CN110252398A - A kind of temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation method and application of/CN composite photo-catalyst - Google Patents
A kind of temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation method and application of/CN composite photo-catalyst Download PDFInfo
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- CN110252398A CN110252398A CN201910421972.0A CN201910421972A CN110252398A CN 110252398 A CN110252398 A CN 110252398A CN 201910421972 A CN201910421972 A CN 201910421972A CN 110252398 A CN110252398 A CN 110252398A
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- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 230000004044 response Effects 0.000 title claims abstract description 29
- 229910000161 silver phosphate Inorganic materials 0.000 claims abstract description 82
- 238000006731 degradation reaction Methods 0.000 claims abstract description 25
- 230000015556 catabolic process Effects 0.000 claims abstract description 22
- 230000003115 biocidal effect Effects 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
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- 239000000463 material Substances 0.000 claims description 19
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229920000877 Melamine resin Polymers 0.000 claims description 16
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 16
- 238000004090 dissolution Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 15
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 13
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 9
- -1 3- (methacryloxypropyl) propyl Chemical group 0.000 claims description 8
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- 238000002604 ultrasonography Methods 0.000 claims description 2
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- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 2
- GWKBSZQPLYRAAH-UHFFFAOYSA-N 6-trimethoxysilylhexyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCCCCOC(=O)C(C)=C GWKBSZQPLYRAAH-UHFFFAOYSA-N 0.000 description 1
- 125000003182 D-alloisoleucine group Chemical group [H]N([H])[C@@]([H])(C(=O)[*])[C@](C([H])([H])[H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- XKJUSNOUOLSNJN-UHFFFAOYSA-N ethyl 2-amino-1h-pyrrole-3-carboxylate Chemical compound CCOC(=O)C=1C=CNC=1N XKJUSNOUOLSNJN-UHFFFAOYSA-N 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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- 229910001961 silver nitrate Inorganic materials 0.000 description 1
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- 230000007704 transition Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
- 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
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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
- 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
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- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
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- Water Supply & Treatment (AREA)
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- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention belongs to technical field of environmental material preparation, provide a kind of temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation method and application of/CN composite photo-catalyst.The present invention includes the preparation of (1) CN；(2)Ag/Ag3PO4The preparation of/CN composite photo-catalyst；(3) temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation of/CN composite photo-catalyst.The present invention prepares out sheet CN by simple one-step calcination method, then has prepared temperature sensitive response type PNIPAM Ag/Ag by chemical precipitation method and emulsion polymerization3PO4/ CN composite photo-catalyst effectively inhibits the combined efficiency of photo-generated carrier in composite system to the controllability, higher visible light-responded ability, excellent electron transport ability of ambient temperature using it to improve PNIPAM@Ag/Ag3PO4The degradation efficiency of/CN composite photo-catalyst.The present invention realizes temperature sensitive response type PNIPAM@Ag/Ag3PO4Purpose of/CN the composite photo-catalyst to antibiotic controllability in degradation sewage.
Description
Technical field
The invention belongs to technical field of environmental material preparation, are related to a kind of temperature sensitive response type PNIPAM@Ag/Ag3PO4/ CN is multiple
The preparation method and applications of light combination catalyst.
Background technique
With the fast development of a large amount of medicine consumption and modern medicine technology, the excessive of antibiotics is got over using phenomenon
Come more serious, the pollution effect for also resulting in antibiotic waste water highlights increasingly.The antibiotic remained in water body can make micro- life
Object and bacterial resistance occurred, upset ambient enviroment and the ecosystem.Antibiotic necessarily appears in people's lives and drinks
In water, and then potential threat is formed to human health by drinking water and food chain.Therefore, there is an urgent need to find one can be effective
The method for handling antibiotic residue.
Currently, the technology of removal antibiotic mainly has membrane separation technique, Technology development, adsorption technology, chemical method, light
Catalysis technique etc..Membrane separation technique is physical method, and is not introduced into poisonous and harmful substances, very popular in water treatment technology, but
Since membrane technology higher cost, and flux is not difficult to be widely used very much；Due to antibiotic waste water have bio-toxicity it is big,
The features such as containing antibacterial substance, traditional Technology development is handling this kind of poisonous organic wastewater difficult to degrade, especially containing residual
Effect is poor when staying the waste water of micro antibiotic；Adsorption technology has easy to operate, inexpensive, high efficiency and does not generate highly toxic
The advantages that by-product, but its mechanical strength stability is poor and is difficult to recycling and reusing；Although chemical method plays antibiotic
Certain removal effect, but its by-product generated all has stronger toxicity；Photocatalysis technology is as a kind of advanced oxidation
Technology has many advantages, such as Strong oxdiative degradation capability, convenient to carry out, is a kind of green environmental protection technique, can be effectively in processing environment
Organic pollutant, be widely used for handle waste water in antibiotic residue.For photocatalysis technology, design a kind of high performance
Catalyst is vital in photocatalysis technology.
