CN109569521A - A kind of rhodanine functionalization MOFs adsorbent and its preparation method and application - Google Patents
A kind of rhodanine functionalization MOFs adsorbent and its preparation method and application Download PDFInfo
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- CN109569521A CN109569521A CN201811500569.9A CN201811500569A CN109569521A CN 109569521 A CN109569521 A CN 109569521A CN 201811500569 A CN201811500569 A CN 201811500569A CN 109569521 A CN109569521 A CN 109569521A
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- 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]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention belongs to Heavy Metals in Waters pollutant absorbent technical field, a kind of rhodanine functionalization MOFs adsorbent and its preparation method and application is provided；The adsorbent includes UiO-66 class MOFs matrix and modification rhodanine group.The UiO-66 class MOFs matrix has many advantages, such as that large specific surface area, porosity height, stable structure, surface are easily modified, and the rhodanine group can be combined by the compound of the group containing rhodanine with the coordination of the Zr-O cluster of UiO-66 class MOFs matrix with UiO-66 class MOFs matrix；Or through the compound of the group containing rhodanine in conjunction with the deamination of UiO-66 class MOFs matrix, by rhodanine base group modification on the surface Zr-MOFs, the high-selectivity adsorption to water body metallic silver is realized.
Description
Technical field
The invention belongs to the technical fields of Heavy Metals in Waters pollutant absorbent, and in particular to a kind of rhodanine functionalization
MOFs adsorbent and its preparation method and application.
Background technique
There is a large amount of silver ions in industrial wastewater, if do not handled it, will be good for ecological environment and human body
The serious influence of Kang Zaocheng.Moreover silver is a kind of precious metal with higher market value, the silver ion in waste water is recycled
Certain economic well-being of workers and staff can be obtained.Absorption method is one of most common method of silver ion in removal water body, has at low cost, effect
Rate height, simple operation and other advantages.Traditional adsorbent material, such as active carbon, silica, carbon nanotube are useless in complicated reality
There are adsorption capacities in water process it is low, the rate of adsorption is slow, selective adsorption capacity is poor the disadvantages of.Therefore, a kind of energy of researching and designing
Enough stable, efficient and high-selectivity adsorption silver ion materials have a very important significance.
Metal-organic framework materials (Metal-organic Framework, MOFs) are one kind by metal ion or metal
The novel crystalline porous material with periodical infinite network structure that cluster and organic ligand are self-assembly of by coordinate bond.Though
So a large amount of experimental study shows MOFs to gas molecule, dyestuff, drug, and it is special that the isomer of even organic matter has
Selection absorption and separating capacity, but stability is poor in aqueous solution for most of MOFs material, this greatly limits it
Application in terms of wastewater treatment；Also, adsorbing separation metal ion is caused since MOFs lacks extra coordination site
It is very weak to the suction-operated of extraneous metal ion, strongly limits application of the MOFs as metal absorbent, and due to
The radius of most of metal ion is all very close, therefore is unable to through hole size advantage and carries out effective absorption point to metal ion
From.For example, 2015, and Cheng etc. [Cheng X, Liu M, Zhang A F, et al, Nanoscale, 2015,7,9738-
9745] sulfydryl modification MIL-53 (Al) is used, successfully synthesizes mercapto-functionalized MIL-53 (Al), with adsorbing metal Ag (I)
Ability, but its drawbacks of that there are adsorption capacities is low, the rate of adsorption is slow, poor selectivity, and water stability is bad that limit its heavy
Multiple Utilization ability.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of rhodanine functionalization MOFs adsorbent and preparation method thereof and
Using rhodanine functionalization MOFs adsorbent adsorption capacity provided by the invention is high, adsorption rate is fast and has height to silver ion
Selective adsorption.
To achieve the goals above, the invention provides the following technical scheme:
The present invention provides a kind of rhodanine functionalization MOFs adsorbents, including UiO-66 class MOFs matrix and modification Luo Dan
Peaceful group.
Preferably, the UiO-66 class MOFs matrix includes UiO-66 or UiO-66-NH2。
The present invention provides the preparation method of rhodanine functionalization MOFs adsorbent described in above-mentioned technical proposal, including it is following
Step:
(1) by ZrCl4Organic solution mixed with carboxylic acids organic ligand, obtain MOFs synthesis feed liquid；
(2) the MOFs synthesis feed liquid and rhodanine acid-mixed obtained the step (1) is closed, and is carried out hydro-thermal reaction, is obtained sieve
Tannin functionalization MOFs adsorbent.
Preferably, carboxylic acids organic ligand includes terephthalic acid (TPA) or 2- amino terephthalic acid (TPA) in the step (1)；
Step (2) the rhodanine acid includes rhodanine -3- acetic acid or rhodanine -3- propionic acid；
Step (2) the rhodanine acid synthesizes ZrCl in feed liquid with MOFs4, carboxylic acids organic ligand molar ratio be 0.1
~10:1:1；
The temperature of hydro-thermal reaction is 110~150 DEG C in the step (2), and the time is 24~72h.
The present invention also provides a kind of preparation method of rhodanine functionalization MOFs adsorbent described in above-mentioned technical proposal, packets
Include following steps:
(1) by ZrCl4Organic solution mixed with carboxylic acids organic ligand, carry out hydro-thermal reaction after filter, obtain UiO-
66 class MOFs；
(2) the UiO-66 class MOFs that the step (1) obtains is mixed with rhodanine acid organic solution, carries out modification synthesis
Reaction, obtains rhodanine functionalization MOFs adsorbent.
Preferably, ZrCl in the step (1)4Molar ratio with carboxylic acids organic ligand is 1:1, carboxylic acids organic ligand
Including terephthalic acid (TPA) or 2- amino terephthalic acid (TPA), the temperature of hydro-thermal reaction is 120 DEG C, time 48h；
Step (2) the rhodanine acid includes rhodanine -3- acetic acid or rhodanine -3- propionic acid；
When the carboxylic acids organic ligand is 2- amino terephthalic acid (TPA), in the step (2) UiO-66 class MOFs with
Before the mixing of rhodanine acid organic solution, the rhodanine acid organic solution is mixed with I-hydroxybenzotriazole alcoholic solution, is obtained
Functionalization feed liquid；Carbodiimide is added after mixing with the functionalization feed liquid with UiO-66 class MOFs, carries out catalysis modification synthesis
Reaction；
The mass ratio of the UiO-66 class MOFs and rhodanine acid is 1:0.2~5；The I-hydroxybenzotriazole alcoholic solution
The molar ratio of middle I-hydroxybenzotriazole and rhodanine acid is 1~1.2:1；The molar ratio of the carbodiimide and rhodanine acid is
1~1.5:1.
The present invention separately provides a kind of preparation method of rhodanine functionalization MOFs adsorbent described in above-mentioned technical proposal, packet
Include following steps:
(1) by ZrCl4Organic solution mixed with carboxylic acids organic ligand, carry out hydro-thermal reaction after filter, obtain UiO-
66 class MOFs；
(2) rhodanine acid organic solution is mixed with thionyl chloride, carries out acyl chloride reaction, obtains rhodanine acyl chlorides；
(3) by the step (2) obtains the organic solution of rhodanine acyl chlorides and the step (1) obtains UiO-66 class
Triethylamine is added after MOFs mixing, generation acyl chlorides is reacted with amine, obtains rhodanine functionalization MOFs adsorbent.
Preferably, ZrCl in the step (1)4Molar ratio with carboxylic acids organic ligand is 1:1；The carboxylic acids is organic
Ligand includes terephthalic acid (TPA) or 2- amino terephthalic acid (TPA)；
The temperature of hydro-thermal reaction is 120 DEG C in the step (1), time 48h；
The molar ratio of rhodanine acid and thionyl chloride is 1:1~2 in the step (2)；
The temperature of acyl chloride reaction is 50~60 DEG C in the step (2), and the time is 6~12h；
The amount ratio of rhodanine acyl chlorides and addition UiO-66 class MOFs in the organic solution of step (3) the rhodanine acyl chlorides
For 1~25mmol:0.5g；
The molar ratio of triethylamine and rhodanine acyl chlorides is 1~1.5:1 in the step (3)；
The reaction temperature of acyl chlorides and amine is 20~25 DEG C in the step (3), and the reaction time is 12~36h.
