CN110433849A - A kind of graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aerogels - Google Patents
A kind of graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aerogels Download PDFInfo
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- 239000001301 oxygen Substances 0.000 title claims abstract description 79
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- 239000002096 quantum dot Substances 0.000 title claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 64
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 64
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title abstract 2
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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
-
- B01J35/39—
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- B01J35/61—
Abstract
The invention discloses a kind of graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aerogels, preparation methods are as follows: using melamine as raw material, by hydro-thermal reaction, PCNO is prepared；Graphite oxide is dispersed in water, stannic oxide/graphene nano piece GO dispersion liquid 1 is prepared, concentrated nitric acid and the concentrated sulfuric acid is added, carries out heating reflux reaction, filtering dialysis is to get ox-GQDs dispersion liquid；PCNO is dispersed in water, is stirred after ox-GQDs dispersion liquid is added, grinding is after washing of precipitate is dry to get PCNGD；PCNGD and graphite oxide are dispersed in water to obtain PCNGD dispersion liquid and GO dispersion liquid 2 respectively, mixing ultrasound sequentially adds ethylenediamine, CTAB and is respectively heated reaction, and cooling PCNGD/GO hydrogel is freeze-dried to obtain PCNGD-GOA photochemical catalyst.This method has the characteristics that efficient, green, mild.
Description
Technical field
The present invention relates to catalysis material technical fields, and self-assembly method and cross-linking method are combined system more particularly, to a kind of
Standby graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aerogels method.
Background technique
Carbonitride is a kind of novel metalloid organic semiconductor visible light catalyst, since it is with cheap, preparation
Simply, the advantages that stability is high, no biotoxicity, degradation of contaminant and in terms of all there is good application value.
But the blocky carbonitride specific surface area of conventional polycondensation method preparation is small, visible light utilization efficiency is low, light induced electron-sky
Cave to easily it is compound, cause its photocatalytic activity not ideal enough.In addition, powder carbon nitride catalyst is unfavorable for recycling, also sternly
The prospect of its practical application is constrained again.Therefore, it develops and has both bigger serface, wide visible spectrum responses range, quickly
Photo-generated carrier transfer ability and the carbonitride based photocatalyst easily recycled are most important.
Graphene oxide quantum dot (ox-GQDs) is a kind of novel graphene-based material of 0D, and partial size is less than 10nm, by having
Have high-crystallinity close to the graphene planes of monatomic thickness and oxygen-containing functional group abundant (including hydroxyl, carboxylic group etc.) group
At these oxygen-containing groups assign the good solubility of ox-GQDs and unique optical and electronic property.Graphene oxide (GO)
Be one kind by carbon atom with sp2Hydridization at the two-dimensional network structure that is arranged in of hexatomic ring, there is bigger serface, excellent lead
Electrically, high mechanical strength and good flexibility, it is considered to be one of most promising material.In recent years, three-dimensional (3D) is more
The GO base aeroge of hole reticular structure is often used as the carrier in photocatalysis, for improving the adsorption energy of supported photochemical catalyst
Power, photocatalysis performance, durability and the rate of recovery.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of graphene oxide quantum dot/oxygen doping is porous by the application
Carbonitride/graphene oxide ternary aerogels.It is an advantage of the invention that it is easy to operate, at low cost, and prepare
PCNGD-GOA photochemical catalyst photocatalysis efficiency it is high, there is a possibility that being mass produced.
Technical scheme is as follows:
A kind of graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aerogels, institute
The preparation method for stating photochemical catalyst includes the following steps:
(1) it using melamine as raw material, is calcined under air atmosphere, prepares blocky carbonitride (BCN), then by gained
Carbonitride (BCN) ultrasonic disperse in water, and carries out hydro-thermal reaction, cooling after having reacted, and be separated by solid-liquid separation and collects precipitating, will
Drying and grinding is precipitated into powder to get oxygen doping nitride porous carbon (PCNO)；
(2) graphite oxide (GO) ultrasonic disperse is obtained into stannic oxide/graphene nano piece (GO) dispersion liquid 1 in water, dense nitre is added
Acid and the concentrated sulfuric acid, and carry out heating reflux reaction, are cooled to room temperature, add pH adjusting agent adjust the pH to 7.0 of dispersion liquid~
9.0, finally by mixture by 0.22 μm of micro-pore-film filtration, and further dialyse in bag filter to get graphene oxide amount
Sub- point (ox-GQDs) dispersion liquid；
(3) gained oxygen doping nitride porous carbon (PCNO) ultrasonic disperse in step (1) in water, is added in step (2)
Gained graphene oxide quantum dot (ox-GQDs) dispersion liquid, is stirred and is reacted, and is separated by solid-liquid separation to collect after reaction and sink
Sediment is washed dry and ground to get graphene oxide quantum dot/oxygen doping nitride porous carbon (PCNGD) by starch；
(4) gained graphene oxide quantum dot/oxygen doping nitride porous carbon (PCNGD) in step (3) is dispersed in water
Graphene oxide quantum dot/oxygen doping nitride porous carbon (PCNGD) dispersion liquid is obtained, while graphite oxide (GO) is dispersed in water
In obtain stannic oxide/graphene nano piece (GO) dispersion liquid 2, by the graphene oxide quantum dot/oxygen doping nitride porous carbon
(PCNGD) dispersion liquid is added in stannic oxide/graphene nano piece (GO) dispersion liquid 2, and mixing ultrasound obtains mixed liquor, and gained is mixed
It closing in liquid and ethylenediamine is added, and carry out heating reaction, cetyl trimethylammonium bromide (CTAB) is added after a certain period of time in reaction,
Carry out heating reaction again, be cooled to room temperature after reaction to get graphene oxide quantum dot/oxygen doping nitride porous carbon/
Graphene oxide hydrogel (PCNGD/GO)；
(5) gained hydrogel with water in step (4) is impregnated, is finally freeze-dried to get graphene oxide quantum dot/oxygen
Adulterate nitride porous carbon/graphene oxide ternary aeroge (PCNGD-GOA) photochemical catalyst.
