CN104353469A - Method for preparing nanocomposite photocatalyst and application of nanocomposite photocatalyst - Google Patents
Method for preparing nanocomposite photocatalyst and application of nanocomposite photocatalyst Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to the technical field of preparation of environmental materials, in particular to a method for preparing a nanocomposite photocatalyst and application of the nanocomposite photocatalyst. The method comprises the following steps: weighing graphene oxide, putting the graphene oxide in a certain amount of deionized water, and performing ultrasound concussion until complete dissolution; respectively adding cadmium chloride and zinc chloride into a graphene oxide solution, and stirring to dissolve and then adding L-cysteine to continue to stir until complete dissolution; then regulating pH to 7 with a sodium hydroxide solution, and adding sodium sulfide and then introducing nitrogen to stir for 10-15min; pouring the solution into a high-pressure reactor, then putting in a high-temperature oven for heat preservation, and finally taking out for natural cooling; after centrifuging, washing and drying the reacted solution, grinding, and thus obtaining the CdS/ZnS nanocomposite photocatalyst loaded with graphene oxide. The prepared CdS/ZnS nanocomposite photocatalyst loaded with graphene oxide can effectively utilize visible light to degrade tetracycline in antibiotic wastewater.
Description
Technical field
The invention belongs to technical field of environmental material preparation, relate to the synthesis of graphene oxide and water heat transfer CdS/ZnS nano composite material load graphene oxide photochemical catalyst and application thereof.
Background technology
Antibiotic (Antibiotics) is the chemical substance produced by certain micro-organisms or animals and plants, can suppress the material of microorganism and other cell proliferations, is widely used in the medicine of the various bacteriological infection for the treatment of or suppression pathogenic microorganism infection.Due to the irrational utilization of antibiotic medicine, larger harm is created to environment, for tetracycline antibiotic, many research reports show that antibiotic extensively exists in soil, surface water, underground water, deposit, municipal sewage and animal excrements oxidation pond; Therefore, the problems such as antibiotic residue brings in environment environmental pollution and food chain product safety of eliminating have been researcher significant problem in the urgent need to address, the means of current wastewater treatment mainly contain Physical, chemical method, biochemical process etc., but numerous wastewater processing technology or to there is operating cost high or with shortcomings such as secondary pollutions, makes treatment effect can not be satisfactory.
Conductor photocatalysis degradation technique is a kind of high-level oxidation technology, is a kind of environmentally-friendly technique most possibly utilizing nature sunshine to realize clean decontamination, has become people at present and paid close attention to more method of wastewater treatment; TiO in numerous photocatalysis semi-conducting material
2photochemical catalyst have cheap, non-secondary pollution, etc. advantage be described as eco-friendly pollution plot material, paid close attention to widely in environmental protection and energy-conservation application prospect, it is mainly used in the fields such as the exploitation of waste water, exhaust-gas treatment and antibacterial, automatically cleaning product; But TiO
2also there is limitation in itself, as its light absorption threshold value be confined to that ultraviolet region, photo-quantum efficiency are lower, photocatalytic degradation lacks selective etc., therefore, have that visible light-responded ability is strong, photocatalytic activity is high, the exploitation of the novel photocatalyst of selective degradation capability becomes the focus of research in recent years.
Graphene oxide (Graphene Oxide), it is the derivative of graphene functionalized, it is alternatively the mono-layer graphite oxide thin slice that graphite oxide obtains through mechanical stripping, structure and the Graphene of graphene oxide (Graphene Oxide) are similar, two-dimensional network structure is presented close to plane, difference is, surface of graphene oxide has multiple oxy radical, as C=O, C-OOH, C-OH etc., these groups are after the oxidized process of flaky graphite, appear at surface and the interlayer of graphite flake, wherein a large amount of hydroxyls and epoxide group are present in plane, and have a small amount of carboxyl, carbonyl, phenylol, ester group and quinonyl are distributed in the edge of lamella, owing to having a large amount of oxy radicals on the surface, graphene oxide has better hydrophily than Graphene, can disperse particularly in water in much solution well, thus can be used for carrying out load matrix.
Cadmium sulfide (CdS) is one more typical Ⅱ – VI piezoelectric semiconductor of race and semiconductor photosensitive material, there is larger band gap width (about 2.45eV), also be a kind of good solar cell window material and nonlinear optical material, because it has excellent optics, electrical properties, be widely used in the fields such as various luminescent device, photovoltaic device, optical detector, light sensor and photocatalysis, but the photoetch that CdS itself has limits its application; ZnS is
-
race's wide bandgap semiconductor compound-material, its Emission in Cubic energy gap 3.7eV, six side's phase energy gaps are 3.8eV.
