CN109569520A - A kind of modified metal organic framework composite material and its preparation method and application - Google Patents
A kind of modified metal organic framework composite material and its preparation method and application Download PDFInfo
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- CN109569520A CN109569520A CN201811294624.3A CN201811294624A CN109569520A CN 109569520 A CN109569520 A CN 109569520A CN 201811294624 A CN201811294624 A CN 201811294624A CN 109569520 A CN109569520 A CN 109569520A
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 117
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003463 adsorbent Substances 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 12
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims abstract description 9
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical class NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 36
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002372 labelling Methods 0.000 claims description 7
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 29
- 239000010931 gold Substances 0.000 abstract description 28
- 229910052737 gold Inorganic materials 0.000 abstract description 28
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 2
- -1 gold ion Chemical class 0.000 description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 7
- 230000009514 concussion Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- JLAMDELLBBZOOX-UHFFFAOYSA-N 3h-1,3,4-thiadiazole-2-thione Chemical class SC1=NN=CS1 JLAMDELLBBZOOX-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005868 electrolysis reaction 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
- HSDVRWZKEDRBAG-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COC(CCCCC)OCC1CO1 HSDVRWZKEDRBAG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a kind of modified metal organic framework composite materials, preparation method and application, belong to porous material preparation technical field；Material structure formula is as follows:；The present invention is by metal organic framework composite material UiO-66-NH2It is added in n,N-Dimethylformamide, ethylene glycol diglycidylether back flow reaction is then added, wash, separate after reaction, is dry, MOF-EGD is made；By MOF-EGD and 2- amino -5- sulfydryl -1,3,4- thiadiazoles sequentially adds the molten middle back flow reaction of n,N-Dimethylformamide, after reaction, washing, separation, dry, obtained modified metal organic framework composite material MOF-EGD-TTA；The method of the present invention is simple to operation, and modified metal organic framework composite material obtained can be used as adsorbent, and the gold ion in adsorbent solution is easy to operate, is readily synthesized, easily separates with aqueous solution, has high adsorption and can be recycled.
Description
Technical field
The present invention relates to a kind of modified metal organic framework composite materials, preparation method and application, belong to porous material system
Standby technical field.
Background technique
In electronic material, jewelry, the fields such as catalyst, the demand to gold is continuously increased.In addition, available gold resource
Start to reduce.Therefore, people are more and more interested in the recycling and enrichment of gold.However, due to complicated chemical property and again
Folded property, the separation of gold ion are a challenge always, have developed many methods to recycle the gold from aqueous solution, such as
Electrolysis, precipitating, solvent extraction and absorption.
In all the above methods, electrolysis method is only applicable to the higher solution of ion solubility, it is difficult to which concentration for the treatment of is lower
Solution；Precipitation process is complicated, time-consuming and laborious, unsuitable industrialization；The object for the treatment of by extraction be mainly ion concentration compared with
High solution.However, absorption is efficient and economic, easily operated because at low cost, the gold of particularly suitable low concentration.Absorption
Separation and concentration method is generally taken seriously due to the features such as selectivity is good, easy to operate.Have at present using wide adsorbent
Nano silica, active carbon, polyurethane foam plastics, chelating resin, metal organic framework composite material etc.；It is each in order to adapt to
Kind purpose and requirement, the effort that people research and develop new adsorbent were never interrupted.
The disclosure of technical solution same as the present invention is had no at present.
Summary of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention provides a kind of modified metal organic backbone composite wood
Material, preparation method and application；Modified metal organic framework composite material of the invention can be used as adsorbent, the gold in adsorbent solution
Ion, it is easy to operate, it is readily synthesized, is easily separated with aqueous solution, there is high adsorption and can be recycled.
