CN109647525A - Utilize the method for deficiency metal organic framework photochemical catalyst photocatalysis degradation organic contaminant - Google Patents
Utilize the method for deficiency metal organic framework photochemical catalyst photocatalysis degradation organic contaminant Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 119
- 230000007812 deficiency Effects 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 46
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 42
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 28
- 230000015556 catabolic process Effects 0.000 title claims abstract description 27
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 25
- 239000000356 contaminant Substances 0.000 title claims abstract description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 30
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 19
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000002351 wastewater Substances 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000013206 MIL-53 Substances 0.000 claims abstract 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- 239000004098 Tetracycline Substances 0.000 claims description 28
- 229960002180 tetracycline Drugs 0.000 claims description 28
- 229930101283 tetracycline Natural products 0.000 claims description 28
- 235000019364 tetracycline Nutrition 0.000 claims description 28
- 150000003522 tetracyclines Chemical class 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 12
- 230000003115 biocidal effect Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000007547 defect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 230000004087 circulation Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000013255 MILs Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010919 dye waste Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- WOSISLOTWLGNKT-UHFFFAOYSA-L iron(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Fe]Cl WOSISLOTWLGNKT-UHFFFAOYSA-L 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-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
- 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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- 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
- 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
- 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
- B01J35/612—Surface area less than 10 m2/g
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of methods using deficiency metal organic framework photochemical catalyst photocatalysis degradation organic contaminant, this method is to carry out photocatalytic degradation to organic pollutant using deficiency metal organic framework photochemical catalyst, wherein deficiency metal organic framework photochemical catalyst is using Iron(III) chloride hexahydrate and terephthalic acid (TPA) as raw material, N, dinethylformamide is solvent, is prepared under the action of acid regulator by solvent thermal reaction；The deficiency metal organic framework photochemical catalyst is deficiency MIL-53 metal organic framework photochemical catalyst.The present invention using the method for deficiency metal organic framework photochemical catalyst photocatalysis degradation organic contaminant have many advantages, such as simple process, it is easy to operate, low in cost, easily recycle and reuse, treatment effeciency is high, degradation rate is high, it can be realized effective fast degradation to organic pollutant, had a good application prospect in the actual treatment of organic pollutant wastewater.
Description
Technical field
The invention belongs to light-catalysed application field, it is related to a kind of urging using deficiency metal organic framework photochemical catalyst light
Change the method for degradable organic pollutant.
Background technique
Photocatalysis technology is a kind of green technology for having important application prospect in the energy and environmental area.In recent years, light
Catalytic applications technical research development is very rapid, this new technology has low energy consumption, operating process is simple, reaction condition is mild etc.
Organic matter in water, air and soil can be completely oxidized to nontoxic, harmless substance at room temperature, avoid secondary dirt by advantage
Dye.It especially has outstanding performance, can effectively degrade useless including antibiotic pharmaceutical wastewater, sulfurous fuels in terms of degradable organic pollutant
A variety of organic wastewaters including water, fermentation class production waste water, Fine Chemistry Wastewater etc., to reach discharge standard.
In recent years, metal organic framework (MOFs) is as one kind by inorganic metal center (metal ion or metal cluster)
The crystalline state porous material with periodic network structure being interconnected to form with the organic ligand of bridging by self assembly, causes
Extensive concern.MILs series (Lai Waxier framework material) is the Antoine Lavoisier that by Versailles, France university headed by Ferey
With trivalent metal ion, (aluminium (Al), iron (Fe), vanadium (V), chromium (Cr) synthesize research work group with Carboxylic acid ligands such as terephthalic acid (TPA)s
A kind of MOF material, the crystal crystal structure having the same synthesized based on different metal centers.MIL-53 is as MIL family
A member, be it is a kind of with Fe (III) for center metal ion, be made of octahedra Fe (III) and Isosorbide-5-Nitrae-terephthalic acid (TPA)
MOF, forbidden bandwidth 2.72eV, have the characteristics that it is visible light-responded, it is still, very fast multiple due to light induced electron and hole
It closes, the photocatalytic activity of MIL-53 is still poor.The existing technology for improving MIL-53 photocatalytic activity mainly includes two kinds, and first
Kind is the additional electron acceptor of addition, such as hydrogen peroxide (H2O2), sulfate persulfate (PS), persulfate
Peroxymonosulfate (PMS) etc. is used as electron acceptor；Second is building heterojunction structure, such as MIL-53/AgI, MIL-
53/Ag3PO4, MIL-53/CdS, MIL-53/SnS etc..However, that there are treatment effects is bad for the technology of addition electron acceptor, preparation
Complexity may have the influence such as potential hazard to environment；And heterojunction photocatalysis is easy to happen photoetch phenomenon, toxic metal ions
It is easy dissolution, environmental hazard is may cause, causes secondary pollution.Therefore, it is necessary to develop a kind of to have even mesoporous structure, compare table
The novel metal organic backbone that area is high, light abstraction width is wide, forbidden bandwidth is small, photoelectric current is big, impedance is small, photocatalytic activity is high
Material, this has a very important significance the organic pollutant in environment of effectively degrading.
