CN113617351A - Graphite-like phase carbon nitride/graphene oxide composite aerogel and method - Google Patents
Graphite-like phase carbon nitride/graphene oxide composite aerogel and method Download PDFInfo
- Publication number
- CN113617351A CN113617351A CN202110995392.XA CN202110995392A CN113617351A CN 113617351 A CN113617351 A CN 113617351A CN 202110995392 A CN202110995392 A CN 202110995392A CN 113617351 A CN113617351 A CN 113617351A
- Authority
- CN
- China
- Prior art keywords
- graphite
- carbon nitride
- graphene oxide
- phase carbon
- aqueous solution
- 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.)
- Pending
Links
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 140
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 120
- 239000004964 aerogel Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 78
- 239000007864 aqueous solution Substances 0.000 claims abstract description 70
- 239000007788 liquid Substances 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000006185 dispersion Substances 0.000 claims abstract description 47
- 239000002135 nanosheet Substances 0.000 claims abstract description 47
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229930003268 Vitamin C Natural products 0.000 claims abstract description 39
- 235000019154 vitamin C Nutrition 0.000 claims abstract description 39
- 239000011718 vitamin C Substances 0.000 claims abstract description 39
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000011240 wet gel Substances 0.000 claims abstract description 18
- 239000004202 carbamide Substances 0.000 claims abstract description 16
- 239000012153 distilled water Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 11
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 13
- 238000007710 freezing Methods 0.000 claims description 11
- 230000008014 freezing Effects 0.000 claims description 11
- 230000010355 oscillation Effects 0.000 claims description 11
- 239000002356 single layer Substances 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000010410 layer Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000000703 high-speed centrifugation Methods 0.000 claims description 3
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000001179 sorption measurement Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002957 persistent organic pollutant Substances 0.000 description 7
- 239000006228 supernatant Substances 0.000 description 7
- 239000000975 dye Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- RAVDHKVWJUPFPT-UHFFFAOYSA-N silver;oxido(dioxo)vanadium Chemical class [Ag+].[O-][V](=O)=O RAVDHKVWJUPFPT-UHFFFAOYSA-N 0.000 description 4
- 239000004966 Carbon aerogel Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002096 quantum dot Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229940072056 alginate Drugs 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000001782 photodegradation Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004965 Silica aerogel Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005406 washing 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- 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
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a preparation method of a graphite-like phase carbon nitride/graphene oxide composite aerogel, which specifically comprises the following steps: 1, grinding urea or melamine or a mixture of urea and melamine in any ratio into powder and heating to prepare graphite-like carbon nitride; step 2, mixing the graphite-like carbon nitride obtained in the step 1 with distilled water; step 3, mixing the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid with the graphene oxide aqueous solution and the vitamin C aqueous solution, and uniformly mixing; step 4, centrifuging the precursor sol at a high speed; and 5, drying the wet gel by using a freeze dryer to obtain the graphite-like phase carbon nitride/graphene oxide composite aerogel. The graphite-like phase carbon nitride/graphene oxide composite aerogel prepared by the method is also provided, and compared with the graphite-like phase carbon nitride, the degradation efficiency and the degradation rate of the photocatalytic material for degrading organic dye are improved.
Description
Technical Field
The invention belongs to the technical field of photocatalyst preparation and structure regulation, and particularly relates to a graphite-like phase carbon nitride/graphene oxide composite aerogel and a preparation method of the graphite-like phase carbon nitride/graphene oxide composite aerogel.
Background
The photocatalysis can directly utilize sunlight to degrade organic pollutants, has the characteristics of low energy consumption, no secondary pollution, wide application range and the like, and is energy-saving and environment-friendly organic pollutantsThe water treatment technology has been widely regarded by various countries and is rapidly becoming a research hotspot in academic circles and industrial circles of various countries. The core of the photocatalytic reaction is a semiconductor photocatalyst, and the photocatalytic efficiency and the cycling stability of the semiconductor photocatalyst are key factors influencing the pollutant removal effect. The earliest and most widely used semiconductor photocatalyst under investigation was TiO2But its photocatalytic efficiency is not high. In recent years, ZnO, CdS, MoS2、Ag3PO4、Bi2WO6And graphite-like phase carbon nitride (g-C)3N4) The new semiconductor photocatalytic materials were developed successively, wherein g-C3N4Has relatively high photocatalytic activity, is cheap and easy to obtain, is safe and nontoxic, and is one of the hotspots of the current research.
g-C at ambient temperature3N4Has a forbidden band width of about 2.7eV, lacks absorption for visible light above 460nm, has poor conductivity, and is easy to recombine photogenerated electron-hole pairs, thereby resulting in g-C3N4The photocatalytic efficiency of (a) is limited. Research shows that nano g-C is dispersed and fixed by using a load material as a supporting framework3N4Is favorable for obtaining higher effective specific surface area to a certain extent to enhance the adsorption capacity, but strong oxidative free radicals generated by the photocatalytic reaction have strong corrosive decomposition effect on a load material, and can cause the nano g-C3N4Shedding, agglomeration and failure, and the corrosion effect is especially obvious for organic load materials. Thus, it can be seen that nano g-C3N4The self-agglomeration and the photo-corrosion effect of the compound can cause the compound not to play a role continuously, and are the main reasons for poor cycle stability of the compound. However, the currently reported g-C3N4The efficiency of photocatalytic degradation of organic pollutants under the irradiation of visible light is generally low, several hours or even longer time is required for thoroughly removing the pollutants, and the circulation stability is not good, so that the g-C is seriously restricted3N4Further application and popularization in the field of photocatalytic treatment of organic pollutants in industrial wastewater, so how to greatly improve g-C3N4The photocatalytic efficiency and the cycling stability of the compound are still the subject of relevant researchersOne of the great challenges.
