CN108355702A - A kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst and its preparation method and application - Google Patents
A kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst and its preparation method and application Download PDFInfo
- Publication number
- CN108355702A CN108355702A CN201810246294.4A CN201810246294A CN108355702A CN 108355702 A CN108355702 A CN 108355702A CN 201810246294 A CN201810246294 A CN 201810246294A CN 108355702 A CN108355702 A CN 108355702A
- Authority
- CN
- China
- Prior art keywords
- graphite phase
- carbon nitride
- phase carbon
- photochemical catalyst
- bigger serface
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 52
- 239000010439 graphite Substances 0.000 title claims abstract description 52
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 230000007547 defect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 5
- 238000006731 degradation reaction Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- -1 carbon nitrides Chemical class 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 12
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 35
- 238000002336 sorption--desorption measurement Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000001772 blood platelet Anatomy 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (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 discloses a kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst and its preparation method and application.The specific steps are：By nitric acid dropping in graphite phase carbon nitride, mixed liquor is obtained；By mixed liquor, hydro-thermal obtains solid powder at a certain temperature, and solid powder is dried to obtain to target product in air atmosphere.Preparation method of the present invention is simple, mild condition, there is good industrial production prospect, the graphite phase carbon nitride photochemical catalyst obtained under the radiation of visible light of 420nm or more degradable isopropanol to acetone.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of bigger serface carbon defects graphite phase carbon nitride
Photochemical catalyst and its preparation method and application.
Background technology
In recent years, a large amount of research has been devoted to develop efficient semiconductor light-catalyst, and it is applied to light
Water, degradation harmful substance and CO is catalytically decomposed2Conversion etc., to solve the energy and environmental problem of global getting worse.Stone
Black phase carbon nitride (g-C3N4) be a kind of to visible light-responded semiconductor light-catalyst, due to very high chemical stability,
The advantages that thermal stability and photoelectric characteristic so that it is widely used in hydrogen production by water decomposition, carbon dioxide reduction and organic contamination
The fields such as object degradation.But due to g-C3N4(it is generally less than 10m with smaller specific surface area2/ g) and photo-generated carrier it is easy
The reasons such as compound, it is relatively low to cause its photo-quantum efficiency, seriously constrains its and further applies.
The specific surface area for improving material is remarkably improved photocatalysis performance, and the catalyst of bigger serface can provide more
Adsorption shortens the diffusion length of photo-generated carrier, to greatly improve the efficiency of catalysis reaction.By catalysis material
It is one of the effective ways for improving its specific surface area to be prepared into porous material, up to the present commonly prepares porous g-C3N4's
Method is mainly hard template method and soft template method.Hard template method generally uses a nanometer casting technique, is with porous silica
Template prepares porous g-C3N4, this method is highly effective, can promote specific surface area to 500m2/ g, but go
As soon as removing template needs dangerous hydrogen fluoride, this hinders further applying for it.Soft template method is mainly lived using surface
Property agent and blocked copolymer, produce porous g-C3N4, however g-C3N4CN structures can extend at high temperature, it is soft
The decomposition temperature of template is with respect to g-C3N4Condensation temperature wants much lower, and removing soft template too early can be such that the hole to be formed is closed again.
Therefore, develop the g-C that a non-template method prepares porous carbon defects3N4It is necessary.
Invention content
The present invention urges in view of the deficienciess of the prior art, providing a kind of bigger serface carbon defects graphite phase carbon nitride light
The preparation method of agent and its application in degradation of small molecular organic matter, the graphite phase carbon nitride photocatalysis that this method is prepared
Agent has high specific surface area, reaches 41-52m2/ g, aperture is in 2-28nm, and preparation method is simple, mild condition, required equipment
Simply, there is good industrial production prospect, visible light of the graphite phase carbon nitride photochemical catalyst obtained in 420nm or more shines
Degradable isopropanol is penetrated down to acetone and carbon dioxide.
The technical solution adopted by the present invention is：It is prepared by a kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst
Method is as follows：
1) by nitric acid dropping in graphite phase carbon nitride, mixed liquor is obtained.