Modified metal organic framework composite material structural formula of the present invention are as follows:
。
Above-mentioned modified metal organic framework composite material the preparation method is as follows:
(1) by metal organic framework composite material UiO-66-NH2It is added in n,N-Dimethylformamide, then adds second
Hexanediol diglycidyl ether, the back flow reaction 15 ~ for 24 hours under conditions of 70 ~ 90 DEG C take out solid matter N, N- after reaction
Dimethyl formamide solution washing, is dried in vacuo after being then centrifuged for separation, is MOF-EGD by obtained Product Labeling；
The metal organic framework composite material UiO-66-NH2Being added to liquid-solid ratio mL:g in N,N-dimethylformamide is 30:
1 ~ 50:1, ethylene glycol diglycidylether and UiO-66-NH2Liquid-solid ratio mL:g be 3:2 ~ 5:2；
(2) that step (1) MOF-EGD and 2- amino -5- sulfydryl -1,3,4- thiadiazoles is sequentially added N,N-dimethylformamide is molten
In, the back flow reaction 15 ~ for 24 hours under conditions of 100 ~ 130 DEG C takes out solid matter n,N-Dimethylformamide after reaction
Solution washing, vacuum drying is labeled as MOF-EGD- to get to modified metal organic framework composite material after being then centrifuged for separation
TTA；
The MOF-EGD and n,N-Dimethylformamide liquid-solid ratio mL:g is 30:1 ~ 50:1, MOF-EGD and 2- amino -5- mercapto
Base -1,3,4- thiadiazoles mass ratio is 2:3 ~ 2:5.
The metal organic framework composite material UiO-66-NH2Preparation method be by zirconium chloride particle and 2- amino pair
Phthalic acid is added in n,N-Dimethylformamide solution, under the conditions of 125 ~ 140 DEG C after back flow reaction 15 ~ for 24 hours, is taken out solid
Body substance is washed with n,N-Dimethylformamide, is dried in vacuo after centrifuge separation, is UiO-66-NH by obtained Product Labeling2；
Wherein zirconium chloride particle and 2- amino terephthalic acid (TPA) mass ratio are 1.5:1 ~ 2:1, n,N-Dimethylformamide solution and chlorination
Zirconium particle liquid-solid ratio mL:g is 20:1 ~ 30:1.
The present invention is another object is that apply the conduct in golden adsorption process for above-mentioned modified metal organic framework composite material
Golden adsorbent.
Mentioned reagent is analytical reagents.
The beneficial effects of the present invention are:
(1) modified metal organic framework composite material of the present invention can be used as adsorbent, high to the adsorption rate of gold ion, in solution
The selectivity of ion is good；
(2) modified metal organic framework composite material of the present invention is nontoxic, and performance is stablized, and is easily isolated, reusable, right
Environment does not cause secondary pollution；
(3) modified metal organic framework composite material of the present invention has very big potentiality, tool in terms of the adsorbing separation of gold ion
There are preferable application and economic value.
Specific embodiment
Below by embodiment, invention is further described in detail, and the scope of the present invention is not limited in described
Hold.
