CN111604070B - Composite membrane photocatalyst and preparation method and application thereof - Google Patents
Composite membrane photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000012528 membrane Substances 0.000 title claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000000725 suspension Substances 0.000 claims abstract description 52
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 238000004070 electrodeposition Methods 0.000 claims abstract description 22
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 22
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 18
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 18
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 18
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 18
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 15
- 238000000151 deposition Methods 0.000 claims abstract description 14
- 238000007747 plating Methods 0.000 claims abstract description 14
- 230000008021 deposition Effects 0.000 claims abstract description 13
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 12
- 229940006460 bromide ion Drugs 0.000 claims abstract description 11
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000015556 catabolic process Effects 0.000 claims abstract description 9
- 238000006731 degradation reaction Methods 0.000 claims abstract description 9
- 238000004321 preservation Methods 0.000 claims abstract description 9
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims abstract description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 30
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 30
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 229910001220 stainless steel Inorganic materials 0.000 claims description 19
- 239000010935 stainless steel Substances 0.000 claims description 19
- 229940091173 hydantoin Drugs 0.000 claims description 18
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000001103 potassium chloride Substances 0.000 claims description 15
- 235000011164 potassium chloride Nutrition 0.000 claims description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 15
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 14
- 229960002317 succinimide Drugs 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000000975 dye Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 150000001469 hydantoins Chemical class 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- -1 silver ions Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 59
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000243 solution Substances 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 14
- 239000002041 carbon nanotube Substances 0.000 description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000010409 thin film Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VMAQYKGITHDWKL-UHFFFAOYSA-N 5-methylimidazolidine-2,4-dione Chemical compound CC1NC(=O)NC1=O VMAQYKGITHDWKL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910001513 alkali metal bromide Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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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
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Abstract
The invention discloses a composite membrane photocatalyst, a preparation method and application thereof. The preparation method of the composite membrane photocatalyst comprises the following steps: forming an electrolyte by using a silver ion source, alkali metal chloride and a complexing agent, adjusting the pH value of the electrolyte to 8-13 to form a plating solution, and performing constant current electrodeposition by using nickel as a cathode to form an Ag/Ni film; forming a suspension by using a bromide ion source, ammonium phosphate and graphene oxide, and forming an electrolytic suspension by using ultrasonic waves of the suspension at a temperature of between 5 and 18 ℃; taking the Ag/Ni film as an anode, taking the electrolytic suspension as plating solution, and performing constant current composite electrodeposition to form the Ag/AgBr/GO/Ni film; wherein the concentration of the graphene oxide in the electrolytic suspension is 0.18-0.28 g.L ‑1 The temperature of the electrolytic suspension is 10-20 ℃; the constant current composite electrodeposition has a current density of 2-2.6mA.cm ‑2 The deposition time is 16-20 min; and carrying out heat preservation treatment on the Ag/AgBr/GO/Ni film at the temperature of 100-180 ℃ to obtain the Ag/AgBr/GO/Ni composite film photocatalyst. The photocatalyst has good degradation effect on rhodamine B.
Description
Technical Field
The invention relates to a composite membrane photocatalyst and a preparation method and application thereof, in particular to an Ag/AgBr/GO/Ni composite membrane photocatalyst and a preparation method and application thereof.
Background
The photocatalytic oxidation can directly utilize sunlight to catalyze and degrade organic pollutants which are difficult to degrade and have low content in water or air, and has remarkable advantages and wide application prospect in environmental purification, especially sewage treatment. The Ag/AgBr surface plasma photocatalyst has strong absorption to visible light due to obvious surface plasma resonance, and has strong photocatalytic activity. Graphene Oxide (GO) is used as a pi system material, and various oxygen-containing groups exist on the skeleton of the graphene oxide, so that a rich practical space is provided for constructing a composite functional material. The graphene oxide has good chemical stability, excellent conductivity and ultra-large specific surface area, so that the light absorption performance of the catalyst can be enhanced, photo-generated electrons can be rapidly transferred, and the catalytic activity can be enhanced.