Calcining described in step (1) includes the heating heating period and constant temperature stage successively carried out；Rank is heated in the heating
The heating rate of section is 1~12 DEG C/min；The temperature in the constant temperature stage is 500~600 DEG C, and constant temperature time is 1~8h；It is described
The mass volume ratio of carbonitride (BCN) and water is 1g:20~150mL；The ultrasonic power is 200~800W, and supersonic frequency is
10~50kHz, ultrasonic time are 5~60min；The hydrothermal temperature is 120~200 DEG C, and the reaction time is 8~16h.
The mass volume ratio of graphite oxide (GO) described in step (2) and water is 1mg:1~10mL, and the ultrasonic power is
200~800W, supersonic frequency are 10~50kHz, 0.5~10h of sonication treatment time；The concentrated nitric acid concentration be 60%~
70%, concentrated sulfuric acid concentration is 90%~99%；The volume ratio of the concentrated nitric acid and graphene oxide dispersion is 1:1~10, institute
The volume ratio for stating the concentrated sulfuric acid and graphene oxide (GO) dispersion liquid 1 is 1:5~15.
The temperature of heating reflux reaction described in step (2) is 50~150 DEG C, and the reaction time is 5~30h；The pH tune
Section agent is at least one of sodium bicarbonate, sodium hydroxide, sodium carbonate；The reservation molecular weight of the dialysis is 1000Da, when dialysis
Between be 5~60h, after dialysis graphene oxide quantum dot (ox-GQDs) dispersion liquid concentration be 0.1~0.01mg/mL.
The mass volume ratio of oxygen doping nitride porous carbon (PCNO) described in step (3) and water is 1g:50~500mL；Institute
Stating ultrasonic power is 200~800W, and supersonic frequency is 10~50kHz, and sonication treatment time is 0.1~5h；The oxygen doping is more
The mass ratio of hole carbonitride (PCNO) and graphene oxide quantum dot (ox-GQDs) are 1:0.001~0.1, reaction temperature 10
~60 DEG C, the reaction time is 5~50h.
Graphene oxide quantum dot described in step (4)/oxygen doping nitride porous carbon (PCNGD) and water mass volume ratio
For 1mg:0.1~1mL, the mass volume ratio of the graphite oxide (GO) and water is 1mg:0.05~0.5mL, graphene oxide amount
The mass ratio of sub- point/oxygen doping nitride porous carbon (PCNGD) and graphite oxide (GO) are 0.1~2:1, and the ultrasonic power is
200~800W, supersonic frequency are 10~50kHz, and sonication treatment time is 0.1~5h；The graphite oxide (GO) and ethylenediamine
Mass volume ratio be the μ L of 1mg:0.5~5, the mass ratio of graphite oxide (GO) and CTAB are 1mg:0.05~0.5mg, it is described plus
Thermal response time range is 0.1~10h, and the temperature range for heating reaction is 50~150 DEG C.
Soaking time described in step (5) is 5~100h, and sublimation drying is 5~100h.
The present invention is beneficial to be had the technical effect that
The present invention, which discloses, a kind of combines self-assembly method and cross-linking method that prepare graphene oxide quantum dot/oxygen doping porous
Carbonitride/graphene oxide ternary aerogels method.Using melamine as raw material, mutually tied by calcining-hydro-thermal
The method of conjunction is prepared for oxygen doping nitride porous carbon (PCNO), is removed graphene oxide (GO) with strong acid by method from top to bottom
Ox-GQDs is modified onto PCNO at ox-GQDs, then by self-assembly method, it is more to be prepared for graphene oxide quantum dot/oxygen doping
Hole carbonitride (PCNGD) composite photo-catalyst, then carry out PCNGD and GO by cross-linking method compound to be prepared for graphene oxide amount
Sub- point/oxygen doping nitride porous carbon/graphene oxide ternary aeroge (PCNGD-GOA) photochemical catalyst.
(1) present invention is combined by self-assembly method and cross-linking method, on the one hand, hydroxyl and amino and ox- in PCNO skeleton
Oxygen-containing functional group (hydroxyl and carboxyl) in GQDs generates hydrogen bond action, π-π effect and chemical bond (- NH-C=O-),
To make ox-GQDs that can not only be contacted with the surface of PCNO, can also pass into inside the duct of PCNO, thus uniform and stable
Ground is deposited on PCNO；On the other hand, it is combined with each other between PCNGD and GO by pi-pi accumulation and hydrogen bond action, while GO piece
The conjugation absorption of layer and being crimped and wrapped enables PCNGD and GO carrier stable bond.
(2) present invention combines self-assembly method and cross-linking method, is prepared for bigger serface, wide visible spectrum responses
Range, quick photo-generated carrier transfer ability and graphene oxide quantum dot/oxygen doping for easily recycling are porous
Carbonitride/graphene oxide ternary aerogels, wherein the 3D reticular structure of aeroge improves PCNGD to pollutant
Adsorption capacity and recovery utilization rate, the high conductivity of ox-GQDs and GO can significantly improve the separation of the photogenerated charge of PCNO
Efficiency and optical response range, to largely improve adsorption capacity of the carbonitride to pollutant, photocatalytic degradation
Energy, antibacterial activity and recovery utilization rate have great importance for the application prospect and practical value that improve photochemical catalyst；Separately
Outside, self-assembly method and cross-linking method have the characteristics that efficient, green, mild.
(3) present invention optimizes the space that carbonitride carries out photocatalysis by porous Morphological control and oxygen element doping
And electronic structure, then the expansion with the compound fast transfer for realizing carbonitride photogenerated charge of ox-GQDs and spectral absorption range,
Then migration rate, optical response range that 3D porous network structure aeroge improves carbonitride photo-generated carrier are cross-linked to form with GO
And recycling ability, it is more to prepare graphene oxide quantum dot/oxygen doping with excellent degradation of contaminant and anti-microbial property
Hole carbonitride/graphene oxide ternary aerogels.
(4) graphene oxide quantum dot provided by the invention/oxygen doping nitride porous carbon/graphene oxide ternary aeroge
Possess compared to graphene oxide quantum dot/more excellent photocatalytic degradation of oxygen doping nitride porous carbon and anti-microbial property；This
The preparation method provided is invented, raw material is inexpensive, simple process, effectively reduces product cost, improves the circulation of product again
Using ability, it is suitable for industrial mass production, there is very high application prospect and practical value.