Embodiment 1: this modified metal organic framework composite material structural formula are as follows:
。
The modified metal organic framework composite material the preparation method is as follows:
2g zirconium chloride particle and 2- amino terephthalic acid (TPA) are added in n,N-Dimethylformamide solution by step 1,140
Under the conditions of DEG C after back flow reaction 15h, takes out solid matter and is washed with n,N-Dimethylformamide, is dried in vacuo after centrifuge separation,
It is UiO-66-NH by obtained Product Labeling2；Wherein zirconium chloride particle and 2- amino terephthalic acid (TPA) mass ratio are 2:1, N,
Dinethylformamide solution and zirconium chloride particle liquid-solid ratio mL:g are 30:1；
Step 2, the 2g metal organic framework composite material UiO-66-NH for obtaining step 12It is added to N,N-dimethylformamide
In, ethylene glycol diglycidylether is then added, back flow reaction for 24 hours, takes out solid after reaction under conditions of 70 DEG C
Substance is washed with n,N-Dimethylformamide solution, is dried in vacuo after being then centrifuged for separation, obtained composite material is labeled as
MOF-EGD；Wherein metal organic framework composite material UiO-66-NH2It is added to liquid-solid ratio mL:g in N,N-dimethylformamide
For 30:1, ethylene glycol diglycidylether and UiO-66-NH2Liquid-solid ratio mL:g be 3:2；
The 2g MOF-EGD that step 2 obtains is added in n,N-Dimethylformamide by step 3, then adds 2- amino -5-
Sulfydryl -1,3,4- thiadiazoles, back flow reaction for 24 hours, takes out solid matter N, N- diformazan after reaction under conditions of 100 DEG C
The washing of base formamide solution, is dried in vacuo, obtained modified metal skeletal composite after being then centrifuged for separation, is labeled as MOF-
EGD-TTA；It is mL:g30:1, MOF-EGD and 2- amino-that wherein MOF-EGD, which is added to liquid-solid ratio in n,N-Dimethylformamide,
5- sulfydryl -1,3,4- thiadiazoles mass ratio is 2:3；
The measurement of ADSORPTION OF GOLD ionic nature:
The gold ion that the MOF-EGD-TTA adsorbent investment initial concentration for taking 10mg the present embodiment to be prepared is 100mg/L is molten
In liquid after concussion absorption 10h, it is centrifugated adsorbent, is 21mg/L with remaining gold ion concentration in ICP-OES measurement filtrate, inhales
Attached rate is 79%；Adsorbent 8 h of agitator treating, then use distillation washing in thiourea solution (0.5M) of gold ion will be adsorbed
It washs 3 times, adsorbent is finally dried in vacuo 8 h at 80 DEG C；Taking above-mentioned 10 mg of adsorbent investment initial concentration is 100mg/L
Gold ion solution in after concussion absorption 10h, adsorbent is centrifugated, with remaining gold ion concentration in ICP-OES measurement filtrate
For 26mg/L, adsorption rate 74%；Illustrate the compound composite material MOF- of modified metal organic backbone of adsorbing separation gold of the invention
EGD-TTA is Ke Xunhuanliyong.
Embodiment 2: this modified metal organic framework composite material structural formula are as follows:
；
The modified metal organic framework composite material the preparation method is as follows:
2g zirconium chloride particle and 2- amino terephthalic acid (TPA) are added in n,N-Dimethylformamide solution by step 1,135
Under the conditions of DEG C after back flow reaction 18h, takes out after solid matter washs centrifuge separation with n,N-Dimethylformamide and be dried in vacuo, it will
Obtained Product Labeling is UiO-66-NH2；Wherein zirconium chloride particle and 2- amino terephthalic acid (TPA) mass ratio are 1.5:1, N,
Dinethylformamide solution and zirconium chloride particle liquid-solid ratio mL:g are 20:1；
Step 2, the 2g metal organic framework composite material UiO-66-NH for obtaining step 12It is added to N,N-dimethylformamide
In, ethylene glycol diglycidylether is then added, back flow reaction 20h under conditions of 80 DEG C takes out solid after reaction
Substance is washed with n,N-Dimethylformamide solution, is dried in vacuo after being then centrifuged for separation, obtained composite material is labeled as
MOF-EGD；Wherein metal organic framework composite material UiO-66-NH2It is added to liquid-solid ratio mL:g in N,N-dimethylformamide
For 40:1mL/g, ethylene glycol diglycidylether and UiO-66-NH2Liquid-solid ratio mL:g be 2:1；
The 2g MOF-EGD that step 2 obtains is added in n,N-Dimethylformamide by step 3, then adds 2- amino -5-