Summary of the invention
The technical problem to be solved by the present invention is to overcome deficiencies in the prior art, provide a kind of with even mesoporous knot
The deficiency gold that structure, specific surface area are high, light abstraction width is wide, forbidden bandwidth is small, photoelectric current is big, impedance is small, photocatalytic activity is high
Belong to organic backbone photochemical catalyst, especially photocatalysis degradation organic contaminant significant effect.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A method of utilizing deficiency metal organic framework photochemical catalyst photocatalysis degradation organic contaminant, the method
It is that photocatalytic degradation is carried out to organic pollutant using deficiency metal organic framework photochemical catalyst；The deficiency metal is organic
Skeleton photochemical catalyst is using Iron(III) chloride hexahydrate and terephthalic acid (TPA) as raw material, and n,N-Dimethylformamide is solvent, in acid
It is prepared under the action of regulator by solvent thermal reaction；The deficiency metal organic framework photochemical catalyst is deficiency
MIL-53 metal organic framework photochemical catalyst.
Above-mentioned method, further improved, the preparation method of the deficiency metal organic framework photochemical catalyst, including
Following steps:
(1) Iron(III) chloride hexahydrate, terephthalic acid (TPA) are dissolved in n,N-Dimethylformamide, obtain mixed solution A；
(2) acid regulator is added toward the mixed solution A that step (1) obtains, obtains mixed solution B；
(3) the mixed solution B for obtaining step (2) carries out solvent thermal reaction, cleans, and filters, dry, obtains deficiency gold
Belong to organic backbone photochemical catalyst.
Above-mentioned method, it is further improved, in the step (1), the Iron(III) chloride hexahydrate, terephthalic acid (TPA) and
The molar ratio of N,N-dimethylformamide is 1: 1: 280.
Above-mentioned method, further improved, in the step (2), the ratio of the mixed solution A and acid regulator is
L~56mL: 100 μ L of 56mL: 10 μ；The acid regulator is HCl solution；The concentration of the HCl solution is 1mol/L~5mol/
L。
Above-mentioned method, further improved, in the step (2), the ratio of the mixed solution A and acid regulator is
L~56mL: 30 μ L of 56mL: 10 μ.
Above-mentioned method, it is further improved, in the step (3), the temperature of the solvent thermal reaction is 150 DEG C~
170℃；The time of the solvent thermal reaction is 15h~for 24 hours.
Above-mentioned method, further improved, the method is using deficiency metal organic framework photochemical catalyst to water
Organic pollutant in body carries out photocatalytic degradation, comprising the following steps: by deficiency metal organic framework photochemical catalyst with have
Machine pollutant water mixing carries out dark reaction, carries out photocatalytic degradation reaction after reaching adsorption-desorption balance, completes in water body
The photocatalytic degradation of organic pollutant.
Above-mentioned method, further improved, the additive amount of the deficiency metal organic framework photochemical catalyst is every liter
0.3g~0.5g is added in organic pollutant water body.
Above-mentioned method, further improved, the organic pollutant water body is antibiotic waste water；The antibiotic waste water
In antibiotic be tetracycline；The concentration of the organic pollutant Organic Pollutants In Water is 10mg/L~40mg/L.