Preferably, the preparation method of the graphite phase carbon nitride is：Melamine is placed in crucible and is put into tube furnace
In, under nitrogen protection, 550 DEG C of roasting 4-6h.
Preferably, the dosage of nitric acid is that nitric acid 1.2-4.0mL is added per 0.6g graphite phase carbon nitrides.
Preferably, by nitric acid dropping in graphite phase carbon nitride, in 80 DEG C of water-baths, heating stirring 1-3h obtains mixed liquor.
2) mixed liquor is put in water heating kettle, heating obtains solid powder.
Specifically, mixed liquor is put in water heating kettle, 120-150 DEG C of hydro-thermal reaction 10-12h obtains solid powder.
3) solid powder is dried to obtain to target product in air atmosphere.
Specifically, by solid powder in air atmosphere, 10-12h is dried at 80-100 DEG C, obtains target product.
The invention has the advantages that：The present invention has obtained the graphite-phase of bigger serface using a non-template method
Carbonitride.Specially using nitric acid treatment graphite phase carbon nitride, (nitric acid has the stronger acid graphite by two-dimensional layered structure
Phase carbon nitride strips off), and cleverly reacted using the carbon atom of the strong oxidizing property of nitric acid and surface and obtain porous carbon
The graphite phase carbon nitride of defect.The benefit of the method is attributable to two aspects：1, blocky graphite phase carbon nitride is shelled due to nitric acid
Taking off into relatively thin nanometer sheet, crystallite dimension becomes smaller simultaneously.Small nano particle results in big specific surface area；2, the strong oxygen of nitric acid
The carbon atom oxidation of material surface is generated carbon dioxide and forms defect by the property changed, these defects are conducive to electronics capture.It obtains more
The graphite phase carbon nitride of the carbon defects of the bigger serface in hole can improve photocatalysis performance.
It not only can avoid using dangerous chemicals using the method for the present invention, but also can avoid forming the porous knot being closed
Structure.Obtained g-C3N4With larger specific surface area (41-52m2/ g), aperture 2-28nm, these porous structures provide
More response locations so that (420nm) degrade rate of isopropanol to acetone reaches under visible light illumination
46.761ppm/min is pure g-C3N49.5 times.
Description of the drawings
Fig. 1 is the XRD diagram of CN-0, ECNV-1.25, ECNV-2.5 and ECNV-3.75.
Fig. 2 is the nitrogen adsorption desorption isotherm of CN-0, ECNV-1.25, ECNV-2.5 and ECNV-3.75 and corresponding hole
Diameter distribution map.
Fig. 3 is the ultraviolet-visible spectrogram of CN-0, ECNV-1.25, ECNV-2.5 and ECNV-3.75.
Fig. 4 is the band gap locations figure of CN-0, ECNV-1.25, ECNV-2.5 and ECNV-3.75.
Fig. 5-1 is that the SEM of CN-0 (a), ECNV-1.25 (b), ECNV-2.5 (c) and ECNV-3.75 (d) scheme.
The TEM that Fig. 5-2 is CN-0 (e) and ECNV-2.5 (f) schemes.
The XPS general figures entirely that Fig. 6 is CN-0 and ECNV-2.5.
Fig. 7 is the comparison diagram that the N element of the XPS of CN-0 and ECNV-2.5 is finely composed.
Fig. 8 is the comparison diagram that the C element of the XPS of CN-0 and ECNV-2.5 is finely composed.
The EPR that Fig. 9 is CN-0 and ECNV-2.5 schemes.
Figure 10 is the pure g-C prepared3N4, ECNV-1.25, ECNV-2.5 and ECNV-3.75 photochemical catalyst in visible light
The lower isopropanol activity contrast schematic diagram of degrading of irradiation.
Figure 11 is the pure g-C prepared3N4, ECNV-1.25, ECNV-2.5 and ECNV-3.75 photochemical catalyst in visible light
The lower degradation isopropanol activity of irradiation compares block diagram.
Specific implementation mode
Pure graphite phase carbon nitride (g-C3N4) preparation：
2.25g melamines are put in alumina crucible, is capped, the alumina crucible of capping is put in tube furnace,
Under nitrogen protection, 550 DEG C are heated to, is kept for 4 hours, heating rate is 5 DEG C/min, obtains pure g-C3N4(being denoted as CV-0).