Sulfydryl -1,3,4- thiadiazoles, back flow reaction 19h under conditions of 110 DEG C take out solid matter N, N- diformazan after reaction
The washing of base formamide solution, is dried in vacuo, obtained modified metal skeletal composite after being then centrifuged for separation, is labeled as MOF-
EGD-TTA；It is 40:1mL/g that wherein MOF-EGD, which is added to liquid-solid ratio mL:g in n,N-Dimethylformamide, and ethylene glycol two shrinks
Glycerin ether and UiO-66-NH2Liquid-solid ratio mL:g be 5:2；
The measurement of ADSORPTION OF GOLD ionic nature:
The gold ion that the MOF-EGD-TTA adsorbent investment initial concentration for taking 10mg the present embodiment to be prepared is 100mg/L is molten
In liquid after concussion absorption 10h, it is centrifugated adsorbent, is 18mg/L with remaining gold ion concentration in ICP-OES measurement filtrate, inhales
Attached rate is 82%；Adsorbent 8 h of agitator treating, then use distillation washing in thiourea solution (0.5M) of gold ion will be adsorbed
It washs 3 times, adsorbent is finally dried in vacuo 8 h at 80 DEG C；Taking above-mentioned 10 mg of adsorbent investment initial concentration is 100mg/L
Gold ion solution in after concussion absorption 10h, adsorbent is centrifugated, with remaining gold ion concentration in ICP-OES measurement filtrate
For 22mg/L, adsorption rate 78%.Illustrate the compound composite material MOF- of modified metal organic backbone of adsorbing separation gold of the invention
EGD-TTA is Ke Xunhuanliyong.
Embodiment 3: this modified metal organic framework composite material structural formula are as follows:
；
The modified metal organic framework composite material the preparation method is as follows:
2g zirconium chloride particle and 2- amino terephthalic acid (TPA) are added in n,N-Dimethylformamide solution by step 1,140
Under the conditions of DEG C after back flow reaction 15h, takes out after solid matter washs centrifuge separation with n,N-Dimethylformamide and be dried in vacuo, it will
Obtained Product Labeling is UiO-66-NH2；Wherein zirconium chloride particle and 2- amino terephthalic acid (TPA) mass ratio are 1.8:1, N,
Dinethylformamide solution and zirconium chloride particle liquid-solid ratio mL:g are 25:1；
Step 2, the 2g metal organic framework composite material UiO-66-NH for obtaining step 12It is added to N,N-dimethylformamide
In, ethylene glycol diglycidylether is then added, back flow reaction 15h under conditions of 90 DEG C takes out solid after reaction
Substance is washed with n,N-Dimethylformamide solution, is dried in vacuo after being then centrifuged for separation, obtained composite material is labeled as
MOF-EGD；Wherein metal organic framework composite material UiO-66-NH2It is added to liquid-solid ratio mL:g in N,N-dimethylformamide
For 50:1, ethylene glycol diglycidylether and UiO-66-NH2Liquid-solid ratio mL:g be 5:2；
The 2g MOF-EGD that step 2 obtains is added in n,N-Dimethylformamide by step 3, then adds 2- amino -5-
Sulfydryl -1,3,4- thiadiazoles, back flow reaction 15h under conditions of 130 DEG C take out solid matter N, N- diformazan after reaction
The washing of base formamide solution, is dried in vacuo, obtained modified metal skeletal composite after being then centrifuged for separation, is labeled as MOF-
EGD-TTA；It is 50:1, MOF-EGD and 2- amino-that wherein MOF-EGD, which is added to liquid-solid ratio mL:g in n,N-Dimethylformamide,
5- sulfydryl -1,3,4- thiadiazoles ratio is 2:5；
The measurement of ADSORPTION OF GOLD ionic nature:
The gold ion that the MOF-EGD-TTA adsorbent investment initial concentration for taking 10mg the present embodiment to be prepared is 100mg/L is molten
In liquid after concussion absorption 10h, it is centrifugated adsorbent, is 17mg/L with remaining gold ion concentration in ICP-OES measurement filtrate, inhales
Attached rate is 83%；Adsorbent 8 h of agitator treating, then use distillation washing in thiourea solution (0.5M) of gold ion will be adsorbed
It washs 3 times, adsorbent is finally dried in vacuo 8 h at 80 DEG C.Taking above-mentioned 10 mg of adsorbent investment initial concentration is 100mg/L
Gold ion solution in after concussion absorption 10h, adsorbent is centrifugated, with remaining gold ion concentration in ICP-OES measurement filtrate
For 22mg/L, adsorption rate 78%；Illustrate the compound composite material MOF- of modified metal organic backbone of adsorbing separation gold of the invention
EGD-TTA is Ke Xunhuanliyong.