Above-mentioned method, further improved, the dark reaction is to be stirred under dark condition；The dark reaction
Time is 30min~60min；The photocatalytic degradation reaction carries out under the visible light conditions of wavelength X > 420；The light is urged
The time for changing degradation reaction is 120min~150min.
Main innovation point of the invention is:
Entirely different with traditional addition electron acceptor and the method for constructing hetero-junctions, the present invention creatively proposes one
The method of the new regulation metal organic framework photochemical catalyst of kind, prepares deficiency metal organic framework light using acid tune strategy for the first time
Catalyst, and its photocatalytic activity is studied for the first time, this will be that tactful modified metal organic backbone photocatalysis is adjusted with acid
Activity is offered reference and basic work.In the present invention, adjust strategy in the synthesis of metal organic framework photochemical catalyst using acid
Defect is introduced in journey, these defects are primarily referred to as missing or offset due to atom in metal organic framework photochemical catalyst or ion
Metal organic framework photocatalyst crystals periodic arrangement is destroyed, wherein introducing defect in metal organic framework photochemical catalyst
Have many advantages, such as, such as: improving the catalytic capability of metal organic framework photochemical catalyst；Metal organic framework photochemical catalyst is improved to gas
Body adsorbance, it may be possible to since defect keeps the cluster of metal organic framework photochemical catalyst not re-closed, be conducive to molecule diffusion；It mentions
High charge transfer ability or Photocatalyzed Hydrogen Production ability；Extended fluorescence lifetime and the property of semiconductor assign its efficient degradation dyestuff
Ability.Therefore, the deficiency metal organic framework photochemical catalyst that strategy preparation is adjusted by acid, with high specific surface area and
Even meso-hole structure, coarse surface, wide light absorption range, narrow forbidden bandwidth can effectively inhibit light induced electron and hole
It is compound, and there are the excellent opticals such as high photoelectric current and small impedance, while there is high photocatalytic activity, Neng Gouyou
Imitate degradable organic pollutant.
Compared with the prior art, the advantages of the present invention are as follows:
(1) deficiency metal organic framework photochemical catalyst photocatalysis degradation organic contaminant is utilized the present invention provides a kind of
Method, by using deficiency metal organic framework photochemical catalyst to organic pollutant carry out photocatalytic degradation, can be realized
Organic pollutant is effectively removed, have simple process, it is easy to operate, low in cost, easily recycle and reuse, treatment effeciency
High, the advantages that degradation rate is high, it can be realized effective fast degradation to organic pollutant, it is useless at organic pollutant (such as tetracycline)
It is had a good application prospect in the actual treatment of water.
(2) in the method for the present invention, deficiency metal organic framework photochemical catalyst used is with Iron(III) chloride hexahydrate and right
Phthalic acid is raw material, and n,N-Dimethylformamide is solvent, is prepared under the action of acid regulator by solvent thermal reaction
It arrives, there is thus obtained deficiency MIL-53 metal organic framework photochemical catalyst even mesoporous structure, specific surface area height, light to inhale
It receives that range is wide, the advantages that forbidden bandwidth is small, photoelectric current is big, impedance is small, photocatalytic activity is high, is that a kind of appearance structure is novel, light
The excellent novel visible catalyst of catalytic performance, there is good use value and application prospect.
