohol or water to obtain C60Can be uniformly dispersed and embedded on the surface of the carbon nitride.
Compared with the prior art, the invention takes the cheap and easily obtained small molecular nitrogen-containing compound as the raw material, and can obviously reduce the production cost; the carbon nitride is ball-milled and compounded after being calcined to directly obtain the multi-defect nano composite carbon nitride material, thereby simplifying the production process. The method is carried out under normal pressure, does not need to use complex equipment, and is easy for industrial production. The red-light-responsive nano composite carbon nitride material obtained by the preparation method disclosed by the invention is used as a catalyst for photodegradation of rhodamine B under red light, has higher catalytic activity and better repeatability, and has potential utilization value in the aspect of sewage treatment. The preparation method is simple, convenient, easy to operate, low in cost and suitable for large-scale production.
Drawings
FIG. 1 is C prepared in example 160X-ray diffraction pattern of composite carbon nitride and carbon nitride prepared in comparative example 1;
FIG. 2 is C prepared in example 160An infrared spectrum of the composite carbon nitride and the carbon nitride prepared in comparative example 1;
FIG. 3 is a drawing showing a preparation process of example 1C is prepared by60Isothermal adsorption-desorption curves of composite carbon nitride and carbon nitride prepared in comparative example 1;
FIG. 4 is C prepared in example 160Electron paramagnetic resonance spectra of composite carbon nitride and carbon nitride prepared in comparative example 1;
FIG. 5(a) is C prepared in example 160UV-VISIBLE ABSORPTION SPECTRUM OF COMPOSITE CARBON NITRIDE AND CARBON NITRIDE PREPARED IN COMPARATIVE EXAMPLE 1, FIG. 5(b) is C prepared in EXAMPLE 160Band gap diagram of composite carbon nitride and carbon nitride prepared in comparative example 1;
FIG. 6(a) is C prepared in example 160Fluorescence emission spectra of composite carbon nitride and carbon nitride prepared in comparative example 1, and FIG. 6(b) is C prepared in example 160Fluorescence emission spectra of the composite carbon nitride under different excitation wavelengths;
FIG. 7 is C prepared in example 160Confocal microscope photograph of the composite carbon nitride under 730nm laser irradiation;
FIGS. 8(a) and 8(b) are transmission electron micrographs of carbon nitride prepared in comparative example 1, and FIGS. 8(C) and 8(d) are C prepared in example 160Transmission electron micrographs of composite carbon nitride;
FIG. 9 is C prepared in example 160An active diagram of red light catalytic degradation of rhodamine B solution by composite carbon nitride;
FIG. 10 is C prepared in example 160And (3) a repeatability chart of red light catalytic degradation of rhodamine B solution by using the composite carbon nitride.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
30g of melamine were ground and uniformly charged into a crucible with a lid, and the crucible was placed in a muffle furnaceAnd (4) roasting, heating the muffle furnace to 700 ℃ at the speed of 2 ℃/min, preserving the heat for 4h, and naturally cooling to obtain the carbon nitride. Carbon nitride, C60And deionized water according to the mass ratio of 5: 0.1: 8, placing the mixture into a ball mill, performing ball milling at the speed of 300 revolutions per minute for 8 hours, and drying to obtain the nano composite carbon nitride material which is marked as CN-700-C60。
To test C prepared in this example60/g-C3N4The material prepared by the embodiment is used for red light catalytic degradation of rhodamine B (RhB), and the photocatalytic activity of the material is tested. 50mL of 10. mu.g/mL rhodamine B aqueous solution is weighed into a test tube, and 0.03g of C prepared in the example is added60/g-C3N4An LED lamp with a wavelength of 660nm and power of 50W is used as a red light source. Opening magnetic stirring, and stirring in dark place for 0.5 hour before illumination to achieve adsorption balance; sampling every 0.5 hour after starting the light, taking 4mL each time, and centrifuging in a high-speed centrifuge of 8000r/min to obtain a clear liquid. The degradation rate is 1.547h-1。
Example 2
And grinding 30g of melamine, uniformly filling the melamine into a crucible with a cover, placing the crucible into a muffle furnace for roasting, heating the muffle furnace to 700 ℃ at the speed of 2 ℃/min, preserving heat for 4h, and naturally cooling to obtain the carbon nitride. Carbon nitride, C60And deionized water according to the mass ratio of 5: 0.05: and 8, placing the carbon powder into a ball mill, performing ball milling at the speed of 300 revolutions per minute for 8 hours, and drying to obtain the nano composite carbon nitride material.