g-C3N4As a kind of New Two Dimensional conductor photocatalysis material, because of its excellent physical characteristic and chemical stability,
It is easy to modify, raw material sources abundant and cheap price, suitable band structure, is led in photocatalysis degradation organic contaminant
Domain has huge research and application value, however pure g-C3N4There are electron-hole recombination rate height, electron transfer rate is slow
It is insufficient, it is therefore desirable to g-C3N4It is modified.Silver orthophosphate has light sensitivity, not only can change g-C3N4Electron-transport road
Diameter, and carrier lifetime can be increased, and then improve the photocatalysis performance of composite material.Improving electron transfer rate can be into
One step improves photocatalysis performance.
However, temperature is an important influence factor in degradation process, due to the uncontrollability of light degradation process, light
The degradation behavior of catalyst is extremely difficult to optimal effectiveness, it is therefore necessary to design a kind of intellectual material modification photochemical catalyst, realize
Controllability of the catalysis material photocatalytic process to temperature.Poly- n-isopropyl acrylamide is a kind of common temperature sensing material, can
Hydrophilic and hydrophobic reversible transformation is realized under the conditions of critical solution temperature (32 DEG C), hydrophily increases with the reduction of temperature
Add, it is caused to change from expanded state to contracted state.Therefore, poly- n-isopropyl acrylamide modification photochemical catalyst not only can be to prevent
Only silver orthophosphate is lost, and also achieves catalyst to the controllability of temperature, has advanced optimized the performance of catalyst.
Summary of the invention
That present invention aim to address electron transfer rates existing for photochemical catalyst is slow, electron-hole recombination rate is high, selection
The technological deficiencies such as property is low prepare temperature sensitive response type PNIPAM Ag/ using chemical precipitation method and emulsion polymerization as technological means
Ag3PO4/ CN composite photo-catalyst, and it is applied to controllability degradation antibiotic.
To reach above-mentioned technical purpose, the technical solution adopted by the present invention the following steps are included:
(1) sheet g-C3N4(CN) preparation:
Melamine and cyanuric acid mixed dissolution are stirred 12 in ethanol~for 24 hours, centrifugal drying is then placed in temperature
It is 4~8h of calcining in 2~2.5 DEG C/min Muffle furnace for 500~600 DEG C, rate, set temperature is 500~600 DEG C, rate 2
~2.5 DEG C/min, the time be 4~8h, obtain sheet g-C3N4That is CN；
(2)Ag/Ag3PO4The preparation of/CN composite photo-catalyst:
CN made from step (1) is dissolved in deionized water, Na is stirring evenly and then adding into3PO4And AgNO3Solution carries out
It after being sufficiently stirred so that reacting progress completely, reacts, is centrifuged after the reaction was completed in the UV lamp, wash and be put into baking oven and do
It is dry, obtain Ag/Ag3PO4/ CN composite photo-catalyst；
(3) temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation of/CN composite photo-catalyst:
By Ag/Ag made from step (2)3PO4/ CN is distributed to ethyl alcohol and 3- (methacryloxypropyl) propyl trimethoxy silicon
In alkane (MPS), under nitrogen protection after water bath with thermostatic control for a period of time, product is centrifuged and is dried, to complete the table of binary material
Face is modified；
Then, n-isopropyl acrylamide (NIPAM) and N, N '-methylene-bisacrylamide (MBA) are mixed into deionization
The modified binary material in surface is added in water, after ultrasound；
Ammonium persulfate ((NH is added in stirring after a certain period of time4)2S2O6) as initiator for reaction 12~for 24 hours；Finally, spending
Ionized water and dehydrated alcohol washed product repeatedly, are dried in vacuo 12h at 60 DEG C for product.
In step (2), the AgNO3And Na3PO4Molar ratio is 3:1；By the way that 0.445~2.213mmol solid is added
Na3PO4Make the Ag/Ag of preparation3PO4Ag in/CN3PO4Mass ratio with CN is 10~50:100.The time reacted under ultraviolet lamp is
20~40min.
