CN109590022A - Stratiform UiO-66/g-C3N4The preparation method and application of/Ag composite material - Google Patents
Stratiform UiO-66/g-C3N4The preparation method and application of/Ag composite material Download PDFInfo
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- 239000013207 UiO-66 Substances 0.000 title claims abstract description 124
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000007146 photocatalysis Methods 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000005588 protonation Effects 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 claims description 4
- 238000006731 degradation reaction Methods 0.000 claims description 4
- 238000011026 diafiltration Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 239000011941 photocatalyst Substances 0.000 claims 2
- 239000000356 contaminant Substances 0.000 claims 1
- 238000002256 photodeposition Methods 0.000 claims 1
- 239000012621 metal-organic framework Substances 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 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 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229910007932 ZrCl4 Inorganic materials 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical group C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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—
-
- B01J35/39—
-
- 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
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
-
- 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
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
-
- 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
Abstract
The invention belongs to nanocomposite technical fields, are related to a kind of stratiform UiO-66/g-C3N4The preparation method and application of/Ag composite material.The present invention is first to being prepared g-C3N4Protonation processing is carried out, g-C will be protonated3N4It is compound with UiO-66, obtain UiO-66/g-C3N4, Ag has successfully been loaded to by UiO-66/g-C using light deposition technology3N4On form a kind of novel trielement composite material UiO-66/g-C3N4/ Ag, and proved using scanning electron microscope (SEM) etc..UiO-66/g-C3N4/ Ag composite material is high-efficiency photocatalysis material, and laminar composite is adsorbing, photocatalysis, is played an important role in the different fields such as energy storage.The present invention will be MOF, g-C3N4Important benchmark is provided with noble metal semiconductor junction synthesis layered nano-structure, to improve the photocatalysis performance of material, thus preferably degradable organic pollutant.
Description
Technical field
The invention belongs to nanocomposite technical fields, are related to a kind of stratiform UiO-66/g-C3N4/ Ag composite material
Preparation method and its performance study.
Background technique
With the continuous consumption of the various energy, social development, a large amount of pollutant removal problem is increasingly studied
The concern of person.Photocatalysis technology is because its is easy to operate, and low energy consumption, without secondary pollution and high efficiency and have been favored by people.So
And such as photoelectron-hole pair Quick Casting, it is seen that some problems such as photoresponse difference and specific surface area deficiency limit many
The application of conventional catalyst.
Metal organic framework (MOFs) is novel microporous material popular in recent years, it is by by organic ligand and transition
Metal ion connection and formed.Since with high surface area, some characteristics of high porosity and adjustability, MOFs is in gas storage
It deposits, adsorbs, many fields such as microelectronics and catalysis occur.In MOFs race, Zr6O4(OH)4With 1,4- terephthalic acid (TPA)
(H2BDC) connector forms highly-filled face-centered cubic (fcc) structure of 12 coordinations (highest of MOF reports coordination), so that Zr
Base MOFs (UiO-66) has unique property, such as rare water stability, excellent thermal stability and chemical stability, even if
High stability is also able to maintain under strong acid and strong alkali environment.Importantly, UiO-66 has microcellular structure, bigger serface and photochemical
Property is learned, hetero-junctions catalyst can be effectively formed, catalysis reaction is steadily carried out in sewage.Graphite carbonitride (g-
C3N4) it is a kind of only carbon containing and nitrogen photochemical catalyst, therefore the characteristics of its low cost and simple synthesis, causes the pass of academia
Note.The band position and gap (2.7eV) appropriate and 2-D formed by the connection of amino on each layer and 5-triazine units, which stacks, ties
Structure makes it have the pi-conjugated electronic structure of π-, high activity, high stability and visible light-responded.However, g-C3N4The low surface of material
Product provides limited catalytic site, and the Quick Casting problem of photoelectron pair also counteracts light-catalyzed reaction.However, recently
Studies have shown that use the MOF with bigger serface combined as semiconductor material with carbonaceous material not only increase it is compound
The active site of material, and the compound of photo-generate electron-hole is also reduced, to enhance visible light reaction.Meanwhile in order to
The extensive research of semiconductor noble metal combination has been carried out in the Quick Casting process for further overcoming photochemical catalyst.At certain
In degree, Nano silver grain (Ag nanoparticle) acts not only as effective electron trap and goes to hinder photo-generate electron-hole pair
Recombination, but also strong visible absorption can be caused due to the surface plasma body resonant vibration (SPR) of Ag atom.Meanwhile light
Deposition can be effectively prevented the aggregation of Ag NPs, so that the active site of dispersed catalyst, is more advantageous to and inhibits photoinduction
Electron-hole is compound.