C prepared in this example60/g-C3N4The material is used for the reaction of catalytic degradation of rhodamine B by red light (660nm), the reaction condition is the same as that of the embodiment 1, the illumination is 90min, and the degradation rate is 1.399h-1。
Example 3
Grinding 30g of melamine, uniformly filling the melamine into a crucible with a cover, placing the crucible into a muffle furnace for roasting, heating the muffle furnace to 550 ℃ at the speed of 2 ℃/min, preserving heat for 3h, and naturally cooling to obtain the carbon nitride. Carbon nitride, C60And deionized water according to the mass ratio of 5: 0.15: 8 is placed in a ball millBall milling at 400 rpm in a ball mill, keeping for 7h, and drying to obtain the nano composite carbon nitride material.
C prepared in this example60/g-C3N4The material is used for the reaction of catalytic degradation of rhodamine B by red light (660nm), the reaction condition is the same as that of the embodiment 1, the illumination is 90min, and the degradation rate is 1.097h-1。
Example 4
Grinding 30g of melamine, uniformly filling the melamine into a crucible with a cover, placing the crucible into a muffle furnace for roasting, heating the muffle furnace to 900 ℃ at the speed of 10 ℃/min, preserving the temperature for 5h, and naturally cooling to obtain the carbon nitride. Carbon nitride, C60And deionized water according to the mass ratio of 5: 0.20: and 8, placing the mixture into a ball mill, performing ball milling at the speed of 500 rpm, keeping for 7 hours, and drying to obtain the nano composite carbon nitride material.
C prepared in this example60/g-C3N4The material is used for the reaction of catalytic degradation of rhodamine B by red light (660nm), the reaction condition is the same as that of the embodiment 1, the illumination is carried out for 90min, and the degradation rate is 1.128h-1。
Example 5
And grinding 30g of melamine, uniformly filling the melamine into a crucible with a cover, placing the crucible into a muffle furnace for roasting, heating the muffle furnace to 650 ℃ at the speed of 5 ℃/min, preserving heat for 6h, and naturally cooling to obtain the carbon nitride. Carbon nitride, C60And deionized water according to the mass ratio of 5: 0.25: and 8, placing the mixture into a ball mill, performing ball milling at the speed of 600 revolutions per minute for 10 hours, and drying to obtain the nano composite carbon nitride material.
C prepared in this example60/g-C3N4The material is used for the reaction of catalytic degradation of rhodamine B by red light (660nm), the reaction condition is the same as that of the embodiment 1, the illumination is 90min, and the degradation rate is 1.116h-1。
Comparative example 1
The roasting temperature of the melamine is 550 ℃, and C is not added60A carbon nitride material, designated CN, was prepared according to the procedure of example 1.
The prepared material is characterized by an X-ray diffraction powder diffractometer, a Fourier infrared spectrometer, a physical adsorption instrument, an electron paramagnetic resonance instrument, an ultraviolet-visible-near infrared spectrophotometer, a fluorescence spectrometer, a confocal microscope, a transmission electron microscope and the like, and figures 1, 2, 3, 4, 5, 6, 7 and 8 are respectively an X-ray diffraction spectrum, a Fourier infrared spectrum, a nitrogen adsorption-desorption isothermal curve, an electron paramagnetic resonance spectrum, an ultraviolet-visible absorption spectrum, a fluorescence emission spectrum, a confocal microscope photo and a transmission electron microscope photo of the material prepared according to the steps of the example 1 and the comparative example 1.