Carbon-based materials, such as fullerene, carbon nanotube, graphene and the like, generally have a large specific surface area and a rich pore structure, and have strong self-corrosion resistance, and thus have wide application in the aspect of adsorbing pollutants. However, the single adsorption makes the adsorption of the pollutants ineffective once reaching a saturation state, and the pollutants cannot be continuously removed, and the synergistic effect of adsorption and photocatalysis has obvious advantages compared with the single adsorption or photocatalysis. The carbon-based material is used as a carrier, so that a supporting framework with a higher specific surface area can be provided for the catalyst, and the catalyst can be effectively prevented from being corroded, so that the cycle stability of the catalyst is improved; after special surface modification, the carbon-based material can selectively adsorb specific organic pollutants from the solution and enrich the specific organic pollutants on the surface, and the collision probability of the photo-generated strong oxidation free radical and organic pollutant molecules is increased to accelerate the reaction rate; the carbon-based material can also capture nano g-C3N4The photo-generated electrons in the conduction band promote photo-generated charge separation, thereby improving the efficiency of the photocatalytic reaction. The aerogel is a nano material with a microporous, mesoporous and macroporous multilevel fractal network structure, in particular to novel carbon-based aerogels such as graphene aerogel, carbon nanotube aerogel and composite carbon aerogel, and has good conductivity, excellent mechanical strength and rich multilevel pore structure, if the carbon-based aerogel is used as the nano g-C3N4A carrier of (2), a nano g-C3N4Effectively combines with the advantages of the carbon-based aerogel to prepare the composite aerogel integrating adsorption and photocatalysis, and is expected to simultaneously solve the problem of nano g-C3N4The problems of low photocatalytic efficiency, poor cycling stability and the like are solved, and a novel efficient and sustainable photocatalytic material is obtained.
Xujing et al (national invention patent publication No. CN110433849A, published: 2020-10-27) prepares PCNO by hydrothermal reaction using melamine as a raw material; dispersing graphite oxide in water to prepare graphene oxide nanosheet GO dispersion liquid 1, adding concentrated nitric acid and concentrated sulfuric acid, performing heating reflux reaction, and filtering and dialyzing to obtain ox-GQDs dispersion liquid; dispersing PCNO in water, adding ox-GQDs dispersion liquid, stirring and mixing, washing and drying a precipitate, and grinding to obtain PCNGD; respectively dispersing PCNGD and graphite oxide in water to obtain a PCNGD dispersion liquid and a GO dispersion liquid 2, performing mixed ultrasound, sequentially adding ethylenediamine and CTAB, respectively performing heating reaction, cooling to obtain a PCNGD/GO hydrogel, and freeze-drying to obtain the PCNGD-GOA photocatalyst.
Taofenanthrene et al (national invention patent publication No. CN111841607A, published: 2020-10-30) use silica aerogel as hard template, and make the precursor enter the pores of the hard template through ultrasonic dispersion, oscillation, and solvothermal; limited domain synthesis of g-C by heat treatment3N4A nanomaterial; removing the hard template by HF solution dipping to obtain porous g-C3N4And (3) nano materials.
Zhuangjiadong et al (national invention patent publication No. CN108686697A, published: 2020-12-29) peel off bulk phase g-C3N4 powder to prepare two-dimensional nano flaky g-C3N4, then disperse the two-dimensional nano flaky g-C3N4 in water uniformly by ultrasonic to prepare suspension, add soluble alginate, pour the obtained mixed solution into a mold after vigorous stirring for freeze drying; and (3) putting the freeze-dried block material into a curing agent solution for curing, and then further performing freeze drying to obtain the alginate-based composite g-C3N4 photocatalytic aerogel material.
Liulin et al (national invention patent publication No. CN106513027A, published: 2017-03-22) use cellulose as a raw material, a sodium hydroxide/urea/water mixed solution as a solvent to dissolve the raw material to obtain a cellulose solution, and prepare cellulose aerogel through simple chemical crosslinking; loading melamine on the cellulose aerogel by adopting an extrusion adsorption method, converting the cellulose aerogel into carbon aerogel by adopting a high-temperature calcination method, simultaneously converting the melamine into graphite-phase carbon nitride, and performing vapor deposition on the carbon aerogel to form g-C with a three-dimensional porous structure3N4and/C aerogel.
Lujian U.S. et al (national invention patent publication No. CN107715910A, published: 2018-02-23) first calcined dicyandiamide as a raw material at a high temperature to prepare flaky carbon nitride; then the perylene tetracarboxylic dianhydride and carbon nitride are used as raw materials, imidazole is used as a solvent, and carbon nitride of the perylene tetracarboxylic dianhydride is prepared under the high-temperature heating condition; uniformly dispersing carbon nitride modified by perylenetetracarboxylic dianhydride and graphene oxide in deionized water, ultrasonically stirring, transferring into a reaction kettle for reaction, and freeze-drying to obtain the aerogel composite material consisting of the carbon nitride modified by perylenetetracarboxylic dianhydride and the graphene oxide.