In step (3), 3- (methacryloxypropyl) propyl trimethoxy silicane MPS, n-isopropyl acrylamide NIPAM,
N, N '-methylene-bisacrylamide MBA, ammonium persulfate (NH4)2S2O6Usage ratio be 5~10mL:0.2~0.5g:0.03
~0.06g:0.01~0.05mmol.
In step (3), Ag/Ag3PO4The dosage of/CN, ethyl alcohol and 3- (methacryloxypropyl) propyl trimethoxy silicane MPS
Ratio is 0.5g:100mL:5~10mL.
The dosage of deionized water is that solute can be made to be completely dissolved in technical solution of the present invention.
The Ag/Ag that preparation method as described above obtains3PO4/ CN composite photo-catalyst, wherein Ag3PO4Shared CN
Mass percent be 10~50%, preferred mass percent be 20%.
The temperature sensitive response type PNIPAM@Ag/Ag that preparation method as described above obtains3PO4/ CN composite photo-catalyst,
Applied to antibiotic of degrading in antibiotic waste water.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) present invention has synthesized CN using method without templet, with blocky g-C3N4It compares, increases contact area, reduce
The transmission range of carrier, increases photocatalysis efficiency, moreover, method is easy, easily largely preparation；
(2)Ag3PO4With light sensitivity, the electron-transport path of CN not only can change, but also can increase the carrier longevity
Life, and then improve the photocatalysis performance of composite material；The present invention is by Ag3PO4After loading on CN, hetero-junctions is formed, is shortened
Forbidden bandwidth excites energy required for electron transition lower in photocatalytic process；Ag3PO4CN is loaded to, not easy to reunite, electronics
Transmission rate, photocatalysis performance are improved.
(3) present invention selects poly- n-isopropyl acrylamide to Ag/Ag3PO4/ CN is modified, poly- N- isopropyl propylene
Amide can prevent Ag3PO4It is lost, can effectively shift electronics, improve the separative efficiency of light induced electron and hole pair, shorten drop
Photocatalytic degradation efficiency is improved while solving the time, but also is able to achieve catalyst in degradation process to the controllability of temperature,
With than CN, Ag/Ag3PO4The higher photocatalytic activity of/CN and practical application value.
(4) temperature sensitive response type PNIPAM@Ag/Ag3PO4/ CN composite photo-catalyst using visible light as excitation, by with dirt
The interfacial interaction of dye object molecule realizes special catalytic effect, and the oxygen of surrounding and hydrone is made to be excited into great oxidizing force
Oxygen radical, hydroxyl radical free radical etc. have strong oxidizing property substance, thus reach degradation environment in harmful organic substances mesh
, it is a kind of green that this method, which will not result in waste of resources and the additional formation polluted, compared with prior art, and easy to operate
The efficient process technology of environmental protection.The present invention realizes PNIPAM@Ag/Ag3PO4/ CN composite photo-catalyst controllability is degraded in sewage
The purpose of antibiotic.
Detailed description of the invention
Fig. 1 is CN, Ag/Ag3PO4- 20/CN, Ag3PO4, PNIPAM@Ag/Ag3PO4The XRD of -20/CN composite photo-catalyst
Figure；
Fig. 2 is (A, B) CN, (C) Ag/Ag3PO4- 20/CN, (D) PNIPAM@Ag/Ag3PO4- 20/CN composite photo-catalyst
SEM figure；
Fig. 3 is Ag3PO4, Ag/Ag3PO4- 20/CN, PNIPAM@Ag/Ag3PO4The UV- of -20/CN, CN composite photo-catalyst
Vis figure；
Fig. 4 is CN, Ag/Ag3PO4- 20/CN, PNIPAM@Ag/Ag3PO4The PL of -20/CN composite photo-catalyst schemes.
Specific embodiment
Combined with specific embodiments below, technical solution of the present invention is described in further detail.Those skilled in the art
It will be clearly understood that the embodiment is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.In following embodiments
Used experimental method is conventional method unless otherwise specified.
Melamine (C used in the present invention3H6N6), cyanuric acid (C3H3N3O3), sodium phosphate (Na3PO4), silver nitrate
(AgNO3), 3- (methacryloxypropyl) propyl trimethoxy silicane (C10H20O5Si8), n-isopropyl acrylamide (C6H11NO)、
N, N '-methylene-bisacrylamide (C7H10N2O2), ammonium persulfate (NH4)2S2O6, dehydrated alcohol (C2H5It OH is) that analysis is pure, purchase
In Sinopharm Chemical Reagent Co., Ltd.；Tetracycline antibiotic is mark product, is purchased from Shanghai along vigorous bioengineering Co., Ltd.