The present invention provides described in rhodanine functionalization MOFs adsorbent described in above-mentioned technical proposal or above-mentioned technical proposal
Application of the rhodanine functionalization MOFs adsorbent that preparation method is prepared in the selection absorption of water body silver ion.
Preferably, the application includes: that the rhodanine functionalization MOFs adsorbent is added to silver ion to be adsorbed
In water body, stirring and adsorbing.
The present invention provides a kind of rhodanine functionalization MOFs adsorbents, including UiO-66 class MOFs matrix and modification Luo Dan
Peaceful group.The UiO-66 class MOFs matrix has many advantages, such as that large specific surface area, porosity height, stable structure, surface are easily modified, institute
Modification rhodanine group is stated to be combined with the coordination of the Zr-O cluster of UiO-66 class MOFs matrix；Or modify rhodanine group and UiO-66 class
The deamination of MOFs matrix combines, and by rhodanine base group modification on the surface Zr-MOFs, realizes to water body metal silver ion
High-selectivity adsorption；The singly-bound S and double bond S that rhodanine group contains in the present invention can be effectively coordinated with Ag.Embodiment result
Show rhodanine functionalization MOFs adsorbent provided by the invention in Ag (I), K (I), Li (I), Pb (II), Ni (II), Co
(II) and the concentration of Cu (II) is when carrying out selection absorption in the mixed solution of 10mmol/L, to Ag (I) with selection absorption
Property, adsorbance reaches as high as 8.5mmol/g, and the adsorbance maximum of other metal ions is only 0.17mmol/g；And this hair
The adsorbent maximum adsorption capacity of bright offer may be up to 923.9mg/g, and 44 times of the maximum adsorption capacity of about original UiO-66.
In addition, the material has the excellent rate of adsorption, it, can to the silver ion removal rate highest that initial concentration is 40mg/L in 2min
Up to 99% or more.
Detailed description of the invention
Fig. 1 is the rhodanine functionalization UiO-66 class MOFs adsorbent and non-rhodanine function that embodiment 1~12 obtains
The UiO-66 and UiO-66-NH of change2XRD diagram；
Fig. 2 is the rhodanine functionalization UiO-66 class MOFs adsorbent and non-rhodanine function that embodiment 13 and 14 obtains
The UiO-66 and UiO-66-NH of change2XRD diagram；
Fig. 3 is the rhodanine functionalization UiO-66 class MOFs adsorbent adsorption-desorption cycle benefit that embodiment 13 and 14 obtains
With the XRD diagram before and after Adsorption For Ag after 5 times；
Fig. 4 is the rhodanine functionalization UiO-66 class MOFs adsorbent and non-rhodanine function that embodiment 23~32 obtains
The UiO-66 and UiO-66-NH of change2XRD diagram；
Fig. 5 is that the rhodanine functionalization UiO-66 class MOFs adsorbent that embodiment 23 and 24 obtains is to initial concentration
The silver ion adsorption dynamics adsorption kinetics figure of 40mg/L.
Specific embodiment
The present invention provides a kind of rhodanine functionalization MOFs adsorbents, including UiO-66 class MOFs matrix and modification Luo Dan
Peaceful group.
In the present invention, the modification rhodanine group and UiO-66 class MOFs matrix are chemically bonded, and are chemically bonded form
Have: being combined with the coordination of the Zr-O cluster of UiO-66 class MOFs matrix；In conjunction with the deamination of UiO-66 class MOFs matrix.
Rhodanine functionalization MOFs adsorbent provided by the invention, including UiO-66 class MOFs matrix and modification rhodanine base
Group.In the present invention, the UiO-66 class MOFs matrix preferably includes UiO-66 and/or UiO-66-NH2；When the MOFs base
When body is UiO-66, the compound of the group containing rhodanine can be coordinated with the Zr-O cluster of UiO-66 to be combined, and realizes the modification Luo Dan
Peaceful group is in conjunction with UiO-66；When the MOFs matrix is UiO-66-NH2When, the compound of the group containing rhodanine is in addition to can be with
UiO-66-NH2Zr-O cluster be coordinated combine, moreover it is possible to UiO-66-NH2Amino occur amidation combine, realize modification sieve
Tannin group and UiO-66-NH2In conjunction with.In the present invention, the compound of the group containing rhodanine can be rhodanine -3- second
Acid, rhodanine -3- propionic acid or the rhodanine acyl chlorides for obtaining rhodanine -3- acetic acid and rhodanine -3- propionic acid chloride etc..
UiO-66 class MOFs matrix is by UiO-66 or UiO-66- in rhodanine functionalization MOFs adsorbent of the present invention
NH2It provides；The UiO-66 class MOFs matrix has many advantages, such as that large specific surface area, porosity height, stable structure, surface are easily modified,
The present invention is combined by the compound of the group containing rhodanine with the coordination of the Zr-O cluster of UiO-66 class MOFs；Or pass through base containing rhodanine
The compound of group with the deamination of UiO-66 class MOFs in conjunction with by rhodanine base group modification on the surface MOFs, realization is to water body
The high-selectivity adsorption of metallic silver.
In the present invention, the complex bound mode of Zr-O cluster of the compound and UiO-66 of the group containing rhodanine has two
Kind: the carboxylic acid compound containing rhodanine can be combined under solvent subsidiary conditions with the Zr coordination in Zr-O cluster；Containing rhodanine
Carboxylic acid compound can also obtain the acyl chloride compound containing rhodanine by acyl chloride reaction, then with the Zr in Zr-O cluster
And μ3- OH coordination combines.
In the present invention, the mass ratio of the Zr in the rhodanine functionalization MOFs adsorbent and S element is preferably 1:
0.02~20, further preferably 1:1.0~18.
In the present invention, there is UiO-66 class MOFs large specific surface area, porosity height, stable structure, surface easily to modify
Advantage is potential excellent water treatment absorbent, and rhodanine contains singly-bound C-S and double bond C=S, can effectively with metal Ag ion
Coordination, so rhodanine modification is realized the high-selectivity adsorption to Ag ion in water body on the surface UiO-66 class MOFs.
The present invention provides the preparation method of rhodanine functionalization MOFs adsorbent described in above-mentioned technical proposal, including it is following
Step:
(1) by ZrCl4Organic solution mixed with carboxylic acids organic ligand, obtain MOFs synthesis feed liquid；
(2) the MOFs synthesis feed liquid and rhodanine acid-mixed obtained the step (1) is closed, and is carried out hydro-thermal reaction, is obtained sieve
Tannin functionalization MOFs adsorbent.
In the present invention, unless otherwise specified, the commercial goods that used raw material is well known to those skilled in the art.
The present invention is by ZrCl4Organic solution mixed with carboxylic acids organic ligand, obtain MOFs synthesis feed liquid.In the present invention
In, the ZrCl4Organic solution in ZrCl4Amount ratio with organic solvent is preferably 1mmol:45~55mL, further preferably
For 1mmol:45~50mL；The organic solvent is preferably n,N-Dimethylformamide (DMF), as the medium of subsequent reactions,
So that sufficiently coordination forms nucleus in a solvent for metal ion and organic ligand, then continues to grow under solvent condition and obtain
MOFs crystal.The present invention is preferably by ZrCl4It is dissolved in n,N-Dimethylformamide (DMF), is obtained after 20~30min is stirred by ultrasonic
To clear ZrCl4Organic solution.
In the present invention, the carboxylic acids organic ligand preferably includes terephthalic acid (TPA) or 2- amino terephthalic acid (TPA)；When
When carboxylic acids organic ligand is terephthalic acid (TPA), the final MOFs adsorbent for obtaining rhodanine functionalization UiO-66, when the carboxylic acid
When class organic ligand is 2- amino terephthalic acid (TPA), finally obtained is rhodanine functionalization UiO-66-NH2MOFs absorption
Agent.
Carboxylic acids organic ligand is preferably added to ZrCl by the present invention4Organic solution carry out 30~40min of ultrasonic agitation,
Realize ZrCl4Organic solution and carboxylic acids organic ligand mixing.In the present invention, ZrCl in the MOFs synthesis feed liquid4With
The molar ratio of carboxylic acids organic ligand is preferably 1:1.
