CN107501565A - Rare earth metal organic framework materials Ho MOF and its preparation method and application - Google Patents
Rare earth metal organic framework materials Ho MOF and its preparation method and application Download PDFInfo
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- CN107501565A CN107501565A CN201710666255.5A CN201710666255A CN107501565A CN 107501565 A CN107501565 A CN 107501565A CN 201710666255 A CN201710666255 A CN 201710666255A CN 107501565 A CN107501565 A CN 107501565A
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- earth metal
- mof
- organic framework
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 128
- 239000000463 material Substances 0.000 title claims abstract description 92
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 76
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000013110 organic ligand Substances 0.000 claims abstract description 24
- 150000000922 Holmium Chemical class 0.000 claims abstract description 16
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 27
- 239000013384 organic framework Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000010919 dye waste Substances 0.000 claims description 10
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical group [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 claims description 9
- 230000000593 degrading effect Effects 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 3
- JTZUUBNBNBFJCX-UHFFFAOYSA-N holmium sulfuric acid Chemical compound [Ho].S(O)(O)(=O)=O JTZUUBNBNBFJCX-UHFFFAOYSA-N 0.000 claims description 3
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000975 dye Substances 0.000 abstract description 13
- 239000002351 wastewater Substances 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 230000003287 optical effect Effects 0.000 abstract description 5
- 230000004044 response Effects 0.000 abstract description 3
- 230000003595 spectral effect Effects 0.000 abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract description 2
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 18
- 229960000907 methylthioninium chloride Drugs 0.000 description 18
- 239000013078 crystal Substances 0.000 description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000356 contaminant Substances 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 150000001261 hydroxy acids Chemical group 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000012917 MOF crystal Substances 0.000 description 2
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical group [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229920001795 coordination polymer Polymers 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical group O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 2
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method 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
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000005837 radical ions Chemical class 0.000 description 1
- -1 rare earth ion Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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]
-
- B01J35/39—
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- 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
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
-
- 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 present invention relates to metal-organic framework material technical field, and in particular to a kind of rare earth metal organic framework materials Ho MOF and its preparation method and application.Rare earth metal organic framework materials Ho MOF provided by the invention, molecular formula are [Ho (H2‑DHBDC)0.5(DHBDC)0.5(H2O)2](H2O)n, its preparation method includes：The dihydric para-phthalic acid of organic ligand 2,5 is added to the water, regulation pH is 6.1 6.5, then adds water-soluble holmium salt and dimethylformamide, carries out hydro-thermal reaction, obtains rare earth metal organic framework materials Ho MOF.Rare earth metal organic framework materials Ho MOF provided by the invention have less optical energy gap and wider spectral response ability, can be as waste water of the degraded of catalysis material rapidly and efficiently containing organic dyestuff.
Description
Technical field
The present invention relates to metal-organic framework material technical field, and in particular to a kind of rare earth metal-organic framework materials
Ho-MOF and its preparation method and application.
Background technology
Dyeing is industrial wastewater discharge rich and influential family, and caused waste water from dyestuff has complicated component, content of organics height, color
Spend height, strong toxicity, change of water quality is big, basicity is big and the features such as difficult for biological degradation, water body can be caused seriously to pollute, be currently most
One of main pollution source of water body.Therefore, the comprehensive regulation of dyeing waste water turns into a problem in the urgent need to address.
At present, domestic treatment of dyeing wastewater means are mainly based on physico-chemical process and biochemical process, but these methods are all present
The problems such as operating cost is high, secondary pollution is heavy, adsorption capacity is low, regeneration is difficult, non-selectivity.And photocatalysis treatment dyeing waste water
It is considered as a kind of brand-new green technique, there is the advantages of environment-friendly, reaction condition is gentle.
Metal-organic framework materials (Metal-Organic Framworks, MOFs) are by inorganic metal center (metal
Ion or metal cluster) it is connected with each other with the organic ligand of bridging by self assembly, one kind of formation has periodic network structure
Crystalline state porous material, generally by transition metal ions and oxygen-containing, nitrogen etc. multiple tooth organic ligand (it is most of be fragrant polyacid and
Polybase), the coordination polymer for the microporous network structure being self-assembly of.Metal-organic framework material not only has varied
Topological structure, but also many-sided if gas absorption separation, catalysis, photoelectricity and magnetic material, sensor etc. are with tempting
Application potential, just developing rapidly as the study hotspot in many fields.