(3) in the method for the present invention, in deficiency metal organic framework photochemical catalyst used, in terms of crystal structure, pass through
Introduce defect, the specific surface area of deficiency metal organic framework photochemical catalyst is from 10.201cm2/ g is increased to 130.958cm2/g；
In terms of pore structure, the pore structure of perfect type MIL-53 metal organic framework photochemical catalyst (MIL-53) is microcellular structure, defect
The pore structure of type metal organic framework photochemical catalyst is meso-hole structure；In terms of optical property, perfect type MIL-53 metal is organic
The resistance of skeleton photochemical catalyst (MIL-53) is 1.0 × 105Ohm, the resistance of deficiency metal organic framework photochemical catalyst are 0.5
×105ohm.The photo-current intensity of this perfect type MIL-53 metal organic framework photochemical catalyst (MIL-53) is 0.05 μ A/cm2, lack
The photoelectric current of swaged metal organic framework photochemical catalyst is increased to 0.20 μ A/cm2, 4 times of photoelectric current raising.It is contaminated in photocatalytic degradation
Material aspect, the photocatalytic activity of perfect type MIL-53 metal organic framework photochemical catalyst (MIL-53) are 59%, deficiency gold
The photocatalytic activity for belonging to organic backbone photochemical catalyst is 90%, and the photocatalytic activity compared to MIL-53 improves 1.5 times
Left and right.As it can be seen that deficiency metal organic framework photocatalysis of the present invention have excellent photocatalytic activity, unique crystal structure,
Excellent optical property, and excellent photocatalytic activity may be related with its unique crystal structure and excellent optical property.
(4) in the method for the present invention, strategy is adjusted to prepare deficiency metal organic framework photochemical catalyst using acid for the first time, i.e., with six
Iron chloride hexahydrate and terephthalic acid (TPA) are raw material, and pattern knot is prepared by solvent thermal reaction under the action of acid regulator
The deficiency metal organic framework photochemical catalyst that structure is novel, photocatalysis performance is excellent.Especially in terms of degradable organic pollutant,
Can by the photocatalytic activity of MIL-53 improve 1.5 times, deficiency metal organic framework photochemical catalyst to organic pollutant
Photocatalysis efficiency is 90%.
Detailed description of the invention
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical scheme in the embodiment of the invention is clearly and completely described.
Fig. 1 is deficiency metal organic framework photochemical catalyst (D-1, D-4) obtained in the embodiment of the present invention 1 and perfect type
The photoelectricity flow graph of MIL-53 metal organic framework photochemical catalyst (MIL-53).
Fig. 2 is deficiency metal organic framework photochemical catalyst (D-1, D-4) obtained in the embodiment of the present invention 1 and perfect type
The impedance diagram of MIL-53 metal organic framework photochemical catalyst (MIL-53).
Fig. 3 is deficiency metal organic framework photochemical catalyst (D-1, D-4) obtained in the embodiment of the present invention 1 and perfect type
The uv drs figure of MIL-53 metal organic framework photochemical catalyst (MIL-53).
Fig. 4 is deficiency metal organic framework photochemical catalyst (D-1, D-4) obtained in the embodiment of the present invention 1 and perfect type
The band structure figure of MIL-53 metal organic framework photochemical catalyst (MIL-53).
Fig. 5 is deficiency metal organic framework photochemical catalyst (D-1, D-2, D-3, D-4, D-5, D- in the embodiment of the present invention 1
10) and perfect type MIL-53 metal organic framework photochemical catalyst (MIL-53) under the visible light conditions of wavelength X > 420nm to four
The photocatalytic degradation effect figure of ring element.
Fig. 6 be the embodiment of the present invention 2 in deficiency metal organic framework photochemical catalyst (D-1) in wavelength X > 420nm can
To the photocatalytic degradation effect figure of various concentration tetracycline under the conditions of light-exposed.
Fig. 7 be the embodiment of the present invention 3 in deficiency metal organic framework photochemical catalyst (D-1) in wavelength X > 420nm can
The circulation degradation effect figure of photocatalytic degradation tetracycline under the conditions of light-exposed.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
In following present invention embodiment, unless otherwise noted, used material and instrument are commercially available, used technique
For common process, used equipment is conventional equipment, and the data obtained is the average value for repeating experiment more than three times.
Embodiment 1:
A method of it is specially sharp using deficiency metal organic framework photochemical catalyst photocatalysis degradation organic contaminant
Photocatalytic degradation, including following step are carried out to the tetracycline in water body with deficiency MIL-53 metal organic framework photochemical catalyst
It is rapid:
Take deficiency metal organic framework photochemical catalyst (D-1, D-2, D-3, D-4, D-5, D-10) and perfect type MIL-53
Metal organic framework photochemical catalyst (MIL-53), each 50mg are added separately to 100mL, the tetracycline that concentration is 20mg/L
In, ultrasound uniformly, reacts 60min (magnetic agitation) under conditions of unglazed, after reaching adsorption-desorption balance, in wavelength X >
Under the visible light conditions of 420nm, illumination 150min carries out photocatalytic degradation reaction, completes the photocatalysis to tetracycline in water body
Degradation.