CdS/ZnS nano composite material load graphene oxide photochemical catalyst catalyst obtained in the present invention, method is simple to operate, effectively reduce photoetch, and have good degradation effect to Fourth Ring and improve catalyst stability simultaneously, and obtained photochemical catalyst have good degradation effect to Fourth Ring.
Summary of the invention
The present invention includes two parts, is the synthesis of graphene oxide and the synthesis of CdS/ZnS nano composite material load graphene oxide photochemical catalyst respectively.
The present invention carries out according to the following steps;
(1) synthesis of graphene oxide: add native graphite and sodium nitrate in the concentrated sulfuric acid, ice bath, slowly add potassium permanganate under stirring condition, keeps stirring 2h at 0-20 DEG C; Then heating water bath 35 DEG C stirring, in solution, add distilled water setting water bath heating temperature is 98 DEG C of maintenance 40min; After end, slowly while stirring add distilled water cessation reaction to solution for continuous, then add the aqueous hydrogen peroxide solution that mass concentration is 30%, leave standstill, outwell supernatant, with concentrated hydrochloric acid and water by 1: 10 the mixed liquor that mixes of volume ratio wash, stir 20-40min, leave standstill, outwell supernatant, and be washed with distilled water to neutrality, be positioned over vacuum drying oven drying and obtain graphene oxide.
(2) synthesis of CdS/ZnS nano composite material load graphene oxide photochemical catalyst: take graphene oxide and be placed in a certain amount of deionized water, ultrasonic vibration is to dissolving completely, caddy and zinc chloride are joined in graphene oxide solution respectively, adds Cys after stirring and dissolving again and continue to be stirred to and dissolve completely; Then regulate pH=7 with sodium hydroxide solution, add vulcanized sodium logical nitrogen gas stirring 10-15min subsequently, above-mentioned solution is poured in autoclave, after being positioned over high temperature oven insulation subsequently, takes out nature cooling; To reacted solution centrifugal, washing, after drying, grinding obtains CdS/ZnS nano composite material load graphene oxide photochemical catalyst.
The mass ratio of potassium permanganate, aqueous hydrogen peroxide solution, the concentrated sulfuric acid, sodium nitrate and native graphite in step (1) is 4:10:30:2.5:1, the mass ratio of the distilled water that first time adds and potassium permanganate is 10:1, and the mass ratio of the distilled water that second time adds and potassium permanganate is 35:1.
The consumption of deionized water described in step (2) dissolves completely to make caddy, zinc chloride, Cys, graphene oxide, vulcanized sodium.
In step (2), optimal oxygen functionalized graphene, caddy, zinc chloride, Cys, vulcanized sodium mass ratio are 6.5-26.25:104:62:439:219, preferred proportion 19.75:104:62:439:219.
Sodium hydroxide solution described in step (2) is concentration is 1mol/L.
Be positioned over described in step (2) in high temperature oven to take out after insulation and refer in 180
oc is incubated 1h.
Washing described in step (2) refers to use respectively deionized water and absolute ethanol washing twice.
Oven dry described in step (2) is 50 DEG C dries 6h.
The CdS/ZnS nano composite material load graphene oxide photochemical catalyst obtained according to preparation method of the present invention, and the application of degraded tetracycline antibiotic.
In the present invention chemicals used be analyze pure, wherein graphite powder, sodium nitrate, potassium permanganate, the concentrated sulfuric acid is purchased in traditional Chinese medicines chemical reagent Co., Ltd; Caddy, zinc chloride, vulcanized sodium is purchased from Aladdin chemical reagent Co., Ltd; Tetracycline antibiotic is mark product, is purchased from Shanghai along vigorous bioengineering Co., Ltd.
Beneficial effect of the present invention:
The object that to present invention achieves with CdS/ZnS nano composite material load graphene oxide be catalyst degradation antibiotic waste water.Semi-conducting material is as photochemical catalyst, visible ray is as exciting, by realizing special catalysis or conversion effet with the interfacial interaction of contaminant molecule, the oxygen of surrounding and hydrone are excited into have the free anion of oxidizing force, thus reach the object of harmful organic substances in degraded environment, the method can not cause the wasting of resources and additional formation of polluting, and easy and simple to handle, is a kind of efficient treatment technology of environmental protection.