CN108525683a discloses a preparation method of a three-dimensional graphene aerogel/silver bromide/silver photocatalyst. Ag and AgBr nano particles are grown on the graphene hydrogel in situ by utilizing the reducibility of the graphene hydrogel and the amphipathy of CTAB, and the three-dimensional GA/AgBr/Ag photocatalyst is prepared through freeze drying. The photocatalyst obtained by the method is in a powder form, is unfavorable for rapid separation, recovery and reuse when the polluted water body is treated, and has poor microstructure controllability for the photocatalyst.
Zhao et al, "visible light high catalytic Activity GO/Ag 3 PO 4 Preparation and Properties of Ni composite film (inorganic chemistry report, volume 36, phase 2, month 2 of 2020) GO/Ag is disclosed 3 PO 4 A method for preparing Ni composite film. An electrochemical method is adopted to prepare the Ag/Ni film. At room temperature, taking an Ag/Ni film as an anode and a stainless steel sheet as a cathode, adding graphene oxide aqueous suspension into an ammonium phosphate solution with pH of 8, and carrying out ultrasonic vibration to prepare an electrolytic suspension. Controlling the current density to be 2.5 mA.cm -2 The electrodeposition time was 30s. The post-treatment condition is that the temperature is kept at 70 ℃ for 1h. The GO/Ag 3 PO 4 The degradation performance of the Ni composite film on rhodamine B is poor.
Li Aichang et al, "preparation and Property of thin film surface plasmon photocatalyst Ag@AgBr/CNT/Ni" (inorganic)The chemistry report, volume 34, 11 th, month 2018) discloses a method for preparing Ag@AgBr/CNT/Ni. An electrochemical method is adopted to prepare the Ag/Ni film. At room temperature, ag/Ni film was used as anode, and stainless steel sheet was used as cathode. Preparing mixed aqueous solutions with the concentration of sodium bromide and ammonium phosphate of 0.3mol/L and 1.0mol/L respectively, adding CNT into the mixed solution, and forming electrolytic suspension by ultrasonic oscillation. Constant current composite electrodeposition is carried out at room temperature under natural light. The distance between the electrodes was 3cm, the pH of the electrolytic suspension was 8, the concentration of CNTs was 1.25g/L, and the anode current density was 3mA cm -2 The deposition time was 18min. The post-treatment condition is that the temperature is kept at 140 ℃ for 1h. The dispersion of the carbon nano tube in water is poor, the formed electrolytic suspension is not uniformly dispersed, the deposition uniformity of the carbon nano tube on the Ag/Ni film is poor, and the degradation performance of the carbon nano tube on rhodamine B is poor.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a method for preparing a composite membrane photocatalyst, which has a good catalytic degradation effect on rhodamine B. Another object of the present invention is to provide a composite film photocatalyst. It is still another object of the present invention to provide a use of a composite membrane photocatalyst in treating organic dye in wastewater.
In one aspect, the invention provides a method for preparing a composite membrane photocatalyst, which comprises the following steps:
(1) Forming an electrolyte by using a silver ion source, alkali metal chloride and a complexing agent, adjusting the pH value of the electrolyte to 8-13 to form a plating solution, and performing constant current electrodeposition by using nickel as a cathode to form an Ag/Ni film;
(2) Forming a suspension by using a bromide ion source, ammonium phosphate and graphene oxide, and forming an electrolytic suspension by using ultrasonic waves of the suspension at a temperature of between 5 and 18 ℃; taking the Ag/Ni film as an anode, taking the electrolytic suspension as plating solution, and performing constant current composite electrodeposition to form the Ag/AgBr/GO/Ni film; wherein the concentration of the graphene oxide in the electrolytic suspension is 0.18-0.28 g.L -1 The temperature of the electrolytic suspension is 10-20 ℃; the constant current composite electrodeposition has a current density of 2-2.6mA.cm -2 The deposition time is 16-20 min;
(3) And carrying out heat preservation treatment on the Ag/AgBr/GO/Ni film at the temperature of 100-180 ℃ to obtain the Ag/AgBr/GO/Ni composite film photocatalyst.
According to the preparation method of the present invention, preferably, the complexing agent is selected from one of succinimide, hydantoin, alkyl-substituted succinimide or alkyl-substituted hydantoin, and the anode is selected from one of stainless steel and graphite.
According to the production method of the present invention, preferably, the silver ion source is selected from at least one of silver nitrate and silver sulfate; the alkali metal chloride is at least one selected from potassium chloride and sodium chloride; the pH of the electrolyte is adjusted using a mixture of an alkali metal hydroxide and an inorganic acid.