Detailed description of the invention
Fig. 1 is graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide prepared by the embodiment of the present invention 1
Oxidation stone prepared by ternary aeroge 30%-PCNGD-GOA, 60%-PCNGD-GOA and 90%-PCNGD-GOA and comparative example 4
Graphite oxide aerogel GOA prepared by black alkene quantum dot/oxygen doping nitride porous carbon PCNGD, comparative example 5 is right under visible light
The degradation property comparison diagram of amaranth；
Fig. 2 is 30%-PCNGD-GOA, 60%-PCNGD-GOA and 90%-PCNGD-GOA and comparison prepared by embodiment 1
PCNGD prepared by example 4 is in visible light to the anti-microbial property comparison diagram of Escherichia coli；
Fig. 3 is 30%-PCNGD-GOA, 60%-PCNGD-GOA, 90%-PCNGD-GOA and comparison prepared by embodiment 1
The XRD comparison diagram of the GOA of PCNGD, the preparation of comparative example 5 prepared by example 4；
The GO of Fig. 4 is 60%-PCNGD-GOA prepared by embodiment 1 and prepared by comparative example 1 PCNO, the preparation of comparative example 2,
The PCNGD of ox-GQDs, the preparation of comparative example 4 prepared by comparative example 3, the TEM photo comparison of the GOA of the preparation of comparative example 5 scheme；Wherein
(a) ox-GQDs, (b) GO, (c) PCNO, (d) ox-GQDs-0.2%/PCNO (PCNGD), (e)-(f) 60%-PCNGD- in Fig. 4
The TEM photo of GOA, (g) the HRTEM photo of 60%-PCNGD-GOA；
The SEM figure that Fig. 5 is 60%-PCNGD-GOA prepared by embodiment 1；
The pore-size distribution comparison diagram for the PCNGD that Fig. 6 is 60%-PCNGD-GOA prepared by embodiment 1 and prepared by comparative example 4；
Fig. 7 is 30%-PCNGD-GOA, 60%-PCNGD-GOA, 90%-PCNGD-GOA and comparison prepared by embodiment 1
The DRS comparison diagram of PCNGD prepared by PCNO and comparative example 4 prepared by example 1；
The photoelectricity of the PCNGD that Fig. 8 is 60%-PCNGD-GOA prepared by embodiment 1 and prepared by comparative example 4 under visible light
Performance comparison figure.
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is specifically described.
Material used in following embodiment and comparative examples, reagent etc., unless otherwise specified, commercially
It arrives.
In following embodiments, using Bruker D2-phaser type X-ray diffractometer (XRD) (Cu K alpha ray), test specimens
The crystalline structure of product；Using JEOL JEM-2100 type transmission electron microscope, beam voltage 200kV, shooting transmission
Electronic Speculum (TEM) image；Scanning electron microscope (SEM) image is shot using FEI Inspect F50 type field emission scanning electron microscope；
Using 3020 type full-automatic chemical adsorption instrument of Micromeritics TriStar II, N is used under liquid nitrogen temperature2Absorption-is de-
Subsidiary formula method measures the BET specific surface area and pore size distribution of sample；Using Shimadzu UV-3600Plus UV, visible light spectrophotometric
The diffusing reflection spectrum (DRS) of meter record sample.
Embodiment 1
A kind of graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aeroge, the photocatalysis
The preparation method of agent includes the following steps:
Firstly, melamine is calcined 4h at 550 DEG C in Muffle furnace, with the heating speed of 10 DEG C/min in air atmosphere
Rate prepares bulk g-C3N4(BCN)；1.5g BCN is dispersed in 135mL water simultaneously ultrasound (560W, 40kHz) 30min, then will be divided
Dispersion liquid is transferred in the stainless steel autoclave of teflon lining, heats 12h at 160 DEG C；Hydro-thermal reaction institute is thoroughly washed with water
It must precipitate, pulverize after dry, obtained pale yellow powder product is oxygen doping nitride porous carbon (PCNO).Then, will
15mg graphite oxide is dispersed in 30mL water and ultrasound (560W, 40kHz) 2h, to obtain small size nanometer sheet GO dispersion liquid 1
(0.5mg/mL)；8mL68% concentrated nitric acid and the 3mL98% concentrated sulfuric acid are mixed into ultrasonic place with prepared nanometer sheet GO dispersion liquid 1
1h is managed, then mixture is transferred in 100 DEG C of oil bath pan and is stirred for 24 hours, after being cooled to room temperature, mixture is placed in mildly
It is ultrasonically treated 20min under ultrasonic wave, after adding sodium carbonate adjusting mixture solution pH to 8.0, mixture is passed through 0.22 μm
Micro-pore-film filtration, and the 48h that further dialyses in bag filter (retaining molecular weight: 1000Da), products therefrom is graphite oxide
Alkene quantum dot (ox-GQDs) dispersion liquid.Then, 0.1g PCNO is dispersed in suitable water and is ultrasonically treated 30min to obtain
Uniform suspension；The ox-GQDs that mass fraction relative to PCNO is 0.2wt% is dispersed in above-mentioned suspension and in room
The total volume of mixed liquor for 24 hours, is maintained at 30mL by the lower stirring of temperature；Again by the way that precipitating is collected by centrifugation, carried out after drying is washed with water
Grinding, products therefrom is graphene oxide quantum dot/oxygen doping nitride porous carbon (PCNGD) photochemical catalyst.Secondly, by 45mg
Graphite oxide powder be dispersed in 3mL, concentration is prepared as the GO dispersion liquid 2 of 15mg/mL in rear ultrasound 2h, then will be relative to
The mass fraction of graphite oxide is respectively 30,60, the PCNGD of 90wt% is dispersed in ultrasound 30min in 2mL water and is prepared three kinds
Above-mentioned GO dispersion liquid 2 is mixed ultrasound with the PCNGD dispersion liquid of three kinds of various concentrations respectively by the PCNGD dispersion liquid of various concentration
30min is then separately added into 80 μ L ethylenediamines, and heats 30min at 95 DEG C, then be separately added into the CTAB of 5mg, and at 95 DEG C
It is lower to heat 7h respectively, obtain three kinds of graphene oxide quantum dots/oxygen doping nitride porous carbon/graphene oxide hydrogel
(PCNGD/GO).It is freeze-dried finally, being soaked in water PCNGD/GO two days to remove extra crosslinking agent, then by three kinds of hydrogels