The pure g-C that will be prepared3N4Carry out nitrogen adsorption desorption test, nitrogen adsorption desorption isotherm and corresponding
Pore-size distribution is as shown in Fig. 2, test result is shown, pure g-C3N4Specific surface area be 5.43m2g-1, the base in terms of graph of pore diameter distribution
Hole is not present in this.
By pure g-C3N4SEM tests are carried out, as a result as shown in (a) in Fig. 5-1, pure g-C is seen from figure3N4It is shown as
The polymer of the bulk of one stratiform, this is the image of a typical graphite phase carbon nitride.Pure g-C3N4TEM figure, such as scheme
In 5-2 shown in (e), pure g-C is as a result shown3N4For a typical non-porous blood platelet shape structure.
By pure g-C3N4UV-vis tests are carried out, test results are shown in figure 3, as seen from the figure pure g-C3N4Suction
It is maximum to receive side, while Fig. 4 shows that band gap locations are 2.76.
A kind of 1 bigger serface carbon defects graphite phase carbon nitride photochemical catalyst (nitric acid=1.25ml) of embodiment
(1) preparation method is as follows：
1) 2.25g melamines are added in alumina crucible, are placed in tube furnace, in nitrogen atmosphere, 550 DEG C of roastings
4h, grinding, obtains uniform powder g-C3N4。
2) 0.6g g-C are added in 1.25ml salpeter solutions3N4In, in 80 DEG C of water-baths, heating stirring 3h obtains mixed liquor.
3) mixed liquor is added in water heating kettle, is put into baking oven, in 120-150 DEG C of hydro-thermal reaction 10-12h, obtains solid powder
End.
4) solid powder is put in open evaporating dish, is placed in baking oven, in air atmosphere, 80-100 DEG C of drying 10-
12h obtains target product, that is, bigger serface carbon defects graphite phase carbon nitride photochemical catalyst g-C3N4(being denoted as ECNV-1.25).
(2) testing result
Product ECNV-1.25 is subjected to XRD tests, test results are shown in figure 1, from figure 1 it appears that the sample prepared
For product there are two diffraction maximums (13 ° and 27 °), this is the diffraction maximum of typical graphite phase carbon nitride, with pure g-C obtained3N4Phase
Seemingly.
Product ECNV-1.25 is subjected to nitrogen adsorption desorption test, the results are shown in Figure 2, and hysteresis loop, explanation are shown in figure
There is ECNV-1.25 porous structure, pore-size distribution to be shown as 2-28nm, the porous ECNV-1.25 that test result display obtains
With 41m2The specific surface area of/g.
Product ECNV-1.25 is subjected to UV-vis tests, test results are shown in figure 3, as seen from the figure compared to pure
g-C3N4ABSORPTION EDGE have occurred blue shift, while Fig. 4 shows that band gap locations are 2.91, illustrates that band gap broadens, and extends photoproduction load
In the service life for flowing son, increase light-catalysed activity.
ECNV-1.25 is subjected to SEM tests, as a result as shown in (b) in Fig. 5-1, ECNV-1.25 is shown as seen from the figure
The polymer of the fritter of one stratiform, this is the image of a graphite phase carbon nitride typically stripped off.
(3) it applies
The ECNV-1.25 photochemical catalysts of preparation are subjected to photocatalytic degradation isopropanol experiment.
Test process is：Using 300W xenon lamps as light source, respectively by the 0.1g photochemical catalysts (ECNV-1.25) of above-mentioned preparation,
Pure g-C3N4It is put in 4cm2In glass guide channel, the glass guide channel of photocatalyst-bearing is put into the 300ml for including an atmospheric air
In reactor, 5ul isopropanol liquids are finally injected into reactor, stand 3 hours, so that system adsorption-desorption is balanced, are then existed
It degrades under radiation of visible light isopropanol.