In the present embodiment, deficiency metal organic framework photochemical catalyst (D-1, D-2, D-3, D-4, D-5, D-10) used,
Specially deficiency MIL-53 metal organic framework photochemical catalyst, be using Iron(III) chloride hexahydrate and terephthalic acid (TPA) as raw material,
N,N-Dimethylformamide is solvent, is prepared under the action of acid regulator by solvent thermal reaction, comprising the following steps:
It (1) is 1: 1: 280 according to the molar ratio of Iron(III) chloride hexahydrate, terephthalic acid (TPA) and n,N-Dimethylformamide,
Iron(III) chloride hexahydrate, terephthalic acid (TPA) are dissolved in n,N-Dimethylformamide, are uniformly mixed, it is molten to form glassy yellow clarification
Liquid, as mixed solution A.
(2) by the 1mol/L HCl solution of 10 μ L, 20 μ L, 30 μ L, 40 μ L, 50 μ L, 100 μ L, it is added separately to 56mL step
Suddenly it in the mixed solution A that (1) obtains, is uniformly mixed, obtains mixed solution B.
(3) the mixed solution B for obtaining step (2) carries out solvent thermal reaction at being 170 DEG C in temperature as in reaction kettle
24, gained crystal is respectively washed three times using DMF and methanol, filtering, and dry 12h, obtains orange-yellow crystal, as at 60 DEG C
Deficiency metal organic framework photochemical catalyst.Wherein the dosage of HCl solution be respectively 10 μ L, 20 μ L, 30 μ L, 40 μ L, 50 μ L,
The corresponding deficiency metal organic framework photochemical catalyst of 100 μ L is named as D-1, D-2, D-3, D-4, D-5, D-10.
In the present embodiment, the preparation method of perfect type MIL-53 metal organic framework photochemical catalyst used, including following step
It is rapid:
It (a) is 1: 1: 280 according to the molar ratio of Iron(III) chloride hexahydrate, terephthalic acid (TPA) and n,N-Dimethylformamide,
Iron(III) chloride hexahydrate, terephthalic acid (TPA) are dissolved in n,N-Dimethylformamide, are uniformly mixed, it is molten to form glassy yellow clarification
Liquid, as mixed solution A.
(b) mixed solution A for obtaining step (a) is placed in reaction kettle, carries out solvent thermal reaction at being 170 DEG C in temperature
24, gained crystal is respectively washed three times using DMF and methanol, filtering, and dry 12h, obtains orange-yellow crystal, as at 60 DEG C
Perfect type metal organic framework photochemical catalyst, is named as MIL-53.
Fig. 1 is deficiency metal organic framework photochemical catalyst (D-1, D-4) obtained in the embodiment of the present invention 1 and perfect type
The photoelectricity flow graph of MIL-53 metal organic framework photochemical catalyst (MIL-53).As shown in Figure 1, the organic bone of perfect type MIL-53 metal
The photo-current intensity of frame photochemical catalyst (MIL-53) is 0.05 μ A/cm2, deficiency metal organic framework photochemical catalyst (D-1)
Photoelectric current is 0.18 μ A/cm2, it is seen then that the photoelectric current of deficiency metal organic framework photochemical catalyst (D-1) significantly increases, may
It is since defect can effectively inhibit light induced electron and hole-recombination.However, compared to perfect type MIL-53 metal organic framework
The photoelectric current of photochemical catalyst (MIL-53), deficiency metal organic framework photochemical catalyst (D-4) reduces, it may be possible to due to excess acid
Crystal structure is affected, crystal face is caused to change, influences light induced electron and hole separation, and then influence photo-current intensity.