48h completely removes the solvent in hydrogel, and products therefrom is graphene oxide quantum dot/oxygen doping nitride porous carbon/oxidation
Graphene ternary aerogels, are respectively designated as 30%-PCNGD-GOA, 60%-PCNGD-GOA, 90%-PCNGD-
GOA。
Embodiment 2
A kind of graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aeroge, the photocatalysis
The preparation method of agent includes the following steps:
Firstly, melamine is calcined 1h at 500 DEG C in Muffle furnace, with the heating speed of 1 DEG C/min in air atmosphere
Rate prepares bulk g-C3N4(BCN)；1.5g BCN is dispersed in 30mL water simultaneously ultrasound (200W, 10kHz) 5min, then will dispersion
Liquid is transferred in the stainless steel autoclave of teflon lining, heats 8h at 120 DEG C；It is heavy obtained by hydro-thermal reaction thoroughly to be washed with water
It forms sediment, pulverizes after dry, obtained pale yellow powder product is oxygen doping nitride porous carbon (PCNO).Then, by 15mg oxygen
Graphite is dispersed in 150mL water and ultrasound (200W, 10kHz) 0.5h, to obtain small size nanometer sheet GO dispersion liquid 1
(0.1mg/mL)；15mL60% concentrated nitric acid and the 10mL90% concentrated sulfuric acid are mixed into ultrasound with prepared nanometer sheet GO dispersion liquid 1
0.5h is handled, then mixture is transferred in 50 DEG C of oil bath pan and stirs 5h, after being cooled to room temperature, mixture is placed in temperature
Be ultrasonically treated 5min under ultrasonic wave, add sodium carbonate adjust mixture solution pH to 7.0 after, by mixture pass through 0.22 μm
Micro-pore-film filtration, and the 5h that further dialyses in bag filter (retaining molecular weight: 1000Da), products therefrom is graphene oxide
Quantum dot (ox-GQDs).Then, 0.1g PCNO is dispersed in suitable water and is ultrasonically treated 6min to obtain uniform hang
Supernatant liquid；The ox-GQDs dispersion liquid that mass fraction is 0.001wt% is dispersed in above-mentioned PCNO suspension and is stirred at 10 DEG C
The total volume of mixed liquor is maintained at 50mL by 5h；Again by the way that precipitating is collected by centrifugation, ground after drying is washed with water, gained
Product is graphene oxide quantum dot/oxygen doping nitride porous carbon (PCNGD) photochemical catalyst.Secondly, by the graphite oxide of 6mg
Powder is dispersed in ultrasound 0.1h in 3mL water and prepares concentration as the GO dispersion liquid 2 of 2mg/mL, then the PCNGD of 0.6mg is dispersed in
Ultrasound 0.1h prepares the PCNGD dispersion liquid of 1mg/mL in 0.6mL water, and above-mentioned PCNGD dispersion liquid and GO dispersion liquid 2 are mixed ultrasound
0.1h is subsequently added into 3 μ L ethylenediamines, and heats 0.1h at 50 DEG C, adds the CTAB of 0.3mg, and heat at 50 DEG C
0.1h obtains graphene oxide quantum dot/oxygen doping nitride porous/graphene oxide hydrogel (PCNGD/GO).Finally, using water
PCNGD/GO 5h is impregnated to remove extra crosslinking agent, then is freeze-dried 5h and completely removes solvent in hydrogel, gained
Product is graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aerogels, as
PCNGD-GOA。
Embodiment 3
A kind of graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aeroge, the photocatalysis
The preparation method of agent includes the following steps:
Firstly, melamine is calcined 8h at 600 DEG C in Muffle furnace, with the heating speed of 12 DEG C/min in air atmosphere
Rate prepares bulk g-C3N4(BCN)；1g BCN is dispersed in 150mL water simultaneously ultrasound (800W, 50kHz) 60min, then will dispersion
Liquid is transferred in the stainless steel autoclave of teflon lining, heats 16h at 200 DEG C；It is thoroughly washed with water obtained by hydro-thermal reaction
Precipitating is pulverized after dry, and obtained pale yellow powder product is oxygen doping nitride porous carbon (PCNO).Then, by 15mg
Graphite oxide is dispersed in 15mL water and ultrasound (800W, 50kHz) 10h, to obtain 1 (1mg/ of small size nanometer sheet GO dispersion liquid
mL)；15mL70% concentrated nitric acid and the 3mL99% concentrated sulfuric acid are mixed to ultrasonic treatment 2h with prepared nanometer sheet GO dispersion liquid 1, with
Mixture is transferred to afterwards in 150 DEG C of oil bath pan and stirs 30h, after being cooled to room temperature, mixture is placed in mild ultrasonic wave
Mixture is passed through 0.22 μm of microporous barrier after adding sodium carbonate adjusting mixture solution pH to 9.0 by lower ultrasonic treatment 60min
Filtering, and the 50h that further dialyses in bag filter (retaining molecular weight: 1000Da), products therefrom is graphene oxide quantum
Point (ox-GQDs).Then, 0.1g PCNO is dispersed in suitable water and is ultrasonically treated 5h to obtain uniform suspension；It will
Mass fraction is that the ox-GQDs of 10.0wt% is dispersed in above-mentioned suspension and stirs 5h at 60 DEG C, by the totality of mixed liquor
Product is maintained at 5mL；Again by the way that precipitating is collected by centrifugation, ground after drying is washed with water, products therefrom is graphene oxide
Quantum dot/oxygen doping nitride porous carbon (PCNGD) composite photo-catalyst.Secondly, the graphite oxide powder of 60mg is dispersed in 3mL
Ultrasound 5h prepares concentration as the GO dispersion liquid 2 of 20mg/mL in water, then the PCNGD of 120mg is dispersed in ultrasound 5h system in 12mL water
The PCNGD dispersion liquid of standby 10mg/mL, mixes ultrasonic 5h for above-mentioned PCNGD dispersion liquid and GO dispersion liquid 2, is subsequently added into 300 μ L second
Diamines, and 10h is heated at 150 DEG C, the CTAB of 30mg is added, and heat 10h at 150 DEG C, obtains graphene oxide amount
Sub- point/oxygen doping nitride porous carbon/graphene oxide hydrogel (PCNGD/GO).Finally, be soaked in water PCNGD/GO 100h with
Extra crosslinking agent is removed, then is freeze-dried 100h and completely removes solvent in hydrogel, products therefrom is to aoxidize stone
Black alkene quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aerogels, as PCNGD-GOA.