As a result as shown in Figure 10 and Figure 11, the rectangular length expression speed that acetone generates under visible light illumination in figure
Rate, the graphite phase carbon nitride of the carbon defects for the bigger serface that as seen from the figure prepared by embodiment 1 show good photocatalysis and live
Property, reach 21.821ppm/min, and pure g-C prepared by conventional method3N4Graphite phase carbon nitride only reaches 4.923ppm/min.
A kind of 2 bigger serface carbon defects graphite phase carbon nitride photochemical catalyst (nitric acid=2.5ml) of embodiment
(1) preparation method is as follows：
1) 2.25g melamines are added in alumina crucible, are placed in tube furnace, in nitrogen atmosphere, 550 DEG C of roastings
4h, grinding, obtains uniform powder g-C3N4。
2) 0.6g g-C are added in 2.5ml salpeter solutions3N4In, in 80 DEG C of water-baths, heating stirring 3h obtains mixed liquor.
3) mixed liquor is added in water heating kettle, is put into baking oven, in 120-150 DEG C of hydro-thermal reaction 10-12h, obtains solid powder
End.
4) solid powder is put in open evaporating dish, is placed in baking oven, in air atmosphere, 80-100 DEG C of drying 10-
12h obtains target product, that is, the graphite phase carbon nitride photochemical catalyst g-C of bigger serface carbon defects3N4(it is denoted as ECNV-
2.5)。
(2) testing result
Product ECNV-2.5 is subjected to XRD tests, test results are shown in figure 1, from figure 1 it appears that the sample prepared
For product there are two diffraction maximums (13 ° and 27 °), this is the diffraction maximum of typical graphite phase carbon nitride, with pure g-C obtained3N4Phase
Seemingly.
Product ECNV-2.5 is subjected to nitrogen adsorption desorption test, the results are shown in Figure 2, and hysteresis loop, explanation are shown in figure
There is ECNV-2.5 porous structure, pore-size distribution to be shown as 2-28nm, the porous ECNV-2.5 tools that test result display obtains
There is 43m2The specific surface area of/g.
Product ECNV-2.5 is subjected to UV-vis tests, test results are shown in figure 3, as seen from the figure compared to pure g-
C3N4ABSORPTION EDGE have occurred blue shift, while Fig. 4 shows that band gap locations are 2.85, illustrates that band gap broadens, extends photoproduction current-carrying
In the service life of son, increase light-catalysed activity.
ECNV-2.5 is subjected to SEM tests, as a result as shown in (c) in Fig. 5-1, ECNV-2.5 is shown as one as seen from the figure
The more tiny bulk polymer of a stratiform, this is the image of a graphite phase carbon nitride typically stripped off.ECNV-2.5
TEM figure, as shown in (f) in Fig. 5-2, for ECNV-2.5 there are many small white spots, these small particles are exactly in embodiment 2
The hole of generation.
Product ECNV-2.5 is subjected to XPS tests, full general survey test result is shown in Fig. 6, as can be seen from Figure 6 ECNV-
1.25 samples contain C, N and O element, with pure g-C3N4It is similar.Finely spectrum is shown in Fig. 7 and Fig. 8, wherein C and N element to element
Combination can all be changed, to illustrate with the presence of carbon defects.
ECNV-2.5 is subjected to EPR tests, Fig. 9 is as a result shown in, can significantly find out in ECNV-2.5 not from Fig. 9
Paired electrons increases, this illustrates defective generation, and this defect is exactly carbon.
(3) it applies
The ECNV-2.5 photochemical catalysts of preparation are subjected to photocatalytic degradation isopropanol experiment.
Test process is：Using 300W xenon lamps as light source, respectively by 0.1g photochemical catalysts (ECNV-2.5) of above-mentioned preparation, pure
G-C3N4It is put in 4cm2In glass guide channel, the glass guide channel of photocatalyst-bearing is put into include an atmospheric air 300ml it is anti-
It answers in device, 5ul isopropanol liquids is finally injected into reactor, standing makes system adsorption-desorption balance for 3 hours, then can
It degrades under light-exposed irradiation isopropanol.