The photocatalytic activity evaluation of prepared photochemical catalyst in the present invention: in DW-01 type photochemical reactor (purchased from raising
State Science and Technology Ltd., university city) in carry out, it is seen that light light irradiation, by 100mL concentration be 20mg/L tetracycline simulated wastewater
It is added in reactor and measures its initial value, be then added photochemical catalyst obtained, magnetic agitation is simultaneously opened aerator and is passed through
Air maintains the catalyst in suspension or afloat, is spaced 15min sampling analysis in During Illumination, takes upper layer after centrifuge separation
Clear liquid is in spectrophotometer λmaxAbsorbance is measured at=357nm, and passes through formula: Dr=[1-Ai/A0] × 100% calculates degradation
Rate, wherein A0The absorbance of tetracycline, A when to reach adsorption equilibriumiFor the extinction of the tetracycline of timing sampling measurement
Degree.
Comparative example 1:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3PO4The preparation of/CN composite photo-catalyst: weighing 0.4g CN and be dissolved in the deionized water of 120mL,
0.073g solid Na is added after being sufficiently stirred3PO4, the AgNO of 2.9mL concentration 1mol/L is added dropwise after stirring 4h3Solution carries out
After being sufficiently stirred so that reacting progress completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is placed in oven and dried,
Obtain Ag/Ag3PO4/ CN composite photo-catalyst；
(3) it takes sample in (2) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to Fourth Ring
The degradation rate of element reaches 64.36% in 2h.
Comparative example 2:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3PO4The preparation of/CN composite photo-catalyst: weighing 0.4g CN and be dissolved in the deionized water of 120mL,
0.109g solid Na is added after being sufficiently stirred3PO4, the AgNO of 4.3mL concentration 1mol/L is added dropwise after stirring 4h3Solution carries out
After being sufficiently stirred so that reacting progress completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is placed in oven and dried,
Obtain Ag/Ag3PO4/ CN composite photo-catalyst；
(3) it takes sample in (2) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to Fourth Ring
The degradation rate of element reaches 77.27% in 2h.
Comparative example 3:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3PO4The preparation of/CN composite photo-catalyst: weighing 0.4g CN and be dissolved in the deionized water of 120mL,
0.145g solid Na is added after being sufficiently stirred3PO4, the AgNO of 5.7mL concentration 1mol/L is added dropwise after stirring 4h3Solution carries out
After being sufficiently stirred so that reacting progress completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is placed in oven and dried,
Obtain Ag/Ag3PO4/ CN composite photo-catalyst；
(3) it takes sample in (2) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to Fourth Ring
The degradation rate of element reaches 84.82% in 2h.
Comparative example 4:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3PO4The preparation of/CN composite photo-catalyst: weighing 0.4g CN and be dissolved in the deionized water of 120mL,
0.181g solid Na is added after being sufficiently stirred3PO4, the AgNO of 7.2mL concentration 1mol/L is added dropwise after stirring 4h3Solution carries out
After being sufficiently stirred so that reacting progress completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is placed in oven and dried,
Obtain Ag/Ag3PO4/ CN composite photo-catalyst；
(3) it takes sample in (2) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to Fourth Ring
The degradation rate of element reaches 79.93% in 2h.
Comparative example 5:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3PO4The preparation of/CN composite photo-catalyst: weighing 0.4g CN and be dissolved in the deionized water of 120mL,
0.218g solid Na is added after being sufficiently stirred3PO4, the AgNO of 8.6mL concentration 1mol/L is added dropwise after stirring 4h3Solution carries out
After being sufficiently stirred so that reacting progress completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is placed in oven and dried,
Obtain Ag/Ag3PO4/ CN composite photo-catalyst；
(3) it takes sample in (2) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to Fourth Ring
The degradation rate of element reaches 76.63% in 2h.
Comparative example 6:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3PO4The preparation of/CN composite photo-catalyst: weighing 0.4g CN and be dissolved in the deionized water of 120mL,
0.292g solid Na is added after being sufficiently stirred3PO4, the AgNO of 11.5mL concentration 1mol/L is added dropwise after stirring 4h3Solution, into
After row is sufficiently stirred so that react progress completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is put into baking oven dry
It is dry, obtain Ag/Ag3PO4/ CN composite photo-catalyst；
(3) it takes sample in (2) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to Fourth Ring
The degradation rate of element reaches 66.27% in 2h.