After obtaining MOFs synthesis feed liquid, the present invention closes MOFs synthesis feed liquid and rhodanine acid-mixed, and it is anti-to carry out hydro-thermal
It answers, obtains rhodanine functionalization MOFs adsorbent.In the present invention, the rhodanine acid preferably include rhodanine -3- acetic acid or
Rhodanine -3- propionic acid；The rhodanine acid synthesizes ZrCl in feed liquid with MOFs4, carboxylic acids organic ligand molar ratio be preferably
0.1~10:1:1, further preferably 3~8:1:1.After the rhodanine acid is preferably added to MOFs synthesis feed liquid by the present invention
20~30min is stirred by ultrasonic, realizes the mixing of MOFs synthesis feed liquid and rhodanine acid.
In the present invention, the temperature of the hydro-thermal reaction is preferably 110~150 DEG C, and further preferably 120 DEG C；It is described
The time of hydro-thermal reaction is preferably 24~72h, further preferably 48h；The hydro-thermal reaction specifically carries out in a kettle.
Present invention one-step synthesis rhodanine functionalization MOFs adsorbent in the hydrothermal reaction process is forming UiO-
While 66 class MOFs matrix, modification of the rhodanine to matrix: the octahedron and μ that 6 Zr atoms are formed is realized3- O and μ3-OH
Coordination forms inorganic metal unit Zr6O4(OH)4After metal cluster, on organic ligand terephthalic acid (TPA) or amino terephthalic acid (TPA)
Two carboxyls and rhodanine acid on a carboxyl coordination；Furthermore a small amount of amino on amino terephthalic acid (TPA) can also be with sieve
Carboxyl on tannic acid combines.
After hydro-thermal reaction, hydro-thermal reaction product is preferably successively filtered, expects washing, dry and grinding admittedly by the present invention,
Obtain rhodanine functionalization MOFs adsorbent.The present invention does not have particular/special requirement to the specific embodiment of the filtering, real with energy
Now it is separated by solid-liquid separation.Present invention preferably employs organic solvents repeatedly to wash solid material, removes unreacted substance；It is described
Washing preferably includes DMF, methanol or methylene chloride with organic solvent.After washing, the present invention is preferably by the solid material of washing 60~80
10~12h of vacuum drying DEG C is carried out, residual solvent is removed.The present invention does not have special want to the specific embodiment of the grinding
It asks, using solid abrasive lapping mode well-known to those skilled in the art, the powder of 50~100nm of partial size can be obtained.
The present invention also provides a kind of preparation method of rhodanine functionalization MOFs adsorbent described in above-mentioned technical proposal, packets
Include following steps:
(1) by ZrCl4Organic solution mixed with carboxylic acids organic ligand, carry out hydro-thermal reaction after filter, obtain UiO-
66 class MOFs；
(2) the UiO-66 class MOFs that the step (1) obtains is mixed with rhodanine acid organic solution, carries out modification synthesis
Reaction, obtains rhodanine functionalization MOFs adsorbent.
In the present invention, the carboxylic acids organic ligand preferably includes terephthalic acid (TPA) or 2- amino terephthalic acid (TPA)；When
When the carboxylic acids organic ligand is 2- amino terephthalic acid (TPA), the present invention is organic by the UiO-66 class MOFs and rhodanine acid
Before solution mixing, the rhodanine acid organic solution is mixed with I-hydroxybenzotriazole alcoholic solution preferably, obtains function material
Liquid；Carbodiimide is added after mixing with the functionalization feed liquid with UiO-66 class MOFs, carries out catalysis modification synthetic reaction.
That is: by ZrCl4Organic solution mixed with carboxylic acids organic ligand, carry out hydro-thermal reaction after filter, obtain UiO-
66 class MOFs；Rhodanine acid organic solution is mixed with I-hydroxybenzotriazole alcoholic solution, obtains functionalization feed liquid；
Carbodiimide is added after the UiO-66 class MOFs is mixed with the functionalization feed liquid, it is anti-to carry out modification synthesis
It answers, obtains rhodanine functionalization MOFs adsorbent.
In the present invention, unless otherwise specified, the commercial goods that used raw material is well known to those skilled in the art.
In the present invention, in the I-hydroxybenzotriazole alcoholic solution I-hydroxybenzotriazole and rhodanine acid molar ratio
Preferably 1~1.2:1；The molar ratio of the carbodiimide and rhodanine acid is preferably 1~1.5:1.
The present invention is by ZrCl4Organic solution mixed with carboxylic acids organic ligand, carry out hydro-thermal reaction after filter, obtain
UiO-66 class MOFs.
In the present invention, the ZrCl4Organic solution in ZrCl4Amount ratio with organic solvent is preferably 1mmol:45
~55mL, further preferably 1mmol:45~50mL；The organic solvent is preferably n,N-Dimethylformamide (DMF), together
Medium of the sample as subsequent reactions then continues so that sufficiently coordination forms nucleus in a solvent for metal ion and organic ligand
Growth obtains MOF crystal under solvent condition.The present invention is preferably by ZrCl4It is dissolved in n,N-Dimethylformamide (DMF), surpasses
Sound obtains clear ZrCl after stirring 20~30min4Organic solution.
In the present invention, when carboxylic acids organic ligand is terephthalic acid (TPA), the Luo Dan that matrix is UiO-66 is finally obtained
Peaceful functionalization MOFs adsorbent, when the carboxylic acids organic ligand is 2- amino terephthalic acid (TPA), finally obtaining matrix is
UiO-66-NH2Rhodanine functionalization MOFs adsorbent.
Carboxylic acids organic ligand is preferably added to ZrCl by the present invention4Organic solution carry out 30~40min of ultrasonic agitation,
Realize ZrCl4Organic solution and carboxylic acids organic ligand mixing.In the present invention, ZrCl in the MOFs synthesis feed liquid4With
The molar ratio of carboxylic acids organic ligand is 1:1.
Mixed liquor is carried out hydro-thermal reaction and generates UiO-66 class MOFs by the present invention；The temperature of the hydro-thermal reaction is preferably
120℃；The time of the hydro-thermal reaction is preferably 48h.
For the present invention in the hydrothermal reaction process, 6 Zr atoms form octahedra and μ3- O and μ3- OH be coordinated to be formed it is inorganic
Metal unit Zr6O4(OH)4After metal cluster, match with two carboxyls on organic ligand terephthalic acid (TPA) or amino terephthalic acid (TPA)
Position, forms the UiO-66 class MOFs of tridimensional network.When the carboxylic acids organic ligand is terephthalic acid (TPA), generation
UiO-66 class MOFs is UiO-66；When the carboxylic acids organic ligand is amino terephthalic acid (TPA), the UiO-66 class of generation
MOFs is UiO-66-NH2。
After obtaining UiO-66 class MOFs, the present invention mixes the UiO-66 class MOFs with rhodanine acid organic solution, into
Row modification synthetic reaction, obtains rhodanine functionalization MOFs adsorbent.
In the present invention, in the rhodanine acid organic solution amount ratio of rhodanine acid and organic solvent be preferably 1~
10mmol:45~55mL, further preferably 1~10mmol:50mL, more preferably 2~5mmol:50mL；The organic solvent
Preferably mixed solvent, including the first solvent and the second solvent, first solvent preferably include methylene chloride, N, N- dimethyl
One of formamide, dimethyl sulfoxide and chloroform are a variety of, and second solvent preferably includes ethyl acetate, methanol and ethyl alcohol
One of or it is a variety of；The volume ratio of first solvent and the second solvent is preferably 1:1~4, further preferably 1:2~3；
The rhodanine acid preferably includes rhodanine -3- acetic acid or rhodanine -3- propionic acid.
In the present invention, the mass ratio of the UiO-66 class MOFs and rhodanine acid is preferably 1:0.2~4, further excellent
It is selected as 1:0.5~3, more preferably 1:2.UiO-66 class MOFs is preferably added in rhodanine acid organic solution by the present invention, into
Row modification synthetic reaction.