On the one hand, MOFs due to it is various receive, the regular pore passage structure of the matrix type of minute yardstick, the specific surface area of super large and
Porosity (up to 0.9) and small density of solid are traditional, make it have adsorption capacity is big, and selectivity is high, and regeneration recovery is easy etc.
Plurality of advantages, to the adsorbing separation of the dye discoloration material in aqueous phase, show good treatment effect.On the other hand, MOFs
Can also be by the way that charge transfer transition between various types of ligand metal occurs, as can be used with adjustable photochemical catalyst
Dyestuff macromolecular in degradation water.Therefore, novel metal-organic framework materials are constructed, and carry out the photocatalysis of waste water from dyestuff
The research of performance, there is important real value and tempting application prospect.
In view of this, the present invention is proposed.
The content of the invention
It is an object of the invention to provide a kind of rare earth metal-organic framework materials Ho-MOF, the rare earth metal-have machine frame
Frame material Ho-MOF has less optical energy gap and wider spectral response ability, can be used as catalysis material rapidly and efficiently
Waste water of the degraded containing organic dyestuff, there is good degrading effect, reaction condition temperature, it is environment-friendly the advantages of.
, should another object of the present invention is to provide a kind of rare earth metal-organic framework materials Ho-MOF preparation method
Preparation method technique is simple, and production cost is low, has good market application foreground.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of rare earth metal-organic framework materials Ho-MOF, the molecular formula of the rare earth metal-organic framework materials are
[Ho(H2-DHBDC)0.5(DHBDC)0.5(H2O)2](H2O)n；
Wherein, H2- DHBDC and DHBDC is respectively the 2,5- dihydroxy terephthaldehydes for losing two protons and four protons
Acid ion；N is the natural number more than or equal to 1.
Wherein, the "-" in " rare earth metal-organic framework materials " refers to that rare earth metal and organic ligand are made by being coordinated
With formation frame material.
Preferably, n is 1-50 natural number.
It is further preferred that n is 2-20 natural number.
A kind of above-mentioned rare earth metal-organic framework materials Ho-MOF preparation method, comprises the following steps：
Organic ligand 2,5-Dihydroxyterephthalic acid is added to the water, regulation pH is 6.1-6.5, is then added water-soluble
Holmium salt and dimethylformamide, hydro-thermal reaction is carried out, obtains rare earth metal-organic framework materials Ho-MOF.
Further, 5-8mL water is added in the 2,5-Dihydroxyterephthalic acid per mmol, is preferably 2 per mmol,
6-7mL water is added in 5- dihydric para-phthalic acids, more preferably in the 2,5-Dihydroxyterephthalic acid per mmol
Add 6.5mL water.
Further, pH is adjusted with strong alkali solution, pH is preferably adjusted using sodium hydrate aqueous solution.
Further, the water-soluble holmium salt is holmium nitrate, sulfuric acid holmium or holmium chloride, preferably holmium nitrate.
Further, the ratio between water-soluble holmium salt and amount of material with organic ligand 2,5-Dihydroxyterephthalic acid are
(2-4)：1, preferably 3:1.
Further, the ratio between volume of dimethylformamide and water is 1：(0.8-1.2), preferably 1:1.
Further, the temperature of hydro-thermal reaction is 100-120 DEG C, preferably 105-115 DEG C, more preferably 110 DEG C.
Further, the time of hydro-thermal reaction is 20-30 hours, preferably 22-28 hours, and more preferably 24 is small
When.
Further, after the completion of the preparation method also includes hydro-thermal reaction, room temperature is cooled to, washing, filters and dries.
Further, the drying uses vacuum drying, and drying temperature is 50-80 DEG C, preferably 60-70 DEG C, further
Preferably 65 DEG C.
Further, drying time is 20-36 hours, preferably 22-30 hours, more preferably 24 hours.
Above-mentioned rare earth metal-applications of the organic framework materials Ho-MOF in degrading organic dye waste water.
Compared with prior art, the beneficial effects of the present invention are：
1. rare earth provided by the invention-metal-organic framework material Ho-MOF has less optical energy gap and wider light
Responding ability is composed, can be as waste water of the degraded of catalysis material rapidly and efficiently containing organic dyestuff.