As can be seen from FIG. 1, CN and CN-700-C60The X-ray diffraction pattern of the sample shows diffraction peaks at 13.0 degrees and 27.5 degrees, and the weak diffraction peak at 13.0 degrees represents the 3-s-triazine structural unit of the plane layer, corresponding to g-C3N4The (100) crystal plane of (A); a strong diffraction peak of 27.5 degrees, which is a characteristic peak of interlayer accumulation of the conjugated aromatic substance and corresponds to a (002) crystal face of graphite-phase carbon nitride; CN-700-C60Diffraction peaks of the sample at 10.9 degrees, 17.7 degrees, 20.7 degrees and 21.7 degrees can be assigned as C60Characteristic peak of (2). FIG. 1 shows that the high temperature calcination of melamine can yield graphite phase carbon nitride, and the ball milling method can be used to successfully prepare C60Incorporation of g-C3N4Among them.
As shown in FIG. 2, CN and CN-700-C60The infrared spectrum characteristic peaks of the samples are almost completely the same, which indicates that C is in the ball milling preparation process60Doping does not alter g-C3N4All samples have similar chemical compositions. In the infrared spectrum, absorption peaks are mainly concentrated in three regions: 810.7cm-1A sharp absorption peak, mainly caused by the bending shock absorption of the triazine cyclic compound; 1240 and 1645cm-1The absorption peak is derived from a typical carbon nitride heterocyclic ring stretching vibration mode; 3000-3300 cm-1The wide absorption peaks correspond to the stretching vibration of O-H and N-H.
As can be seen from FIG. 3, N in both samples2Physical adsorption isotherms are classified according to IUPAC, and belong to class IV isotherms. And CN-700-C60The sample exhibited a typical hysteresis loop of type H1, which can be in the pore size distribution phaseThe shape and size of the hysteresis ring are consistent with the texture parameter analysis. CN and CN-700-C60The BET specific surface areas of the samples were 6.53m, respectively2G and 37.34m2(ii) in terms of/g. The results show that the ball milling is compounded with C60The specific surface area of the carbon nitride can be greatly increased.
As can be seen from FIG. 4, the electron paramagnetic resonance spectrum can reflect the existence of defect sites in the samples, and the two samples have similar Lorentz signals, CN-700-C60The signal intensity of the sample is higher, which indicates that the surface of the sample has more defect sites.
As can be seen from FIG. 5(a) in FIG. 5, the CN sample showed a distinct absorption edge around 467nm, C60The doping of (A) makes its absorption edge largely "red-shifted" to 722nm and CN-700-C is found60The absorption of the sample to visible light is greatly enhanced in the interval of 460nm-750 nm. The forbidden band width of the sample is calculated according to the semiconductor forbidden band derivation formula, and as shown in FIG. 5(b), the forbidden band width of CN is 2.66eV, and CN-700-C60The forbidden band width of the crystal is reduced to 1.72eV, namely C60The ball milling doping greatly improves the utilization rate of the sample to visible light, and has the capability of utilizing red light.
As can be seen from FIG. 6, FIG. 6(a) shows CN and CN-700-C measured at an excitation wavelength of 360nm60The fluorescence emission spectrum of the sample generally indicates that the lower the intensity of the emission peak of the sample is, the lower the recombination rate of the photo-generated electron-hole pairs in the sample is. As can be seen from the figure, the CN sample has a strong fluorescence emission peak near 468nm, and CN-700-C60The PL signal intensity of the sample is greatly reduced, and obvious quenching phenomenon occurs, which shows that C60The doping of (2) can accelerate electron transfer, and the defect sites brought by ball milling doping effectively prevent the recombination of photon-generated carriers. Further, CN-700-C was studied using PL60The upconversion property of (A) is shown in FIG. 6(b), with an excitation wavelength of 620-780nm for CN-700-C60The test was performed with emission wavelengths centered around 468 nm. As can be seen, CN is subjected to a long wavelength of (>600nm) and low-energy red light, and emits short-wavelength (468nm) and high-energy blue light. The results show CN-700-C60The samples had upconversion properties.