In the present invention, the temperature of the modification synthetic reaction is preferably 20~25 DEG C；It is described modification synthetic reaction when
Between preferably 12~36h, further preferably 15~30h.Modification synthetic reaction of the present invention is preferably in the condition of condensing reflux
Lower progress；The present invention is in modification synthetic reaction process, the Zr-O cluster coordination of the carboxyl and MOFs material of rhodanine acid or and ammonia
Base condensation generates amide, forms rhodanine functionalization MOFs adsorbent.Specifically, UiO-66 and UiO-66-NH2It is assisted in solvent
Under the conditions of, on a small quantity
Terephthalic acid (TPA) (the BDC of deprotonation2-) dissociation can occur so that Zr-O metal cluster is there are unoccupied orbital, can and Luo Dan
- COOH coordination on peaceful acid (rhodanine -3- acetic acid or rhodanine -3- propionic acid), by rhodanine base group modification in MOFs material table
Face.
When the carboxylic acids organic ligand be amino terephthalic acid (TPA) when, the present invention preferably by rhodanine acid organic solution with
The mixing of I-hydroxybenzotriazole alcoholic solution, obtains functionalization feed liquid.In the present invention, Luo Dan in the rhodanine acid organic solution
Peaceful acid is consistent with preceding solution with the amount ratio of organic solvent, and details are not described herein.
In the present invention, the volume ratio of I-hydroxybenzotriazole and alcoholic solvent is excellent in the I-hydroxybenzotriazole alcoholic solution
It is selected as 1mmol:1.5~5mL, further preferably 1mmol:2.0~4mL；The alcoholic solvent is preferably methanol and/or ethyl alcohol；
I-hydroxybenzotriazole is preferably added in alcoholic solvent by the present invention, and 15~20min of ultrasonic agitation obtains clear 1- hydroxy benzenes
And triazole alcoholic solution.
I-hydroxybenzotriazole alcoholic solution is preferably added in rhodanine acid organic solution by the present invention, is stirred by ultrasonic
10~15min realizes the mixing of rhodanine acid organic solution and I-hydroxybenzotriazole alcoholic solution, obtains functionalization feed liquid.?
In the present invention, the I-hydroxybenzotriazole plays the role of promoting amino and carboxyl reaction.
In the present invention, in the I-hydroxybenzotriazole alcoholic solution I-hydroxybenzotriazole and rhodanine acid molar ratio
Preferably 1~1.2:1.
After obtaining UiO-66 class MOFs and functionalization feed liquid, the present invention is preferably by the UiO-66 class MOFs and function material
Carbodiimide is added after liquid mixing, carries out catalysis modification synthetic reaction, obtains rhodanine functionalization MOFs adsorbent.
In the present invention, the mass ratio of the UiO-66 class MOFs and rhodanine acid in functionalization feed liquid are preferably 1:0.2
~4, further preferably 1:0.5~3, more preferably 1:2.UiO-66 class MOFs is preferably added to functionalization feed liquid by the present invention
10~15min is stirred afterwards, obtains the mixed liquor of UiO-66 class MOFs and functionalization feed liquid.
The present invention mixes mixed liquor with carbodiimide, carries out catalysis modification synthetic reaction, obtains rhodanine functionalization
MOFs adsorbent.In the present invention, the molar ratio of the carbodiimide and rhodanine acid is preferably 1~1.5:1.In the present invention
In, the carbodiimide preferably includes two cyclohexyl carbon dimethylamine or 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide acid
Salt.
In the present invention, the catalysis modification synthetic reaction is acted in catalyst carbon diimine and I-hydroxybenzotriazole
Under, modification synthetic reaction occurs.In the present invention, the temperature of the catalysis modification synthetic reaction is preferably 20~25 DEG C；It is described
The time for modifying synthetic reaction is preferably 12~36h, further preferably 15~30h.Modification synthetic reaction of the present invention is excellent
It is selected under the conditions of being condensed back and carries out；Carboxylic of the present invention in modification synthetic reaction process, on carbodiimide activation rhodanine acid
Base, the intermediate product of generation react to obtain active ester with I-hydroxybenzotriazole, which reacts with amine is converted into amide；Sieve
The Zr-O cluster coordination of the carboxyl and MOFs material of tannic acid is condensed generation amide with amino, forms rhodanine functionalization MOFs and inhales
Attached dose.Specifically, UiO-66 and UiO-66-NH2Under solvent subsidiary conditions, a small amount of BDC2-Dissociation can occur so that Zr-O metal
There are unoccupied orbitals for cluster, can be coordinated with-the COOH on rhodanine sour (rhodanine -3- acetic acid or rhodanine -3- propionic acid), by rhodanine
Base group modification is in MOFs material surface；In addition, UiO-66-NH2Free-the NH in surface2Can under the conditions of activator with rhodanine-
- COOH on 3- acetic acid or rhodanine -3- propionic acid occurs heterogeneous amide and reacts to obtain the modified UiO-66-NH of rhodanine2-
Rd。
After modifying synthetic reaction or catalysis modification synthetic reaction, the present invention preferably preferably successively carried out reaction product
Filter, solid material washing, dry and grinding, obtain rhodanine functionalization MOFs adsorbent.Specific implementation of the present invention to the filtering
Mode does not have particular/special requirement, to be able to achieve separation of solid and liquid.Present invention preferably employs organic solvents repeatedly to wash solid material
It washs, removes unreacted substance；The washing preferably includes DMF, methanol or methylene chloride with organic solvent.After washing, this hair
It is bright that the solid material of washing is preferably subjected to 10~12h of vacuum drying at 60~80 DEG C, remove residual solvent.The present invention is to the grinding
Specific embodiment does not have particular/special requirement, using solid abrasive lapping mode well-known to those skilled in the art, can obtain partial size
The powder of 50~100nm.
For ease of description, the reaction mechanism of step modification synthesis of the invention, as shown in formula I:
When (a) refers to that carboxylic acids organic ligand is terephthalic acid (TPA) in formula I, after being initially formed UiO-66, by rhodanine acid
Step modification is implemented in combination with by the Zr-O cluster coordination on carboxyl and UiO-66 to synthesize, and obtains rhodanine functionalization MOFs.
When (b) refers to that carboxylic acids organic ligand is amino-terephthalic acid (TPA) in formula I, it is initially formed UiO-66-NH2Afterwards, will
Rhodanine acid passes through carboxyl and UiO-66-NH2On Zr-O cluster be coordinated and combine, while and UiO-66-NH2On deamination
In conjunction with realization one step modification synthesis obtains rhodanine functionalization MOFs.
The present invention also provides a kind of preparation method of rhodanine functionalization MOFs adsorbent described in above-mentioned technical proposal, packets
Include following steps:
(1) by ZrCl4Organic solution mixed with carboxylic acids organic ligand, carry out hydro-thermal reaction after filter, obtain UiO-
66 class MOFs；
(2) rhodanine acid organic solution is mixed with thionyl chloride, carries out acyl chloride reaction, obtains rhodanine acyl chlorides；
(3) by the step (2) obtains the organic solution of rhodanine acyl chlorides and the step (1) obtains UiO-66 class
Triethylamine is added after MOFs mixing, generation acyl chlorides is reacted with amine, obtains rhodanine functionalization MOFs adsorbent；
In the present invention, unless otherwise specified, the commercial goods that used raw material is well known to those skilled in the art.
The present invention is by ZrCl4Organic solution mixed with carboxylic acids organic ligand, carry out hydro-thermal reaction after filter, obtain
UiO-66 class MOFs.In the present invention, the preparation of the UiO-66 class MOFs and UiO-66 in aforementioned preparation process technical solution
Preparing for class MOFs is consistent, and details are not described herein.
The present invention mixes rhodanine acid organic solution with thionyl chloride, carries out acyl chloride reaction, obtains rhodanine acyl chlorides.
In the present invention, the amount ratio of rhodanine acid and organic solvent is 1~10mmol:50mL in the rhodanine acid organic solution；
The organic solvent is mixed solvent, including the first solvent and the second solvent, first solvent include methylene chloride, N, N- bis-
One of methylformamide, dimethyl sulfoxide and chloroform are a variety of, and second solvent includes ethyl acetate, methanol and ethyl alcohol
One of or it is a variety of；The mixed solvent is more preferably methylene chloride and ethyl acetate；First solvent and the second solvent
Volume ratio be 1:1~4；The rhodanine acid includes rhodanine -3- acetic acid or rhodanine -3- propionic acid.In the present invention, described
The molar ratio of rhodanine acid and thionyl chloride is preferably 1:1~2 in rhodanine acid organic solution.
