CN109046435A - A kind of preparation method of nitrogen defect modification counter opal structure carbonitride - Google Patents
A kind of preparation method of nitrogen defect modification counter opal structure carbonitride Download PDFInfo
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- CN109046435A CN109046435A CN201811061911.XA CN201811061911A CN109046435A CN 109046435 A CN109046435 A CN 109046435A CN 201811061911 A CN201811061911 A CN 201811061911A CN 109046435 A CN109046435 A CN 109046435A
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 230000007547 defect Effects 0.000 title claims abstract description 37
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000012986 modification Methods 0.000 title claims abstract description 14
- 230000004048 modification Effects 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 7
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 229910052681 coesite Inorganic materials 0.000 claims 1
- 229910052906 cristobalite Inorganic materials 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 229910052682 stishovite Inorganic materials 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 229910052905 tridymite Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 230000003115 biocidal effect Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 238000005121 nitriding Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 3
- 229960001180 norfloxacin Drugs 0.000 description 3
- 239000011022 opal Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001795 light effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- UIOFUWFRIANQPC-JKIFEVAISA-N Floxacillin Chemical compound N([C@@H]1C(N2[C@H](C(C)(C)S[C@@H]21)C(O)=O)=O)C(=O)C1=C(C)ON=C1C1=C(F)C=CC=C1Cl UIOFUWFRIANQPC-JKIFEVAISA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 229960004273 floxacillin Drugs 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation methods of nitrogen defect modification counter opal structure carbonitride.This method is by hard template method, by silica template, carbon nitride precursor and nitrogen defect forming agent mixed grinding, obtains the counter opal structure carbonitride of nitrogen defect modification after calcining in an inert atmosphere, then after etched dose of etching.The method of the invention can introduce nitrogen defect in the case where guaranteeing counter opal structure and significantly improve activity, the catalyst of the rich defect of preparation has excellent photoelectric properties, it is applied to photocatalytic degradation antibiotic and shows very efficient catalytic activity, the material is in Photocatalyzed Hydrogen Production, reduction CO2, produce H2O2Etc. photocatalysis fields also have a good application prospect.
Description
Technical field
The present invention relates to a kind of photochemical catalysts that can be used for efficient degradation antibiotic, belong to photocatalysis technology field.
Background technique
In recent years, with a large amount of growths of population, the quickening of process of industrialization, due to a large amount of industrial wastewaters and sanitary sewage
Untreated qualified discharge, all kinds of organic pollutants enter in environment, bring greatly to drinking water safety and agricultural product security
Threat.Wherein, all kinds of organic pollutants such as incretion interferent, antibiotic, pesticide a large amount of detections in the environment.For example,
Norfloxacin causes the drug resistance of bacterium to enhance as one of the people's antibiotic being widely used, extensive use, environment
In residual concentration level it is higher and higher, seriously threaten the healthy and safe of the mankind.Simultaneously as killing of having of antibiotic itself
Bacterium characteristic can not be completely removed in the biological treatment process of municipal sewage plant, therefore, explored and be suitable for by antibiosis
The method for treating water of element pollution, efficient, the adaptable environment functional material of exploitation novel green and the place for being used for polluted water body
Reason has research significance outstanding and application value.
Photocatalitic Technique of Semiconductor has the characteristics that environmental-friendly and efficient as research hotspot now, shows huge
Big application potential.In numerous materials, graphite phase carbon nitride (g-C3N4) material preparation process is simple, photocatalytic activity is high.
Due to containing only two kinds of rich secondary element C and N on the earth, so be a kind of environmentally protective catalyst that not will cause secondary pollution,
And preparation cost is lower.But higher electron-hole recombination rate, the disadvantages of lower specific surface area, seriously limit nitridation
The advantage of carbon.And in the application of photocatalytic pollutant degradation, the method for most applied metal or nonmetal doping enhances
Activity, more or less can all introduce other elements or even precious metal element, this results in high expensive.This catalyst utilizes system
The mode for making nitrogen defect and counter opal structure modification is not only able to retain the characteristic of carbonitride, can also effectively improve carbonitride
Photocatalysis performance.
In this invention, we modify counter opal structure carbonitride using nitrogen defect.The introducing of nitrogen defect can increase
The active site of reaction reduces electron-hole recombinations, enhances electron lifetime, promotes photoelectric properties；And counter opal structure can be with
Increase specific surface area of catalyst, be conducive to mass transfer, enhances absorption property, while can also generate counter opal structures such as " slow light effects "
Inherent characteristic enhances light percent of pass and utilization rate, increases active site, enhances photocatalytic activity.In the process of degradation antibiotic
In, the degradation efficiency of pollutant can be greatly improved in the synergistic effect of two kinds of characteristics, hence it is evident that be better than other types catalyst, from now
From the point of view of some research, report not yet was carried out to the counter opal structure carbonitride of nitrogen defect modification.