FIG. 7 shows CN-700-C60The confocal microscope photo of the sample can emit blue fluorescence after being excited by laser with the wavelength of 730nm, and the sample is proved to have the up-conversion performance more intuitively.
FIG. 8 shows CN sample and CN-700-C60Transmission electron micrograph of sample. As can be seen from fig. 8(a-b), the CN sample was massive and uneven in thickness, and the stripe-shaped distribution zone with a deep contrast was a thick portion of the sample. After grinding and doping, CN-700-C60As shown in FIG. 8(C-d), the bulk structure of the sample was found to be exfoliated, thin and uniform, and C was found60High dispersion on the flaky carbon nitride.
FIG. 9 shows C prepared in example 160/g-C3N4The reaction activity diagram of the material for catalyzing and degrading the RhB solution under 660nm red light irradiation. As can be seen from fig. 9, the concentration of the red light hardly changes under the irradiation of red light without adding a catalyst; dark adsorption phase CN-700-C60The adsorption capacity is strong and is related to the larger specific surface, under 660nm red light irradiation, two samples can degrade RhB solution, but CN-700-C60The photocatalytic activity of the photocatalyst is obviously superior to that of CN; through calculation, the red light degradation reaction process conforms to a quasi-first-order kinetic model, and the degradation rate constant of the CN sample is 0.159h-1，CN-700-C60Sample 1.547h-1About 9.73 times the rate of degradation of CN. Certificate C60Ball milling doping can greatly enhance the ability of the sample to utilize red light.
FIG. 10 shows C prepared in this example60/g-C3N4The material is used for a repeatability chart of catalytic degradation RhB under red light (660nm) irradiation. As can be seen from FIG. 10, the activity was almost unchanged after repeating 3 times, indicating that the composite material was stable and could be used many times.
The invention takes cheap and easily obtained small molecular nitrogen-containing compound as raw material, which can obviously reduce the production cost; the carbon nitride is ball-milled and compounded after being calcined to directly obtain the multi-defect nano composite carbon nitride material, thereby simplifying the production process. The method is carried out under normal pressure, does not need to use complex equipment, and is easy for industrial production. The red-light-responsive nano composite carbon nitride material obtained by the preparation method disclosed by the invention is used as a catalyst for photodegradation of rhodamine B under red light, has higher catalytic activity and better repeatability, and has potential utilization value in the aspect of sewage treatment. The preparation method is simple, convenient, easy to operate, low in cost and suitable for large-scale production.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes in the embodiments and/or modifications of the invention can be made, and equivalents and modifications of some features of the invention can be made without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a nano composite carbon nitride catalytic material is characterized by comprising the following steps:
s1, putting the measured small molecular nitrogen-containing compound into a container, putting the container into a muffle furnace for roasting, preserving heat for a period of time, and cooling to room temperature to obtain carbon nitride;
s2, mixing carbon nitride with C60After uniform mixing, a small amount of deionized water or alcohol is dripped, the mixture is placed in a ball mill for ball milling for a period of time, and the nano composite carbon nitride catalytic material is obtained after drying.
2. The method for preparing a nanocomposite carbon nitride catalytic material according to claim 1, wherein: the small molecular nitrogen-containing compound is one or more of melamine, urea, dicyandiamide and thiourea.
3. The method for preparing a nanocomposite carbon nitride catalytic material according to claim 1, wherein: in step S1, the temperature of the roasting is raised to 550-900 ℃ at a rate of 2-10 ℃/min, and the temperature is maintained for 3-6 h.
4. The method for preparing a nanocomposite carbon nitride catalytic material according to claim 3, wherein: in step S1, the temperature of the calcination is raised to 700 ℃ at the rate of 2 ℃/min, and the heat preservation period is 4 h.
5. The method for preparing a nanocomposite carbon nitride catalytic material according to claim 1, wherein: in step S2, the carbon nitride, C60And the mass ratio of the alcohol to the deionized water is 5: 0.1-0.25: 8; the ball milling speed is 300-600 r/m, and the ball milling time is 2-12 h.