Summary of the invention
The purpose of the present invention is to provide a kind of novel lamellar UiO-66/g-C3N4/ Ag composite material and preparation method with
And performance study, obtained composite material are conducive to improve visible absorption, have good photo-catalysis capability.
In order to achieve the above purpose, present invention employs technical solutions below:
A kind of stratiform UiO-66/g-C of in-situ method preparation3N4/ Ag composite material, UiO-66 and g-C3N4Quality score
Not Wei 1:0.1,1:0.15,1:0.2, prepared sample UiO-66/g-C3N4/ Ag is denoted as UiO-66/g-C respectively3N4/Ag
(X%) X% is g-C3N4Account for the mass percent of UiO-66, X%=10%, 15% or 20%.
Stratiform UiO-66/g-C of the present invention3N4The preparation method of/Ag composite material, comprising the following steps:
(1) melamine is distributed in the HCl solution of 2mol/L and is stirred 2 hours, then filtered, be washed with deionized water
It washs and is dried to obtain white powder under the conditions of 100 DEG C；
(2) white powder is uniformly placed in sealed crucible and is warming up to 550 DEG C with 5 DEG C/min, and forged in tube furnace
It burns 4 hours, obtains a kind of flaxen powder, as g-C3N4；
(3) by g-C3N4Ultrasonic disperse is then charged into the HCl solution of 6mol/L in reaction kettle and with 100 DEG C of temperature
Heating, it is cooling after heating, obtain g-C3N4Mixture is simultaneously cleaned with deionized water to solution neutral, obtains protonation g-C3N4, it is added
In water, g-C must be protonated3N4Nanometer sheet suspension；
(4) by UiO-66 powder and protonation g-C3N4Nanometer sheet suspension is encased in round-bottomed flask, and by round-bottomed flask
2h is stirred in 70 DEG C of oil bath pan, is filtered after obtaining mixed liquor, with deionized water and ethyl alcohol diafiltration and dries, obtains UiO-66/g-
C3N4；
(5) PEG 2000 of mass fraction 10% is added to 1g/L AgNO330 are stirred in solution and under dark condition
Minute, obtain mixed liquor；
(6) then above-mentioned mixed liquor is poured into containing UiO-66/g-C3N4In teat glass, test tube is put into a dress
2h is irradiated in the reactor for having 350Xe lamp, collects mixture；
(7) it is dried with deionized water and ethyl alcohol washed mixture and under the conditions of 100 DEG C, obtains stratiform UiO-66/g-
C3N4/ Ag composite material.
The beneficial effects of the present invention are:
(1) UiO-66/g-C is prepared using simple protonation coating and light deposition technology3N4/ Ag composite material, pattern are
Layer structure cooperates between synthesis, so that the material to be formed is had many advantages, such as that visible light catalytic performance is high, stability is good.This
Invented technology is simple, and raw materials are cheap and easy to get, at low cost, meets environmental-friendly requirement.Since the preparation method is novel,
Material innovation has reference function to the exploitation of environmentally conscious materials；
(2) g-C that the present invention protonates3N4It is compound well with UiO-66 progress, then in g-C3N4/ UiO-66 entirety table
Face modifies Ag layers, is mutually cooperateed between each layer, is formed by structure with excellent absorption and photocatalysis effect；
(3) present invention is using light deposition Ag in g-C3N4The surface /UiO-66 deposits Ag compared to chemical reduction method, not only grasps
Make simply, and Ag can be made uniformly more to be distributed, improves photocatalysis effect and adsorption effect.