Summary of the invention
A kind of preparation method of the counter opal structure carbonitride for being designed to provide nitrogen defect modification of the invention.It should
The counter opal structure of material is and to mix NH using silica as hard template4Then Cl passes through lithographic method after high-temperature calcination
Prepare the counter opal structure carbonitride IO g-C of nitrogen defect modification3N4Nv。
The counter opal carbonitride IO g-C of the modification of nitrogen defect provided by the invention3N4The preparation process of Nv is as follows: by one
Quantitative dicyanodiamine, silicon oxide pellets, ammonium chloride are mixed together, and are ground and are uniformly mixed, etching washing drying after calcining
Obtain sample.The quality of dicyanodiamine is 0.6g, and the quality of silicon oxide pellets is 1g, and the quality of ammonium chloride is 0.6g.Dioxy
The diameter of SiClx bead is about 200nm.The method for preparing silica is as follows: 8mL tetraethyl orthosilicate is added in 92mL ethyl alcohol,
Stirring makes it uniformly form solution A.Then 56.6mL ethyl alcohol, 29.4mL water and 14mL ammonium hydroxide are separately added into the round bottom of 250mL
Flask forms solution B.A liquid is rapidly added in B liquid and is stirred 24 hours in 25 DEG C of oil baths.Sample is through being centrifuged after the reaction was completed
After washing drying, silicon ball is dispersed in water according to mass fraction 5%, 10mL straight screw socket vial is added to, is placed in 110 DEG C
Arrangement is evaporated in electric heating bellows, the solid for being evaporated rear glass wall is the SiO of marshalling2Bead solid.
Above-mentioned preparation method, calcination process carry out in tube-type atmosphere furnace, from room temperature with 2 DEG C of heating rates per minute
520 DEG C are risen to, keeps the temperature 2 hours, then rises to 550 DEG C with 4 DEG C of heating rates per minute and keeps the temperature 2 hours.Calcining whole process is in argon gas
It is carried out in air-flow protection, 0.2 Liter Per Minute of gas flow rate.
Above-mentioned preparation method, the ammonium hydrogen fluoride solution etching through 50mL 4mol/L after the sample after calcining need to be ground
48 hours, the sample after etching need to be washed several times, to remove the interference of heteroion.Washing is centrifuge washing, and revolving speed is
12500r/min, centrifugation time 15min.
Advantage of the invention is embodied in:
1, the invention material has counter opal structure, can increase specific surface area of catalyst, is conducive to mass transfer, enhancing absorption
Performance, while the counter opal structures inherent characteristic such as " slow light effect " can be also generated, enhance light percent of pass and utilization rate, increases work
Property site, enhance photocatalytic activity.
2, (Elemental Analysis) is tested according to elemental analysis, the carbon-nitrogen ratio of blank graphite phase carbon nitride exists
0.67, the carbon-nitrogen ratio of this catalyst can reach 0.74, which effectively passes through nitrogen defect, introduce activated centre, photoelectricity
It has excellent performance, conducive to electronics and the fast transfer of hole in the material, greatly reduces answering for material internal photo-generate electron-hole
It closes, further increases photocatalytic activity.
3, material of the present invention effectively passes through counter opal structure policy optimization materials band structure, enhances light absorption energy
Power enhances the degradation property to organic matter using quantum confined effect.
4, the present invention is by small by the way that the silica of arrangement is added in dicyanodiamine during carbonitride synthesizes
Ball is sintered, the dicyanodiamine in raw material can aggregate into trimerization at 234 DEG C jointly as template under ammonium chloride and argon atmosphere
Cyanamide, and NH4Cl can be decomposed at 337 DEG C.In dicyanodiamine heat polymerization process, undecomposed NH4Cl will be played in space
The effect of intermediate derived from some dicyanodiamine crystal grain and dicyanodiamine is separated, so that long-range be inhibited to polymerize, leads to nitrogen defect,
Nitrogen defect is effectively introduced in the product.
5, raw material economics involved in the invention material preparation process is easy to get, and experimental procedure is simply easily operated.