2. above-mentioned rare earth metal-organic framework materials Ho-MOF provided by the invention preparation method, the preparation method work
Skill is simple, and reaction condition is gentle, environmentally friendly, and production cost is low, has good market application foreground.
Brief description of the drawings
, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical scheme of the prior art
The required accompanying drawing used is briefly described in embodiment or description of the prior art, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is rare earth metal-organic framework materials Ho-MOF coordination context diagram；
Fig. 2 is rare earth metal-organic framework materials Ho-MOF three-dimensional frame structure schematic diagram；
Fig. 3 is rare earth metal-organic framework materials Ho-MOF X-ray powder diffraction figure；
Fig. 4 is rare earth metal-organic framework materials Ho-MOF UV-vis DRS spectrogram, wherein, (a) rare earth gold
Category-organic framework materials Ho-MOF UV-vis spectrograms；(b) rare earth metal-organic framework materials Ho-MOF Kubelka-
Munk changes the spectrogram that diffuses；
Fig. 5 is the UV-visible spectrum of degraded target contaminant methylene blue solution in embodiment 1；
Fig. 6 is that the pseudo-first-order dynamics of light-catalyzed reaction in embodiment 1 is fitted spectrogram；
Fig. 7 is the UV-visible spectrum of comparative example degraded target contaminant methylene blue.
Embodiment
Technical scheme is clearly and completely described below in conjunction with embodiment and accompanying drawing, it is clear that retouched
The embodiment stated is part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, this area
The every other embodiment that those of ordinary skill is obtained under the premise of creative work is not made, belongs to protection of the present invention
Scope.
On the one hand, metal-organic framework material MOFs due to it is various receive, the regular pore passage structure of the matrix type of minute yardstick,
The specific surface area and porosity (up to 0.9) of super large and small density of solid tradition, it is big to make it have adsorption capacity, selectivity
Many advantages, such as easy, is reclaimed in height, regeneration, to the adsorbing separation of the dye discoloration material in aqueous phase, shows good processing effect
Fruit.On the other hand, MOFs can also be by occurring charge transfer transition between various types of ligand metal, as can band
The dyestuff macromolecular that adjustable photochemical catalyst is used in degradation water.
The invention provides a kind of rare earth metal-organic framework materials Ho-MOF, the rare earth metal-organic framework materials
Molecular formula be [Ho (H2-DHBDC)0.5(DHBDC)0.5(H2O)2](H2O)n；
Wherein, H4- DHBDC is 2,5- dihydric para-phthalic acids；H2- DHBDC and DHBDC is respectively to lose two protons
With 2,5- dihydric para-phthalic acid's radical ions of four protons；N is the natural number more than or equal to 1.
In a kind of optional embodiment of the present invention, n is 1-50 natural number.
In a kind of preferred embodiment of the present invention, n is 2-20 natural number.
As shown in figure 1, in the rare earth metal-organic framework materials Ho-MOF asymmetric cell, Ho matches somebody with somebody using eight
Bit pattern, with five carboxyl oxygen atoms from four organic ligands, (wherein O4, O4B, O5B use μ2:η1:η2Coordination mode；
O1, O2A use μ2:η1:η1Coordination mode) and a phenol oxygen atom (O6), and two hydrone (O7, O8) coordinations, to H2-
DHBDC parts, its two hydroxy-acid groups use identical coordination mode, and two oxygen atoms of each hydroxy-acid group are respectively with two
Individual metal ion forms coordination；And to DHBDC parts, the oxygen atom and a metallic ion coordination of each hydroxy-acid group,
A remaining oxygen atom chelates a metal ion with adjacent hydroxyl oxygen atom.
As shown in Fig. 2 two kinds of organic ligand connection Ho3+Ion forms one-dimensional rare earth chain, adjacent one-dimensional interchain along c-axis
Connected further through two kinds of organic ligands, form three-dimensional organic frame.
The rare earth metal-organic framework materials Ho-MOF belongs to monoclinic system, P21/ c space groups, cell parameter difference
For：α=90 °, β=103.067 (4) °, γ=
90°。
2,5-Dihydroxyterephthalic acid because it introduces miscellaneous function base hydroxyl in phthalic acid, can be formed monodentate,
Various coordination mode of bidentate, bridging and chelating, and then constitutionally stable complex is combined to form with rare earth ion, help
In coordination polymer of the synthesis with novelty structure and performance.