Above the embodiment of the present invention is explained in detail, but the present invention is not limited to above-mentioned embodiment party
Formula can also be made without departing from the purpose of the present invention within the knowledge of a person skilled in the art
Various change out.
Claims (6)
1. a kind of modified metal organic framework composite material, which is characterized in that structural formula is as follows:
。
2. the preparation method of modified metal organic framework composite material described in claim 1, it is characterised in that including following step
It is rapid:
(1) by metal organic framework composite material UiO-66-NH2It is added in n,N-Dimethylformamide, then adds second two
Alcohol diglycidyl ether, the back flow reaction 15 ~ for 24 hours under conditions of 70 ~ 90 DEG C take out solid matter N, N- bis- after reaction
The washing of methylformamide solution, is dried in vacuo after being then centrifuged for separation, is MOF-EGD by obtained Product Labeling；
(2) that step (1) MOF-EGD and 2- amino -5- sulfydryl -1,3,4- thiadiazoles is sequentially added N,N-dimethylformamide is molten
In, the back flow reaction 15 ~ for 24 hours under conditions of 100 ~ 130 DEG C takes out solid matter n,N-Dimethylformamide after reaction
Solution washing, vacuum drying is labeled as MOF-EGD- to get to modified metal organic framework composite material after being then centrifuged for separation
TTA。
3. the preparation method of modified metal organic framework composite material according to claim 2, it is characterised in that: metal has
Machine skeletal composite UiO-66-NH2Being added to liquid-solid ratio mL:g in n,N-Dimethylformamide is 30:1 ~ 50:1, ethylene glycol
Diglycidyl ether and UiO-66-NH2Liquid-solid ratio mL:g be 3:2 ~ 5:2.
4. the preparation method of modified metal organic framework composite material according to claim 2, it is characterised in that: step
(2) MOF-EGD and n,N-Dimethylformamide liquid-solid ratio mL:g is sulfydryl -1 30:1 ~ 50:1, MOF-EGD and 2- amino -5- in,
3,4- thiadiazoles mass ratio is 2:3 ~ 2:5.
5. the preparation method of modified metal organic framework composite material according to claim 2, it is characterised in that: metal has
Machine skeletal composite UiO-66-NH2Preparation method be that zirconium chloride particle and 2- amino terephthalic acid (TPA) are added to N, N-
In dimethyl formamide solution, under the conditions of 125 ~ 140 DEG C after back flow reaction 15 ~ for 24 hours, solid matter N, N- dimethyl are taken out
Formamide washing, is dried in vacuo after centrifuge separation, is UiO-66-NH by obtained Product Labeling2；Wherein zirconium chloride particle and 2-
Amino terephthalic acid (TPA) mass ratio is 1.5:1 ~ 2:1, and n,N-Dimethylformamide solution is with zirconium chloride particle liquid-solid ratio mL:g
20:1~30:1。
6. modified metal organic framework composite material described in claim 1 is as the application in golden adsorbent.