Detailed description of the invention
Fig. 1 is scanning electron microscope (SEM) figure for the nitrogen defect counter opal structure carbonitride that embodiment obtains
Fig. 2 is the nitrogen defect counter opal structure carbonitride x-ray photoelectron spectroscopy (XPS) that embodiment obtains, and X-ray is spread out
Penetrate map (XRD) and electron paramagnetic resonance map (EPR)
Fig. 3 is that the degradation of blank nitriding carbon and nitrogen defect counter opal structure carbonitride that comparative example and embodiment obtain is real
Test figure
Fig. 4 is the photoelectric current of blank nitriding carbon and nitrogen defect counter opal structure carbonitride that comparative example and embodiment obtain
Spectrogram, impedance diagram, fluorogram, ultraviolet-visible absorption spectra figure, Mo Te-Schottky spectrogram and band structure schematic diagram
Specific embodiment
The present invention will be described in more detail below by specific embodiment, but protection scope of the present invention not by
It is limited to these embodiments.
Embodiment
The preparation of nitrogen defect counter opal structure carbonitride
By the dicyanodiamine of 0.6g, the ammonium chloride of silicon oxide pellets and 0.6g that 1.0g diameter is about 200nm mixes together
It closes, grinds and be uniformly mixed, be placed in porcelain Noah's ark, after closeing the lid, be placed in tube furnace and calcine.2 DEG C of heating rate are per minute,
2h is kept the temperature after rising to 520 DEG C, then is warming up to 550 DEG C per minute with 4 DEG C, keeps the temperature 2h, and whole process is continually fed into the argon gas of 0.2L/min.
After its cooled to room temperature after the ammonium acid fluoride aqueous solution of 50mL 4mol/L etches 48h, centrifuge washing revolving speed is
12500r/min, centrifugation time are 15min centrifuge washing, dry, obtain IO g-C3N4Nv。
Comparative example
The preparation of blank nitriding carbon
It takes the dicyanodiamine of 0.6g to be placed in porcelain Noah's ark, after closeing the lid, is placed in Muffle furnace and calcines, 5 DEG C of heating rate
Per minute, 2h is kept the temperature after rising to 550 DEG C, grinding washing is dried to obtain Bulk g-C after its cooled to room temperature3N4。
Experiment and data
It is as follows that the counter opal structure carbonitride photocatalytic activity of nitrogen defect modification provided by the invention investigates method:
It takes 25mg catalyst to be sufficiently mixed in photocatalysis pipe with 50mL concentration for the Norfloxacin aqueous solution of 10mg/L, hides
20 minutes are adsorbed under luminous environment secretly to reach adsorption equilibrium.Using 300W Xe lamp as lamp source, add 420 optical filter simulated visible lights,
Prolonged exposure 90min, preceding 30min take 1.5ml liquid every 10min, and rear 60 minutes per half an hour take 1.5mL liquid, detect promise
The concentration of Flucloxacillin.
The measurement side of the counter opal structure carbonitride photocatalytic degradation Norfloxacin of nitrogen defect modification provided by the invention
Method is as follows:
1.5ml reaction solution is taken, is taken on 1ml with 12000r/min revolving speed centrifugation 8min with completing to be separated by solid-liquid separation through centrifuge
Clear liquid is put into be measured in liquid phase bottle after 0.22 μm of membrane filtration.
Liquid chromatogram test condition is as follows, and mobile phase 20% is acetonitrile, and 80% is 0.2% aqueous formic acid, flow velocity 1mL/
Min, each 10 μ L of sample introduction detect appearance situation in 278nm, using external standard method, calculate concentration according to working curve and degradation is imitated
Rate.
Fig. 1 is scanning electron microscope (SEM) figure for the nitrogen defect counter opal structure carbonitride that embodiment obtains.It can be with from figure
Clearly see counter opal structure, and as can be seen from the figure counter opal structure aperture is 200nm or so.
Fig. 2 is the nitrogen defect counter opal structure carbonitride x-ray photoelectron spectroscopy (XPS) that embodiment obtains, and X-ray is spread out
Penetrate map (XRD) and electron paramagnetic resonance map (EPR).From a, b figure be can be seen that, there are nitrogen defects；It can be seen that from c figure, originally urge
Agent still has the basic chemical skeleton of carbonitride, but peak intensity decrease illustrates the formation of defect state.It can be seen that from d figure, originally urge
The epr signal of agent enhances, the generation of description defect state.(Elemental Analysis) is tested according to elemental analysis, blank
For the carbon-nitrogen ratio of graphite phase carbon nitride 0.67, the carbon-nitrogen ratio of this catalyst can reach 0.74.