Accompanying drawing explanation
Fig. 1 is the XRD figure of graphene oxide, CdS, ZnS, CdS/ZnS and CdS/ZnS nano composite material load graphene oxide photochemical catalyst.
Fig. 2 is the TEM figure of graphene oxide-CdS/ZnS; A, graphene oxide TEM scheme; B, c, the TEM figure of graphene oxide-CdS/ZnS; E, d, for the HRTEM of graphene oxide-CdS/ZnS schemes.
Fig. 3 is the fluorescence emission spectrum of graphene oxide, graphene oxide-CdS/ZnS, CdS/ZnS.
Fig. 4 is the contrast schematic diagram of the degraded tetracycline of the graphene oxide of CdS/ZnS load different content.
Fig. 5 is the contrast schematic diagram of different photochemical catalyst to tetracycline degradation behavior.
Fig. 6 is graphene oxide-CdS/ZnS photochemical catalyst recovery experiment schematic diagram.
Detailed description of the invention
Photocatalytic activity evaluation: carry out in DW-01 type photochemical reaction instrument (purchased from city Co., Ltd of Yangzhou University), visible lamp irradiates, 100mL tetracycline simulated wastewater to be added in reactor and to measure its initial value, then composite photo-catalyst is added, magnetic agitation and open aerator pass into air keep catalyst be in suspension or afloat, 10min sample analysis in interval in During Illumination, gets supernatant liquor at spectrophotometer λ after centrifugation
max=278nm place measures absorbance, and passes through formula:
DR=[（A
0-A
i）/A
0]×100%
Calculate degradation rate, wherein A
0the absorbance of occrycetin solution during for reaching adsorption equilibrium, A
ifor the absorbance of the occrycetin solution that timing sampling measures.
Below in conjunction with concrete embodiment, the present invention will be further described.
embodiment 1:
The preparation of graphene oxide:
In the there-necked flask filling the 30g concentrated sulfuric acid, add 1g native graphite and 2.5g sodium nitrate, ice bath, under stirring condition, slowly add 4g potassium permanganate, under the condition of 15 DEG C, keep 2h.Then heating water bath 35 DEG C stirs 30min solution and becomes and blackish greenly have bubble formation simultaneously, adds 40ml distilled water and set water bath heating temperature to be 98 DEG C and to keep 40min in solution, and solution becomes khaki; After end, slowly while stirring in solution, add 140ml distilled water cessation reaction, then add 10g, 30% aqueous hydrogen peroxide solution, solution becomes golden yellow, leave standstill, outwell supernatant, wash with the mixed liquor that concentrated hydrochloric acid and water mix by the volume ratio of 1:10, stir 30min, leave standstill, outwell supernatant, and be washed with distilled water to neutrality, be positioned over vacuum drying oven drying and obtain graphene oxide.
embodiment 2:
(1) take obtained graphene oxide 0.0026g in embodiment 1 and add deionized water ultrasonic vibration to dissolving completely, form uniform solution; Add 0.0416g caddy and 0.0248g zinc chloride, be stirred to after dissolving completely, add 0.1756g Cys to be stirred to and to dissolve completely, abundant stirring regulates pH=7 of solution afterwards with the sodium hydroxide solution of 1mol/L, then 0.0876g vulcanized sodium is joined in above-mentioned solution, pass into nitrogen gas stirring 15min, to pour in 50mL autoclave 180 into
oc is incubated 1h, takes out nature cooling, by cooled solution centrifugal, wash and puts into vacuum drying chamber and grind after 50 DEG C of 6h are dried and obtain CdS/ZnS nano composite material load graphene oxide photochemical catalyst.
(2) get sample in (1) and carry out photocatalytic degradation test in 0.05g photochemical reaction instrument, record the degradation rate of this photochemical catalyst to 10mg/L tetracycline antibiotic and reach 79.89% in 60min.
embodiment 3:
By the step in embodiment 2, unlike the amount 0.0053g choosing graphene oxide in (1), the wherein mass conservation of caddy, zinc chloride, Cys, vulcanized sodium, reaction terminates rear taking-up and naturally cools, by cooled solution centrifugal, wash and put into vacuum drying chamber dry grinding after obtain photochemical catalyst.
(2) get sample 0.05g in (1) and carry out photocatalytic degradation test in photochemical reaction instrument, record the degradation rate of obtained photochemical catalyst to 10mg/L tetracycline antibiotic and reach 82.06% in 60min.
embodiment 4:
By the step in embodiment 2, unlike choosing graphene oxide 0.0079g Kaolinite Preparation of Catalyst in (1), take out nature cooling, by cooled solution centrifugal, wash and put into vacuum drying chamber dry grind after obtain photochemical catalyst.