Detailed description of the invention:
Fig. 1 is UiO-66/g-C3N4The SEM spectrum of/Ag (15) composite material.
Fig. 2 is UiO-66/g-C3N4The TEM map of/Ag (15) composite material.
Fig. 3 is UiO-66, UiO-66/Ag, UiO-66/g-C3N4, UiO-66/g-C3N4/ Ag (10), UiO-66/g-C3N4/
Ag (15), UiO-66/g-C3N4/ Ag (20), g-C3N4XRD diagram picture.
Fig. 4 is UiO-66, UiO-66/g-C3N4, UiO-66/g-C3N4/ Ag (10), UiO-66/g-C3N4/ Ag (15),
UiO-66/g-C3N4/ Ag (20), g-C3N4EIS image.
Fig. 5 is UiO-66/g-C3N4, UiO-66/g-C3N4/ Ag (10), UiO-66/g-C3N4/ Ag (15), UiO-66/g-
C3N4/ Ag (20), g-C3N4PL image.
Fig. 6 is UiO-66, UiO-66/g-C3N4, UiO-66/g-C3N4/ Ag (10), UiO-66/g-C3N4/ Ag (15),
UiO-66/g-C3N4/ Ag (20), g-C3N4The image of photocatalytic degradation RhB.
Specific embodiment:
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited to following embodiments.
Embodiment 1:
Protonate g-C3N4Pass through conventional solvent-thermal process.Specifically carry out as follows:
(1) 5g melamine is distributed in 300ml HCl solution (2M) and is stirred 2 hours, then filtered, use deionization
Water diafiltration is simultaneously dried to obtain white powder for 100 DEG C.
(2) white powder above is uniformly placed in 6 sealed crucibles and is calcined 4 hours (550 in tube furnace
DEG C, 5 DEG C/min), to obtain a kind of flaxen powder, as g-C3N4。
(3) protonation process is as follows: by the g-C of 1g3N4Ultrasonic disperse is then charged into in 60ml HCl solution (6M)
In 100ml reaction kettle and with the heating of 100 DEG C of temperature.
(4) then by cooling g-C3N4Mixture is cleaned with deionized water until solution neutral, then in vacuum oven
In it is dry with 100 DEG C of temperature, obtain protonation g-C3N4。
UiO-66 is also to pass through solvent structure.Specifically sequentially include the following steps:
(1) by 0.386g (1.67mmol) ZrCl4, 0.276g (1.67mmol) H2BDC and 6.118g (50.1mmol) benzene first
Acid dissolution is poured into the stainless steel autoclave equipped with polytetrafluoroethyllining lining after mixing evenly in 50ml DMF solution.
Wherein ZrCl4: H2BDC: the molar ratio of benzoic acid is 1:1:30；
(2) then reaction kettle is placed in air dry oven and is heated 24 hours with 120 DEG C.After reaction kettle is cooled to room temperature
Centrifugation obtains white crystal.
(3) then obtained white crystal is washed with DMF and methanol and is immersed in 100ml methanol solution and anti-afterwards three times
It answers in kettle and handles 12 hours for 100 DEG C.
(4) above-mentioned powder is immersed in chloroform 5 days.Then sample is centrifuged with methanol, finally 100 DEG C in vacuum drying oven
Dry 12 hours to obtain UiO-66.