The thionyl chloride is preferably added drop-wise in rhodanine acid organic solution by the present invention, is condensed in a nitrogen atmosphere
Acyl chloride reaction occurs for reflux, obtains rhodanine acyl chlorides.The present invention improves amide reaction efficiency for after carboxyl chloride, can be big
It is big to improve the amount for being supported on rhodanine on the surface UiO-66 class MOFs.
After obtaining UiO-66 class MOFs and rhodanine acyl chlorides, the present invention is by the organic solution and UiO- of the rhodanine acyl chlorides
Triethylamine is added after 66 class MOFs mixing, generation acyl chlorides is reacted with amine, obtains rhodanine functionalization MOFs adsorbent.
In the present invention, organic solvent is preferably methylene chloride or tetrahydro furan in the organic solution of the rhodanine acyl chlorides
It mutters；The amount ratio of rhodanine acyl chlorides and organic solvent is preferably 1~25mmol in the organic solution of the rhodanine acyl chlorides:
60mL can be realized the abundant dissolution to rhodanine acyl chlorides.After rhodanine acyl chlorides is preferably added to organic solvent by the present invention, surpass
Sound stirs 15~20min, obtains the organic solution of rhodanine acyl chlorides.
The present invention preferably by UiO-66 class MOFs be added to ultrasonic agitation 15 after the organic solution of rhodanine acyl chlorides~
20min realizes uniform the mixing of the organic solution with UiO-66 class MOFs, obtains mixed liquor.
Triethylamine is added into the mixed liquor by the present invention, and generation acyl chlorides is reacted with amine, obtains rhodanine functionalization
MOFs adsorbent.In the present invention, the molar ratio of the triethylamine and rhodanine acyl chlorides in mixed liquor is preferably 1~1.5:1,
Further preferably 1~1.2:1.In the present invention, the triethylamine plays the role of acid binding agent, institute can be reacted with amine with acyl chlorides
The HCl of generation reacts, and then promotes the progress of goal response；Reacting for acyl chlorides and amine occur for the present invention, rhodanine acyl chlorides with
UiO-66 class MOFs reaction realizes that the Zr-O cluster of group containing rhodanine and MOFs material is coordinated or generates amide with amino condensation,
Form rhodanine functionalization MOFs adsorbent.
After the reacting of acyl chlorides and amine, reaction product is preferably successively filtered by the present invention, material washing, dry and grind admittedly
Mill, obtains rhodanine functionalization MOFs adsorbent.The present invention does not have particular/special requirement to the specific embodiment of the filtering, with energy
It realizes and is separated by solid-liquid separation.Present invention preferably employs organic solvents repeatedly to wash solid material, removes unreacted substance；Institute
It states washing and preferably includes DMF, methanol, tetrahydrofuran or methylene chloride with organic solvent.After washing, the present invention is preferably solid by washing
Material carries out 10~12h of vacuum drying at 60~80 DEG C, removes residual solvent.The present invention does not have the specific embodiment of the grinding
There is particular/special requirement, using solid abrasive lapping mode well-known to those skilled in the art, the powder of 50~100nm of partial size can be obtained
?.
For ease of description, the reaction mechanism of multi step modification synthesis of the present invention, as shown in formula II, formula III and formula IV:
Carboxylic acids organic ligand in reaction is terephthalic acid (TPA) and amino-terephthalic acid (TPA), is first formed with metal Zr
UiO-66 class MOFs carries out subsequent modification synthesis again.Rhodanine acid is initially formed rhodanine acyl chlorides (such as formula II), then by rhodanine acyl
μ in Zr-O cluster on chlorine and MOFs matrix3- OH and Zr coordination, obtains rhodanine functionalization MOFs (formula III)；In addition, rhodanine
Acyl chlorides can also be with UiO-66-NH2On amino occur amidation process, by rhodanine base group modification in the surface MOFs (formula IV).
The present invention also provides the rhodanine functionalization MOFs adsorbents or above-mentioned technical proposal described in above-mentioned technical proposal
Application of the rhodanine functionalization MOFs adsorbent that the preparation method is prepared in the selection absorption of water body silver ion；Institute
It states to apply and preferably include: the rhodanine functionalization MOFs adsorbent being added in silver ion water body to be adsorbed, stirring is inhaled
It is attached.The present invention does not have particular/special requirement to the source of the silver ion water body to be adsorbed, need to arbitrarily carry out silver ion selection absorption
Water body；In an embodiment of the present invention, Cu, Co, Ni, Pb, Li, K and Ag various metals pair can be contained in the water body
The ion answered；The concentration of every metal ion species is preferably 0.1~10mmol/L in the water body, further preferably 1.0~
8.0mmol/L.In the present invention, the dosage of the rhodanine functionalization MOFs adsorbent is with the body of silver ion water body to be adsorbed
Product meter, preferably 1g:500~2500mL, further preferably 1g:1500~2500mL.
In the present invention, the time of the stirring and adsorbing is preferably 5~8h, further preferably 5.5~7.5h, more preferably
For 6~7h；The stirring and adsorbing preferably carries out at room temperature, and without additional heating, cost is relatively low.After the stirring and adsorbing, this
Invention, which is preferably filtered, realizes recycling to adsorbent, and then water body after being adsorbed.The present invention is specific to the filtering
Embodiment does not have particular/special requirement, using mode well-known to those skilled in the art.
In order to further illustrate the present invention, with reference to the accompanying drawings and examples to rhodanine functionalization provided by the invention
MOFs adsorbent and its preparation method and application is described in detail, but they cannot be interpreted as to the scope of the present invention
Restriction.
A. the peaceful functionalization UiO-66 class MOFs adsorbent of the direct synthesizing rhodamine of one step hydro thermal method:
Embodiment 1
(1) by 0.24g (about 1.03mmol) ZrCl4Solve homogeneously in 50mLN, in dinethylformamide (DMF), ultrasound
Clear solution is obtained after stirring 20min, then 0.18g (about 1.08mmol) organic ligand 2- amino terephthalic acid (TPA) is added, after
Continuous ultrasonic agitation 30min, is completely dissolved to solid, obtains mixed liquor；
(2) 0.96g (5mmol) rhodanine -3- acetic acid is added in mixed liquor obtained in step (1), continues to surpass
Sound stirring 30min is transferred in 100mL reaction kettle after solid is completely dissolved to obtain clear solution, is put into 120 DEG C of baking ovens
React 48h；
(3) it is filtered after being cooled to room temperature, obtained sediment DMF, methanol and methylene chloride mixed organic solvents are anti-
After backwashing is washed repeatedly；
(4) product after washing is put into 80 DEG C of vacuum ovens dry 12h, grinding, obtaining partial size is 50~100nm's
Lavender powder is that rhodanine functionalization UiO-66 class MOFs adsorbent (is denoted as UiO-66-NH2-5Rd-A)。
Embodiment 2
Rhodanine functionalization MOFs adsorbent is prepared in the way of embodiment 1, difference is, in step (1), uses
Organic ligand is terephthalic acid (TPA), dosage 0.16g.It obtains rhodanine functionalization UiO-66 class MOFs adsorbent and (is denoted as UiO-
66-5Rd-A)。
Embodiment 3~7
Rhodanine functionalization MOFs adsorbent is prepared in the way of embodiment 1, difference is, in step (2), addition
Rhodanine -3- acetic acid dosage is respectively 0.096g, 0.192g, 0.576g, 1.536g and 1.92g, obtained rhodanine function
Change UiO-66 class MOFs adsorbent and is denoted as UiO-66-NH respectively2-0.5Rd-A、UiO-66-NH2-1Rd-A、UiO-66-NH2-
3Rd-A、UiO-66-NH2-8Rd-A、UiO-66-NH2-10Rd-A。
Embodiment 8~12
Rhodanine functionalization MOFs adsorbent is prepared in the way of embodiment 2, difference is, the rhodanine -3- of addition
Acetic acid dosage is respectively 0.096g, 0.192g, 0.576g, 1.536g and 1.92g, obtained rhodanine functionalization UiO-66 class
MOFs adsorbent is denoted as UiO-66-0.5Rd-A, UiO-66-1Rd-A, UiO-66-3Rd-A, UiO-66-8Rd-A, UiO- respectively
66-10Rd-A。
The UiO-66 and UiO-66-NH of adsorbent and non-rhodanine functionalization that embodiment 1~12 is obtained2, respectively
Carry out silver ion absorption.