Comparative example 1
Hydro-thermal method prepares oxygen doping nitride porous carbon
Firstly, melamine is calcined 4h at 550 DEG C in Muffle furnace, with the heating speed of 10 DEG C/min in air atmosphere
Rate prepares bulk g-C3N4(BCN)；1.5g BCN is dispersed in 135mL water simultaneously ultrasound (560W, 40kHz) 30min, then will be divided
Dispersion liquid is transferred in the stainless steel autoclave of teflon lining, heats 12h at 160 DEG C；Hydro-thermal reaction institute is thoroughly washed with water
It must precipitate, pulverize after dry, obtained pale yellow powder product is oxygen doping nitride porous carbon (PCNO).
Comparative example 2
Ultrasonic method prepares stannic oxide/graphene nano piece dispersion liquid
15mg graphite oxide is dispersed in 30mL water simultaneously ultrasound (560W, 40kHz) 2h, to obtain small size graphite oxide
Alkene nanometer sheet (GO) dispersion liquid (0.5mg/mL).
Comparative example 3
Sour stripping method prepares graphene oxide quantum dot
15mg graphite oxide is dispersed in 30mL water simultaneously ultrasound (560W, 40kHz) 2h, to obtain small size nanometer sheet GO
Dispersion liquid (0.5mg/mL)；8mL68% concentrated nitric acid and the 3mL98% concentrated sulfuric acid are mixed with prepared nanometer sheet GO dispersion liquid and surpassed
Mixture is then transferred in 100 DEG C of oil bath pan and stirs for 24 hours, after being cooled to room temperature, mixture is placed in by sonication 1h
Mixture is passed through 0.22 μm of micropore after adding sodium carbonate adjusting mixture solution pH to 8.0 by 20min under mild ultrasonic wave
Film filtering, and the 48h that further dialyses in bag filter (retaining molecular weight: 1000Da), products therefrom is graphene oxide amount
Sub- point (ox-GQDs).
Comparative example 4
Self-assembly method prepares graphene oxide quantum dot/oxygen doping nitride porous carbon
Firstly, melamine is calcined 4h at 550 DEG C in Muffle furnace, with the heating speed of 10 DEG C/min in air atmosphere
Rate prepares bulk g-C3N4(BCN)；1.5g BCN is dispersed in 135mL water simultaneously ultrasound (560W, 40kHz) 30min, then will be divided
Dispersion liquid is transferred in the stainless steel autoclave of teflon lining, heats 12h at 160 DEG C；Hydro-thermal reaction institute is thoroughly washed with water
It must precipitate, pulverize after dry, obtained pale yellow powder product is oxygen doping nitride porous carbon (PCNO).Secondly, will
15mg graphite oxide is dispersed in 30mL water and ultrasound (560W, 40kHz) 2h, to obtain small size nanometer sheet GO dispersion liquid
(0.5mg/mL)；8mL68% concentrated nitric acid and the 3mL98% concentrated sulfuric acid are mixed into ultrasonic treatment with prepared nanometer sheet GO dispersion liquid
Mixture is then transferred in 100 DEG C of oil bath pan and stirs for 24 hours by 1h, after being cooled to room temperature, mixture is placed in mild super
Mixture is passed through 0.22 μm of micro-pore-film filtration after adding sodium carbonate adjusting mixture solution pH to 8.0 by 20min under sound wave,
And the 48h that further dialyses in bag filter (retaining molecular weight: 1000Da), products therefrom is graphene oxide quantum dot (ox-
GQDs).Finally, 0.1g PCNO is dispersed in suitable water and is ultrasonically treated 30min to obtain uniform suspension；By phase
Mass fraction for PCNO is respectively that the ox-GQDs of 0.2wt% is dispersed in above-mentioned suspension and is stirred at room temperature for 24 hours,
The total volume of mixed liquor is maintained at 30mL；Again by the way that precipitating is collected by centrifugation, ground after drying is washed with water, products therefrom
As graphene oxide quantum dot/oxygen doping nitride porous carbon composite photocatalyst, as PCNGD.
Comparative example 5
Cross-linking method prepares graphite oxide aerogel
The graphite oxide powder of 45mg is dispersed in ultrasound 2h in 3mL water and prepares the graphene oxide that concentration is 15mg/mL
Nanometer sheet (GO) dispersion liquid adds 80 μ L ethylenediamines, and heats 30min at 95 DEG C, is subsequently added into the CTAB of 5mg, and
7h is heated at 95 DEG C, obtains GO hydrogel.Then, be soaked in water GO hydrogel two days to remove extra crosslinking agent, then by its
Freeze-drying 48h completely removes the solvent in hydrogel, and products therefrom is graphite oxide aerogel, as GOA.
Test case
1, photocatalytic pollutant degradation performance test
Using amaranth as target degradation product, the degradation for investigating PCNGD-GOA composite photo-catalyst under visible light is living
Property, it is seen that gloss is that light source adds 420nm optical filter, average intensity 30mW/cm with the xenon lamp of 500W2；Take 2.0 × 10-5The amaranth of M
The red solution 50mL of dish, is added the photochemical catalyst of 5.0mg, first by solution ultrasonic disperse 15min, then stirs in dark room conditions
50min to reach adsorption equilibrium between photochemical catalyst and target contaminant；It opens xenon source and starts light-catalyzed reaction, every
10min takes 2mL reaction solution, with the photochemical catalyst in centrifuge centrifugation (revolving speed 11000rpm/min) removal solution, supernatant
The concentration of amaranth measures the suction at 521nm wavelength using Shimadzu UV-1800 type ultraviolet-uisible spectrophotometer in liquid
The variation of luminosity.