According to the production method of the present invention, it is preferable that the constant current electrodeposition in the step (1) has a current density of 1 to 3 mA.cm -2 The deposition time is 20-40 min.
According to the preparation method of the present invention, preferably, the silver ion source is silver nitrate, the alkali chloride is potassium chloride, and the complexing agent is hydantoin; the concentration of silver nitrate in the electrolyte is 12-25 g/L, the concentration of potassium chloride is 5-15 g/L, and the concentration of hydantoin is 25-55 g/L.
According to the production method of the present invention, preferably, the bromide ion source is at least one selected from sodium bromide and potassium bromide; the molar ratio of the bromide ion to the ammonium phosphate is (1-6): 10.
According to the preparation method of the present invention, preferably, the cathode in the step (2) is selected from one of stainless steel and graphite; the concentration of bromide ions in the electrolytic suspension is 0.1-0.6 mol/L, the concentration of ammonium phosphate is 0.5-1.5 mol/L, and the pH value of the electrolytic suspension is 7-10.
According to the preparation method of the present invention, preferably, the time of the heat-retaining treatment is 0.5 to 2 hours.
In another aspect, the invention provides a composite membrane photocatalyst, which is prepared by the preparation method.
In yet another aspect, the invention provides the use of a composite membrane photocatalyst in the treatment of organic dyes in wastewater.
According to the invention, bromide ions and graphene oxide are deposited on an Ag/Ni film by adopting a constant current composite electrodeposition method, so that an Ag/AgBr/GO/Ni composite film photocatalyst is formed, and various parameters in the preparation process are controlled, so that the Ag/AgBr/GO/Ni composite film photocatalyst has a good photocatalytic decomposition effect on rhodamine B.
Drawings
FIG. 1 is a scanning electron microscope image of an Ag/AgBr/Ni thin film photocatalyst prepared in comparative example 9 of the present invention.
FIG. 2 is a scanning electron microscope image of the Ag/AgBr/GO/Ni composite film photocatalyst prepared in example 1 of the present invention.
FIG. 3 is a graph showing the photocatalytic activity of rhodamine B by the catalyst film prepared in example 1 and comparative example 9 of the present invention.
FIG. 4 is a graph of photocatalytic activity against Congo red for the catalyst films prepared in example 1 and comparative example 9 of the present invention.
FIG. 5 is a graph showing the photocatalytic activity of rhodamine B by the catalyst films prepared in example 1, comparative examples 2 to 4, and comparative example 9 of the present invention. ( Example 1 go=0.2 g/L; comparative example 2 go=0.04 g/L; comparative example 3 go=0.1 g/L; comparative example 4 go=0.3 g/L; comparative example 9 go=0 g/L )
Detailed Description
The present invention will be further described with reference to specific examples, but the scope of the present invention is not limited thereto.
The preparation method of the composite membrane photocatalyst comprises the following steps: (1) preparation of Ag/Ni film; (2) preparation of Ag/AgBr/GO/Ni film; (3) a step of post-treatment. The following is a detailed description.
< preparation of Ag/Ni film >
And (3) forming an electrolyte by using a silver ion source, alkali metal chloride and a complexing agent, regulating the pH value of the electrolyte to 8-13 to form a plating solution, and performing constant current electrodeposition by using nickel as a cathode to form an Ag/Ni film.
The silver ion source in the present invention may be an inorganic salt of silver, such as silver nitrate, silver sulfate, or the like. According to one embodiment of the invention, the silver ion source is silver nitrate. The concentration of silver nitrate in the electrolyte can be 12-25 g/L; preferably 14-20 g/L; more preferably 15 to 18g/L.
The alkali metal chloride of the present invention may be selected from at least one of potassium chloride or sodium chloride. According to one embodiment of the invention, the alkali metal chloride is potassium chloride. The concentration of potassium chloride in the electrolyte can be 5-15 g/L; preferably 7-13 g/L; more preferably 7 to 11g/L.