Zhuyong et al (national invention patent publication No. CN108479833A, published: 2018-09-04) calcine a mixture of dicyandiamide and thiourea in a muffle furnace to obtain a bulk-phase carbon nitride, then disperse the bulk-phase carbon nitride in deionized water and transfer the bulk-phase carbon nitride to a hydrothermal kettle to keep the bulk-phase carbon nitride at a certain temperature for a certain time, freeze-dry the obtained sample, and then calcine the sample for a second time in a nitrogen atmosphere to obtain the oxygen-doped carbon nitride aerogel.
Lujian America et al (national invention patent publication No. CN108855191A, published: 2020-09-08) prepares carbon nitride nanosheets by twice calcining dicyandiamide as a precursor; dispersing carbon nitride nanosheets in water, growing silver metavanadate quantum dots in situ, and preparing a silver metavanadate quantum dot/carbon nitride nanosheet composite material; carrying out hydrothermal reaction on the silver metavanadate quantum dot/carbon nitride nanosheet composite material and graphene oxide, and then freezing and drying to prepare the silver metavanadate quantum dot/carbon nitride nanosheet/graphene hybrid aerogel which is a visible light response hybrid aerogel.
However, the aerogel materials involved in the above reports have insufficient adsorption capacity for dyes in photocatalytic experiments, and have low photocatalytic efficiency.
Disclosure of Invention
The invention aims to provide a graphite-like phase carbon nitride/graphene oxide composite aerogel, which improves the degradation efficiency and the degradation rate of a photocatalytic material for degrading organic dyes compared with the graphite-like phase carbon nitride.
The second purpose of the invention is to provide a preparation method of the graphite-like phase carbon nitride/graphene oxide composite aerogel.
The technical scheme adopted by the invention is that the preparation method of the graphite-like phase carbon nitride/graphene oxide composite aerogel specifically comprises the following steps:
step 1, grinding urea or melamine or a mixture of urea and melamine in any ratio into powder, heating the powder from room temperature to 530-570 ℃ at a heating rate of 8-10 ℃/min, and keeping the temperature of 530-570 ℃ for 3-4h to obtain the graphite-like carbon nitride;
step 2, mixing the graphite-like phase carbon nitride obtained in the step 1 with distilled water, and performing ultrasonic oscillation on the mixed liquid for 4-6 hours to obtain a graphite-like phase carbon nitride nanosheet water system dispersion liquid;
step 3, mixing the graphite-like phase carbon nitride nanosheet water-based dispersion liquid obtained in the step 2 with a graphene oxide aqueous solution and a vitamin C aqueous solution, stirring for 0.5-1h to fully and uniformly mix the mixture, and then putting the mixed liquid into a drying oven at the temperature of 45-55 ℃ for heat treatment for 0.5-2.0h to obtain precursor sol;
step 4, performing high-speed centrifugation on the precursor sol obtained in the step 3 at the rotating speed of 4000-;
and 5, drying the wet gel obtained in the step 4 by using a freeze dryer to obtain the graphite-like phase carbon nitride/graphene oxide composite aerogel.
The alumina crucible may be 50mL or 100mL in volume.
The present invention is also characterized in that,
in the step 2, the mass ratio of the graphite-like phase carbon nitride to the distilled water is 1: 2000.
In the step 3, the concentration of the graphene oxide in the graphene oxide aqueous solution is 6 mg/mL; in the step 3, the concentration of the vitamin C in the vitamin C aqueous solution is 100 mg/mL;
in the step 3, the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 6-120:10: 3.
In the step 3, the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid obtained in the step 2, the graphene oxide aqueous solution and the vitamin C aqueous solution are mixed under the condition of a water bath at 25-28 ℃.
In step 3, the graphene oxide is a single-layer graphene oxide or a few-layer industrial-grade graphene oxide.
In the step 4, the centrifugation time is 3-10 min.
In the step 5, the quick freezing time in a freeze dryer is 2-3 h; the freeze drying is vacuum freeze drying for 24-26 hr.
The second technical scheme adopted by the invention is that the graphite-like phase carbon nitride/graphene oxide composite aerogel is prepared by adopting the preparation method.
The invention has the beneficial effects that:
(1) the preparation method of the graphite-like phase carbon nitride/graphene oxide composite aerogel provided by the invention effectively solves the problem of low photocatalysis efficiency of the graphite-like phase carbon nitride, and simultaneously organically combines the graphite-like phase carbon nitride and the carbon-based aerogel, improves the degradation efficiency of the photocatalytic material for degrading organic dye, and obtains the material which is environment-friendly and efficient and is used for purifying organic sewage.