Fig. 2 is deficiency metal organic framework photochemical catalyst (D-1, D-4) obtained in the embodiment of the present invention 1 and perfect type
The impedance diagram of MIL-53 metal organic framework photochemical catalyst (MIL-53).As shown in Figure 2, deficiency metal organic framework photocatalysis
The impedance of agent (D-1, D-4) is uniformly distributed, and in the two sides of perfect type MIL-53 metal organic framework photochemical catalyst (MIL-53), is said
The impedance of bright deficiency metal organic framework photochemical catalyst (D-1) is less than perfect type MIL-53 metal organic framework photochemical catalyst
(MIL-53), and the impedance of deficiency metal organic framework photochemical catalyst (D-4) be greater than perfect type MIL-53 metal organic framework
Photochemical catalyst (MIL-53), it may be possible to which the defect as caused by low amounts (10 μ L) hydrochloric acid blender (acid regulator) is conducive to electronics
With the separation and transmitting in hole, and a large amount (40 μ L) hydrochloric acid blender (acid regulator) may influence crystal structure, be unfavorable for electricity
The separation of son and hole.
Fig. 3 is deficiency metal organic framework photochemical catalyst (D-1, D-4) obtained in the embodiment of the present invention 1 and perfect type
The uv drs figure of MIL-53 metal organic framework photochemical catalyst (MIL-53).From the figure 3, it may be seen that perfect type MIL-53 metal has
There is absorption peak in 445nm in machine skeleton photochemical catalyst (MIL-53), shows that it has absorption to visible light, is a kind of potential half
Conductor material.Also there is absorption peak, and deficiency gold in 445nm in deficiency metal organic framework photochemical catalyst (D-1, D-4)
The absorption peak for belonging to organic backbone photochemical catalyst (D-1) is better than perfect type MIL-53 metal organic framework photochemical catalyst (MIL-53),
And the weak perfect type MIL-53 metal organic framework photochemical catalyst of absorption peak of deficiency metal organic framework photochemical catalyst (D-4)
(MIL-53), it may be possible to the different crystal structure as caused by different sour dosages, it may be related with photocatalytic activity.
Fig. 4 is deficiency metal organic framework photochemical catalyst (D-1, D-4) obtained in the embodiment of the present invention 1 and perfect type
The band structure figure of MIL-53 metal organic framework photochemical catalyst (MIL-53).As shown in Figure 4, perfect type MIL-53 metal is organic
The position valence band VB of skeleton photochemical catalyst (MIL-53) is in 2.10eV, deficiency metal organic framework photochemical catalyst (D-1, D-4)
The position valence band VB faint variation has occurred, move to 2.00eV, be less than E (OH-/ OH) 2.16eV, it is not possible to and OH-Reaction
Generate OH.The position conduction band CB of perfect type MIL-53 metal organic framework photochemical catalyst (MIL-53) is less than E in -0.56eV
(O2/·O2 -) -0.33eV, can and O2Reaction generates O2 -, O2 -Participate in the photocatalytic degradation reaction of tetracycline.Deficiency gold
Faint variation has occurred in the position conduction band CB for belonging to organic backbone photochemical catalyst (D-1, D-4), moves to -0.58eV respectively, -
0.68eV is less than E (O2/·O2 -) -0.33eV, can and O2Reaction generates O2 -, O2 -Participate in the photocatalytic degradation of tetracycline
Reaction.As it can be seen that different band structures may be related from different hydrochloric acid dosages.