Present invention also offers a kind of above-mentioned rare earth metal-organic framework materials Ho-MOF preparation method, including it is as follows
Step：
Organic ligand 2,5-Dihydroxyterephthalic acid is added to the water, regulation pH is 6.1-6.5, is then added water-soluble
Holmium salt and dimethylformamide, hydro-thermal reaction is carried out, obtains rare earth metal-organic framework materials Ho-MOF.
The present invention is by organic ligand 2,5- dihydric para-phthalic acids and water-soluble holmium salt in specific pH and solvent two
In the presence of NMF, hydro-thermal reaction is carried out, rare earth metal-organic framework materials Ho-MOF can be obtained.
The pH of solution can influence the structure of growth from solution primitive, and the present invention selects specific pH value 6.1-6.5, makes to have
Machine part and water-soluble holmium salt can obtain rare earth metal-organic framework materials Ho-MOF of the present invention.The present invention adds diformazan
The purpose of base formamide is in order to increase the solubility property of system, crystal is easily grown, if using other solvents, it is difficult to grow
Crystal, simply powder.Meanwhile preparation method technique of the invention is simple, reaction condition is gentle, environmentally friendly, production cost
It is low, there is good market application foreground.
As the optional embodiment of the present invention, 5-8mL water is added in the 2,5-Dihydroxyterephthalic acid per mmol.
The volume that water is added in 2,5- dihydric para-phthalic acids per mmol is typical but non-limiting be：5mL、5.5mL、6mL、
6.5mL, 7mL, 7.5mL or 8mL.As the preferred embodiments of the invention, in the 2,5-Dihydroxyterephthalic acid per mmol
Add 6.5mL water.Add the amount of water number can influence the concentration of reactant, it is very few or excessive, all can cause crystal very
Small or even precipitation, or do not go out crystal.
As the optional embodiment of the present invention, pH is adjusted with strong alkali solution, preferably using sodium hydrate aqueous solution
Adjust pH.
As the optional embodiment of the present invention, the water-soluble holmium salt is holmium nitrate, sulfuric acid holmium or holmium chloride.It is used as this
The preferred embodiment of invention, the water-soluble holmium salt are holmium nitrate.
As the optional embodiment of the present invention, the water-soluble holmium salt and organic ligand 2,5-Dihydroxyterephthalic acid
The ratio between the amount of material be (2-4)：1.The water-soluble holmium salt and the material of organic ligand 2,5- dihydric para-phthalic acids
Typical but non-limiting the ratio between amount is 2:1、2.1:1、2.2:1、2.3:1、2.4:1、2.5:1、2.6:1、2.7:1、2.8:1、
2.9:1、3:1、3.1:1、3.2:1、3.3:1、3.4:1、3.5:1、3.6:1、3.7:1、3.8:1、3.9:1 or 4:1.It is used as this hair
The ratio between bright preferred embodiment, the water-soluble holmium salt and amount of material of organic ligand 2,5-Dihydroxyterephthalic acid are
3:1.The dosage of only water-soluble holmium salt and organic ligand within the specific limits, can just grow crystal, otherwise be clear liquid or powder
End.
As the optional embodiment of the present invention, the ratio between volume of dimethylformamide and water is 1：(0.8-1.2), the two
The ratio between volume is typical but non-limiting content is 1:0.8、1:0.9、1:1、1:1.1 or 1:1.2.As being preferable to carry out for the present invention
The ratio between volume of mode, dimethylformamide and water is 1:1.The dosage of dimethylformamide is very few to influence the molten of organic ligand
Xie Liang, cause to be not easily formed crystal.
As the optional embodiment of the present invention, the temperature of hydro-thermal reaction is 100-120 DEG C.The temperature typical case of hydro-thermal reaction
It is but non-limiting to be：100℃、101℃、102℃、103℃、104℃、105℃、106℃、107℃、108℃、109℃、110
DEG C, 111 DEG C, 112 DEG C, 113 DEG C, 114 DEG C, 115 DEG C, 116 DEG C, 117 DEG C, 118 DEG C, 119 DEG C or 120 DEG C.As the present invention's
Preferred embodiment, the temperature of hydro-thermal reaction is 110 DEG C.Under general condition, the speed of growth of crystal is with hydrothermal temperature
Rise, but reaction speed is too high causes crystal size uneven.Temperature from hydro-thermal reaction is 100-120 DEG C, can be caused
To the crystal of high yield, high quality.