(2) According to the invention, graphene oxide and graphene are used as carrier materials of the graphite-like phase carbon nitride catalyst, and the graphite-like phase carbon nitride, the graphene oxide and the graphene are compounded, so that the efficiency of photocatalytic degradation of organic dye by the graphite-like phase carbon nitride is improved. The aerogel prepared by the invention has high photocatalytic efficiency, the removal rate of rhodamine B dye can reach more than 96.1% after illumination for 30min under the condition of visible light, and the photocatalytic reaction kinetic constant is 2.42h-1Compared with the similar graphite phase carbon nitride under the same test conditions, the photodegradation efficiency is improved by 23.5 percent, and the reaction rate is improved by 30.4 percent.
(3) According to the method, the graphite-like phase carbon nitride, the graphene and the graphene oxide are assembled into the graphite-like phase carbon nitride/graphene oxide composite aerogel with the three-dimensional porous structure, so that the defects in the reports can be overcome, and the organic pollutants in the water body can be efficiently removed under the condition of visible light.
Drawings
FIG. 1 is a flow chart of the production process of the present invention;
FIG. 2 is an SEM image (10 μm on a scale) of an aerogel prepared in example 1 of the present invention;
FIG. 3 is an SEM image (scale bar: 1 μm) of an aerogel prepared in example 1 of the present invention;
FIG. 4 is a TEM image (scale: 100nm) of an aerogel prepared in example 1 of the present invention;
FIG. 5 is a TEM image (scale: 5nm) of an aerogel prepared in example 1 of the present invention;
FIG. 6 is a graph of the effect of an experiment for degrading rhodamine B through photocatalysis by using aerogel prepared by the invention;
FIG. 7 is a graph showing the effect of the experiment of photocatalytic degradation of rhodamine B by graphite-like carbon nitride prepared by the invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of a graphite-like phase carbon nitride/graphene oxide composite aerogel, which specifically comprises the following steps as shown in figure 1:
step 1, grinding urea or melamine or a mixture of urea and melamine in any ratio into powder, placing the powder into an alumina crucible, placing the crucible into a muffle furnace, heating the crucible from room temperature to 530-570 ℃ at a heating rate of 8-10 ℃/min, and keeping the temperature at 530-570 ℃ for 3-4h to obtain graphite-like phase carbon nitride; the alumina crucible may be 50mL or 100mL in volume.
Step 2, mixing the graphite-like phase carbon nitride obtained in the step 1 with distilled water, and performing ultrasonic oscillation on the mixed liquid for 4-6 hours to obtain a graphite-like phase carbon nitride nanosheet water system dispersion liquid;
in the step 2, the mass ratio of the graphite-like phase carbon nitride to the distilled water is 1: 2000.
Step 3, mixing the graphite-like phase carbon nitride nanosheet water-based dispersion liquid obtained in the step 2 with a graphene oxide aqueous solution and a vitamin C aqueous solution, stirring for 0.5-1h to fully and uniformly mix the mixture, and then putting the mixed liquid into a drying oven at the temperature of 45-55 ℃ for heat treatment for 0.5-2.0h to obtain precursor sol;
in the step 3, the concentration of the graphene oxide in the graphene oxide aqueous solution is 6 mg/mL; in the step 3, the concentration of the vitamin C in the vitamin C aqueous solution is 100 mg/mL;
in the step 3, the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 6-120:10: 3.
In the step 3, the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid obtained in the step 2, the graphene oxide aqueous solution and the vitamin C aqueous solution are mixed under the condition of a water bath at 25-28 ℃.
In step 3, the graphene oxide is a single-layer graphene oxide or a few-layer industrial-grade graphene oxide.
Step 4, performing high-speed centrifugation on the precursor sol obtained in the step 3 at the rotating speed of 4000-; in the step 4, the centrifugation time is 3-10 min.
And 5, drying the wet gel obtained in the step 4 by using a freeze dryer to obtain the graphite-like phase carbon nitride/graphene oxide composite aerogel.
In the step 5, the quick freezing time in a freeze dryer is 2-3 h; the freeze drying is vacuum freeze drying for 24-26 hr.
The invention also provides a graphite-like phase carbon nitride/graphene oxide composite aerogel prepared by the preparation method.
Example 1
Preparing the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 12:10: 3.
Firstly, grinding 30g of urea into powder, placing the powder into an alumina crucible with the volume of 50mL, placing the crucible into a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 10 ℃/min, and keeping the temperature at 550 ℃ for 4h to obtain the graphite-like phase carbon nitride.
Secondly, mixing the graphite-like phase carbon nitride with distilled water according to the mass ratio of 1:2000, and carrying out ultrasonic oscillation on the mixed liquid for 4 hours to obtain 0.5mg/mL graphite-like phase carbon nitride nanosheet water-based dispersion liquid.
Thirdly, mixing 0.5mg/mL of graphite-like phase carbon nitride nanosheet water-based dispersion liquid, 6mg/mL of graphene oxide aqueous solution and 100mg/mL of vitamin C aqueous solution according to a volume ratio of 12:10:3, stirring for 0.5h under a water bath condition at 25 ℃ to fully and uniformly mix the mixture, and then putting the mixed liquid into a drying oven at 50 ℃ for heat treatment for 0.5h to obtain precursor sol; the graphene oxide is a single layer of graphene oxide.
Fourthly, centrifuging the precursor sol at the high speed of 4200r/min for 3min, and removing the supernatant to obtain the wet gel.