Isothermal adsorption process are as follows: be added in 100mL conical flask 20mg adsorbent and 20mL various concentration (50~
Ag (I) solution 1000mg/L), shakes 6h in 25 DEG C of constant temperature oscillation boxes, up to adsorption equilibrium after filter, use atomic absorption spectrum
Instrument measures the concentration of Ag in filtrate (I) under certain condition；To be the absorption feelings of 50 and 500mg/L silver ion to initial concentration
For condition, the adsorption capacity of every kind of adsorbent is as shown in table 1.
The UiO-66 and UiO-66-NH of adsorbent and non-rhodanine functionalization that 1 embodiment 1~12 of table obtains2To first
Beginning concentration is the absorption situation of 50 and 500mg/L silver ion
As shown in Table 1, with the increase for adding rhodanine amount, preparation-obtained adsorbent is to silver-colored adsorption capacity also phase
It is slightly reduced after should first increasing, adds 5mmol rhodanine amount to be optimal and add ratio；Add the case where rhodanine is isodose
Under, the adsorption capacity of the adsorbent being prepared containing amino ligands will be than the adsorbent adsorption capacity that obtains without amino more
Greatly.
The Ag that dynamic absorption experiment: being added 100mg adsorbent in 250mL beaker and 100mL concentration is 40mg/L
(I) solution, magnetic agitation, takes out certain volume solution at regular intervals at room temperature, and filtering is existed with Atomic Absorption Spectrometer
The concentration of Ag (I) in filtrate is measured under certain condition, and calculates adsorption capacity.
The adsorption kinetic data is carried out according to the adsorbent obtained to embodiment 1~12, obtains time of equilibrium adsorption；Simultaneously
Adsorption isotherm experiment is carried out, maximum adsorption capacity is obtained.The results showed that the adsorbent that the embodiment 1 obtains can be in 15min
Inside reach adsorption equilibrium, and maximum adsorption capacity is up to 100.25mg/g, 5 times of about original UiO-66 adsorption capacity, UiO-
66-NH22 times of adsorption capacity.When adsorbent is in Ag (I), K (I), Li (I), Pb (II), Ni (II), Co (II) and Cu (II)
When concentration is in the mixed solution of 1mmol/L, there is Selective adsorption, adsorbance 0.58mmol/g to Ag (I), and other are golden
The adsorbance maximum for belonging to ion is only 0.09mmol/g.
The UiO-66 and UiO-66-NH of adsorbent and non-rhodanine functionalization that embodiment 1~12 is obtained2Material into
The analysis of row XRD characterization.Fig. 1 is all adsorbent materials and the XRD diagram for simulating the UiO-66 being calculated.As can be seen from Figure 1: institute
There is the sorbent material being prepared consistent with the characteristic peak of UiO-66 that simulation calculates, the UiO-66 after rhodanine load is still
Original characteristic peak is maintained, illustrates that adsorbent and UiO-66's flutters that open up structure identical.
B. the step modification peaceful functionalization UiO-66 class MOFs adsorbent of synthesizing rhodamine is modified afterwards:
Embodiment 13
(1) by 0.48g ZrCl4It solves homogeneously in 100mL DMF, obtains clear solution after 20min is stirred by ultrasonic, then
0.36g 2- amino terephthalic acid (TPA) is added, continues that 30min is stirred by ultrasonic, is put into reaction kettle after solid is completely dissolved,
48h is reacted in 120 DEG C of baking oven, is filtered after being cooled to room temperature, the repeated multiple times washing of DMF of obtained sediment is removed
Unreacting substance, filtered product are dried in vacuo under 100 DEG C of baking ovens, grinding, and obtaining partial size is the faint yellow of 50~100nm
Powder is UiO-66-NH2；
(2) 0.96g (5mmol) rhodanine -3- acetic acid is dispersed in the mixing of 25mL methylene chloride Yu 25mL ethyl acetate
In solvent, 10min is stirred by ultrasonic, is completely dissolved to it；
(3) 0.75g I-hydroxybenzotriazole is dissolved in 10mL methanol solution, 15min is stirred by ultrasonic, it is clear to solution
It is added in above-mentioned steps (2) after clear, 10min is stirred by ultrasonic, be uniformly mixed solution；
(4) the material UiO-66-NH for taking 0.5g above-mentioned steps (1) to synthesize2, it is resulting to be dispersed in above-mentioned steps (3)
In mixed solution, it is slowly added to 1.15g carbodiimide after stirring 10min, is condensed back at room temperature for 24 hours；
(5) the repeated multiple times washing of product methanol that will be obtained by filtration after reaction；
(6) filtered product is ground after being put into 80 DEG C of vacuum ovens dry 12h, and obtained partial size is 50~
100nm khaki powder is that rhodanine functionalization UiO-66 class MOFs adsorbent (is denoted as UiO-66-NH2-5Rd-B)。
Embodiment 14
Rhodanine functionalization MOFs adsorbent is prepared in the way of embodiment 13, difference is: in step (1), using
Organic ligand be terephthalic acid (TPA), dosage 0.32g；Step (3) does not need to carry out；Step (4) does not need that two Asia of carbon is added
Amine directly takes the material UiO-66 synthesized in 0.5g above-mentioned steps (1), and it is molten to be dispersed in the resulting mixing of above-mentioned steps (2)
In liquid, it is condensed back at room temperature for 24 hours.Obtain rhodanine functionalization UiO-66 class MOFs adsorbent (being denoted as UiO-66-5Rd-B).
Embodiment 15~18
Rhodanine functionalization MOFs adsorbent is prepared in the way of embodiment 13, difference is: in step (2), being added
Rhodanine -3- acetic acid dosage be respectively 0.192g, 0.576g, 1.536g and 1.92g；In step (3), the 1- hydroxyl of addition
Benzotriazole dosage is respectively 0.15g, 0.45g, 1.2g and 1.5g；In step (4), the carbodiimide dosage of addition is respectively
0.23g, 0.69g, 1.84g and 2.3g.Obtained rhodanine functionalization UiO-66 class MOFs adsorbent is denoted as UiO-66- respectively
NH2-1Rd-B、UiO-66-NH2-3Rd-B、UiO-66-NH2-8Rd-B、UiO-66-NH2-10Rd-B。
Embodiment 19~22
Rhodanine functionalization MOFs adsorbent is prepared in the way of embodiment 14, difference is, in step (2), is added
Rhodanine -3- acetic acid dosage be respectively 0.192g, 0.576g, 1.536g and 1.92g.Obtained rhodanine functionalization UiO-
66 class MOFs adsorbents are denoted as UiO-66-1Rd-B, UiO-66-3Rd-B, UiO-66-8Rd-B, UiO-66-10Rd-B respectively.
The UiO-66 and UiO-66-NH of adsorbent and non-rhodanine functionalization that embodiment 13~22 is obtained2, respectively
Carry out silver ion adsorption experiment.Isothermal adsorption and dynamics adsorption experiment are consistent in embodiment 1~12, no longer superfluous herein
It states.
For during isothermal adsorption to initial concentration being the absorption situation of 50 and 500mg/L silver ion, every kind of absorption
The adsorption capacity of agent is as shown in table 2.
The UiO-66 and UiO-66-NH of adsorbent and non-rhodanine functionalization that 2 embodiment 13~22 of table obtains2To first
Beginning concentration is the absorption situation of 50 and 500mg/L silver ion
As shown in Table 2, with the increase of modification rhodanine amount, preparation-obtained adsorbent is to silver-colored adsorption capacity also phase
It is slightly reduced after should first increasing, modification 5mmol rhodanine amount adds ratio to be optimal；Modify the case where rhodanine is isodose
Under, the adsorption capacity of the adsorbent being prepared containing amino ligands will be than the adsorbent adsorption capacity that obtains without amino more
Greatly.