In the present embodiment, every 30min samples 3mL, and the spy of tetracycline in solution is measured using ultraviolet-visible spectrophotometer
Peak value is levied, concentration is scaled, calculates degradation rate
Fig. 5 is deficiency metal organic framework photochemical catalyst (D-1, D-2, D-3, D-4, D-5, D- in the embodiment of the present invention 1
10) and perfect type MIL-53 metal organic framework photochemical catalyst (MIL-53) under the visible light conditions of wavelength X > 420nm to four
The photocatalytic degradation effect figure of ring element.As shown in figure 5, the drop of D-1, D-2, D-3, MIL-53, D-4, D-5, D-10 to tetracycline
Solution rate is respectively 90.17%, 79.8%, 69%, 59%, 52%, 42.7% and 39%.Cloudy, turbid phase, different materials are to four
Ring is known as adsorption effect, this is because different materials are porous structure, is conducive to adsorb.Perfect type MIL-53 metal organic framework
The photocatalysis efficiency of photochemical catalyst (MIL-53) is 59%, shows that MIL-53 is kind of a photocatalysis for potential degrading organic dye waste water
Agent.The deficiency metal organic framework photochemical catalyst (D-1, D-2, D-3) that acid is adjusted is 90.17% to the degradation rate of tetracycline,
79.8% and 69%, the photocatalytic activity of MIL-53 can be improved, it is living to illustrate that acid adjusts strategy to improve metal organic framework photocatalysis
Property is feasible.But deficiency metal organic framework photochemical catalyst (D-4, D-5, D-10) distinguishes the degradation rate of tetracycline
It is 52%, 42.7% and 39%, is lower than MIL-53, illustrates that excessive acid will affect crystal structure, reduce photocatalytic activity.Therefore,
It is adjusted in strategy in acid, sour amount has important influence to photocatalytic activity, needs to select suitable sour dosage.
Embodiment 2:
A method of it is specially sharp using deficiency metal organic framework photochemical catalyst photocatalysis degradation organic contaminant
Photocatalytic degradation is carried out with tetracycline water body of the deficiency MIL-53 metal organic framework photochemical catalyst to various concentration, including with
Lower step:
Deficiency metal organic framework photochemical catalyst (D-1) obtained, every part of 50mg in 4 parts of embodiments 1 is taken to be separately added into
It is in the tetracycline (volume 100mL) of 10mg/L, 20mg/L, 30mg/L, 40mg/L to concentration, ultrasound is uniform, in nothing
60min (magnetic agitation) is reacted under conditions of light, after reaching adsorption-desorption balance, in the visible light conditions of wavelength X > 420nm
Under, illumination 150min carries out photocatalytic degradation reaction, completes the photocatalytic degradation to tetracycline in water body.
Every 30min samples 3mL, and the characteristic peaks of tetracycline in solution are measured using ultraviolet-visible spectrophotometer, converts
For concentration, degradation rate is calculated.
Fig. 6 be the embodiment of the present invention 2 in deficiency metal organic framework photochemical catalyst (D-1) in wavelength X > 420nm can
To the photocatalytic degradation effect figure of various concentration tetracycline under the conditions of light-exposed.As shown in fig. 6, deficiency metal organic framework light is urged
Agent (D-1) is respectively to the degradation rate of tetracycline that initial concentration is 10mg/L, 20mg/L, 30mg/L, 40mg/L
96.93%, 90.17%, 84.51%, 79.0%, this raising of explanation with tetracycline concentration, deficiency metal organic framework
The photocatalysis effect of photochemical catalyst (D-1) reduces；Meanwhile also description defect type metal organic framework photochemical catalyst (D-1) can be with
Handle the tetracycline of higher concentration.
Embodiment 3:
A method of it is specially sharp using deficiency metal organic framework photochemical catalyst photocatalysis degradation organic contaminant
Degradation tetracycline is recycled with deficiency MIL-53 metal organic framework photochemical catalyst, comprising the following steps:
(1) take deficiency metal organic framework photochemical catalyst (D-1) obtained in 50mg embodiment 1, be added to 100mL,
Concentration is in the tetracycline of 20mg/L, and ultrasound uniformly, reacts 60min (magnetic agitation) under conditions of unglazed, reaches suction
After attached desorption balance, under the visible light conditions of wavelength X > 420nm, illumination 150min carries out photocatalytic degradation reaction, completes
To the photocatalytic degradation of tetracycline in water body.
(2) photocatalytic degradation of step (1) after the reaction was completed, collects remaining sample, dries, to four under same experimental conditions
Ring element water body carries out photocatalytic degradation, recycles 4 times altogether.
Every 30min samples 3mL, and the characteristic peaks of tetracycline in solution are measured using ultraviolet-visible spectrophotometer, converts
For concentration, the degradation rate of different circulations is calculated.