And finally, freezing the obtained wet gel in a vacuum drier for 2h, vacuumizing for 24h after the sample is completely solidified, and thus obtaining the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 12:10: 3. Fig. 2 to 3 are SEM images of the graphite-like phase carbon nitride/graphene oxide composite aerogel prepared according to the present invention, and fig. 4 to 5 are TEM images of the graphite-like phase carbon nitride/graphene oxide composite aerogel prepared according to the present invention, and it can be seen from fig. 2 to 5 that the graphite-like phase carbon nitride is more uniformly dispersed on the graphene sheet layer, and the graphene and graphene oxide are assembled into the graphite-like phase carbon nitride/graphene oxide composite aerogel having a three-dimensional porous structure, thereby avoiding the problem of stacking of the graphite-like phase carbon nitride into large particles, and improving the uniformity of the dispersion of the graphite-like phase carbon nitride in the system.
As shown in fig. 6, the aerogel prepared in this embodiment has a very high photocatalytic efficiency, under visible light conditions, the removal rate of rhodamine B dye after 30min of illumination can reach more than 96.1%, and the photocatalytic reaction kinetic constant is 2.42h-1The photodegradation efficiency was improved compared to the graphite-like phase carbon nitride under the same test conditions (as shown in FIG. 7)The reaction rate is improved by 23.5 percent and 30.4 percent.
Example 2
Preparing the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 6:10: 3.
Firstly, grinding 30g of urea into powder, placing the powder in an alumina crucible with the volume of 50mL, placing the crucible in a muffle furnace, heating the crucible from room temperature to 530 ℃ at the heating rate of 8 ℃/min, and keeping the temperature at 530 ℃ for 4h to obtain the graphite-like phase carbon nitride.
Secondly, mixing the graphite-like phase carbon nitride with distilled water according to the mass ratio of 1:2000, and carrying out ultrasonic oscillation on the mixed liquid for 6 hours to obtain 0.5mg/mL graphite-like phase carbon nitride nanosheet water-based dispersion liquid.
Thirdly, mixing 0.5mg/mL of graphite-like phase carbon nitride nanosheet water-based dispersion liquid, 6mg/mL of graphene oxide aqueous solution and 100mg/mL of vitamin C aqueous solution according to a volume ratio of 6:10:3, stirring for 1h under the condition of 28 ℃ water bath to fully and uniformly mix the mixture, and then putting the mixed liquid into a 45 ℃ oven for heat treatment for 2h to obtain precursor sol; the graphene oxide is a few-layer industrial-grade graphene oxide.
Fourthly, centrifuging the precursor sol at a high speed of 4000r/min for 10min, and removing supernatant to obtain wet gel.
And finally, freezing the obtained wet gel in a vacuum drier for 3 hours, vacuumizing for 26 hours after the sample is completely solidified, and thus obtaining the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 6:10: 3.
Example 3
Preparing the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 120:10: 3.
Firstly, grinding 30g of urea into powder, placing the powder in an alumina crucible with the volume of 50mL, placing the crucible in a muffle furnace, raising the temperature from room temperature to 570 ℃ at the temperature raising rate of 9 ℃/min, and keeping the temperature at 570 ℃ for 3.5h to obtain the graphite-like phase carbon nitride.
Secondly, mixing the graphite-like phase carbon nitride with distilled water according to the mass ratio of 1:2000, and carrying out ultrasonic oscillation on the mixed liquid for 5 hours to obtain 0.5mg/mL graphite-like phase carbon nitride nanosheet water-based dispersion liquid.
Thirdly, mixing 0.5mg/mL of graphite-like phase carbon nitride nanosheet water-based dispersion liquid, 6mg/mL of graphene oxide aqueous solution and 100mg/mL of vitamin C aqueous solution according to a volume ratio of 120:10:3, stirring for 0.75h under a water bath condition at 26 ℃ to fully and uniformly mix the mixture, and then putting the mixed liquid into a drying oven at 55 ℃ for heat treatment for 1h to obtain precursor sol; the graphene oxide is a single layer of graphene oxide.
Fourthly, centrifuging the precursor sol at a high speed of 4100r/min for 8min, and removing supernatant to obtain wet gel.
And finally, freezing the obtained wet gel in a vacuum drier for 2.5 hours, vacuumizing for 25 hours after the sample is completely solidified, and thus obtaining the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet water-based dispersion liquid to the graphene oxide water solution to the vitamin C water solution is 120:10: 3.
Example 4
Preparing the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 12:10: 1.
Firstly, grinding 30g of urea into powder, placing the powder into an alumina crucible with the volume of 50mL, placing the crucible into a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 10 ℃/min, and keeping the temperature at 550 ℃ for 4h to obtain the graphite-like phase carbon nitride.
Secondly, mixing the graphite-like phase carbon nitride with distilled water according to the mass ratio of 1:2000, and carrying out ultrasonic oscillation on the mixed liquid for 4 hours to obtain 0.5mg/mL graphite-like phase carbon nitride nanosheet water-based dispersion liquid.