Fig. 1 is 30%-PCNGD-GOA, 60%-PCNGD-GOA and 90%-PCNGD-GOA and comparison prepared by embodiment 1
The GOA of PCNGD, the preparation of comparative example 5 prepared by example 4 are under visible light to the degradation property comparison diagram of amaranth.By scheming in Fig. 1
(a) it is found that PCNGD-GOA, which proceeds to 50min in dark reaction, basically reaches adsorption equilibrium, however after radiation of visible light 50min,
The PCNGD-GOA compound of different proportion all shows photocatalysis performance more better than PCNGD, GOA to amaranth.With
PCNGD content increases to 90% from 30%, and the degradation efficiency of compound first increases to be reduced afterwards, shows that PCNGD is most in compound
Good ratio is 60%, is 99.3% to the degradation rate of amaranth in 50min, corresponding degradation rate constant is
0.0844min-1, it is 29.6 times of PCNGD, is 13.1 times of GOA.In addition, testing composite material by 5 circulation degradation experiments
Stability (in Fig. 1 scheme (b)), 60%-PCNGD-GOA aeroge after the 5th wheel circulation to the removal rate of amaranth hardly
Become, shows that it recycles ability with outstanding.Prove compared to graphene oxide quantum dot/oxygen doping nitride porous carbon and
Graphite oxide aerogel, graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aeroge photocatalysis
Agent possesses more excellent photocatalytic pollutant degradation performance and recycling ability.
2, photocatalysis antibacterial performance test
Gram-E. coli selected as model bacterium analyze the anti-microbial property of sample.Bacterium is existed first
It is incubated in 100mL Luria-Bertani (LB) nutrient solution, then vibrates 4h at 37 DEG C.After centrifugation, by bacterium cell pellet
It is washed twice with Sterile Saline (0.9%NaCl) solution, is then resuspended in sterile saline solution.Pass through photochemical reactor
(XPA-7) the 420nm edge filter and 500W xenon lamp being furnished in survey to the photocatalysis antibacterial performance of Bacillus coli cells
Examination.Bacterial cell density and photocatalyst concentrations respectively may be about 5 × 106CFU/mL and 0.1mg/mL.During radiation of visible light
Suspension is extracted at a time interval as sample liquid, then uses sterile saline solution serial dilution.Later, 100 μ L are diluted
Suspension on LB solid medium, be then incubated for 12h at 37 DEG C.Large intestine bar living is estimated using colony counting method
The cell density of bacterium (in terms of CFU).Meanwhile under visible light illumination, experiment of photoswitch is carried out in the case where no photochemical catalyst,
And dark control experiment is carried out to be compared with prepared 60%-PCNGD-GOA photochemical catalyst in the dark.Each antibacterial is real
Test triplicate progress.In order to ensure sterile, all glasswares are sterilized in autoclave 20min at 121 DEG C.
Fig. 2 is 30%-PCNGD-GOA, 60%-PCNGD-GOA and 90%-PCNGD-GOA and comparison prepared by embodiment 1
PCNGD prepared by example 4 is in visible light to the anti-microbial property comparison diagram of Escherichia coli.As shown in Figure 2, photocontrol experiment shows visible
Light does not influence bacterium, while still having about 93.2% bacterium residual to show that light is urged after 80min in dark control experiment
Agent itself is to Escherichia coli without apparent bio-toxicity.After radiation of visible light 80min, PCNGD can only make about 15.9%
Bacillus coli cells inactivation, and the antibacterial activity of 30%-PCNGD-GOA, 60%-PCNGD-GOA and 90%-PCNGD-GOA with
The increase of load percentage can make the Escherichia coli of about 86.2%, 99.8% and 93.2% in the trend reduced afterwards is first increased respectively
Cell inactivation.Therefore, PCNGD-GOA ratio PCNGD has superior anti-microbial property, the result of this and photocatalytic degradation amaranth
Unanimously.Prove that graphene oxide quantum dot/oxygen doping is porous compared to graphene oxide quantum dot/oxygen doping nitride porous carbon
Carbonitride/graphene oxide ternary aerogels possess more excellent photocatalysis antibacterial performance.
Fig. 3 is 30%-PCNGD-GOA, 60%-PCNGD-GOA and 90%-PCNGD-GOA and comparison prepared by embodiment 1
The XRD comparison diagram of the GOA of PCNGD, the preparation of comparative example 5 prepared by example 4.From the figure 3, it may be seen that PCNO is 13.0 ° (100) and 27.4 °
(002) two different diffraction maximums are shown at, respectively correspond and the flat of aromatic rings is stacked and be conjugated in the plane of 3-s- 5-triazine units
It is stacked between face, 10.6 ° of weak peak represents the oxygen-containing group formed in water-heat process.The diffraction maximum of PCNGD and PCNO are essentially identical,
But it almost disappears at 10.6 ° of peak, this is because ox-GQDs and PCNO interaction causes oxygen-containing functional group to reduce.Another party
Face, GO has sharp diffraction maximum at 10.8 °, and peak value of the GOA at 001 becomes 12.9 ° from 10.8 ° and become wide diffraction
Peak shows to retain the loose stacking of major part GO original oxygen-containing functional group and GO nanometer sheet in gel structure in GOA structure.
PCNGD-GOA has characteristic peak identical with GOA at 001, shows the characteristic peak of corresponding PCNGD at 27.4 °, and with
The increase of PCNGD content, peak value of the PCNGD-GOA at 001 gradually dies down, and the peak value at 002 is remarkably reinforced, and shows GO
Lamella and PCNGD lamella can steadily be crosslinked combination.Prove that the present invention can will aoxidize stone by self-assembly method and cross-linking method
Black alkene quantum dot, oxygen doping nitride porous carbon and graphene oxide are successfully combined into ternary aerogel material.