As the optional embodiment of the present invention, the time of hydro-thermal reaction is 20-30 hours.The time typical case of hydro-thermal reaction
It is typical single it is non-limiting be 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, it is 28 small
When, 29 hours or 30 hours.As the preferred embodiment of the present invention, the time of hydro-thermal reaction is 24 hours.During hydro-thermal reaction
Between it is too short, crystal does not also form complete structure and yield is few；The hydro-thermal reaction time is long, and reaction efficiency is low, high energy consumption.
In a kind of optional embodiment of the present invention, hydrothermal synthesis reaction enters in the reactor of polytetrafluoroethyllining lining
OK.
Further, after the completion of the preparation method also includes hydro-thermal reaction, room temperature is cooled to, washing, filters and dries.
As the optional embodiment of the present invention, adopt and be washed with deionized 3-5 times.
As the optional embodiment of the present invention, the drying uses vacuum drying, and drying temperature is 50-80 DEG C.Drying
Temperature is typical but non-limiting to be：50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C.As being preferable to carry out for the present invention
Mode, drying temperature are 65 DEG C.The crystal structure that can make Ho-MOF from 50-80 DEG C of drying temperature is not damaged, and energy
Enough rapid draing.
As the optional embodiment of the present invention, drying time is 20-36 hours.Drying time is typical but non-limiting
For：20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, it is 30 small
When, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours or 36 hours.As the preferred embodiment of the present invention, when drying
Between be 24 hours.
Above-mentioned rare earth metal-applications of the organic framework materials Ho-MOF in degrading organic dye waste water.The present invention's
In optional embodiment, the organic dye waste water includes cationic dyes and heterocyclic dye.In being preferable to carry out for the present invention
In mode, the organic dye waste water is the cationic dyes using methylene blue as representative.Present invention methylene blue solution
Organic dye waste water is simulated, investigates the performance of rare earth metal-organic framework materials Ho-MOF degrading organic dye waste waters.
Embodiment 1
The rare earth metal of embodiment 1-organic framework materials Ho-MOF preparation method, comprises the following steps：
(a) 0.198g organic ligand 2,5-Dihydroxyterephthalic acids are weighed, and are added in 6.5mL deionized waters, are stirred
Uniformly, 0.1mol/L sodium hydrate aqueous solution is added dropwise under agitation, and is with acidometer monitoring system pH value
6.4, stir, obtain light green mixed solution；
(b) 0.951g holmium nitrate solids are weighed, is added in the mixed liquor of step (a), adds dimethylformamide
6.5mL, it is uniformly mixed, is then transferred in reactor and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 105 DEG C, reaction
Time is 24 hours；
(c) after the completion for the treatment of hydro-thermal reaction, room temperature is cooled to, is washed with deionized and obtains orange red post after filtering 4 times
Shape crystal, then vacuum drying 24 hours at 65 DEG C, produce rare earth metal-organic framework materials Ho-MOF.
Embodiment 2
The rare earth metal of embodiment 2-organic framework materials Ho-MOF preparation method, comprises the following steps：
(a) 0.198g organic ligand 2,5-Dihydroxyterephthalic acids are weighed, and are added in 6mL deionized waters, stirring is equal
It is even, 0.1mol/L sodium hydrate aqueous solution is added dropwise under agitation, and be 6.2 with acidometer monitoring system pH value,
Stir, obtain light green mixed solution；
(b) 0.634g holmium nitrate solids are weighed, is added in the mixed liquor of step (a), adds dimethylformamide
5mL, it is uniformly mixed, is then transferred in reactor and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 100 DEG C, during reaction
Between be 30 hours；
(c) after the completion for the treatment of hydro-thermal reaction, room temperature is cooled to, is cooled to room temperature, is washed with deionized and is obtained after filter 23 time
To orange red column crystal, then vacuum drying 36 hours at 50 DEG C, produce rare earth metal-organic framework materials Ho-MOF.