Thirdly, mixing 0.5mg/mL of graphite-like phase carbon nitride nanosheet water-based dispersion liquid, 6mg/mL of graphene oxide aqueous solution and 100mg/mL of vitamin C aqueous solution according to a volume ratio of 12:10:1, stirring for 0.5h under a water bath condition at 25 ℃ to fully and uniformly mix the graphene oxide aqueous solution and the vitamin C aqueous solution, and then putting the mixed liquid into a drying oven at 50 ℃ for heat treatment for 0.5h to obtain precursor sol; the graphene oxide is a single layer of graphene oxide.
Fourthly, centrifuging the precursor sol at the high speed of 4200r/min for 3min, and removing the supernatant to obtain the wet gel.
And finally, freezing the obtained wet gel in a vacuum drier for 2h, vacuumizing for 24h after the sample is completely solidified, and thus obtaining the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 12:10: 1.
Example 5
Preparing the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 12:10: 5.
Firstly, grinding 30g of urea into powder, placing the powder into an alumina crucible with the volume of 50mL, placing the crucible into a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 10 ℃/min, and keeping the temperature at 550 ℃ for 4h to obtain the graphite-like phase carbon nitride.
Secondly, mixing the graphite-like phase carbon nitride with distilled water according to the mass ratio of 1:2000, and carrying out ultrasonic oscillation on the mixed liquid for 4 hours to obtain 0.5mg/mL graphite-like phase carbon nitride nanosheet water-based dispersion liquid.
Thirdly, mixing 0.5mg/mL of graphite-like phase carbon nitride nanosheet water-based dispersion liquid, 6mg/mL of graphene oxide aqueous solution and 100mg/mL of vitamin C aqueous solution according to a volume ratio of 12:10:5, stirring for 0.5h under a water bath condition at 25 ℃ to fully and uniformly mix the graphene oxide aqueous solution and the vitamin C aqueous solution, and then putting the mixed liquid into a drying oven at 50 ℃ for heat treatment for 0.5h to obtain precursor sol; the graphene oxide is a single layer of graphene oxide.
Fourthly, centrifuging the precursor sol at the high speed of 4200r/min for 3min, and removing the supernatant to obtain the wet gel.
And finally, freezing the obtained wet gel in a vacuum drier for 2h, vacuumizing for 24h after the sample is completely solidified, and thus obtaining the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 12:10: 5.
Example 6
Preparing the graphite-like phase carbon nitride/graphene oxide composite aerogel with the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution being 12:10:3 without heat treatment.
Firstly, grinding 30g of urea into powder, placing the powder into an alumina crucible with the volume of 50mL, placing the crucible into a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 10 ℃/min, and keeping the temperature at 550 ℃ for 4h to obtain the graphite-like phase carbon nitride.
Secondly, mixing the graphite-like phase carbon nitride with distilled water according to the mass ratio of 1:2000, and carrying out ultrasonic oscillation on the mixed liquid for 4 hours to obtain 0.5mg/mL graphite-like phase carbon nitride nanosheet water-based dispersion liquid.
Thirdly, mixing 0.5mg/mL of graphite-like phase carbon nitride nanosheet water-based dispersion liquid, 6mg/mL of graphene oxide aqueous solution and 100mg/mL of vitamin C aqueous solution according to the volume ratio of 12:10:3, and stirring for 0.5h under the condition of water bath at 25 ℃ to fully and uniformly mix the mixture to obtain precursor sol; the graphene oxide is a single layer of graphene oxide.
Fourthly, centrifuging the precursor sol at the high speed of 4200r/min for 3min, and removing the supernatant to obtain the wet gel.
And finally, freezing the obtained wet gel in a vacuum drier for 2h, vacuumizing for 24h after the sample is completely solidified, and thus obtaining the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 12:10: 3.
Example 7
Preparing the graphite-like phase carbon nitride/graphene oxide composite aerogel with the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution being 12:10:3, and carrying out heat treatment for 2 h.
Firstly, grinding 30g of urea into powder, placing the powder into an alumina crucible with the volume of 50mL, placing the crucible into a muffle furnace, raising the temperature from room temperature to 550 ℃ at the heating rate of 10 ℃/min, and keeping the temperature at 550 ℃ for 4h to obtain the graphite-like phase carbon nitride.
Secondly, mixing the graphite-like phase carbon nitride with distilled water according to the mass ratio of 1:2000, and carrying out ultrasonic oscillation on the mixed liquid for 4 hours to obtain 0.5mg/mL graphite-like phase carbon nitride nanosheet water-based dispersion liquid.
Thirdly, mixing 0.5mg/mL of graphite-like phase carbon nitride nanosheet water-based dispersion liquid, 6mg/mL of graphene oxide aqueous solution and 100mg/mL of vitamin C aqueous solution according to a volume ratio of 12:10:3, stirring for 0.5h under a water bath condition at 25 ℃ to fully and uniformly mix the mixture, and then putting the mixed liquid into a drying oven at 50 ℃ for heat treatment for 2h to obtain precursor sol; the graphene oxide is a single layer of graphene oxide.
Fourthly, centrifuging the precursor sol at the high speed of 4200r/min for 3min, and removing the supernatant to obtain the wet gel.
And finally, freezing the obtained wet gel in a vacuum drier for 2h, vacuumizing for 24h after the sample is completely solidified, and thus obtaining the graphite-like phase carbon nitride/graphene oxide composite aerogel, wherein the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 12:10: 3.