The complexing agent of the invention can be selected from one of succinimide, hydantoin, alkyl-substituted succinimide or alkyl-substituted hydantoin; preferably, the complexing agent is selected from one of succinimide, hydantoin, 5-methylhydantoin; more preferably, the complexing agent is hydantoin. The concentration of hydantoin in the electrolyte can be 25-55 g/L; preferably 30-50 g/L; more preferably 35 to 45g/L. This helps to improve the quality of the Ag/Ni film.
The pH of the electrolyte of the invention may be 8 to 13; preferably 9 to 12; more preferably 10 to 11. This helps to obtain a stable quality Ag/Ni film.
The pH of the electrolyte may be adjusted by a mixture of an alkali metal hydroxide and an inorganic acid. Examples of alkali metal hydroxides include, but are not limited to, sodium hydroxide, potassium hydroxide. Examples of mineral acids include, but are not limited to, nitric acid, sulfuric acid, hydrochloric acid. According to one embodiment of the invention, the pH of the electrolyte may be adjusted by a mixture of potassium hydroxide and nitric acid.
The anode may be an inert electrode such as stainless steel, graphite, or the like. Preferably, the anode is stainless steel. According to one embodiment of the present invention, the anode is a stainless steel plate of (1 to 6 cm) × (2 to 7 cm).
The cathode is nickel. According to one embodiment of the present invention, the cathode is a nickel plate of (0.2 to 3 cm) × (0.5 to 5 cm). The distance between the cathode and the anode can be 0.5-7 cm; preferably 1 to 5cm; more preferably 2 to 4cm.
The constant current electrodeposit has a current density of 1-3 mA cm -2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably 1.5 to 2.5 mA.cm -2 The method comprises the steps of carrying out a first treatment on the surface of the More preferably 1.8 to 2.2mA·cm -2 . Such conditions help to control the microstructure of the Ag/Ni film, resulting in an Ag/Ni film suitable for use in preparing composite film photocatalysts.
The deposition time of constant current electrodeposition can be 20-40 min; preferably 25 to 35 minutes; more preferably 22 to 33 minutes. Such conditions help to control the microstructure of the Ag/Ni film, resulting in an Ag/Ni film suitable for use in preparing composite film photocatalysts.
< preparation of Ag/AgBr/GO/Ni film >
Forming a suspension by using a bromide ion source, ammonium phosphate and graphene oxide, and forming an electrolytic suspension by using ultrasonic waves of the suspension at a temperature of between 5 and 18 ℃; taking the Ag/Ni film as an anode, taking the electrolytic suspension as plating solution, and performing constant current composite electrodeposition to form the Ag/AgBr/GO/Ni film; wherein the concentration of the graphene oxide in the electrolytic suspension is 0.18-0.28 g.L -1 The temperature of the electrolytic suspension is 10-20 ℃; the constant current composite electrodeposition has a current density of 2-2.6mA.cm -2 The deposition time is 16-20 min.
The bromide ion source in the present invention may be an alkali metal bromide, such as sodium bromide, potassium bromide, or the like. According to one embodiment of the invention, the bromide ion source is sodium bromide. The concentration of bromide ions in the electrolytic suspension may be 0.1 to 0.6mol/L, preferably 0.1 to 0.4mol/L; more preferably 0.2 to 0.4mol/L.
The molar ratio of the bromide ion to the ammonium phosphate can be (1-6): 10; preferably (1-4): 10; more preferably (2-4): 10. This helps to increase the catalytic activity of the composite film photocatalyst.
The concentration of ammonium phosphate in the electrolytic suspension may be 0.5 to 1.5mol/L, preferably 0.7 to 1.3mol/L; more preferably 0.8 to 1.2mol/L.
According to the invention, graphene oxide is adopted to replace the carbon nanotubes, so that agglomeration of the carbon nanotubes is avoided, and the catalytic activity of the composite film photocatalyst is higher. The concentration of the graphene oxide in the electrolytic suspension is 0.18-0.28 g.L -1 The method comprises the steps of carrying out a first treatment on the surface of the Preferably 0.18 to 0.25 g.L -1 The method comprises the steps of carrying out a first treatment on the surface of the More preferably 0.18 to 0.22 g.L -1 . This helps to increase the catalytic activity of the composite film photocatalyst.
The pH of the electrolytic suspension may be 7 to 10; preferably 7 to 9; more preferably 7.5 to 8.5.