As a result as shown in Figure 10 and Figure 11, the rectangular length expression speed that acetone generates under visible light illumination in figure
Rate, the graphite phase carbon nitride of the carbon defects for the bigger serface that as seen from the figure prepared by embodiment 2 show good photocatalysis and live
Property, reach 46.76ppm/min, and graphite phase carbon nitride prepared by conventional method only reaches 4.923ppm/min.
A kind of 3 bigger serface carbon defects graphite phase carbon nitride photochemical catalyst (nitric acid=3.75ml) of embodiment
(1) preparation method is as follows
1) 2.25g melamines are added in alumina crucible, are placed in tube furnace, in nitrogen atmosphere, 550 DEG C of roastings
4h, grinding, obtains uniform powder g-C3N4。
2) 0.6g g-C are added in 3.75ml salpeter solutions3N4In, in 80 DEG C of water-baths, heating stirring 3h obtains mixed liquor.
3) mixed liquor is added in water heating kettle, is put into baking oven, in 120-150 DEG C of hydro-thermal reaction 10-12h, obtains solid powder
End.
4) solid powder is put in open evaporating dish, is placed in baking oven, in air atmosphere, 80-100 DEG C of drying 10-
12h obtains target product, that is, the graphite phase carbon nitride photochemical catalyst g-C of bigger serface carbon defects3N4(it is denoted as ECNV-
3.75)。
(2) testing result
Product ECNV-3.75 is subjected to XRD tests, test results are shown in figure 1, from figure 1 it appears that the sample prepared
For product there are two diffraction maximums (13 ° and 27 °), this is the diffraction maximum of typical graphite phase carbon nitride, with pure g-C obtained3N4Phase
Seemingly.
Product ECNV-3.75 is subjected to nitrogen adsorption desorption test, the results are shown in Figure 2, and hysteresis loop, explanation are shown in figure
There is ECNV-3.75 porous structure, pore-size distribution to be shown as 2-28nm, the porous ECNV-3.75 that test result display obtains
With 52m2The specific surface area of/g.
Product ECNV-3.75 is subjected to UV-vis tests, test results are shown in figure 3, as seen from the figure compared to pure
g-C3N4ABSORPTION EDGE have occurred blue shift, while Fig. 4 shows that band gap locations are 2.86, illustrates that band gap broadens, and extends photoproduction load
In the service life for flowing son, increase light-catalysed activity.
ECNV-3.75 obtained is subjected to SEM tests, as shown in (d) in Fig. 5-1, with pure g-C3N4SEM figures compare,
ECNV-3.75 shows a kind of loose, thin, cellular and surface, and there are the structures of many holes.
(3) it applies
G-CNA-3 photochemical catalysts prepared by the present embodiment 3 carry out photocatalytic degradation isopropanol experiment.
Test process is：Using 300W xenon lamps as light source, respectively by the 0.1g photochemical catalysts (ECNV-3.75) of above-mentioned preparation,
g-C3N4It is put in 4cm2In glass guide channel, the glass guide channel of photocatalyst-bearing is put into the 300ml reactions for including an atmospheric air
In device, 5ul isopropanol liquids are finally injected into reactor, standing 3 hours makes system adsorption-desorption balance, then visible
The lower isopropanol of degrading of light irradiation.
As shown in Figure 10 and Figure 11, the rectangular length expression rate that acetone generates under visible light illumination in figure, by
The graphite phase carbon nitride of bigger serface prepared by embodiment 3 known to figure shows good photocatalytic activity, reaches
Graphite phase carbon nitride prepared by 30.789ppm/min and conventional method only reaches 4.923ppm/min.
Claims (10)
1. a kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst, it is characterised in that：Preparation method is as follows：
1) by nitric acid dropping in graphite phase carbon nitride, mixed liquor is obtained；
2) mixed liquor is put in water heating kettle, heating obtains solid powder；
3) solid powder is dried to obtain to target product in air atmosphere.
2. a kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst according to claim 1, which is characterized in that
The bigger serface carbon defects graphite phase carbon nitride photochemical catalyst, specific surface area 41-52m2/ g, aperture 2-28nm.
3. a kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst according to claim 1, which is characterized in that
In step 1), the preparation method of the graphite phase carbon nitride is：Melamine is placed in crucible and is put into tube furnace, in nitrogen
Under gas shielded, 550 DEG C of roasting 4-6h.