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| CN201811294624.3A CN109569520B (en) | 2018-11-01 | 2018-11-01 | Modified metal organic framework composite material and preparation method and application thereof |
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| CN201811294624.3A CN109569520B (en) | 2018-11-01 | 2018-11-01 | Modified metal organic framework composite material and preparation method and application thereof |
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| CN111001392A (en) * | 2019-12-30 | 2020-04-14 | 中山大学 | Preparation method and application of modified zirconium-based metal organic framework adsorbent for gold ion adsorption |
| CN113045767A (en) * | 2021-03-24 | 2021-06-29 | 肇庆市武大环境技术研究院 | Nitrogen heterocyclic ring molecule modified UiO-66-NH with stable structure2Material and method for the production thereof |
| CN113117652A (en) * | 2021-05-26 | 2021-07-16 | 中国地质大学（北京） | DMTD-COFs material and modification method and application thereof |
| US11124530B1 (en) | 2019-10-22 | 2021-09-21 | King Fahd University Of Petroleum And Minerals | Zirconium metal-organic framework and a method of detecting copper and chromate ions |
| CN113634233A (en) * | 2021-07-29 | 2021-11-12 | 昆明理工大学 | Zirconium-based metal coordination polymer adsorbent, preparation method and application thereof |
| CN113663648A (en) * | 2021-07-29 | 2021-11-19 | 昆明理工大学 | Post-synthesis modified MOF material adsorbent, preparation method and application thereof |
| CN114471731A (en) * | 2022-03-02 | 2022-05-13 | 淮阴师范学院 | Preparation method, product and application of Cu (I) catalyst |
| CN115554989A (en) * | 2022-11-08 | 2023-01-03 | 昆明理工大学 | Pre-modified zirconium-based MOF adsorbent and preparation method and application thereof |
| CN116328736A (en) * | 2022-11-23 | 2023-06-27 | 中国原子能科学研究院 | MOF composite adsorbent loaded with imidazole-4, 5-dicarboxylic acid and preparation method and application thereof |
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| CN110128669A (en) * | 2019-05-13 | 2019-08-16 | 多助科技(武汉)有限公司 | A kind of modified zirconium base MOFs material and its preparation and application |
| US11124530B1 (en) | 2019-10-22 | 2021-09-21 | King Fahd University Of Petroleum And Minerals | Zirconium metal-organic framework and a method of detecting copper and chromate ions |
| CN111001392A (en) * | 2019-12-30 | 2020-04-14 | 中山大学 | Preparation method and application of modified zirconium-based metal organic framework adsorbent for gold ion adsorption |
| CN113045767A (en) * | 2021-03-24 | 2021-06-29 | 肇庆市武大环境技术研究院 | Nitrogen heterocyclic ring molecule modified UiO-66-NH with stable structure2Material and method for the production thereof |
| CN113117652A (en) * | 2021-05-26 | 2021-07-16 | 中国地质大学（北京） | DMTD-COFs material and modification method and application thereof |
| CN113117652B (en) * | 2021-05-26 | 2022-07-19 | 中国地质大学（北京） | DMTD-COFs material and modification method and application thereof |
| CN113663648A (en) * | 2021-07-29 | 2021-11-19 | 昆明理工大学 | Post-synthesis modified MOF material adsorbent, preparation method and application thereof |
| CN113634233A (en) * | 2021-07-29 | 2021-11-12 | 昆明理工大学 | Zirconium-based metal coordination polymer adsorbent, preparation method and application thereof |
| CN114471731A (en) * | 2022-03-02 | 2022-05-13 | 淮阴师范学院 | Preparation method, product and application of Cu (I) catalyst |
| CN114471731B (en) * | 2022-03-02 | 2022-10-04 | 淮阴师范学院 | Preparation method, product and application of Cu (I) catalyst |
| CN115554989A (en) * | 2022-11-08 | 2023-01-03 | 昆明理工大学 | Pre-modified zirconium-based MOF adsorbent and preparation method and application thereof |
| CN115554989B (en) * | 2022-11-08 | 2023-09-05 | 昆明理工大学 | Pre-modified zirconium-based MOF adsorbent and preparation method and application thereof |
| CN116328736A (en) * | 2022-11-23 | 2023-06-27 | 中国原子能科学研究院 | MOF composite adsorbent loaded with imidazole-4, 5-dicarboxylic acid and preparation method and application thereof |
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