Stratiform UiO-66/g-C3N4Composite material passes through in-situ method for the g-C of above-mentioned synthesis3N4It is combined into UiO-66
Function preparation, comprising the following steps:
(1) by the g-C of the UiO-66 powder of the above-mentioned synthesis of 100mg and protonation3N4Nanometer sheet suspension is encased in 250ml
In round-bottomed flask, and round-bottomed flask is stirred into 2h in 70 DEG C of oil bath pan, obtains mixed liquor.
(2) it and then by mixed liquor filtering deionized water and ethyl alcohol diafiltration and dries, to obtain UiO-66/g-C3N4。
Stratiform UiO-66/g-C3N4/ Ag composite material passes through in-situ method for the UiO-66/g-C of above-mentioned synthesis3N4It is tied with Ag
It closes and successfully prepares, comprising the following steps:
(1) 1ml PEG 2000 (10% concentration) is added to the AgNO of 8ml3In solution (1g/L) and under dark condition
Stirring 30 minutes.
(2) mixed liquor after stirring pours into the UiO-66/g-C containing 100mg3N4In teat glass, which is placed into one
2h is irradiated in a reactor equipped with 350Xe lamp, collects mixture.
(3) it is dried under the conditions of 100 DEG C with after deionized water and ethyl alcohol washed mixture, to obtain stratiform UiO-66/g-
C3N4/Ag(15)。
Embodiment 2
Using preparation method same as Example 1, change g-C3N4The additional amount of solution, is prepared into UiO-66/g-
C3N4/Ag(10)。
Embodiment 3
Using preparation method same as Example 1, change g-C3N4The additional amount of solution, is prepared into UiO-66/g-
C3N4/Ag(20)。
Comparative example 1
It prepares UiO-66/Ag: using preparation method same as Example 1, g-C is not added3N4, it is prepared into UiO-66/Ag
UiO-66 is also to pass through solvent structure.Specifically sequentially include the following steps:
(1) by 0.386g (1.67mmol) ZrCl4, 0.276g (1.67mmol) H2BDC and 6.118g (50.1mmol) benzene first
Acid dissolution is poured into the stainless steel autoclave equipped with polytetrafluoroethyllining lining after mixing evenly in 50ml DMF solution.
Wherein ZrCl4: H2BDC: the molar ratio of benzoic acid is 1:1:30；
(2) then reaction kettle is placed in air dry oven and is heated 24 hours with 120 DEG C.After reaction kettle is cooled to room temperature
Centrifugation obtains white crystal.
(3) then obtained white crystal is washed with DMF and methanol and is immersed in 100ml methanol solution and anti-afterwards three times
It answers in kettle and handles 12 hours for 100 DEG C.
(4) above-mentioned powder is immersed in chloroform 5 days.Then sample is centrifuged with methanol, finally 100 DEG C in vacuum drying oven
Dry 12 hours to obtain UiO-66.
Prepare UiO-66/Ag
(1) 1ml PEG 2000 (10% concentration) is added to the AgNO of 8ml3In solution (1g/L) and under dark condition
Stirring 30 minutes.
(2) mixed liquor after stirring is poured into containing in UiO-66 teat glass, which is placed into one equipped with 350Xe lamp
Reactor in irradiate 2h, collect mixture.
(3) it is dried under the conditions of 100 DEG C with after deionized water and ethyl alcohol washed mixture, to obtain stratiform UiO-66/Ag.
Comparative example 2
Prepare UiO-66/Ag/g-C3N4
(1)g-C3N4It is same as Example 1 by conventional solvent-thermal process step；
(2) UiO-66 solvent structure step is same as Example 1；
(3) first it is prepared into Ag/g-C3N4, then it is prepared into UiO-66/Ag/g-C3N4。
Ag/g-C is found during the experiment3N4Add UiO-66 that can reduce its photocatalysis performance again after synthesis, carries out characterization hair
Existing UiO-66/Ag/g-C3N4Middle Ag's falls off, this is because Ag/g-C3N4Stirring 2 hours at 70 DEG C of oil bath pan will form Ag's
It falls off, the compound of Ag is not easy high temperature and acutely operates, and influences the formation of structure.So the UiO-66/Ag/g- that synthesis obtains
C3N4Photocatalysis performance will be greatly reduced.