Embodiment 3
The rare earth metal of embodiment 3-organic framework materials Ho-MOF preparation method, comprises the following steps：
(a) 0.198g organic ligand 2,5-Dihydroxyterephthalic acids are weighed, and are added in 4mL deionized waters, stirring is equal
It is even, 0.1mol/L sodium hydrate aqueous solution is added dropwise under agitation, and be 6.4 with acidometer monitoring system pH value,
Stir, obtain light green mixed solution；
(b) 1.2g holmium nitrate solids are weighed, are added in the mixed liquor of step (a), add dimethylformamide 5mL,
It is uniformly mixed, is then transferred in reactor and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 110 DEG C, and the reaction time is
20 hours；
(c) after the completion for the treatment of hydro-thermal reaction, room temperature is cooled to, is washed with deionized and obtains orange red post after filtering 5 times
Shape crystal, then vacuum drying 20 hours at 80 DEG C, produce rare earth metal-organic framework materials Ho-MOF.
1 rare earth metal of test example-organic framework materials Ho-MOF crystal structure determination
The rare earth metal provided using Bruker Smart ApexII X-rays single crystal diffractometer measure embodiment 1-have
Machine frame frame material Ho-MOF crystal structure.Using the molybdenum target Mo-K alpha rays of graphite monochromator monochromatization as radiation source, in temperature
Under 296K, point diffraction is collected using ω -2 θ scan modes.Crystal structure is solved using SHELXTL-97 program bag direct methods.First
All non-oxygen atomic coordinates, and hydrogen atom position is obtained with theoretical hydrogenation method are determined with difference function method and least square method, so
Crystal structure is modified with least square method afterwards.
Fig. 1 is rare earth metal-organic framework materials Ho-MOF coordination context diagram.Fig. 2 is rare earth metal-organic frame material
Expect Ho-MOF three-dimensional crystalline structure schematic diagram.
As shown in figure 1, in the rare earth metal-organic framework materials Ho-MOF asymmetric cell, Ho matches somebody with somebody using eight
Bit pattern, with five carboxyl oxygen atoms from four organic ligands, (wherein O4, O4B, O5B use μ2:η1:η2Coordination mode；
O1, O2A use μ2:η1:η1Coordination mode) and a phenol oxygen atom (O6), and two hydrone (O7, O8) coordinations, to H2-
DHBDC parts, its two hydroxy-acid groups use identical coordination mode, and two oxygen atoms of each hydroxy-acid group are respectively with two
Individual metal ion forms coordination；And to DHBDC parts, the oxygen atom and a metallic ion coordination of each hydroxy-acid group,
A remaining oxygen atom chelates a metal ion with adjacent hydroxyl oxygen atom.
As shown in Fig. 2 two kinds of organic ligand connection Ho3+Ion forms one-dimensional rare earth chain, adjacent one-dimensional interchain along c-axis
Connected further through two kinds of organic ligands, form three-dimensional organic frame.
The rare earth metal-organic framework materials Ho-MOF belongs to monoclinic system, P21/ c space groups, cell parameter difference
For：α=90 °, β=103.067 (4) °, γ=
90°。
Test example 2Ho-MOF X-ray powder diffraction figure measure
Using Powder X-ray Diffractometer (Powder X-Ray Diffraction, PXRD, INSTRUMENT MODEL：Rigaku
DMAX- III A, Cu K α radiation) measure embodiment 1 provide rare earth metal-organic framework materials Ho-MOF thing phase.Rare earth gold
Category-organic framework materials Ho-MOF X-ray powder diffraction figure is shown in Fig. 3.
From figure 3, it can be seen that the diffraction maximum in X-ray powder diffraction experiment spectrogram and analogue spectrums is coincide substantially, do not have
Have and observe obvious miscellaneous peak, show that the phase purity of complex is very high, material structure is [Ho (H2-DHBDC)0.5(DHBDC)0.5
(H2O)2](H2O)n。
Test example 3Ho-MOF UV-vis DRS spectrogram measure
Using 650 ultraviolet-visibles of Lambda-near infrared spectrometer, integrating sphere diameter 90cm, embodiment 1 is measured
The rare earth metal of offer-diffusing reflection data of the organic framework materials Ho-MOF samples in the range of 200-800nm.Using BaSO4
For reference (reflectivity 100%).