The adsorption kinetic data is carried out by the adsorbent obtained to embodiment 13~22, obtains time of equilibrium adsorption；Simultaneously
By adsorption isotherm experiment, maximum adsorption capacity is obtained.The results showed that adsorbent can reach adsorption equilibrium in 10min, and
Maximum adsorption capacity is up to 149.6mg/g, and 7 times of about original UiO-66 adsorption capacity, UiO-66-NH2The 3 of adsorption capacity
Times；When adsorbent Ag (I), K (I), Li (I), Pb (II), Ni (II), Co (II) and Cu (II) and concentration be 1mmol/L
Mixed solution in when, there is Selective adsorption, adsorbance 0.78mmol/g, and the adsorbance of other metal ions to Ag (I)
Maximum is only 0.03mmol/g.
Fig. 2 is the UiO-66 class MOFs adsorbent for the modification 5mmol rhodanine amount that embodiment 13 and 14 obtains, simulation UiO-
66 and non-rhodanine functionalization UiO-66 and UiO-66-NH2XRD diagram.From figure 3, it can be seen that after grafting rhodanine
Material characteristics peak do not change, adsorbent maintains identical flutter of UiO-66 and opens up structure after illustrating grafting.
Fig. 3 is that the rhodanine functionalization MOFs adsorbent adsorption-desorption cycle that embodiment 13 and 14 obtains is inhaled using the 5th
XRD diagram (the UiO-66-NH in Fig. 3 of attached silver front and back2Before -5Rd-B and UiO-66-5Rd-B respectively indicates circulation absorption the 5th
XRD diagram, UiO-66-NH2- 5Rd-B@Ag (I) and UiO-66-5Rd-B@Ag (I) respectively indicate the XRD after circulation absorption the 5th
Figure).From figure 3, it can be seen that characteristic peak remains unchanged, illustrate that material has excellent water stability.In addition, embodiment 13 is made
When adsorption-desorption cycle utilizes the 4th time, adsorption capacity is still able to maintain original standby rhodanine functionalization MOFs adsorbent
85% or more, illustrate that material has good regenerability.
C. modification multistep reaction modifies the peaceful functionalization UiO-66 class MOFs adsorbent of synthesizing rhodamine afterwards:
Embodiment 23
(1) by 0.48g ZrCl4It solves homogeneously in 50mLDMF, obtains clear solution after 20min is stirred by ultrasonic, then will
0.36g 2- amino terephthalic acid (TPA) is added, and continues that 30min is stirred by ultrasonic, is put into reaction kettle after solid is completely dissolved,
48h is reacted in 120 DEG C of baking oven, is filtered after being cooled to room temperature, the organic solvents such as obtained sediment methylene chloride are anti-
Multiple repeatedly washing removes unreacting substance, and filtered product is dried in vacuo under 100 DEG C of baking ovens, is ground, and obtained partial size is
50~100nm pale yellow powder is UiO-66-NH2；
(2) 3.84g (20mmol) rhodanine -3- acetic acid is dispersed in the mixed solution of 30mL chloroform Yu 30mL ethyl acetate
In, after 20min is stirred by ultrasonic, it is completely dissolved to solid；
(3) it is slowly dropped into 4mL thionyl chloride in above-mentioned (2) mixed solution, is condensed back to for 60 DEG C under the conditions of nitrogen protection
12h is flowed, 40 DEG C of revolvings after cooling, 60 DEG C of revolvings, obtain rhodanine -3- chloroacetic chloride after again with toluene dissolution；
(4) rhodanine -3- chloroacetic chloride obtained above is dissolved in 60mL dichloromethane solvent, 20min is stirred by ultrasonic,
After solution is uniform, the 0.5g UiO-66-NH of above-mentioned steps (1) preparation is added2Material, stirring 10min divide material uniformly
It dissipates；
(5) 4mL triethylamine, 25 DEG C of condensing refluxes under the conditions of nitrogen protection are slowly dropped into above-mentioned (4) mixed solution
36h；
(6) the repeated multiple times washing of product tetrahydrofuran that will be obtained by filtration after reaction；
(7) filtered product is ground after being put into 80 DEG C of vacuum ovens dry 12h, and obtained brown-black powder is sieve
Tannin functionalization UiO-66 class MOFs adsorbent (is denoted as UiO-66-NH2-20Rd-C)。
Embodiment 24
Rhodanine functionalization MOFs adsorbent is prepared in the way of embodiment 23, difference is: in step (1), using
Organic ligand be terephthalic acid (TPA), dosage 0.32g；In step (4), the UiO-66 of 0.5g above-mentioned steps (1) preparation is added
Material, stirring 10min keep material evenly dispersed.It obtains rhodanine functionalization UiO-66 class MOFs adsorbent and (is denoted as UiO-66-
20Rd-C)。
Embodiment 25~28
Rhodanine functionalization MOFs adsorbent is prepared in the way of embodiment 23, difference is: in step (2), being added
Rhodanine -3- acetic acid dosage be respectively 0.96g, 1.92g, 2.88g and 4.8g；In step (3), the thionyl chloride of addition is used
Amount is respectively 1mL, 2mL, 3mL and 5mL；In step (5), the triethylamine dosage of addition be respectively 1mL, 2mL, 3mL and
5mL.Obtained rhodanine functionalization UiO-66 class MOFs adsorbent is denoted as UiO-66-NH respectively2-5Rd-C、UiO-66-NH2-
10Rd-C、UiO-66-NH2-15Rd-C、UiO-66-NH2-25Rd-C。
Embodiment 29~32
Rhodanine functionalization MOFs adsorbent is prepared in the way of embodiment 24, difference is: in step (2), being added
Rhodanine -3- acetic acid dosage be respectively 0.96g, 1.92g, 2.88g and 4.8g；In step (3), the thionyl chloride of addition is used
Amount is respectively 1mL, 2mL, 3mL and 5mL；In step (5), the triethylamine dosage of addition be respectively 1mL, 2mL, 3mL and
5mL.Obtained rhodanine functionalization UiO-66 class MOFs adsorbent be denoted as respectively UiO-66-5Rd-C, UiO-66-10Rd-C,
UiO-66-15Rd-C、UiO-66-25Rd-C。
The UiO-66 and UiO-66-NH of adsorbent and non-rhodanine functionalization that embodiment 23~32 is obtained2, respectively
Carry out silver ion adsorption experiment.Isothermal adsorption and dynamics adsorption experiment are consistent in embodiment 1~12, no longer superfluous herein
It states.
For during isothermal adsorption to initial concentration being the absorption situation of 50 and 800mg/L silver ion, every kind of absorption
The adsorption capacity of agent is as shown in table 3.
The UiO-66 and UiO-66-NH of adsorbent and non-rhodanine functionalization that 3 embodiment 23~32 of table obtains2To first
Beginning concentration is the absorption situation of 50 and 800mg/L silver ion
As shown in Table 3, modified material adsorption capacity significantly improves, and when grafting amount is 20mmol rhodanine, material
Up to maximum, and when continuing growing rhodanine amount, the adsorbance of material significantly reduces the adsorption capacity of material.In addition, modification rhodanine
In the case where for isodose, the adsorption capacity of the adsorbent being prepared containing amino ligands will be than the absorption that obtain without amino
Agent adsorption capacity is bigger.
The UiO-66 and UiO-66-NH of adsorbent and non-rhodanine functionalization that embodiment 23~32 is obtained2It carries out
XRD characterization analysis, as a result as shown in Figure 4.Figure 4, it is seen that material when increasing to 20mmol of grafting rhodanine amount
The peak material XRD that is still obtained with the peak dosage that is consistent, and continues growing rhodanine of simulation UiO-66 of characteristic peak occur
Variation, illustrates that material structure is collapsed after continuing increasing amount.