4. a kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst according to claim 1, which is characterized in that
In step 1), the dosage of nitric acid is that nitric acid 1.2-4.0mL is added per 0.6g graphite phase carbon nitrides.
5. a kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst according to claim 1, which is characterized in that
Step 1) is specifically, by nitric acid dropping in graphite phase carbon nitride, and in 80 DEG C of water-baths, heating stirring 1-3h obtains mixed liquor.
6. a kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst according to claim 1, which is characterized in that
For step 2) specifically, mixed liquor is put in water heating kettle, 120-150 DEG C of hydro-thermal reaction 10-12h obtains solid powder.
7. a kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst according to claim 1, which is characterized in that
Step 3) dries 10-12h at 80-100 DEG C, obtains target product specifically, by solid powder in air atmosphere.
8. claim 1-7 any one of them bigger serface carbon defects graphite phase carbon nitride photochemical catalysts are in degradation of small molecular
Application in organic matter.
9. application according to claim 8, which is characterized in that the small organic molecule is isopropanol.
10. application according to claim 9, which is characterized in that method is as follows, under visible light illumination, by Large ratio surface
Carbon distribution defect graphite phase carbon nitride photochemical catalyst is placed in the confined space containing isopropanol gas, is adsorbed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810246294.4A CN108355702B (en) | 2018-03-23 | 2018-03-23 | Graphite-phase carbon nitride photocatalyst with large specific surface area carbon deposition defects and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810246294.4A CN108355702B (en) | 2018-03-23 | 2018-03-23 | Graphite-phase carbon nitride photocatalyst with large specific surface area carbon deposition defects and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108355702A true CN108355702A (en) | 2018-08-03 |
| CN108355702B CN108355702B (en) | 2020-08-25 |
Family
ID=63001478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810246294.4A Active CN108355702B (en) | 2018-03-23 | 2018-03-23 | Graphite-phase carbon nitride photocatalyst with large specific surface area carbon deposition defects and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108355702B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126853A (en) * | 2018-09-12 | 2019-01-04 | 华东理工大学 | A kind of counter opal g-C with carbon defects3N4The preparation method of photochemical catalyst |
| CN109351362A (en) * | 2018-10-15 | 2019-02-19 | 广州中国科学院沈阳自动化研究所分所 | A kind of porous molecular doping carbon nitride photocatalyst and the preparation method and application thereof |
| CN109433246A (en) * | 2018-12-26 | 2019-03-08 | 台州学院 | Nanometer sheet C containing carbon vacancy3N4Photochemical catalyst and preparation method |
| CN109701583A (en) * | 2019-02-25 | 2019-05-03 | 武汉理工大学 | A kind of defect regulation high activity graphite phase carbon nitride and preparation method thereof |
| CN109884010A (en) * | 2019-02-27 | 2019-06-14 | 黑龙江大学 | A kind of preparation method of high specific surface area porous carbonitride and method using its fluorescence detection TNP |
| CN111004625A (en) * | 2019-11-19 | 2020-04-14 | 福州大学 | Method for enhancing graphite phase carbon nitride defect state electrochemiluminescence |
| CN111071999A (en) * | 2019-11-20 | 2020-04-28 | 嘉兴学院 | Synthesis method of mesoporous graphite-like carbon nitride nanosheet with low metal content |
| CN111250138A (en) * | 2020-02-28 | 2020-06-09 | 韶关学院 | Porous nano flaky graphite phase carbon nitride and preparation method and application thereof |
| CN113680373A (en) * | 2021-09-28 | 2021-11-23 | 中化学朗正环保科技有限公司 | Graphite phase carbon nitride photocatalyst for sewage treatment and preparation method and application thereof |