(2) get sample 0.05g in (1) and carry out photocatalytic degradation test in photochemical reaction instrument, record the degradation rate of obtained photochemical catalyst to 10mg/L tetracycline antibiotic the highest, and reach 87.08% in 60min.
embodiment 5:
By the step in embodiment 2, be 0.0105g unlike graphene oxide in (1), photocatalysis synthesis and other condition do not change.
(2) get sample 0.05g in (1) and carry out photocatalytic degradation test in photochemical reaction instrument, record the degradation rate of this photochemical catalyst to 15mg/L tetracycline antibiotic and reach 74.97% in 60min.
embodiment 6:
By the step in embodiment 2, do not add graphene oxide unlike in (1), photocatalysis synthesis and other condition do not change.
(2) get sample 0.05g in (1) and carry out photocatalytic degradation test in photochemical reaction instrument, record this photochemical catalyst and in 60min, reach 69.59% to the degradation rate of 10mg/L tetracycline antibiotic.
embodiment 7:
(1) 0.08332g caddy is joined in deionized water, be stirred to after dissolving completely, add pH=7 that 0.1756g Cys fully stirs the sodium hydroxide solution adjustment solution of rear 1mol/L, then 0.0876g vulcanized sodium is joined in above-mentioned solution, pass into nitrogen gas stirring 15min, to pour in 50mL autoclave 180 into
oc is incubated 1h, takes out nature cooling, by cooled solution centrifugal, washs and put into vacuum drying chamber and dry in 50 DEG C of 6h, obtain CdS photochemical catalyst.
(2) get sample in (1) and carry out photocatalytic degradation test in photochemical reaction instrument, record when to deserve photochemical catalyst consumption be 0.05g and in 60min, 60.74% is reached to the degradation rate of 10mg/L tetracycline antibiotic.
embodiment 8:
(1) 0.0497g zinc chloride is added in deionized water, be stirred to after dissolving completely, add pH=7 that 0.1756g Cys fully stirs the sodium hydroxide solution adjustment solution of rear 1mol/L, then 0.0876g vulcanized sodium is joined in above-mentioned solution, pass into nitrogen gas stirring 15min, to pour in 50mL autoclave 180 into
oc is incubated 1h, takes out nature cooling, by cooled solution centrifugal, washs and put into vacuum drying chamber and dry in 50 DEG C of 6h, obtain ZnS photochemical catalyst.
(2) get sample 0.05g in (1) and carry out photocatalytic degradation test in photochemical reaction instrument, record the degradation rate of this photochemical catalyst to 10mg/L tetracycline antibiotic and reach 17.86% in 60min.
Fig. 1 is the XRD figure of graphene oxide, CdS, ZnS, CdS/ZnS and CdS/ZnS nano composite material load graphene oxide photochemical catalyst, very clearly presents the characteristic peak of each material in figure; As shown in Figure 1, the characteristic peak of the CdS/ZnS heterojunction structure obtained is fairly obvious, peak sharply there is no any assorted peak illustrate product degree of crystallinity and purity all higher, and the peak that graphene oxide-CdS/ZnS characteristic peak obviously weakens even GO disappears, may be due in course of reaction, the existence of the destructurized and graphene oxide of graphene oxide also causes the peak of CdS/ZnS to weaken.
The TEM figure of Fig. 2 graphene oxide-CdS/ZnS. the TEM that a. graphene oxide TEM schemes b, c. graphene oxide-CdS/ZnS schemes the HRTEM figure that e, d. are graphene oxide-CdS/ZnS; Graphene oxide slabbing structure can be found out from a figure, and the existence of pleated structure describes graphene oxide good elasticity, as can be seen from b figure, CdS/ZnS is evenly distributed on surface of graphene oxide, and granular size is homogeneous, the spacing of lattice that HRTEM shows CdS/ZnS heterojunction structure is obvious, and wherein (101) crystal face of CdS and (111) crystal face of ZnS overlap, and demonstrate the existence of heterojunction structure.
Fig. 3 is the fluorescence emission spectrum of graphene oxide, graphene oxide-CdS/ZnS, CdS/ZnS; As can be seen from the figure because the fluorescence intensity adding CdS/ZnS heterojunction structure of graphene oxide reduces, describe the compound that graphene oxide prevents wherein electron hole pair to a certain extent, improve the ability of the anti-light corrosion of photochemical catalyst.