And Kubelka-Munk functions corresponding to incident wavelength can be calculated by UV-vis reflected spectrum datas, will
Kubelka-Munk (F) maps to incident photon energy Eg (eV), F-E curves is obtained, to characterize the optical absorption characteristics of sample.F-
There is an absworption peak in UV-vis areas in E curves, and tangent line is done along this absworption peak edge, corresponding to tangent line and the intersection point of E axles
The energy gap (Eg) of energy, as sample.
Fig. 4 is rare earth metal-organic framework materials Ho-MOF UV-vis DRS spectrogram, wherein (a) rare earth metal-
Organic framework materials Ho-MOF UV-vis spectrograms；(b) rare earth metal-organic framework materials Ho-MOF Kubelka-Munk turns
Change the spectrogram that diffuses.
Combine (a) and (b) from Fig. 4 as can be seen that rare earth metal-organic framework materials Ho-MOF of the present invention have compared with
Wide spectral response ability and less optical energy gap (Eg=2.16eV), it is a kind of potential novel photocatalyst of tool.
Rare earth metal prepared by the embodiment 1 of test example 4-organic framework materials Ho-MOF degraded wastewater containing methylene blues
Organic dye waste water is simulated with methylene blue solution, investigating rare earth metal-organic framework materials Ho-MOF degradeds has
The performance of machine waste water from dyestuff.
Weigh rare earth metal made from embodiment 1-organic framework materials Ho-MOF 40mg and be added to 40mL as catalyst
Concentration is 3.12 × 10-2In mmol/L methylene blue solution.First in the dark magnetic agitation 20min, it is ensured that adsorption equilibrium is complete
Into.Then under ultraviolet light, at interval of 30min, take 2mL solution to be analyzed, determine the ultra-violet absorption spectrum of solution, profit
With the concentration of absorbance detection methylene blue.Using concentration proportion C/C0Is weighed by degradation efficiency and is mapped for time t curve.
After the reaction time reaches 120min, 40 μ L hydrogen peroxide is added into reaction system, per minor tick 15min, takes 2mL solution
Analyzed, determine the ultra-violet absorption spectrum of solution, utilize the concentration of absorbance detection methylene blue.Using concentration proportion C/C0
Is weighed by degradation efficiency and is mapped for time t curve.
Fig. 5 is the UV-visible spectrum of degraded target contaminant methylene blue solution in embodiment 1.Wherein, in Fig. 5-
The UV-visible spectrum of methylene blue solution when 20min refers to not adding Ho-MOF materials, and Ho- is added after a measurement
MOF；0min refers to adding the UV-visible spectrum of solution (i.e. when Ho-MOF completes absorption) after Ho-MOF20min, Cat
30min, Cat 60min, Cat 75min, Cat 90min, Cat 105min and Cat 120min refer to after the completion of absorption respectively
The UV-visible spectrum of solution when 30min, 60min, 75min, 90min, 105min and 120min, and after the completion of absorption
H is added after 120min2O2；Cat/H2O2135min, Cat/H2O2150min, Cat/H2O2165min and Cat/H2O2
180min refers to respectively adds H2O2The UV-visible spectrum of solution when 15min, 30min, 45min and 60min.
Fig. 6 is that the pseudo-first-order dynamics of light-catalyzed reaction in embodiment 1 is fitted spectrogram.
Absorption values and calculating with reference to Fig. 5, to the clearance of target contaminant methylene blue solution, in the reaction time
After reaching 120min, the clearance to target contaminant methylene blue solution is 35.0%, and the hydrogen peroxide for adding 40 μ L is molten
Liquid, by after 60min, the clearance to target contaminant methylene blue solution is 83.0%.
As can be seen from Figure 6 pseudo-first-order is met using rare earth metal-organic framework materials Ho-MOF light-catalyzed reaction
Kinetics equation, speed constant are 4.33 × 10-3min-1, after adding hydrogen peroxide, light-catalyzed reaction meets pseudo-first-order dynamics
Equation, speed constant are 2.57 × 10-2min-1, degradation rate substantially increases, it is seen that rare earth metal-organic framework materials Ho-
MOF can be rapidly and efficiently in the presence of hydrogen peroxide degrading organic dye waste water.