Ultrasound may be performed in an ice-water bath. The ultrasonic temperature is 5-18 ℃; preferably 5-15 ℃; more preferably 8 to 12 ℃. This helps to increase the catalytic activity of the composite film photocatalyst. The present invention finds that the ultrasound temperature has an important influence on the composite membrane. The ultrasonic temperature is lower than 5 ℃, which is unfavorable for the formation of a composite film; the ultrasonic temperature is higher than 18 ℃, and the catalytic activity of the composite membrane is deteriorated.
The temperature of the electrolytic suspension is 10-20 ℃; preferably 15-20 ℃; more preferably 17 to 20 ℃. This helps to increase the catalytic activity of the composite film photocatalyst. The present invention has found that the temperature of the electrolytic suspension has an important effect on the composite membrane. The temperature of the electrolytic suspension is lower than 10 ℃, which is unfavorable for the formation of a composite film; the temperature of the electrolytic suspension is higher than 20 ℃, and the catalytic activity of the composite membrane is deteriorated.
The cathode may be an inert electrode such as stainless steel, graphite, or the like. Preferably, the cathode is stainless steel. According to one embodiment of the invention, the cathode is a stainless steel plate. The distance between the cathode and the anode can be 0.5-7 cm; preferably 1 to 5cm; more preferably 2 to 4cm.
The current density of constant current composite electrodeposition can be 2-2.6mA.cm -2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably 2.2 to 2.6 mA.cm -2 The method comprises the steps of carrying out a first treatment on the surface of the More preferably 2.3 to 2.6 mA.cm -2 . Such conditions help to control the microstructure of the composite thin film photocatalyst and enhance the catalytic activity.
The deposition time of constant current composite electrodeposition can be 16-20 min; preferably 17 to 20 minutes; more preferably 17 to 19 minutes. Such conditions help to control the microstructure of the composite thin film photocatalyst and enhance the catalytic activity.
< step of post-treatment >
And carrying out heat preservation treatment on the Ag/AgBr/GO/Ni film at the temperature of 100-180 ℃ to obtain the Ag/AgBr/GO/Ni composite film photocatalyst.
In the invention, the temperature of the heat preservation treatment can be 100-180 ℃; preferably 120-160 ℃; more preferably 130 to 150 ℃. The heat preservation treatment time can be 0.5-2 h; preferably 0.7 to 1.5 hours; more preferably 0.8 to 1.2 hours. Thus being beneficial to improving the catalytic activity of the Ag/AgBr/GO/Ni composite film photocatalyst.
The Ag/AgBr/GO/Ni composite film photocatalyst is prepared by the method, and the degradation rate of rhodamine B in 15min can reach more than 98%.
The Ag/AgBr/GO/Ni composite film photocatalyst has good catalytic activity on organic dyes, so that the photocatalyst can be used for treating the organic dyes in wastewater, and is preferably rhodamine B.
Example 1 and comparative examples 1 to 8
(1) Forming an electrolyte from silver nitrate, potassium chloride and hydantoin at room temperature (the concentration of the silver nitrate is 17g/L, the concentration of the potassium chloride is 9g/L, and the concentration of the hydantoin is 40 g/L); the pH of the electrolyte was adjusted to 10.5 with potassium hydroxide and nitric acid to form a plating solution. Stainless steel plate (3 cm. Times.4 cm) is used as anode, nickel plate (1 cm. Times.2 cm) is used as cathode, non-working surface of cathode is sealed with insulating tape, distance between two electrodes is 3cm, and current density is 2.0mA.cm -2 And performing constant current deposition for 30min to obtain the Ag/Ni film.
(2) Sodium bromide, ammonium phosphate and graphene oxide are formed into a suspension, and the suspension is subjected to ultrasonic vibration to form an electrolytic suspension (NaBr concentration is 0.3mol/L, ammonium phosphate concentration is 1.0mol/L, and pH of the electrolytic suspension is 8). And (3) carrying out constant current composite electrodeposition by taking the Ag/Ni film as an anode, taking the stainless steel sheet as a cathode, taking the electrolytic suspension as a plating solution, wherein the distance between the cathode and the anode is 3cm, and forming the Ag/AgBr/GO/Ni film.