Fig. 3 is that the degradation of blank nitriding carbon and nitrogen defect counter opal structure carbonitride that comparative example and embodiment obtain is real
Test figure.It can be seen from the figure that nitrogen defect counter opal structure carbonitride shows comparable advantage, contaminant degradation efficiency is mentioned
It rises obvious.
Fig. 4 is the photoelectric current of blank nitriding carbon and nitrogen defect counter opal structure carbonitride that comparative example and embodiment obtain
Spectrogram, impedance diagram, fluorogram, ultraviolet-visible absorption spectra figure, Mo Te-Schottky spectrogram and band structure schematic diagram.Comparison
In blank nitriding carbon, nitrogen defect counter opal structure carbonitride photo-current intensity with higher illustrates stronger light induced electron
Ability；Lesser impedance illustrates that electric conductivity is good；Lower fluorescence intensity, it is meant that good electron hole separative efficiency.It says
Bright catalyst has preferable photoelectric properties.By d, the forbidden bandwidth of e Tu Ke get Ben catalyst and conduction band positions, from e figure energy band
Structural schematic diagram can illustrate that the increase of forbidden bandwidth is the embodiment due to the quantum confined effect of counter opal structure, conduction band
Reduction explanation have stronger reducing property.The reason of to illustrate efficient degradation pollutant.
Claims (7)
1. a kind of preparation method of the counter opal structure carbonitride of nitrogen defect modification, it is characterised in that this method takes following step
Rapid: by a certain amount of dicyanodiamine, silicon oxide pellets, ammonium chloride is mixed together, and is ground and is uniformly mixed, and is protected in argon stream
In shield after 520-550 DEG C of calcining, obtained product obtains the anti-albumen of the nitrogen defect modification through over etching, washing, drying
Stone structure carbonitride；Wherein the silicon oxide pellets are prepared by the following method: tetraethyl orthosilicate being added in ethyl alcohol, stirring is equal
It is even, form solution A；Then it is added separately to water and ammonium hydroxide to form solution B in ethyl alcohol；Solution A is rapidly added in solution B simultaneously
It stirring in oil bath, silicon ball is dispersed in water by sample after centrifugation washing drying according to certain mass score after the reaction was completed,
Evaporation arrangement at a certain temperature, obtains the SiO of marshalling after being evaporated2Bead.
2. preparation method according to claim 1, it is characterised in that: wherein the quality of dicyanodiamine is 0.6g, titanium dioxide
The quality of silicon bead is 1g, and the quality of ammonium chloride is 0.6g.
3. preparation method according to claim 1 to 2, it is characterised in that: the diameter of the silicon oxide pellets is about
200nm, the method for preparing the silicon oxide pellets are as follows: 8mL tetraethyl orthosilicate being added in 92mL ethyl alcohol, stirring makes it
It is even, form solution A；Then it is added separately to 29.4mL water and 14mL ammonium hydroxide to form solution B in 56.6mL ethyl alcohol；By solution A
It is rapidly added in solution B and is stirred 24 hours in 25 DEG C of oil baths；Sample is after centrifugation washing drying after the reaction was completed, by silicon ball
It is dispersed in water according to mass fraction 5%, is placed in 110 DEG C of electric heating bellows and evaporates arrangement, obtain marshalling after being evaporated
SiO2Bead.
4. preparation method according to claim 1 to 3, calcination process carries out in tube-type atmosphere furnace, every with 2 DEG C from room temperature
The heating rate of minute rises to 520 DEG C, keeps the temperature 2 hours, then rises to 550 DEG C with 4 DEG C of heating rates per minute and keep the temperature 2 hours,
Calcining is whole to be carried out in argon stream protection, 0.2 Liter Per Minute of gas flow rate.
5. preparation method described in -4 according to claim 1, the product calcined is polished, the ammonium acid fluoride through 4mol/L
Solution etches 48 hours, the product after etching was washed several times, dries the counter opal structure for obtaining the nitrogen defect and modifying
Carbonitride.
6. preparation method described in -5 according to claim 1, the washing is centrifuge washing, and centrifuge washing revolving speed is 12500r/
Min, centrifugation time 15min.
7. a kind of counter opal structure carbonitride of nitrogen defect modification, it is characterised in that the carbon-nitrogen ratio in the carbonitride is
0.74, carbonitride preparation method as described in claim 1-6 is prepared.
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| CN112473712A (en) * | 2020-11-23 | 2021-03-12 | 南京大学 | CeO treated with different atmospheres2/g-C3N4Heterojunction material, preparation method and application thereof |
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