| CN116020516A (en) * | 2023-01-17 | 2023-04-28 | 齐鲁工业大学(山东省科学院) | Graphite-phase carbon nitride photocatalyst with controllable size and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084228A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof |
| CN104289244A (en) * | 2014-09-15 | 2015-01-21 | 浙江大学 | Preparation method for porous g-C3N4/AgBr nanometer composite material |
| CN105944748A (en) * | 2016-06-14 | 2016-09-21 | 辽宁大学 | Graphite-phase carbon nitride photocatalyst with large specific surface area and preparation method and application thereof |
| CN106238085A (en) * | 2016-07-28 | 2016-12-21 | 安徽师范大学 | A kind of oxygen doping nitrogen carbide noble metal composite photo-catalyst, preparation method and application |
| CN106423244A (en) * | 2016-10-09 | 2017-02-22 | 辽宁大学 | Porous g-C3N4 nano slice light catalyst and preparation method thereof and application |
-
2018
- 2018-03-23 CN CN201810246294.4A patent/CN108355702B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084228A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof |
| CN104289244A (en) * | 2014-09-15 | 2015-01-21 | 浙江大学 | Preparation method for porous g-C3N4/AgBr nanometer composite material |
| CN105944748A (en) * | 2016-06-14 | 2016-09-21 | 辽宁大学 | Graphite-phase carbon nitride photocatalyst with large specific surface area and preparation method and application thereof |
| CN106238085A (en) * | 2016-07-28 | 2016-12-21 | 安徽师范大学 | A kind of oxygen doping nitrogen carbide noble metal composite photo-catalyst, preparation method and application |
| CN106423244A (en) * | 2016-10-09 | 2017-02-22 | 辽宁大学 | Porous g-C3N4 nano slice light catalyst and preparation method thereof and application |
Non-Patent Citations (3)
| Title |
|---|
| HONGTAO WEI ET AL: "Enhancement of the Cr(VI) adsorption and photocatalytic reduction activity of g-C3N4by hydrothermal treatment in HNO3 aqueous solution", 《APPLIED CATALYSIS A: GENERAL》 * |
| LEI SHI ET AL: "In site acid template induced facile synthesis of porous graphitic carbon nitride with enhanced visible-light photocatalytic activity", 《CATALYSIS COMMUNICATIONS》 * |
| 吴思展: "类石墨氮化碳（g-C3N4）的合成、加工处理、修饰及其光催化性能的研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109126853A (en) * | 2018-09-12 | 2019-01-04 | 华东理工大学 | A kind of counter opal g-C with carbon defects3N4The preparation method of photochemical catalyst |
| CN109351362A (en) * | 2018-10-15 | 2019-02-19 | 广州中国科学院沈阳自动化研究所分所 | A kind of porous molecular doping carbon nitride photocatalyst and the preparation method and application thereof |
| CN109433246B (en) * | 2018-12-26 | 2021-07-16 | 台州学院 | Carbon vacancy-containing nanosheet C3N4Photocatalyst and preparation method thereof |
| CN109433246A (en) * | 2018-12-26 | 2019-03-08 | 台州学院 | Nanometer sheet C containing carbon vacancy3N4Photochemical catalyst and preparation method |
| CN109701583A (en) * | 2019-02-25 | 2019-05-03 | 武汉理工大学 | A kind of defect regulation high activity graphite phase carbon nitride and preparation method thereof |
| CN109884010A (en) * | 2019-02-27 | 2019-06-14 | 黑龙江大学 | A kind of preparation method of high specific surface area porous carbonitride and method using its fluorescence detection TNP |
| CN111004625A (en) * | 2019-11-19 | 2020-04-14 | 福州大学 | Method for enhancing graphite phase carbon nitride defect state electrochemiluminescence |
| CN111004625B (en) * | 2019-11-19 | 2022-12-16 | 福州大学 | Method for enhancing graphite phase carbon nitride defect state electrochemiluminescence |
| CN111071999A (en) * | 2019-11-20 | 2020-04-28 | 嘉兴学院 | Synthesis method of mesoporous graphite-like carbon nitride nanosheet with low metal content |
| CN111250138A (en) * | 2020-02-28 | 2020-06-09 | 韶关学院 | Porous nano flaky graphite phase carbon nitride and preparation method and application thereof |
| CN113680373A (en) * | 2021-09-28 | 2021-11-23 | 中化学朗正环保科技有限公司 | Graphite phase carbon nitride photocatalyst for sewage treatment and preparation method and application thereof |
| CN116020516A (en) * | 2023-01-17 | 2023-04-28 | 齐鲁工业大学(山东省科学院) | Graphite-phase carbon nitride photocatalyst with controllable size and preparation method thereof |