Comparative example 7:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3PO4The preparation of/CN composite photo-catalyst: weighing 0.4g CN and be dissolved in the deionized water of 120mL,
0.363g solid Na is added after being sufficiently stirred3PO4, the AgNO of 14.3mL concentration 1mol/L is added dropwise after stirring 4h3Solution, into
After row is sufficiently stirred so that react progress completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is put into baking oven dry
It is dry, obtain Ag/Ag3PO4/ CN composite photo-catalyst；
(3) it takes sample in (2) to carry out photocatalytic degradation test in photochemical reactor, measures the photochemical catalyst to Fourth Ring
The degradation rate of element reaches 61.70% in 2h.
Embodiment 1:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3VO4The preparation of/CN composite photo-catalyst:
Ag/Ag3PO4The preparation of/CN composite photo-catalyst: it weighs 0.4g CN and is dissolved in the deionized water of 120mL, sufficiently
0.145g solid Na is added after stirring3PO4, the AgNO of 5.7mL concentration 1mol/L is added dropwise after stirring 4h3Solution carries out abundant
After stirring is so that reaction carries out completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is placed in oven and dried, obtains
Ag/Ag3PO4/ CN composite photo-catalyst, at this time Ag3PO4Quality account for the 20% of CN, behind be referred to as Ag/Ag3PO4-20/CN；
(3) temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation of -20/CN composite photo-catalyst:
By 0.5g Ag/Ag3PO4- 20/CN is distributed to 100mL ethyl alcohol and 10mL3- (methacryloxypropyl) propyl trimethoxy
In base silane, 50 DEG C of water bath with thermostatic control 12h, product is centrifuged and is dried under nitrogen protection, and the surface for completing binary material is modified.
Then, the n-isopropyl acrylamide and 0.03g N, N '-methylene-bisacrylamide of 0.2g are weighed, 50mL deionized water is added
The modified binary material in surface is added after ultrasonic 30min.0.1mL ammonium persulfate (0.1mol/L) is added as initiation after stirring 2h
12h is reacted in agent.Finally, product is dried in vacuo 12h at 60 DEG C with deionized water and dehydrated alcohol washed product repeatedly.
(4) it takes sample in (3) to keep temperature for 20 DEG C of progress photocatalytic degradation tests in photochemical reactor, measures this
Photochemical catalyst reaches 88.96% to the degradation rate of tetracycline in 2h.
Embodiment 2:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3VO4The preparation of/CN composite photo-catalyst:
Ag/Ag3PO4The preparation of/CN composite photo-catalyst: it weighs 0.4g CN and is dissolved in the deionized water of 120mL, sufficiently
0.145g solid Na is added after stirring3PO4, the AgNO of 5.7mL concentration 1mol/L is added dropwise after stirring 4h3Solution carries out abundant
After stirring is so that reaction carries out completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is placed in oven and dried, obtains
Ag/Ag3PO4/ CN composite photo-catalyst, at this time Ag3PO4Quality account for the 20% of CN, behind be referred to as Ag/Ag3PO4-20/CN；
(3) temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation of -20/CN composite photo-catalyst:
By 0.5g Ag/Ag3PO4- 20/CN is distributed to 100mL ethyl alcohol and 10mL3- (methacryloxypropyl) propyl trimethoxy
In base silane, 50 DEG C of water bath with thermostatic control 12h, product is centrifuged and is dried under nitrogen protection, and the surface for completing binary material is modified.
Then, the n-isopropyl acrylamide and 0.03g N, N '-methylene-bisacrylamide of 0.2g are weighed, 50mL deionized water is added
The modified binary material in surface is added after ultrasonic 30min.0.1mL ammonium persulfate (0.1mol/L) is added as initiation after stirring 2h
12h is reacted in agent.Finally, product is dried in vacuo 12h at 60 DEG C with deionized water and dehydrated alcohol washed product repeatedly.
(4) it takes sample in (3) to keep temperature for 25 DEG C of progress photocatalytic degradation tests in photochemical reactor, measures this
Photochemical catalyst reaches 82.42% to the degradation rate of tetracycline in 2h.
Embodiment 3:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3VO4The preparation of/CN composite photo-catalyst:
Ag/Ag3PO4The preparation of/CN composite photo-catalyst: it weighs 0.4g CN and is dissolved in the deionized water of 120mL, sufficiently
0.145g solid Na is added after stirring3PO4, the AgNO of 5.7mL concentration 1mol/L is added dropwise after stirring 4h3Solution carries out abundant
After stirring is so that reaction carries out completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is placed in oven and dried, obtains
Ag/Ag3PO4/ CN composite photo-catalyst, at this time Ag3PO4Quality account for the 20% of CN, behind be referred to as Ag/Ag3PO4-20/CN；
(3) temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation of -20/CN composite photo-catalyst:
By 0.5g Ag/Ag3PO4- 20/CN is distributed to 100mL ethyl alcohol and 10mL3- (methacryloxypropyl) propyl trimethoxy
In base silane, 50 DEG C of water bath with thermostatic control 12h, product is centrifuged and is dried under nitrogen protection, and the surface for completing binary material is modified.