6. The method for preparing a nanocomposite carbon nitride catalytic material according to claim 1 or 5, wherein: said C is60The doping amount of the catalyst is 0.1 to 10 percent.
7. A nano composite carbon nitride catalytic material is characterized in that: the preparation method comprises the step of preparing the nano composite carbon nitride catalytic material by the preparation method of any one of claims 1 to 6.
8. The nanocomposite, carbon nitride catalytic material of claim 7, wherein: the shape of the nano composite carbon nitride catalytic material is uniform lamellar, C60High dispersion on the flaky carbon nitride.
9. The application of the nano composite carbon nitride catalytic material as claimed in claim 7 or 8 in catalytic degradation of rhodamine B under red light irradiation.
10. Use according to claim 9, characterized in that: the wavelength of the red light is 660 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111177905.2A CN113941354B (en) | 2021-10-09 | 2021-10-09 | Nano composite carbon nitride catalytic material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111177905.2A CN113941354B (en) | 2021-10-09 | 2021-10-09 | Nano composite carbon nitride catalytic material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113941354A true CN113941354A (en) | 2022-01-18 |
| CN113941354B CN113941354B (en) | 2022-04-19 |
Family
ID=79329437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111177905.2A Active CN113941354B (en) | 2021-10-09 | 2021-10-09 | Nano composite carbon nitride catalytic material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113941354B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104174437A (en) * | 2014-09-10 | 2014-12-03 | 天津工业大学 | Graphene/C60/g-C3N4 heterojunction composite film and preparation method thereof |
| CN105664996A (en) * | 2016-03-09 | 2016-06-15 | 中国科学院地球环境研究所 | Preparation method and application of g-C3N4/TiO2 heterojunction photocatalytic film |
| CN107890878A (en) * | 2017-10-20 | 2018-04-10 | 浙江工商大学 | A kind of carbon ball azotized carbon nano material and its preparation and application |
| CN110026229A (en) * | 2019-05-23 | 2019-07-19 | 重庆工商大学 | A kind of preparation method and applications of the mesoporous carbonitride of nitrogenous defect |
| CN110560120A (en) * | 2019-08-16 | 2019-12-13 | 徐州工程学院 | Preparation method of porous carbon nitride material, porous carbon nitride material and application thereof |
| CN110589806A (en) * | 2019-07-25 | 2019-12-20 | 武汉大学 | Efficient purification method of water-dispersible carbon nano material |
| FR3095598A1 (en) * | 2019-05-02 | 2020-11-06 | IFP Energies Nouvelles | PHOTOCATALYTICAL REDUCTION PROCESS OF CARBON DIOXIDE IN THE PRESENCE OF AN EXTERNAL ELECTRIC FIELD |
-
2021
- 2021-10-09 CN CN202111177905.2A patent/CN113941354B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104174437A (en) * | 2014-09-10 | 2014-12-03 | 天津工业大学 | Graphene/C60/g-C3N4 heterojunction composite film and preparation method thereof |
| CN105664996A (en) * | 2016-03-09 | 2016-06-15 | 中国科学院地球环境研究所 | Preparation method and application of g-C3N4/TiO2 heterojunction photocatalytic film |
| CN107890878A (en) * | 2017-10-20 | 2018-04-10 | 浙江工商大学 | A kind of carbon ball azotized carbon nano material and its preparation and application |
| FR3095598A1 (en) * | 2019-05-02 | 2020-11-06 | IFP Energies Nouvelles | PHOTOCATALYTICAL REDUCTION PROCESS OF CARBON DIOXIDE IN THE PRESENCE OF AN EXTERNAL ELECTRIC FIELD |
| CN110026229A (en) * | 2019-05-23 | 2019-07-19 | 重庆工商大学 | A kind of preparation method and applications of the mesoporous carbonitride of nitrogenous defect |
| CN110589806A (en) * | 2019-07-25 | 2019-12-20 | 武汉大学 | Efficient purification method of water-dispersible carbon nano material |