The UiO-66 and UiO-66-NH of adsorbent and non-rhodanine functionalization that embodiment 23 and 24 is prepared2
The competitive Adsorption experiment of hybrid ionic is carried out.50mg adsorbent is added in 100mL conical flask and 50mL contains Ag (I), K
(I), Li (I), Pb (II), Ni (II), Co (II) and Cu (II) concentration are the mixed solution of 10mmol/L, are shaken in 25 DEG C of constant temperature
Swing and shake 6h in case, up to adsorption equilibrium after filter, with Atomic Absorption Spectrometer under certain condition come measure in filtrate metal from
The concentration of son, the results are shown in Table 4 for adsorption capacity.As can be seen from Table 4, the rhodanine that embodiment 23 is prepared is modified
Adsorbent has high selection adsorptivity, adsorbance 8.5mmol/g to Ag (I), and the adsorbance maximum of other metal ions is only
0.17mmol/g。
The rhodanine functionalization UiO-66 class MOFs adsorbent and non-rhodanine functionalization that 4 embodiment 23 and 24 of table obtains
UiO-66 and UiO-66-NH2It is the selective absorption situation of 10mmol/L hybrid ionic to initial concentration
The UiO-66 and UiO-66-NH of the adsorbent and non-rhodanine functionalization that be prepared by embodiment 23 and 242
The dynamic absorption of progress is tested, and dynamic absorption figure is obtained, as a result as shown in figure 5, from figure 5 it can be seen that rhodanine changes
The rate of adsorption of material significantly improves after property, and removal rate may be up to 99% or more in 2min.
The adsorption kinetic data is carried out by the adsorbent obtained to embodiment 23~32, obtains time of equilibrium adsorption；Simultaneously
By adsorption isotherm experiment, maximum adsorption capacity is obtained.The results showed that the maximum adsorption capacity of adsorbent is up to 923.9mg/
G, 44 times of about original UiO-66 adsorption capacity, UiO-66-NH217 times of adsorption capacity.When adsorbent Ag (I), K (I),
Concentration when being in the mixed solution of 10mmol/L of Li (I), Pb (II), Ni (II), Co (II) and Cu (II), have Ag (I)
There are Selective adsorption, adsorbance 8.5mmol/g, and the adsorbance maximum of other metal ions is only 0.17mmol/g；In addition, should
Material has the excellent rate of adsorption, in 2min, may be up to 99.2% to the silver ion removal rate that initial concentration is 40mg/L.
The rhodanine functionalization MOFs adsorbent that above embodiments obtain is detected by XPS elemental analysis, it was demonstrated that
The mass ratio of the obtained Zr and S element in rhodanine functionalization MOFs adsorbent is 1:0.02~20.
As seen from the above embodiment, rhodanine functionalization MOFs adsorbent provided by the invention is with stable Zr-MOFs
Base material and Rhodanine derivates are the functional group for having targeting characterization of adsorption to Ag, and rhodanine is introduced into Zr-
In MOF structure, rhodanine functionalization MOFs adsorbent is obtained, realizes the selective absorption of Ag in water body.
Reaction raw material sources used in preparation process of the present invention are abundant, and inexpensively, production cost is low for price, is easy to
Scale business application.
Although above-described embodiment is made that detailed description to the present invention, it is only a part of the embodiment of the present invention,
Rather than whole embodiments, people can also obtain other embodiments under the premise of without creativeness according to the present embodiment, these
Embodiment belongs to the scope of the present invention.
Claims (10)
1. a kind of rhodanine functionalization MOFs adsorbent, including UiO-66 class MOFs matrix and modification rhodanine group.
2. rhodanine functionalization MOFs adsorbent according to claim 1, which is characterized in that the UiO-66 class MOFs base
Body includes UiO-66 or UiO-66-NH2。
3. a kind of preparation method of rhodanine functionalization MOFs adsorbent as claimed in claim 1 or 2, comprising the following steps:
(1) by ZrCl4Organic solution mixed with carboxylic acids organic ligand, obtain MOFs synthesis feed liquid；
(2) the MOFs synthesis feed liquid and rhodanine acid-mixed obtained the step (1) is closed, and is carried out hydro-thermal reaction, is obtained rhodanine
Functionalization MOFs adsorbent.
4. preparation method according to claim 3, which is characterized in that carboxylic acids organic ligand includes in the step (1)
Terephthalic acid (TPA) or 2- amino terephthalic acid (TPA)；
Step (2) the rhodanine acid includes rhodanine -3- acetic acid or rhodanine -3- propionic acid；
Step (2) the rhodanine acid synthesizes ZrCl in feed liquid with MOFs4, carboxylic acids organic ligand molar ratio be 0.1~10:
1:1；
The temperature of hydro-thermal reaction is 110~150 DEG C in the step (2), and the time is 24~72h.
5. a kind of preparation method of rhodanine functionalization MOFs adsorbent as claimed in claim 1 or 2, comprising the following steps:
(1) by ZrCl4Organic solution mixed with carboxylic acids organic ligand, carry out hydro-thermal reaction after filter, obtain UiO-66 class
MOFs；
(2) the UiO-66 class MOFs that the step (1) obtains is mixed with rhodanine acid organic solution, it is anti-carries out modification synthesis
It answers, obtains rhodanine functionalization MOFs adsorbent.
6. preparation method according to claim 5, which is characterized in that ZrCl in the step (1)4With carboxylic acids is organic matches
The molar ratio of body is 1:1, and carboxylic acids organic ligand includes terephthalic acid (TPA) or 2- amino terephthalic acid (TPA), the temperature of hydro-thermal reaction
It is 120 DEG C, time 48h；
Step (2) the rhodanine acid includes rhodanine -3- acetic acid or rhodanine -3- propionic acid；
When the carboxylic acids organic ligand is 2- amino terephthalic acid (TPA), UiO-66 class MOFs and Luo Dan in the step (2)
Before peaceful acid organic solution mixing, the rhodanine acid organic solution is mixed with I-hydroxybenzotriazole alcoholic solution, obtains function
Material liquid；Carbodiimide is added after mixing with the functionalization feed liquid with UiO-66 class MOFs, carries out catalysis modification synthetic reaction；
The mass ratio of the UiO-66 class MOFs and rhodanine acid is 1:0.2~5；1- in the I-hydroxybenzotriazole alcoholic solution
The molar ratio of hydroxybenzotriazole and rhodanine acid is 1~1.2:1；The molar ratio of the carbodiimide and rhodanine acid for 1~
1.5:1。
7. a kind of preparation method of rhodanine functionalization MOFs adsorbent as claimed in claim 1 or 2, comprising the following steps:
(1) by ZrCl4Organic solution mixed with carboxylic acids organic ligand, carry out hydro-thermal reaction after filter, obtain UiO-66 class
MOFs；
(2) rhodanine acid organic solution is mixed with thionyl chloride, carries out acyl chloride reaction, obtains rhodanine acyl chlorides；
(3) the UiO-66 class MOFs that the step (2) obtains the organic solution of rhodanine acyl chlorides and the step (1) obtains is mixed
Triethylamine is added after conjunction, generation acyl chlorides is reacted with amine, obtains rhodanine functionalization MOFs adsorbent.
8. preparation method according to claim 7, which is characterized in that ZrCl in the step (1)4With carboxylic acids is organic matches
The molar ratio of body is 1:1；The carboxylic acids organic ligand includes terephthalic acid (TPA) or 2- amino terephthalic acid (TPA)；
The temperature of hydro-thermal reaction is 120 DEG C in the step (1), time 48h；
The molar ratio of rhodanine acid and thionyl chloride is 1:1~2 in the step (2)；
Step (2) the rhodanine acid includes rhodanine -3- acetic acid or rhodanine -3- propionic acid；
The temperature of acyl chloride reaction is 50~60 DEG C in the step (2), and the time is 6~12h；
The amount ratio of rhodanine acyl chlorides and addition UiO-66 class MOFs are 1 in the organic solution of step (3) the rhodanine acyl chlorides
~25mmol:0.5g；
The molar ratio of triethylamine and rhodanine acyl chlorides is 1~1.5:1 in the step (3)；
The reaction temperature of acyl chlorides and amine is 20~25 DEG C in the step (3), and the reaction time is 12~36h.
9. described in the described in any item rhodanine functionalization MOFs adsorbents of claim 1~2 or any one of claim 3~8
Application of the rhodanine functionalization MOFs adsorbent that is prepared of preparation method in the selection absorption of water body silver ion.
10. application according to claim 9, which is characterized in that the application includes: by the rhodanine functionalization MOFs
Adsorbent is added in silver ion water body to be adsorbed, stirring and adsorbing.
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