Then, the n-isopropyl acrylamide and 0.03g N, N '-methylene-bisacrylamide of 0.2g are weighed, 50mL deionized water is added
The modified binary material in surface is added after ultrasonic 30min.0.1mL ammonium persulfate (0.1mol/L) is added as initiation after stirring 2h
12h is reacted in agent.Finally, product is dried in vacuo 12h at 60 DEG C with deionized water and dehydrated alcohol washed product repeatedly.
(4) it takes sample in (3) to keep temperature for 30 DEG C of progress photocatalytic degradation tests in photochemical reactor, measures this
Photochemical catalyst reaches 76.54% to the degradation rate of tetracycline in 2h.
Embodiment 4:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3VO4The preparation of/CN composite photo-catalyst:
Ag/Ag3PO4The preparation of/CN composite photo-catalyst: it weighs 0.4g CN and is dissolved in the deionized water of 120mL, sufficiently
0.145g solid Na is added after stirring3PO4, the AgNO of 5.7mL concentration 1mol/L is added dropwise after stirring 4h3Solution carries out abundant
After stirring is so that reaction carries out completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is placed in oven and dried, obtains
Ag/Ag3PO4/ CN composite photo-catalyst, at this time Ag3PO4Quality account for the 20% of CN, behind be referred to as Ag/Ag3PO4-20/CN；
(3) temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation of -20/CN composite photo-catalyst:
By 0.5g Ag/Ag3PO4- 20/CN is distributed to 100mL ethyl alcohol and 10mL3- (methacryloxypropyl) propyl trimethoxy
In base silane, 50 DEG C of water bath with thermostatic control 12h, product is centrifuged and is dried under nitrogen protection, and the surface for completing binary material is modified.
Then, the n-isopropyl acrylamide and 0.03g N, N '-methylene-bisacrylamide of 0.2g are weighed, 50mL deionized water is added
The modified binary material in surface is added after ultrasonic 30min.0.1mL ammonium persulfate (0.1mol/L) is added as initiation after stirring 2h
12h is reacted in agent.Finally, product is dried in vacuo 12h at 60 DEG C with deionized water and dehydrated alcohol washed product repeatedly.
(4) it takes sample in (3) to keep temperature for 35 DEG C of progress photocatalytic degradation tests in photochemical reactor, measures this
Photochemical catalyst reaches 69.97% to the degradation rate of tetracycline in 2h.
Embodiment 5:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3VO4The preparation of/CN composite photo-catalyst:
Ag/Ag3PO4The preparation of/CN composite photo-catalyst: it weighs 0.4g CN and is dissolved in the deionized water of 120mL, sufficiently
0.145g solid Na is added after stirring3PO4, the AgNO of 5.7mL concentration 1mol/L is added dropwise after stirring 4h3Solution carries out abundant
After stirring is so that reaction carries out completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is placed in oven and dried, obtains
Ag/Ag3PO4/ CN composite photo-catalyst, at this time Ag3PO4Quality account for the 20% of CN, behind be referred to as Ag/Ag3PO4-20/CN；
(3) temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation of -20/CN composite photo-catalyst:
By 0.5g Ag/Ag3PO4- 20/CN is distributed to 100mL ethyl alcohol and 10mL3- (methacryloxypropyl) propyl trimethoxy
In base silane, 50 DEG C of water bath with thermostatic control 12h, product is centrifuged and is dried under nitrogen protection, and the surface for completing binary material is modified.
Then, the n-isopropyl acrylamide and 0.03g N, N '-methylene-bisacrylamide of 0.2g are weighed, 50mL deionized water is added
The modified binary material in surface is added after ultrasonic 30min.0.1mL ammonium persulfate (0.1mol/L) is added as initiation after stirring 2h
12h is reacted in agent.Finally, product is dried in vacuo 12h at 60 DEG C with deionized water and dehydrated alcohol washed product repeatedly.
(4) it takes sample in (3) to keep temperature for 40 DEG C of progress photocatalytic degradation tests in photochemical reactor, measures this
Photochemical catalyst reaches 65.87% to the degradation rate of tetracycline in 2h.