Fig. 7 be the embodiment of the present invention 3 in deficiency metal organic framework photochemical catalyst (D-1) in wavelength X > 420nm can
The circulation degradation effect figure of photocatalytic degradation tetracycline under the conditions of light-exposed.As shown in fig. 7, drop of four circulation degradations to tetracycline
Solution rate is respectively 90.17%, 88.64%, 84.42% and 75.24%, description defect type metal organic framework photochemical catalyst (D-
1) there is good reusable property, can be used in practical water body.
In summary, deficiency metal organic framework photochemical catalyst of the present invention has good crystal structure, high ratio table
Area, uniform meso-hole structure, while having response to visible light, preferable photo-generated carrier separation and transport efficiency, bloom are urged
Change active photochemical catalyst, can degradable organic pollutant rapidly and efficiently, meet practical application request, there is good use
Value and application prospect.
Above embodiments are only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned reality
Apply example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that being led for this technology
For the those of ordinary skill in domain, improvements and modifications without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of method using deficiency metal organic framework photochemical catalyst photocatalysis degradation organic contaminant, feature exist
In the method is to carry out photocatalytic degradation to organic pollutant using deficiency metal organic framework photochemical catalyst；It is described to lack
Swaged metal organic framework photochemical catalyst is the n,N-Dimethylformamide using Iron(III) chloride hexahydrate and terephthalic acid (TPA) as raw material
For solvent, it is prepared under the action of acid regulator by solvent thermal reaction；The deficiency metal organic framework photocatalysis
Agent is deficiency MIL-53 metal organic framework photochemical catalyst.
2. the method according to claim 1, wherein the preparation of the deficiency metal organic framework photochemical catalyst
Method, comprising the following steps:
(1) Iron(III) chloride hexahydrate, terephthalic acid (TPA) are dissolved in n,N-Dimethylformamide, obtain mixed solution A；
(2) acid regulator is added toward the mixed solution A that step (1) obtains, obtains mixed solution B；
(3) the mixed solution B for obtaining step (2) carries out solvent thermal reaction, cleans, and filters, and dry, obtaining deficiency metal has
Machine skeleton photochemical catalyst.
It is the Iron(III) chloride hexahydrate, right 3. according to the method described in claim 2, it is characterized in that, in the step (1)
The molar ratio of phthalic acid and N,N-dimethylformamide is 1: 1: 280.
4. according to the method described in claim 2, it is characterized in that, the mixed solution A and acid are adjusted in the step (2)
The ratio of agent is L~56mL: 100 μ L of 56mL: 10 μ；The acid regulator is HCl solution；The concentration of the HCl solution is
1mol/L~5mol/L.
5. according to the method described in claim 4, it is characterized in that, the mixed solution A and acid are adjusted in the step (2)
The ratio of agent is L~56mL: 30 μ L of 56mL: 10 μ.
6. according to the method described in claim 2, it is characterized in that, in the step (3), the temperature of the solvent thermal reaction is
150 DEG C~170 DEG C；The time of the solvent thermal reaction is 15h~for 24 hours.
7. method described according to claim 1~any one of 6, which is characterized in that the method is using deficiency metal
Organic backbone photochemical catalyst carries out photocatalytic degradation to the organic pollutant in water body, comprising the following steps: by deficiency metal
Organic backbone photochemical catalyst and organic pollutant water mixing carry out dark reaction, carry out photocatalysis drop after reaching adsorption-desorption balance
Solution reaction, completes the photocatalytic degradation to Organic Pollutants In Water.
8. the method according to the description of claim 7 is characterized in that the addition of the deficiency metal organic framework photochemical catalyst
Amount is addition 0.3g~0.5g in every liter of organic pollutant water body.
9. according to the method described in claim 8, it is characterized in that, the organic pollutant water body is antibiotic waste water；It is described
Antibiotic in antibiotic waste water is tetracycline；The concentration of the organic pollutant Organic Pollutants In Water be 10mg/L~
40mg/L。
10. method according to claim 8 or claim 9, which is characterized in that the dark reaction is to be stirred under dark condition
It mixes；The time of the dark reaction is 30min~60min；Visible light conditions of the photocatalytic degradation reaction in wavelength X > 420
Lower progress；The time of the photocatalytic degradation reaction is 120min~150min.
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