Claims (7)
1. A preparation method of a graphite-like phase carbon nitride/graphene oxide composite aerogel is characterized by comprising the following steps:
step 1, grinding urea or melamine or a mixture of urea and melamine in any ratio into powder, heating the powder from room temperature to 530-570 ℃ at a heating rate of 8-10 ℃/min, and keeping the temperature of 530-570 ℃ for 3-4h to obtain the graphite-like carbon nitride;
step 2, mixing the graphite-like phase carbon nitride obtained in the step 1 with distilled water, and performing ultrasonic oscillation on the mixed liquid for 4-6 hours to obtain a graphite-like phase carbon nitride nanosheet water system dispersion liquid;
step 3, mixing the graphite-like phase carbon nitride nanosheet water-based dispersion liquid obtained in the step 2 with a graphene oxide aqueous solution and a vitamin C aqueous solution, stirring for 0.5-1h to fully and uniformly mix the mixture, and then putting the mixed liquid into a drying oven at the temperature of 45-55 ℃ for heat treatment for 0.5-2.0h to obtain precursor sol;
step 4, performing high-speed centrifugation on the precursor sol obtained in the step 3 at the rotating speed of 4000-;
and 5, drying the wet gel obtained in the step 4 by using a freeze dryer to obtain the graphite-like phase carbon nitride/graphene oxide composite aerogel.
2. The preparation method of the graphite-like phase carbon nitride/graphene oxide composite aerogel according to claim 1, wherein in the step 2, the mass ratio of the graphite-like phase carbon nitride to the distilled water is 1: 2000.
3. The method for preparing the graphite-phase carbon nitride/graphene oxide composite aerogel according to claim 1, wherein in the step 3, the concentration of graphene oxide in the graphene oxide aqueous solution is 6 mg/mL; in the step 3, the concentration of the vitamin C in the vitamin C aqueous solution is 100 mg/mL;
in the step 3, the volume ratio of the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid to the graphene oxide aqueous solution to the vitamin C aqueous solution is 6-120:10: 3.
In the step 3, the graphite-like phase carbon nitride nanosheet aqueous dispersion liquid obtained in the step 2, the graphene oxide aqueous solution and the vitamin C aqueous solution are mixed under the condition of a water bath at 25-28 ℃.
4. The method for preparing the graphite-phase carbon nitride/graphene oxide composite aerogel according to claim 1, wherein in the step 3, the graphene oxide is single-layer graphene oxide or few-layer industrial-grade graphene oxide.
5. The preparation method of the graphite-phase carbon nitride/graphene oxide composite aerogel according to claim 1, wherein in the step 4, the centrifugation time is 3-10 min.
6. The preparation method of the graphite-like carbon nitride/graphene oxide composite aerogel according to claim 1, wherein in the step 5, the rapid freezing time in a freeze dryer is 2-3 h; the freeze drying is vacuum freeze drying for 24-26 hr.
7. The graphite-like phase carbon nitride/graphene oxide composite aerogel is characterized by being prepared by the preparation method according to any one of claims 1 to 6.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110995392.XA CN113617351A (en) | 2021-08-27 | 2021-08-27 | Graphite-like phase carbon nitride/graphene oxide composite aerogel and method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110995392.XA CN113617351A (en) | 2021-08-27 | 2021-08-27 | Graphite-like phase carbon nitride/graphene oxide composite aerogel and method |
Publications (1)
Publication Number | Publication Date |
---|---|
CN113617351A true CN113617351A (en) | 2021-11-09 |
Family
ID=78388051
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110995392.XA Pending CN113617351A (en) | 2021-08-27 | 2021-08-27 | Graphite-like phase carbon nitride/graphene oxide composite aerogel and method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113617351A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114368741A (en) * | 2021-12-31 | 2022-04-19 | 深圳市翔丰华科技股份有限公司 | Preparation method of graphene/carbon nanotube/silicon dioxide aerogel material |
CN115010123A (en) * | 2022-06-14 | 2022-09-06 | 中北大学 | Sulfonated reduced graphene oxide and laser preparation method thereof |
CN115212909A (en) * | 2022-07-14 | 2022-10-21 | 湖南工程学院 | Cauliflower-shaped CdS/C 3 N 4 Hydrothermal synthesis method and application of composite material |
CN115282725A (en) * | 2022-08-31 | 2022-11-04 | 滨州学院 | Composite nano material for air purification and preparation method thereof |
CN116322007A (en) * | 2023-02-23 | 2023-06-23 | 之江实验室 | NiFe-CNTs-RGO composite aerogel material with three-dimensional interconnected pore structure, and preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103769187A (en) * | 2013-12-18 | 2014-05-07 | 江苏悦达新材料科技有限公司 | Preparation method of graphene/g-C3N4 compound photocatalyst |
CN105562053A (en) * | 2016-01-04 | 2016-05-11 | 西南石油大学 | Preparation method of macroscopic aerogel photocatalyst material |