Stratiform UiO-66/g-C prepared by embodiment 13N4/ Ag (15) composite material by scanning electron microscope (SEM),
Transmission electron microscope (TEM), X-ray diffraction (XRD), EIS nyquist diagram and photoluminescence spectra (PL) prove.
Fig. 1 is stratiform UiO-66/g-C3N4The SEM spectrum of/Ag composite material, SEM spectrum illustrate the UiO-66/g- of preparation
C3N4/ Ag has apparent support structures, and Ag particle makes material surface become smooth.
Fig. 2 is stratiform UiO-66/g-C3N4The TEM of/Ag composite material schemes, and TEM map illustrates UiO-66 nano particle and Ag
It equably modifies in g-C3N4Surface, it was demonstrated that UiO-66 is successfully supported on g-C3N4On layer.
Fig. 3 is UiO-66, UiO-66/Ag, UiO-66/g-C3N4, UiO-66/g-C3N4/ Ag (10), UiO-66/g-C3N4/
Ag (15), UiO-66/g-C3N4/ Ag (20), g-C3N4XRD diagram picture, XRD spectra finds out g-C3N4It is appeared in the crystal face of Ag
On UiO-66, illustrate g-C3N4The surface of UiO-66 is successfully attached to Ag.
Fig. 4 is UiO-66, UiO-66/g-C3N4, UiO-66/g-C3N4/ Ag (10), UiO-66/g-C3N4/ Ag (15),
UiO-66/g-C3N4/ Ag (20), g-C3N4EIS nyquist diagram, EIS nyquist diagram illustrates UiO-66/g-C3N4/ Ag can
With fast transfer interface charge and electron-hole pair is efficiently separated, to promote photocatalysis performance.
Fig. 5 is UiO-66/g-C3N4, UiO-66/g-C3N4/ Ag (10), UiO-66/g-C3N4/ Ag (15), UiO-66/g-
C3N4/ Ag (20), g-C3N4PL image, the bright UiO-66/g-C of PL chart3N4The upper electron-hole of/Ag is to the ability recombined
Greatly inhibited, to promote photocatalysis performance.
The present invention also provides above-mentioned composite materials in visible light photocatalysis field, to the waste water containing rhdamine B
Degradation property research.
Degradation property evaluation: catalytic test carries out in photo catalysis reactor.By 20mg above-mentioned material catalyst and add
Into the rhodamine B solution (initial concentration=20mg/l) of 50ml, test tube is had reached for magnetic agitation 1 hour under dark condition
Adsorption equilibrium.The H of 1ml 3% is added2O2It is small that 3 are irradiated into test tube solution and with the Xe lamp source that 350W includes 420nm optical filter
When, keep the circulation of magnetic agitation and water to keep environment temperature.Then it is used in combination at regular intervals with syringe extraction supernatant
0.22 μm of syringe filter filters out solution, using UV-2550 ultraviolet-visible spectrophotometer 554nm maximum wavelength
The absorbance of lower measurement rhodamine B.Absorbance measurement is carried out to the rhodamine B solution of various concentration, draws standard curve.According to
The absorbance detected calculates the concentration of rhodamine B, is denoted as Ct.Initial concentration 20mg/l is denoted as C0。
By UiO-66, UiO-66/g-C3N4, UiO-66/g-C3N4/ Ag (10), UiO-66/g-C3N4/ Ag (15), UiO-
66/g-C3N4/ Ag (20), g-C3N4, it is measured using above-mentioned biodegrading process, the photocatalytic degradation RhB of measurement result such as Fig. 6
Image shown in.