(3) And cleaning the Ag/AgBr/GO/Ni film, and then performing heat preservation treatment to obtain the Ag/AgBr/GO/Ni composite film photocatalyst.
The specific process parameters are shown in table 1.
TABLE 1
Comparative example 9
(1) Forming an electrolyte from silver nitrate, potassium chloride and hydantoin at room temperature (the concentration of the silver nitrate is 17g/L, the concentration of the potassium chloride is 9g/L, and the concentration of the hydantoin is 40 g/L); the pH of the electrolyte was adjusted to 10.5 with potassium hydroxide and nitric acid to form a plating solution. Stainless steel plate (3 cm. Times.4 cm) is used as anode, nickel plate (1 cm. Times.2 cm) is used as cathode, non-working surface of cathode is sealed with insulating tape, distance between two electrodes is 3cm, and current density is 2.0mA.cm -2 And performing constant current deposition for 30min to obtain the Ag/Ni film.
(2) Sodium bromide and ammonium phosphate were formed into a mixed aqueous solution (NaBr concentration was 0.3mol/L, ammonium phosphate concentration was 1.0 mol/L), and the pH of the mixed aqueous solution was adjusted to 8 to form a plating solution. Taking an Ag/Ni film as an anode, taking a stainless steel sheet as a cathode, wherein the distance between the cathode and the anode is 3cm, and the current density is 2.0mA.cm -2 And (3) performing constant current electrodeposition for 18min to form the Ag/AgBr/Ni film.
(3) And cleaning the Ag/AgBr/Ni film, and then performing heat preservation treatment at 140 ℃ for 1h to obtain the Ag/AgBr/Ni film catalyst.
Comparative example 10
Example 1 was repeated except that graphene oxide was replaced with carbon nanotubes.
Experimental example
Taking the initial concentration C at room temperature 0 Initial concentration C of rhodamine B solution or equal volume=6 mg/L 0 Congo red solution=20mg/L was added to the reactor and the absorbance of the solution at this time was recorded as A 0 . Immersing the catalyst film in the solution completely, introducing O 2 (flow rate 50 mL/min) absorbance of the solution after 30min was A' 0 . After the adsorption is finished, a xenon lamp light source (lambda=420 nm) is started to perform photocatalytic degradation, and the light intensity is 110mW cm -2 . Sampling at regular intervals, measuring absorbance of degraded solution as A i (corresponding to the concentration of the organic dye in the solution of C). According to the formula x= (1-a i /A 0 ) The degradation rate was calculated as x 100%. The results obtained are shown in FIGS. 3 to 5 and Table 2.
TABLE 2
| Sequence number | Degradation rate of rhodamine B at 15min | Degradation rate of Congo red at 60min |
| Example 1 | 98.0％ | 87.4％ |
| Comparative example 1 | 67.5％ | -- |
| Comparative example 2 | 73.3％ | -- |
| Comparative example 3 | 78.1％ | -- |
| Comparative example 4 | 81.5％ | -- |
| Comparative example 5 | 58.6％ | -- |
| Comparative example 6 | 63.5％ | -- |
| Comparative example 7 | 61.4％ | -- |
| Comparative example 8 | 45.3％ | -- |
| Comparative example 9 | 72.7％ | 68.7％ |
| Comparative example 10 | 72.8％ | -- |
The present invention is not limited to the above-described embodiments, and any modifications, improvements, substitutions, and the like, which may occur to those skilled in the art, fall within the scope of the present invention without departing from the spirit of the invention.
Claims (11)
1. The preparation method of the composite membrane photocatalyst is characterized by comprising the following steps of:
(1) Forming an electrolyte by using a silver ion source, alkali metal chloride and a complexing agent, adjusting the pH value of the electrolyte to 8-13 to form a plating solution, and performing constant current electrodeposition by using nickel as a cathode to form an Ag/Ni film;
(2) Forming a suspension by using a bromide ion source, ammonium phosphate and graphene oxide, and forming an electrolytic suspension by using ultrasonic waves of the suspension at the temperature of 10 ℃; taking the Ag/Ni film as an anode, taking the electrolytic suspension as plating solution, and performing constant current composite electrodeposition to form the Ag/AgBr/GO/Ni film; wherein the concentration of graphene oxide in the electrolytic suspension is 0.2 g.L -1 The temperature of the electrolytic suspension is 18 ℃; constant current composite electrodepositingThe current density was 2.5 mA.cm -2 The deposition time is 18min;
(3) Carrying out heat preservation treatment on the Ag/AgBr/GO/Ni film at 140 ℃ to obtain an Ag/AgBr/GO/Ni composite film photocatalyst;
the degradation rate of the Ag/AgBr/GO/Ni composite film photocatalyst to rhodamine B in 15min reaches more than 98%.