Fig. 4 is the degraded tetracycline spectrogram of the graphene oxide of CdS/ZnS load different content; As can be seen from the figure along with the increase of graphene oxide amount, degradation efficiency first increases and subtracts afterwards, and wherein when graphene oxide content is 0.0079g, degradation effect is best.
Fig. 5 is the degradation behavior contrast schematic diagram of different catalysts to tetracycline; Known by figure, CdS/ZnS nano material to the degradation efficiency of tetracycline apparently higher than CdS, ZnS, and along with graphene oxide to add degradation efficiency higher, also illustrate that the formation of the CdS/ZnS heterojunction structure of non-combined oxidation Graphene simultaneously.
Fig. 6 is graphene oxide-CdS/ZnS photochemical catalyst recovery experiment schematic diagram; Through 5 circulation and stress experiments, the efficiency of photochemical catalyst, without obvious reduction, illustrates that the stability of graphene oxide-CdS/ZnS photochemical catalyst is better.
Claims (10)
1. the preparation method of a nano composite material photocatalyst, it is characterized in that step is as follows: take graphene oxide and be placed in a certain amount of deionized water, ultrasonic vibration is to dissolving completely, caddy and zinc chloride are joined in graphene oxide solution respectively, adds Cys after stirring and dissolving again and continue to be stirred to and dissolve completely; Then regulate pH=7 with sodium hydroxide solution, add vulcanized sodium logical nitrogen gas stirring 10-15min subsequently, above-mentioned solution is poured in autoclave, after being positioned over high temperature oven insulation subsequently, takes out nature cooling; To reacted solution centrifugal, washing, after drying, grinding obtains CdS/ZnS nano composite material load graphene oxide photochemical catalyst.
2. the preparation method of a kind of nano composite material photocatalyst as claimed in claim 1, is characterized in that:
The synthetic method of described graphene oxide is as follows: in the concentrated sulfuric acid, add native graphite and sodium nitrate, ice bath, slowly add potassium permanganate under stirring condition, keeps stirring 2h at 0-20 DEG C; Then heating water bath 35 DEG C stirring, in solution, add distilled water setting water bath heating temperature is 98 DEG C of maintenance 40min; After end, slowly while stirring add distilled water cessation reaction to solution for continuous, then add the aqueous hydrogen peroxide solution that mass concentration is 30%, leave standstill, outwell supernatant, with concentrated hydrochloric acid and water by 1: 10 the mixed liquor that mixes of volume ratio wash, stir 20-40min, leave standstill, outwell supernatant, and be washed with distilled water to neutrality, be positioned over vacuum drying oven drying and obtain graphene oxide.
3. the preparation method of a kind of nano composite material photocatalyst as claimed in claim 2, is characterized in that:
The mass ratio of described potassium permanganate, aqueous hydrogen peroxide solution, the concentrated sulfuric acid, sodium nitrate and native graphite is 4:10:30:2.5:1, the mass ratio of the distilled water that first time adds and potassium permanganate is 10:1, and the mass ratio of the distilled water that second time adds and potassium permanganate is 35:1.
4. the preparation method of a kind of nano composite material photocatalyst as claimed in claim 1, is characterized in that: the consumption of described deionized water dissolves completely to make caddy, zinc chloride, Cys, graphene oxide, vulcanized sodium.
5. the preparation method of a kind of nano composite material photocatalyst as claimed in claim 1, it is characterized in that: graphene oxide, caddy, zinc chloride, Cys, vulcanized sodium mass ratio are 6.5-26.25:104:62:439:219, preferred proportion 19.75:104:62:439:219.
6. the preparation method of a kind of nano composite material photocatalyst as claimed in claim 1, is characterized in that: described sodium hydroxide solution is concentration is 1mol/L.
7. the preparation method of a kind of nano composite material photocatalyst as claimed in claim 1, is characterized in that: described in be positioned in high temperature oven insulation after take out and refer in 180
oc is incubated 1h.
8. the preparation method of a kind of nano composite material photocatalyst as claimed in claim 1, is characterized in that: described washing refers to use respectively deionized water and absolute ethanol washing twice.
9. the preparation method of a kind of nano composite material photocatalyst as claimed in claim 1, is characterized in that: described oven dry is 50 DEG C dries 6h.
10. the application of the nano composite material photocatalyst prepared of preparation method in degraded tetracycline antibiotic as claimed in claim 1.
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