Embodiment 6:
(1) melamine and cyanuric acid dissolution the preparation of CN: are stirred into 12h, centrifugal drying, then in temperature in ethanol
Degree is 550 DEG C, calcines 8h in the Muffle furnace that rate is 2.5 DEG C/min, and obtained product is fully ground, CN is obtained；
(2)Ag/Ag3VO4The preparation of/CN composite photo-catalyst:
Ag/Ag3PO4The preparation of/CN composite photo-catalyst: it weighs 0.4g CN and is dissolved in the deionized water of 120mL, sufficiently
0.145g solid Na is added after stirring3PO4, the AgNO of 5.7mL concentration 1mol/L is added dropwise after stirring 4h3Solution carries out abundant
After stirring is so that reaction carries out completely, the reaction was continued in the UV lamp 20min, centrifugation is washed and is placed in oven and dried, obtains
Ag/Ag3PO4/ CN composite photo-catalyst, at this time Ag3PO4Quality account for the 20% of CN, behind be referred to as Ag/Ag3PO4-20/CN；
(3) temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation of -20/CN composite photo-catalyst:
By 0.5g Ag/Ag3PO4- 20/CN is distributed to 100mL ethyl alcohol and 10mL3- (methacryloxypropyl) propyl trimethoxy
In base silane, 50 DEG C of water bath with thermostatic control 12h, product is centrifuged and is dried under nitrogen protection, and the surface for completing binary material is modified.
Then, the n-isopropyl acrylamide and 0.03g N, N '-methylene-bisacrylamide of 0.2g are weighed, 50mL deionized water is added
The modified binary material in surface is added after ultrasonic 30min.0.1mL ammonium persulfate (0.1mol/L) is added as initiation after stirring 2h
12h is reacted in agent.Finally, product is dried in vacuo 12h at 60 DEG C with deionized water and dehydrated alcohol washed product repeatedly.
(4) it takes sample in (3) to keep temperature for 45 DEG C of progress photocatalytic degradation tests in photochemical reactor, measures this
Photochemical catalyst reaches 56.73% to the degradation rate of tetracycline in 2h.
Fig. 1 is CN, Ag/Ag3PO4- 20/CN, Ag3PO4, PNIPAM@Ag/Ag3PO4The XRD of -20/CN composite photo-catalyst,
What be will be apparent that in figure presents CN and Ag3PO4Characteristic peak, Ag/Ag3PO4- 20/CN composite photo-catalyst has been detected CN
And Ag3PO4Characteristic peak, but fail to detect the characteristic peak of Ag, it may be possible to because the few reason of Ag nano-particle content causes
, furthermore we find that temperature sensitive response type PNIPAM@Ag/Ag3PO4- 20/CN composite photo-catalyst does not change Ag/Ag3PO4-
The crystalline structure of 20/CN photochemical catalyst.
Fig. 2 is (A, B) CN, (C) Ag/Ag3PO4- 20/CN, (D) PNIPAM@Ag/Ag3PO4- 20/CN composite photo-catalyst
SEM figure, from A and B figure available pattern be sheet CN, (C) figure Ag3PO4Particle is evenly dispersed on CN, (D)
Scheme Ag/Ag3PO4There is layer of substance on particle and the surface CN, illustrate Ag/Ag3PO4/ CN has succeeded to be repaired by n-isopropyl acrylamide
Decorations.
Fig. 3 is Ag3PO4, Ag/Ag3PO4- 20/CN, PNIPAM@Ag/Ag3PO4The UV- of -20/CN, CN composite photo-catalyst
Vis schemes, and illustrates PNIPAM@Ag/Ag in figure3PO4- 20/CN photoresponse ability has compared to monomer CN to be greatly enhanced, and is occurred
Apparent red shift, illustrates that the band gap of catalyst becomes smaller, and excitation electronics needs lower energy, improves photocatalysis performance.
Fig. 4 is CN, Ag/Ag3PO4- 20/CN, PNIPAM@Ag/Ag3PO4The PL of -20/CN composite photo-catalyst schemes, in figure
It shows that the strong emission peak of CN concentrates on 460nm, shows that the recombination probability of photo-generate electron-hole pairs is very high, however composite photo-catalyst
Carrier withdrawal efficiency be significantly improved.Show that the photo-generate electron-hole pairs of composite material can efficiently turn in heterojunction boundary
It moves, and has than CN, Ag/Ag3PO4The higher photocatalytic activity of -20/CN.