| CN110560120A (en) * | 2019-08-16 | 2019-12-13 | 徐州工程学院 | Preparation method of porous carbon nitride material, porous carbon nitride material and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| BO CHAI ET AL: ""Fullerene modified C3N4 composites with enhanced photocatalytic activity under visible light irradiation"", 《DALTON TRANSACTIONS》 * |
| XIANG CHEN ET AL: ""a facile mechanochemical route to a covalently bonded graphitic carbon nitride (g-C3N4) and fullerene hybrid toward enhanced visible light photocatalytic hydrogen produciton"", 《NANOSCALE》 * |
| 章单伟: ""纳米光催化材料的改性及降解有机染料废水研究"", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113941354B (en) | 2022-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Das et al. | Effect of cobalt doping into graphitic carbon nitride on photo induced removal of dye from water | |
| CN110339853B (en) | C3N5Material, preparation method and application thereof | |
| CN107837816B (en) | Fe2O3/g-C3N4Composite system, preparation method and application | |
| CN110756215B (en) | CoP-HCCN composite photocatalyst and preparation method and application thereof | |
| CN113318764A (en) | Preparation method and application of nitrogen defect/boron doped tubular carbon nitride photocatalyst | |
| CN107876079B (en) | Preparation method and application of sulfur-doped zinc oxide quantum dot modified porous graphite phase nitrogen carbide composite material | |
| CN107774294A (en) | A kind of novel photochemical catalyst K g C3N4And its prepare and apply | |
| CN109665560B (en) | Carbon and nitrogen doped BiOCl with full-spectrum absorption and preparation method and application thereof | |
| CN102728342A (en) | Preparation method of bismuth vanadate visible light photocatalysis material | |
| CN107262132B (en) | Sulfur-doped g-C3N4Preparation method of zinc-cadmium sulfide composite photocatalyst | |
| CN105772056A (en) | Preparation method and application of graphite-phase carbon nitride photocatalysis material | |
| CN108325555A (en) | Nitrogen auto-dope is graphitized azotized carbon nano piece photochemical catalyst and its preparation method and application | |
| CN102698784B (en) | Visible light response catalyst and preparation method thereof | |
| CN114377711A (en) | Simple preparation method and application of high-crystallinity graphite carbon nitride | |
| Guo et al. | Probing the effect of P-doping in polymeric carbon nitride on CO 2 photocatalytic reduction | |
| CN112007679B (en) | Co/V bimetal doped g-C3N4Photocatalyst and preparation method and application thereof | |
| CN114669315A (en) | Preparation method of all-organic composite photocatalytic material for photocatalytic hydrogen peroxide production | |
| Yu et al. | One-step solution combustion synthesis of Bi/BiOCl nanosheets: Reaction mechanism and photocatalytic RhB degradation | |
| CN106311306A (en) | Method for preparing lithium-doped graphite phase carbon nitride material | |
| CN113941354B (en) | Nano composite carbon nitride catalytic material and preparation method and application thereof | |
| CN106964388A (en) | A kind of preparation method of the two-dimentional graphite phase carbon nitride composite photo-catalyst of wolframic acid stannous doping | |
| CN106732726A (en) | A kind of photochemical catalyst CNB BA and preparation method thereof | |
| CN113578368B (en) | g-C 3 N 4 /Ag 3 PO 4 /BiFeO 3 Preparation method and application of composite visible light catalyst | |
| CN113509952B (en) | Ytterbium and erbium co-doped Yb-Er/g-C 3 N 4 Photocatalyst and synthesis method and application thereof | |
| CN108654669A (en) | A kind of doped zinc sulphide catalyst and preparation method for solar hydrogen making |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231208 Address after: 221433 Xulou village, yaowan Town, Xinyi City, Xuzhou City, Jiangsu Province Patentee after: Xinyi lvkang biomass energy Co.,Ltd. Address before: 221000 Lishui Road, Yunlong District, Xuzhou, Jiangsu 2 Patentee before: XUZHOU University OF TECHNOLOGY |
|
| TR01 | Transfer of patent right |