The rare earth metal of embodiment 2 and embodiment 3-organic framework materials Ho-MOF is degraded according to the method for test example 4
Wastewater containing methylene blue, it can also obtain higher degradation efficiency.
Comparative experimental example
Rare earth metal-organic framework materials the Ho-MOF prepared without using embodiment 1, the hydrogen peroxide for only adding 40 μ L arrive
40mL concentration is 3.12 × 10-2In mmol/L methylene blue solution, under ultraviolet light, at interval of 30min, take 2mL molten
Liquid is analyzed, and determines the ultra-violet absorption spectrum of solution, utilizes the concentration of absorbance detection methylene blue.Using concentration proportion C/
C0Is weighed by degradation efficiency and is mapped for time t curve.
Fig. 7 is the UV-visible spectrum of degraded target contaminant methylene blue solution in embodiment 1.Can be with from Fig. 7
Find out, after the reaction time reaches 120min, the clearance to target contaminant methylene blue is only 36.0%.
Relatively found out by test example 4 and comparative experimental example, rare earth metal of the invention-organic framework materials Ho-MOF energy
Enough quickly and efficiently degrading organic dye waste waters.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of rare earth metal-organic framework materials Ho-MOF, it is characterised in that the rare earth metal-organic framework materials
Molecular formula is [Ho (H2-DHBDC)0.5(DHBDC)0.5(H2O)2](H2O)n；
Wherein, H2- DHBDC and DHBDC be respectively lose the 2,5- dihydric para-phthalic acids root of two protons and four protons from
Son；N is the natural number more than or equal to 1.
2. rare earth metal according to claim 1-organic framework materials Ho-MOF, it is characterised in that the n is 1-50's
The natural number of natural number, preferably 2-20.
3. a kind of rare earth metal-organic framework materials Ho-MOF as claimed in claim 1 or 2 preparation method, its feature exist
In comprising the following steps：
Organic ligand 2,5-Dihydroxyterephthalic acid is added to the water, regulation pH is 6.1-6.5, then adds water-soluble holmium salt
And dimethylformamide, hydro-thermal reaction is carried out, obtains rare earth metal-organic framework materials Ho-MOF.
4. rare earth metal according to claim 3-organic framework materials Ho-MOF preparation method, it is characterised in that every
5-8mL water is added in mmol 2,5-Dihydroxyterephthalic acid, is preferably the 2,5-Dihydroxyterephthalic acid per mmol
6.5mL water is added in middle addition 6-7mL water, the more preferably 2,5-Dihydroxyterephthalic acid per mmol；
And/or pH is adjusted with strong alkali solution, pH is preferably adjusted using sodium hydrate aqueous solution.
5. rare earth metal according to claim 3-organic framework materials Ho-MOF preparation method, it is characterised in that institute
It is holmium nitrate, sulfuric acid holmium or holmium chloride, preferably holmium nitrate to state water-soluble holmium salt；
And/or the ratio between amount of material of the water-soluble holmium salt and organic ligand 2,5-Dihydroxyterephthalic acid is (2-4)：
1, preferably 3:1.
6. rare earth metal according to claim 3-organic framework materials Ho-MOF preparation method, it is characterised in that institute
It is 1 to state the ratio between the volume of dimethylformamide with adding water：(0.8-1.2), preferably 1:1.
7. rare earth metal according to claim 3-organic framework materials Ho-MOF preparation method, it is characterised in that institute
The temperature for stating hydro-thermal reaction is 100-120 DEG C, preferably 105-115 DEG C, more preferably 110 DEG C；
And/or the time of hydro-thermal reaction is 20-30 hours, preferably 22-28 hours, more preferably 24 hours.
8. rare earth metal according to claim 3-organic framework materials Ho-MOF preparation method, it is characterised in that also
After the completion of hydro-thermal reaction, room temperature is cooled to, washing, filters and dries.
9. rare earth metal according to claim 8-organic framework materials Ho-MOF preparation method, it is characterised in that institute
State to dry and use vacuum drying, drying temperature is 50-80 DEG C, preferably 60-70 DEG C, more preferably 65 DEG C；
And/or drying time is 20-36 hours, preferably 22-30 hours, more preferably 24 hours.
10. rare earth metal as claimed in claim 1 or 2-organic framework materials Ho-MOF is in degrading organic dye waste water
Using.
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