Stratiform UiO-66/g-C prepared by the present invention3N4/ Ag composite material especially UiO-66/g-C3N4/ Ag (15) exists
To the degradation rate of rhodamine B up to 92% after catalysis 3 hours.
The embodiment is a preferred embodiment of the present invention, but present invention is not limited to the embodiments described above, not
In the case where substantive content of the invention, any conspicuous improvement that those skilled in the art can make, replacement
Or modification all belongs to the scope of protection of the present invention.
Claims (8)
1. stratiform UiO-66/g-C3N4The preparation method of/Ag composite material, which is characterized in that by g-C3N4By protonation after and
UiO-66 is prepared into UiO-66/g-C3N4, and UiO-66/g-C is obtained with Photodeposition loaded Ag particle3N4/ Ag (X%), institute
Stating X% is g-C3N4Account for the mass percent of UiO-66, wherein X%=10%, 15% or 20%.
2. stratiform UiO-66/g-C according to claim 13N4The preparation method of/Ag composite material, which is characterized in that tool
Preparation step are as follows:
(1) melamine is distributed in HCl solution and is stirred 2 hours, then filtered, is washed with deionized and at 100 DEG C
Under the conditions of be dried to obtain white powder；
(2) white powder is uniformly placed in sealed crucible and is calcined in tube furnace, obtain a kind of flaxen powder, i.e.,
For g-C3N4；
(3) by g-C3N4Ultrasonic disperse is then charged into reaction kettle and is heated with 100 DEG C of temperature, after heating into HCl solution
It is cooling, obtain g-C3N4Mixture is simultaneously cleaned with deionized water to solution neutral, obtains protonation g-C3N4, it is added to the water, obtains proton
Change g-C3N4Nanometer sheet suspension；
(4) by UiO-66 powder and protonation g-C3N4Nanometer sheet suspension is encased in round-bottomed flask, and by round-bottomed flask 70
DEG C oil bath pan in stir 2h, filtered after obtaining mixed liquor, with deionized water and ethyl alcohol diafiltration and dry, obtain UiO-66/g-C3N4；
(5) AgNO for being added to PEG 20003It is stirred 30 minutes in solution and under dark condition；
(6) mixed liquor after stirring is poured into containing UiO-66/g-C3N4In teat glass, test tube is put into one equipped with 350Xe lamp
Reactor in irradiate 2h, collect mixture；
(7) it is dried under the conditions of 100 DEG C with after deionized water and ethyl alcohol washed mixture, obtains stratiform UiO-66/g-C3N4/Ag
Composite material.
3. stratiform UiO-66/g-C according to claim 23N4The preparation method of/Ag composite material, which is characterized in that
UiO-66/g-C3N4In/Ag (15%) composite photocatalyst material, UiO-66:g-C3N4: the mass ratio of Ag is 100:15:8.
4. stratiform UiO-66/g-C according to claim 23N4The preparation method of/Ag composite material, which is characterized in that step
Suddenly melamine described in (1) is distributed in the HCl solution of 2mol/L.
5. stratiform UiO-66/g-C according to claim 23N4The preparation method of/Ag composite material, which is characterized in that step
Suddenly calcination temperature described in (2) is 550 DEG C, and heating rate is 5 DEG C/min, and calcination time is 4 hours.
6. stratiform UiO-66/g-C according to claim 23N4The method of/Ag composite material preparation, which is characterized in that step
Suddenly g-C described in (3)3N4Ultrasonic disperse carries out protonation processing into 6mol/LHCl solution.
7. method according to claim 1-6 prepares stratiform UiO-66/g-C3N4The application of/Ag composite material,
It is characterized in that, layered UiO-66/g-C3N4/ Ag composite material is as composite photocatalyst material.
8. stratiform UiO-66/g-C according to claim 73N4The application of/Ag composite material, which is characterized in that the layer
Shape UiO-66/g-C3N4/ Ag composite material is used for photocatalysis degradation organic contaminant.
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