The GO of Fig. 4 is 60%-PCNGD-GOA prepared by embodiment 1 and prepared by comparative example 1 PCNO, the preparation of comparative example 2,
The PCNGD of ox-GQDs, the preparation of comparative example 4 prepared by comparative example 3, the TEM photo comparison of the GOA of the preparation of comparative example 5 scheme.By Fig. 4
(a) it is found that ox-GQDs diameter is about 3nm and is uniformly dispersed, can be observed respectively in the upper half figure and lower half figure of Fig. 4 (b)
The transparent laminar GO and PCNO in porous flake；By Fig. 4 (c) it is found that ox-GQDs is uniformly deposited on the surface of PCNO
On duct；By Fig. 4 (d) and Fig. 4 (e) it is found that PCNGD is evenly dispersed on the substrate of GO, PCNGD or it is stacked on GO lamella
Upper (as shown in orange circle), or be encapsulated in GO lamella (as shown in red circle), to make ternary complex PCNGD-
GOA has multiple overlapping layers, this shows that the PCNGD of laminated structure and GO are successfully made stacking crosslinking；From the macro of PCNGD-GOA
Piece (upper right corner Fig. 4 (d)) is taken into consideration as can be seen that PCNGD lamella and the finally formed macroscopical aeroge of GO lamella interconnection stacking are in
It is now consistent cylindric with reaction vessel shape；By Fig. 4 (f) it is found that having apparent heterogeneous interface between PCNGD and GO,
Facilitate the migration of composite inner photo-generated carrier, and then improves the photocatalysis performance of PCNGD-GOA.Prove that the present invention is logical
It crosses self-assembly method and cross-linking method can be compound by the success of graphene oxide quantum dot, oxygen doping nitride porous carbon and graphene oxide
At the ternary aerogel material of 3D reticular structure.
The SEM figure that Fig. 5 is 60%-PCNGD-GOA prepared by embodiment 1.As shown in Figure 5,60%-PCNGD-GOA is shown
For reticulated porous structures, this is mainly to be stacked and be cross-linked to form mutually by PCNGD lamella and GO lamella.Prove that the present invention passes through
Graphene oxide quantum dot/oxygen doping nitride porous carbon and graphene oxide can be successfully combined into 3D reticular structure by cross-linking method
Ternary aerogel material.
The pore-size distribution comparison diagram for the PCNGD that Fig. 6 is 60%-PCNGD-GOA prepared by embodiment 1 and prepared by comparative example 4.
As shown in fig. 6, the aperture of PCNGD is mainly distributed at about 3.7nm, illustrate the presence for having mesoporous in its structure, and 60%-
PCNGD-GOA shows apparent pore size distribution within the scope of 1.8~25nm, and peak value is located at about 3.7nm, shows composite aerogel
There is the presence of micropore and mesoporous in structure, this some holes is mainly handed over by the pore structure of PCNGD itself and GO lamella and PCNGD lamella
The slit pore structure composition that connection assembling generates.In addition, due to the 3D reticular structure of aeroge, so that 60%-PCNGD-GOA
BET specific surface area (1571.23m2/ g) it significantly increases, it is the BET specific surface area (40.55m of PCNGD2/ g) 38.75 times.It proves
Graphene oxide quantum dot/oxygen doping nitride porous carbon and graphene oxide can be successfully combined into 3D with cross-linking method by the present invention
The ternary aerogel material of reticulated porous structures.
Fig. 7 is 30%-PCNGD-GOA, 60%-PCNGD-GOA and 90%-PCNGD-GOA and comparison prepared by embodiment 1
The DRS comparison diagram of PCNGD prepared by example 4.As shown in fig. 7, all PCNGD-GOA, which are all shown, to be significantly increased compared to PCNGD
Visible absorption and ABSORPTION EDGE all there is red shift, the most obvious with the red shift degree of 60%-PCNGD-GOA, this may be
As incident light in the 3D holey of aeroge multiple reflections and refraction caused by.This result also illustrates 60%-PCNGD-
GOA have it is optimal visible light-responded, reason may be the 3D reticular structure of 60%-PCNGD-GOA than other ratio compounds
Structure be more conducive to the reflection and refraction of incident light.Prove graphene oxide quantum dot/oxygen doping nitride porous carbon/graphite oxide
Light absorpting ability of the alkene ternary aerogels in visible-range significantly increases, thus with more excellent visible
Photocatalytic pollutant degradation and anti-microbial property.
3, photoelectric properties are tested
Photoelectricity flow measurement carries out on CHI 660B electrochemical workstation (Chenhua Instrument), standard three electrode
System includes to electrode i.e. platinum filament, reference electrode, that is, saturated calomel electrode and working electrode, while by 0.1M Na2SO4Solution is made
For electrolyte.Following preparation work electrode: by 2mg sample dispersion in 2mL ethanol solution, then suspension is existed
On the ito glass substrate of 20mm × 40mm, active region is about 20mm × 30mm, and the dry 5h at 180 DEG C.Using having
The 300W xenon lamp (CEL-HXF 300, Ceaulight) of 400nm edge filter is used as visible light source.Photocurrent response test exists
It is carried out under 0.0V.Electrochemical impedance spectroscopy (EIS) spectrum records under the AC voltage of 5mV and in the range of 0.05Hz to 105Hz.
The photoelectricity of the PCNGD that Fig. 8 is 60%-PCNGD-GOA prepared by embodiment 1 and prepared by comparative example 4 under visible light
Performance comparison figure.As shown in Fig. 8 (a), the transient photocurrents density of PCNGD is greater than PCNO, and this is mainly due to the height of ox-GQDs
The migration of photogenerated charge can be improved in conductivity.In addition, 60%-PCNGD-GOA shows highest photo-current intensity, it is respectively
2 times of PCNGD and PCNO and 18 times, this enhancing may be since the 3D reticular structure being cross-linked to form between GO and PCNGD can
To accelerate the separation of photo-generate electron-hole pair.Meanwhile as shown in Fig. 8 (b), in Nyquist figure, PCNGD has more than PCNO
The EIS circular curve of minor radius, and have the smallest EIS circular arc of radius bent compared to PCNO, PCNGD, 60%-PCNGD-GOA
Line further demonstrates the high conductivity of ox-GQDs and GO.Proof 3D porous network structure is graphene oxide quantum dot/oxygen
Doping nitride porous carbon/graphene oxide ternary aerogels photo-generated carrier provides transfering channel abundant,
The transport efficiency of its photogenerated charge is significantly increased, to more excellent catalyzing and degrading pollutant by visible light and resist
Bacterium performance.