Claims (10)
1. a kind of temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation method of/CN composite photo-catalyst, which is characterized in that including
Following steps:
(1) g-C of sheet is prepared3N4, i.e. CN is spare；
(2)Ag/Ag3PO4The preparation of/CN composite photo-catalyst:
CN made from step (1) is dissolved in deionized water, Na is stirring evenly and then adding into3PO4And AgNO3Solution carries out abundant
Stirring is reacted in the UV lamp, is centrifuged after the reaction was completed, wash and be placed in oven and dried, obtain so that after reaction progress completely
To Ag/Ag3PO4/ CN composite photo-catalyst；
(3) temperature sensitive response type PNIPAM@Ag/Ag3PO4The preparation of/CN composite photo-catalyst:
By Ag/Ag made from step (2)3PO4/ CN is distributed to ethyl alcohol and 3- (methacryloxypropyl) propyl trimethoxy silicane
(MPS) in, under nitrogen protection after water bath with thermostatic control for a period of time, product is centrifuged and is dried, to complete the surface of binary material
It is modified；
Then, n-isopropyl acrylamide (NIPAM) and N, N '-methylene-bisacrylamide (MBA) are mixed into deionized water,
The modified binary material in surface is added after ultrasound；
Ammonium persulfate ((NH is added in stirring after a certain period of time4)2S2O6) as initiator for reaction 12~for 24 hours, finally, using deionized water
It is with dehydrated alcohol washed product repeatedly, product vacuum is dry, obtain PNIPAM@Ag/Ag3PO4/CN。
2. temperature sensitive response type PNIPAM@Ag/Ag as described in claim 13PO4The preparation method of/CN composite photo-catalyst,
Be characterized in that, in step (1), it is described CN's the preparation method comprises the following steps: by melamine and cyanuric acid dissolution stir in ethanol
Then 12h, centrifugal drying calcine 8h in the Muffle furnace that temperature is 550 DEG C, rate is 2.5 DEG C/min, by obtained product into
Row is fully ground, and obtains CN.
3. temperature sensitive response type PNIPAM@Ag/Ag as described in claim 13PO4The preparation method of/CN composite photo-catalyst,
It is characterized in that, in step (2), the AgNO3And Na3PO4Molar ratio is 3:1；
By the way that 0.445~2.213mmol solid Na is added3PO4Make the Ag/Ag of preparation3PO4Ag in/CN3PO4With the mass ratio of CN
For 10~50:100.
4. temperature sensitive response type PNIPAM@Ag/Ag as described in claim 13PO4The preparation method of/CN composite photo-catalyst,
It is characterized in that, in step (2), the time reacted under ultraviolet lamp is 20~40min.
5. temperature sensitive response type PNIPAM@Ag/Ag as described in claim 13PO4The preparation method of/CN composite photo-catalyst,
Be characterized in that, in step (3), 3- (methacryloxypropyl) propyl trimethoxy silicane MPS, n-isopropyl acrylamide NIPAM,
N, N '-methylene-bisacrylamide MBA, ammonium persulfate (NH4)2S2O6Usage ratio be 5~10mL:0.2~0.5g:0.03
~0.06g:0.01~0.05mmol.
6. temperature sensitive response type PNIPAM@Ag/Ag as described in claim 13PO4The preparation method of/CN composite photo-catalyst,
It is characterized in that, in step (3), Ag/Ag3PO4The use of/CN, ethyl alcohol and 3- (methacryloxypropyl) propyl trimethoxy silicane MPS
Amount ratio is 0.5g:100mL:5~10mL.
7. temperature sensitive response type PNIPAM@Ag/Ag as described in claim 13PO4The preparation method of/CN composite photo-catalyst,
It is characterized in that, in step (3), vacuum drying temperature is 60 DEG C, time 12h.
8. a kind of temperature sensitive response type PNIPAM@Ag/Ag3PO4/ CN composite photo-catalyst, which is characterized in that be by claim 1
Made from~7 described in any item preparation methods, Ag3PO4The mass percent of shared CN is 10~50%.
9. a kind of temperature sensitive response type PNIPAM@Ag/Ag as claimed in claim 83PO4/ CN composite photo-catalyst, feature exist
In Ag3PO4The mass percent of shared CN is 20%.
10. by temperature sensitive response type PNIPAM@Ag/Ag according to any one of claims 83PO4/ CN composite photo-catalyst is useless for antibiotic
The purposes of degradation antibiotic in water.
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| CN111569949B (en) * | 2020-04-15 | 2023-12-15 | 深圳万知达科技有限公司 | Preparation method and application of magnetic temperature-sensitive imprinting material polymerized by microwave initiation |
| CN112934146A (en) * | 2021-02-09 | 2021-06-11 | 江南大学 | Optical drive photocatalytic reactor and preparation method thereof |
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