2. The preparation method according to claim 1, wherein the complexing agent is selected from one of succinimide, hydantoin, alkyl-substituted succinimide or alkyl-substituted hydantoin, and the anode in the step (1) is selected from one of stainless steel and graphite.
3. The method according to claim 1, wherein the silver ion source is at least one selected from the group consisting of silver nitrate and silver sulfate; the alkali metal chloride is at least one selected from potassium chloride and sodium chloride; the pH of the electrolyte is adjusted using a mixture of an alkali metal hydroxide and an inorganic acid.
4. The method according to claim 1, wherein the constant current electrodeposited in step (1) has a current density of 1 to 3mA cm -2 The deposition time is 20-40 min.
5. The method of claim 1, wherein the source of silver ions is silver nitrate, the alkali chloride is potassium chloride, and the complexing agent is hydantoin; the concentration of silver nitrate in the electrolyte is 12-25 g/L, the concentration of potassium chloride is 5-15 g/L, and the concentration of hydantoin is 25-55 g/L.
6. The method according to claim 1, wherein the bromide ion source is at least one selected from sodium bromide and potassium bromide; the molar ratio of the bromide ion to the ammonium phosphate is (1-6): 10.
7. The method according to claim 1, wherein the cathode in the step (2) is one selected from stainless steel and graphite; the concentration of bromide ions in the electrolytic suspension is 0.1-0.6 mol/L, the concentration of ammonium phosphate is 0.5-1.5 mol/L, and the pH value of the electrolytic suspension is 7-10.
8. The method according to any one of claims 1 to 7, wherein the time for the heat-retaining treatment is 0.5 to 2 hours.
9. The preparation method of the composite membrane photocatalyst is characterized by comprising the following steps of:
(1) At room temperature, silver nitrate, potassium chloride and hydantoin form electrolyte; regulating the pH value of the electrolyte to 10.5 by potassium hydroxide and nitric acid to form a plating solution; the stainless steel plate is used as an anode, the nickel sheet is used as a cathode, the non-working surface of the cathode is sealed by an insulating tape, the distance between the two electrodes is 3cm, and the current density is 2.0 mA.cm -2 Depositing for 30min under constant current to obtain an Ag/Ni film;
wherein, the concentration of silver nitrate in the electrolyte is 17g/L, the concentration of potassium chloride is 9g/L, and the concentration of hydantoin is 40g/L; the stainless steel plate has a size of 3cm by 4cm; the size of the nickel sheet is 1cm multiplied by 2cm;
(2) Sodium bromide, ammonium phosphate and graphene oxide are formed into a suspension, and the suspension is subjected to ultrasonic vibration at 10 ℃ to form an electrolytic suspension; taking an Ag/Ni film as an anode, taking a stainless steel sheet as a cathode, taking an electrolytic suspension as a plating solution, and carrying out constant current composite electrodeposition with the distance between the cathode and the anode being 3cm to form an Ag/AgBr/GO/Ni film;
wherein the concentration of NaBr in the electrolytic suspension is 0.3mol/L, the concentration of ammonium phosphate is 1.0mol/L, the concentration of graphene oxide is 0.2g/L, and the pH of the electrolytic suspension is 8; the temperature of the electrolytic suspension is 18 ℃; the constant current composite electrodeposition has a current density of 2.5 mA.cm -2 The deposition time is 18min;
(3) And cleaning the Ag/AgBr/GO/Ni film, and then carrying out heat preservation treatment at 140 ℃ to obtain the Ag/AgBr/GO/Ni composite film photocatalyst.
10. A composite film photocatalyst, characterized in that the composite film photocatalyst is prepared by the preparation method of any one of claims 1 to 9.
11. Use of the composite membrane photocatalyst according to claim 10 for treating organic dyes in wastewater.
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