Claims (7)
1. a kind of graphene oxide quantum dot/oxygen doping nitride porous carbon/graphene oxide ternary aerogels, special
Sign is that the preparation method of the photochemical catalyst includes the following steps:
(1) it using melamine as raw material, is calcined under air atmosphere, prepares blocky carbonitride, then gained carbonitride is surpassed
Sound is dispersed in water, and carries out hydro-thermal reaction, cooling after having reacted, and be separated by solid-liquid separation and is collected precipitating, will precipitate drying and grinding
At powder to get oxygen doping nitride porous carbon；
(2) graphite oxide ultrasonic disperse is obtained into stannic oxide/graphene nano piece dispersion liquid 1 in water, concentrated nitric acid and the concentrated sulfuric acid is added,
And heating reflux reaction is carried out, it is cooled to room temperature, adds the pH to 7.0~9.0 that pH adjusting agent adjusts dispersion liquid, will finally mix
Object is closed by 0.22 μm of micro-pore-film filtration, and is further dialysed in bag filter to get graphene oxide quantum dot dispersion liquid；
(3) in water by gained oxygen doping nitride porous carbon ultrasonic disperse in step (1), gained in step (2) is added and aoxidizes stone
Black alkene quantum dot dispersion liquid, is stirred and is reacted, and is separated by solid-liquid separation collects sediment after reaction, sediment is washed dry
Dry and grinding is to get graphene oxide quantum dot/oxygen doping nitride porous carbon；
(4) it is dispersed in water gained graphene oxide quantum dot/oxygen doping nitride porous carbon in step (3) to obtain graphite oxide
Alkene quantum dot/oxygen doping nitride porous carbon dispersion liquid, while graphite oxide being dispersed in water to obtain stannic oxide/graphene nano piece
The stannic oxide/graphene nano piece is added in the graphene oxide quantum dot/oxygen doping nitride porous carbon dispersion liquid by dispersion liquid 2
In dispersion liquid 2, mixing ultrasound obtains mixed liquor, ethylenediamine is added in gained mixed liquor, and carry out heating reaction, one timing of reaction
Between after be added cetyl trimethylammonium bromide, carry out heating reaction again, be cooled to room temperature after reaction to get oxidation stone
Black alkene quantum dot/oxygen doping nitride porous carbon/graphene oxide hydrogel；
(5) gained hydrogel with water in step (4) is impregnated, is finally freeze-dried to get graphene oxide quantum dot/oxygen doping
Nitride porous carbon/graphene oxide ternary aerogels.
2. photochemical catalyst according to claim 1, which is characterized in that calcining described in step (1) includes successively carrying out
It heats up heating period and constant temperature stage；The heating rate of the heating heating period is 1~12 DEG C/min；The constant temperature stage
Temperature is 500~600 DEG C, and constant temperature time is 1~8h；The mass volume ratio of the carbonitride and water is 1g:20~150mL；Institute
Stating ultrasonic power is 200~800W, and supersonic frequency is 10~50kHz, and ultrasonic time is 5~60min；The hydrothermal temperature
It is 120~200 DEG C, the reaction time is 8~16h.
3. photochemical catalyst according to claim 1, which is characterized in that the quality of graphite oxide and water described in step (2)
Volume ratio is 1mg:1~10mL, and the ultrasonic power is 200~800W, and supersonic frequency is 10~50kHz, sonication treatment time
0.5~10h；The concentrated nitric acid concentration is 60%~70%, and concentrated sulfuric acid concentration is 90%~99%；The concentrated nitric acid and oxidation stone
The volume ratio of black alkene dispersion liquid is 1:1~10, and the volume ratio of the concentrated sulfuric acid and graphene oxide dispersion is 1:5~15.
4. photochemical catalyst according to claim 1, which is characterized in that the temperature of heating reflux reaction described in step (2)
It is 50~150 DEG C, the reaction time is 5~30h；The pH adjusting agent is sodium bicarbonate, at least one in sodium hydroxide, sodium carbonate
Kind；The reservation molecular weight of the dialysis is 1000Da, and dialysis time is 5~60h, graphene oxide quantum dot dispersion liquid after dialysis
Concentration is 0.1~0.01mg/mL.
5. photochemical catalyst according to claim 1, which is characterized in that oxygen doping nitride porous carbon described in step (3) with
The mass volume ratio of water is 1g:50~500mL；The ultrasonic power is 200~800W, and supersonic frequency is 10~50kHz, ultrasound
The processing time is 0.1~5h；The mass ratio of the oxygen doping nitride porous carbon and graphene oxide quantum dot be 1:0.001~
0.1, reaction temperature is 10~60 DEG C, and the reaction time is 5~50h.
6. photochemical catalyst according to claim 1, which is characterized in that graphene oxide quantum dot/oxygen described in step (4)
The mass volume ratio of nitride porous carbon and water is adulterated as 1mg:0.1~1mL, the mass volume ratio of the graphite oxide and water is
The mass ratio of 1mg:0.05~0.5mL, graphene oxide quantum dot/oxygen doping nitride porous carbon and graphite oxide is 0.1~2:
1, the ultrasonic power is 200~800W, and supersonic frequency is 10~50kHz, and sonication treatment time is 0.1~5h；The oxidation
The mass volume ratio of graphite and ethylenediamine is the μ L of 1mg:0.5~5, the mass ratio of graphite oxide and cetyl trimethylammonium bromide
For 1mg:0.05~0.5mg, the heating reaction time range is 0.1~10h, and the temperature range for heating reaction is 50~
150℃。
7. photochemical catalyst according to claim 1, which is characterized in that soaking time described in step (5) is 5~100h,
Sublimation drying is 5~100h.
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