CN107185576A (en) * | 2017-05-24 | 2017-09-22 | 上海大学 | A kind of preparation method of carbonitride/graphene composite material of three-dimensional structure |
CN110694664A (en) * | 2019-10-22 | 2020-01-17 | 邢台学院 | Preparation method and application of graphite-phase carbon nitride/graphene composite photocatalyst |
-
2021
- 2021-08-27 CN CN202110995392.XA patent/CN113617351A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103769187A (en) * | 2013-12-18 | 2014-05-07 | 江苏悦达新材料科技有限公司 | Preparation method of graphene/g-C3N4 compound photocatalyst |
CN105562053A (en) * | 2016-01-04 | 2016-05-11 | 西南石油大学 | Preparation method of macroscopic aerogel photocatalyst material |
CN107185576A (en) * | 2017-05-24 | 2017-09-22 | 上海大学 | A kind of preparation method of carbonitride/graphene composite material of three-dimensional structure |
CN110694664A (en) * | 2019-10-22 | 2020-01-17 | 邢台学院 | Preparation method and application of graphite-phase carbon nitride/graphene composite photocatalyst |
Non-Patent Citations (2)
Title |
---|
白苗苗;阮萱颖;王宇慧;孟宇;马向荣;邢艳;: "三维网络结构石墨烯/氮化碳气凝胶的制备及其光催化性能", 化工科技, no. 01 * |
马新月;徐文博;成双婵;丁玮帅;林真伊;谭诗杨;: "g-C_3N_4/石墨烯水凝胶复合光催化剂降解四环素研究", 环境保护与循环经济, no. 08, pages 19 - 21 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114368741A (en) * | 2021-12-31 | 2022-04-19 | 深圳市翔丰华科技股份有限公司 | Preparation method of graphene/carbon nanotube/silicon dioxide aerogel material |
CN115010123A (en) * | 2022-06-14 | 2022-09-06 | 中北大学 | Sulfonated reduced graphene oxide and laser preparation method thereof |
CN115212909A (en) * | 2022-07-14 | 2022-10-21 | 湖南工程学院 | Cauliflower-shaped CdS/C 3 N 4 Hydrothermal synthesis method and application of composite material |
CN115282725A (en) * | 2022-08-31 | 2022-11-04 | 滨州学院 | Composite nano material for air purification and preparation method thereof |
CN116322007A (en) * | 2023-02-23 | 2023-06-23 | 之江实验室 | NiFe-CNTs-RGO composite aerogel material with three-dimensional interconnected pore structure, and preparation method and application thereof |
CN116322007B (en) * | 2023-02-23 | 2023-12-29 | 之江实验室 | NiFe-CNTs-RGO composite aerogel material with three-dimensional interconnected pore structure, and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN113617351A (en) | Graphite-like phase carbon nitride/graphene oxide composite aerogel and method | |
US11192093B2 (en) | Two-dimensional nitrogen-doped carbon-based titanium dioxide composite material, and preparation method and application thereof for degrading and removing organic pollutants in water | |
CN110342477B (en) | Oxygen-doped porous carbon nitride nanosheet and preparation method thereof | |
CN107115884B (en) | g-C3N4/TiO2Nano-wire assembled structure photocatalyst | |
CN109395763B (en) | Sulfur-doped g-C3N4C-dot porous composite photocatalyst and preparation method and application thereof | |
CN107473261A (en) | A kind of preparation method of zinc oxide/redox graphene composite | |
CN103011264B (en) | Preparation method of one-dimensional metal titanate nanorods | |
CN104692344A (en) | Preparation method of mesoporous graphite-phase carbon nitride material | |
CN107837816B (en) | Fe2O3/g-C3N4Composite system, preparation method and application | |
CN109876845B (en) | M-g-C3N4Preparation method and application of/rGOA composite adsorption visible light catalytic material | |
CN103861630A (en) | Copolymerization-modified graphite-phase carbon nitride hollow ball visible light-driven photocatalyst | |
CN113649044A (en) | Nitrogen-sulfur double-doped porous carbon material catalyst and preparation method thereof | |
CN110841670A (en) | Zero-dimensional black phosphorus quantum dot/one-dimensional tubular carbon nitride composite photocatalyst and preparation method thereof | |
CN111111638B (en) | Preparation method of fly ash photocatalytic material | |
CN110193362A (en) | A kind of zinc oxide/carbon composite photocatalyst and preparation method thereof | |
CN111285368A (en) | Preparation method of nitrogen-boron double-doped porous hollow carbon nano-capsule material | |
CN108745405B (en) | Carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst and preparation method thereof | |
CN105879855B (en) | A kind of graphene-γ-bismuth molybdate nanocomposite and its preparation method and application | |
CN109621975B (en) | Supported ozone catalytic oxidation catalyst and preparation method and application thereof | |
CN110142042B (en) | RGO/TiO2Preparation method and application of/Ag aerogel photocatalyst | |
WO2024011905A1 (en) | Metal-supported spinel nickel manganite nanosphere aerogel, preparation method therefor and use thereof | |
CN115212884B (en) | Preparation method and application of catalyst based on metal ion reinforced free radical domination | |
CN114192145B (en) | GQDs/TiO 2 Preparation method of alpha-FeOOH three-composite photocatalyst | |
CN108793312B (en) | Method for removing antibiotics by using carbon nitride/nitrogen doped hollow mesoporous carbon/bismuth trioxide ternary Z-shaped photocatalyst | |
CN113842938A (en) | Novel g-C3N4Method for preparing derived carbonaceous adsorbent and photocatalytic material |
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 |