| CN116020516B (en) * | 2023-01-17 | 2023-10-20 | 齐鲁工业大学(山东省科学院) | Graphite-phase carbon nitride photocatalyst with controllable size and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108355702B (en) | 2020-08-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108355702A (en) | A kind of bigger serface carbon defects graphite phase carbon nitride photochemical catalyst and its preparation method and application | |
| CN105944748B (en) | A kind of bigger serface graphite phase carbon nitride photochemical catalyst and its preparation method and application | |
| Xia et al. | Localized π-conjugated structure and EPR investigation of g-C3N4 photocatalyst | |
| Li et al. | C3N4 with engineered three coordinated (N3C) nitrogen vacancy boosts the production of 1O2 for Efficient and stable NO photo-oxidation | |
| Hu et al. | Dramatic promotion of visible-light photoreactivity of TiO2 hollow microspheres towards NO oxidation by introduction of oxygen vacancy | |
| Yang et al. | Porous carbon-doped TiO2 on TiC nanostructures for enhanced photocatalytic hydrogen production under visible light | |
| US20220355284A1 (en) | Perylene imide and composite photocatalytic material thereof, preparation method therefor and application thereof in removing organic pollutants from water | |
| CN106423244B (en) | A kind of porous g-C3N4Nanosheet photocatalyst and its preparation method and application | |
| Shi et al. | N-doping Ta2O5 nanoflowers with strong adsorption and visible light photocatalytic activity for efficient removal of methylene blue | |
| CN108355701A (en) | Ag supports two-dimentional graphite phase carbon nitride nanosheet photocatalyst and its preparation method and application | |
| Wang et al. | Simple synthesis of Zr-doped graphitic carbon nitride towards enhanced photocatalytic performance under simulated solar light irradiation | |
| Hu et al. | Insight into the kinetics and mechanism of visible-light photocatalytic degradation of dyes onto the P doped mesoporous graphitic carbon nitride | |
| CN104722325B (en) | Three-dimensional macro-scale porous graphite phase carbon nitride photocatalyst and preparation and application of photocatalyst | |
| CN112675894B (en) | Hollow annular carbon nitride photocatalyst and preparation method thereof | |
| Chen et al. | Cyano-rich mesoporous carbon nitride nanospheres for visible-light-driven photocatalytic degradation of pollutants | |
| Zhang et al. | Synthesis of g-C3N4 microrods with superficial C, N dual vacancies for enhanced photocatalytic organic pollutant removal and H2O2 production | |
| CN108993574B (en) | Preparation method of high-performance graphite-phase carbon nitride photocatalytic material | |
| Sreethawong et al. | Investigation of thermal treatment effect on physicochemical and photocatalytic H2 production properties of mesoporous-assembled Nb2O5 nanoparticles synthesized via a surfactant-modified sol–gel method | |
| CN113198496B (en) | Metallic indium-doped lead cesium bromide perovskite quantum dot photocatalyst, preparation method and application thereof in reduction of carbon dioxide | |
| Sun et al. | Generated gas molecules-modified carbon nitride nanosheets with nitrogen vacancies and high efficient photocatalytic hydrogen evolution | |
| Zhao et al. | Salt-air template synthesis of Na and O doped porous graphitic carbon nitride nanorods with exceptional photocatalytic H2 evolution activity | |
| Liang et al. | Hydroxyl/amino and Fe (III) co-grafted graphite carbon nitride for photocatalytic removal of volatile organic compounds | |
| Nunes et al. | Ultrafast microwave synthesis of WO3 nanostructured films for solar photocatalysis | |
| Yang et al. | Nanopore enriched hollow carbon nitride nanospheres with extremely high visible-light photocatalytic activity in the degradation of aqueous contaminants of emerging concern | |
| Kumar et al. | Hierarchically Structured CuO/gC 3N4 Heterogeneous Semiconductor Photocatalyst with Improved Photocatalytic Activity and Stability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |