CN113000036A - Bis-thiourea modified Zr-MOF adsorption material, preparation method and application - Google Patents

Bis-thiourea modified Zr-MOF adsorption material, preparation method and application Download PDF

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CN113000036A
CN113000036A CN202110333858.XA CN202110333858A CN113000036A CN 113000036 A CN113000036 A CN 113000036A CN 202110333858 A CN202110333858 A CN 202110333858A CN 113000036 A CN113000036 A CN 113000036A
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郭军康
范小虎
张蕾
王家园
王磊
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Shaanxi University of Science and Technology
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Abstract

The invention discloses a dual-thiourea modified Zr-MOF adsorbing material, a preparation method and application. According to the preparation method of the bis-thiourea modified Zr-MOF adsorption material, bis-thiourea molecules are grafted on a metal organic framework through an amine-aldehyde condensation reaction, the synthesis method is simple, the cost is low, and the method is used for large-scale production. According to the dual-thiourea modified Zr-MOF adsorption material, due to the introduction of dual-thiourea molecules, the adsorption performance of MOF is greatly improved. The application of the dual-thiourea modified Zr-MOF adsorbing material is not interfered by metal ions such as Cu (II), Fe (III), Zn (II), Mn (II) and the like, has extremely high selectivity on Au (III), has extremely strong reducibility on UiO-66-BTU, preferentially reduces Au (III) into simple substances, and saves a large number of complicated subsequent steps compared with the traditional gold recovery process.

Description

Bis-thiourea modified Zr-MOF adsorption material, preparation method and application
Technical Field
The invention belongs to the field of Zr-MOF modification, and particularly relates to a dual-thiourea modified Zr-MOF adsorption material, and a preparation method and application thereof.
Background
Gold has been playing a role in jewelry and currency in human society. In recent decades, the gold demand has increased dramatically, especially due to the explosive increase in high-tech fields such as catalysis, electronic and electrical devices, aerospace, medical treatment, etc., which is irreplaceable. However, the current gold supply is not able to meet the ever increasing demand and the reserves of gold ores are constantly decreasing, so there has been a great interest in developing efficient and economical methods for recovering gold from industrial wastes, mine tailings and leach residues.
At present, various technologies such as extraction, electrodeposition, membrane separation, adsorption and the like are developed and adopted to recover gold ions in wastewater. Among these methods, the adsorption method is an attractive option because of its simplicity of operation, economy and environmental friendliness. The application of the traditional adsorbents such as chitosan resin, porous carbon, nano materials and the like in the recovery of the waste gold is researched. However, the recovery of gold is seriously hindered by low adsorption amount, poor selectivity, weak binding affinity and high energy consumption in industrial production.
Disclosure of Invention
The invention aims to overcome the defects of low adsorption capacity and poor selectivity of the existing gold adsorbent and provides a dual-thiourea modified Zr-MOF adsorption material, a preparation method and application.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a preparation method of a dual-thiourea modified Zr-MOF adsorption material comprises the following steps of using UiO-66-NH2Is a metal organic framework, glyoxal is a cross-linking agent, and a bithiourea molecule is grafted on UiO-66-NH through an amine-aldehyde condensation reaction2Thus, UiO-66-BTU was obtained.
Further, the specific operation is as follows:
mixing UiO-66-NH2And dispersing the dithiourea into deionized water, adding glyoxal, heating in a water bath, reacting under stirring, washing after the reaction is finished, and drying to obtain UiO-66-BTU.
Further, the method comprises3g of UiO-66-NH2And 3g of dithiourea are uniformly dispersed in 100mL of deionized water, heated and stirred at 60 ℃ for 20min, then 16mL of glyoxal is added dropwise, and the mixture reacts for 6h under the condition of heating and stirring in a water bath at 60 ℃.
Further, the UiO-66-NH2The preparation method comprises the following steps:
reacting ZrCl4And NH2-BDC is dissolved in DMF, then hydrochloric acid and acetic acid are added to obtain reaction liquid, the reaction liquid is transferred to a polytetrafluoroethylene high-pressure tank and heated in a microwave extraction instrument, and a reactant is obtained after the reaction is finished; then washing and drying to obtain UiO-66-NH2。
Furthermore, 699mg ZrCl was added to the reaction solution per 70mL DMF4、543mg NH2-BDC, 0.5mL hydrochloric acid and 3mL acetic acid;
wherein, the concentration of the hydrochloric acid is concentrated hydrochloric acid, and the concentration of the acetic acid is 36%.
Further, the reaction conditions are as follows: heating with microwave at 120 deg.C for 45 min.
Further, the washing operation is: washed with DMF, methanol and dichloromethane.
The invention discloses a dual-thiourea modified Zr-MOF adsorbing material which is prepared according to the preparation method.
Further, the metal ion selective adsorbent is used for selectively adsorbing gold ions and reducing the gold ions into gold simple substances.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the bis-thiourea modified Zr-MOF adsorption material, bis-thiourea molecules are grafted on a metal organic framework through an amine-aldehyde condensation reaction, the synthesis method is simple, the cost is low, and the method is used for large-scale production.
According to the dual-thiourea modified Zr-MOF adsorption material, due to the introduction of dual-thiourea molecules, the adsorption performance of MOF is greatly improved.
The application of the dual-thiourea modified Zr-MOF adsorbing material is not interfered by Cu (II), Fe (III), Zn (II) and Mn (II) metal ions, has extremely high selectivity on Au (III), has extremely strong reducibility on UiO-66-BTU, can preferentially reduce Au (III) into simple substances, and saves a large number of complicated subsequent steps compared with the traditional gold recovery process.
Drawings
FIG. 1 shows UiO-66-NH of example 12FIG. 1(a) is a field emission scanning electron microscope image of UiO-66-NH2, FIG. 1(b) is a field emission scanning electron microscope image of UiO-66-NH2, FIG. 1(d) is a transmission electron microscope image of UiO-66-BTU, and FIG. 1(e) is an EDS energy spectrum analysis of UiO-66-BT;
FIG. 2 shows UiO-66-NH in example 12And the adsorption performance diagram of UiO-66-BTU to Au (III);
FIG. 3 shows UiO-66-NH in example 12Selective adsorption of Au (III) by UiO-66-BTU.
Wherein, UiO-66-NH2Namely Zr-MOF.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
Preparation of bis-Thiourea modified Zr-MOF adsorbing Material (UiO-66-BTU)
699mg of ZrCl4、543mg NH2Dissolving the mixture of-BDC in 70mL of DMF, adding 0.5mL of hydrochloric acid and 3mL of acetic acid, stirring uniformly to obtain a reaction solution, transferring the reaction solution into a polytetrafluoroethylene high-pressure tank, heating for 45min at 120 ℃ by using microwave, washing and precipitating by using DMF, methanol and dichloromethane for at least three times, and finally drying the solid powder by using an oven to obtain UiO-66-NH2；
3g of UiO-66-NH2And 3g of dithiourea are uniformly dispersed in 100mL of deionized water, heated and stirred at 60 ℃ for 20min, then 16mL of glyoxal is slowly added, heated in a water bath at 60 ℃ and stirred for 6h, the obtained precipitate is washed by the deionized water for multiple times, and finally dried by an oven to obtain UiO-66-BTU.
UiO-66-NH was observed by FE-SEM and TEM as shown in FIG. 12And the surface topography of UiO-66-BTU. As shown in FIGS. 1(a) - (d), UiO-66-NH2And UiO-66-BTU are all octahedral shapes, formed from nano-scale tiny particles. UiO-66-NH2And UiO-66-BTU were not significantly different in size and shape, indicating that the entering of dithiourea did not destroy UiO-66-NH2The microstructure of (1). In addition, the degree of modification was evaluated using the results of energy spectrum (EDS) analysis of UiO-66-BTU, and as shown in FIG. 1(e), UiO-66-BTU mainly contained carbon (57.6% by weight), oxygen (25.4% by weight), zirconium (10.7% by weight), nitrogen (4.9% by weight), and sulfur (1.4% by weight), confirming that dithiourea was successfully crosslinked in UiO-66-NH2On the skeleton.
Example 2
Adsorption experiment for Au (III)
10mg of UiO-66-BTU sample is mixed with 20mL of 400mg/L Au (III) solution, the mixture is shaken for 20-1440min under the conditions of pH 2.0 and 25 ℃, and after filtration, the filtrate at each time period is measured by a flame atomic absorption spectrometer.
As shown in FIG. 2, the adsorption of Au (III) is very fast within the initial 240min, accounting for about 93% of the total Au (III). During this time, the UiO-66-BTU surface has enough adsorption sites to bind with Au (III) ions. Then, since most adsorption sites are occupied, the adsorption process is slowly performed with the increase of the contact time, and the equilibrium adsorption amount is reached after 300 min. The adsorption quantity of the UiO-66-BTU to the Au (III) is 657.45mg/g which is higher than that of the UiO-66-NH2(253.45 mg/g). The high adsorption rate within the initial 240min is attributed to the porous MOF structure, which penetrates deeper and deeper into the inner pores.
Example 3
Selective adsorption experiment for Au (III)
The selectivity was measured by adding 10mg of UiO-66-BTU to a solution of 50mg/L of Zn (II), Fe (III), Cu (II), and Mn (II) coexisting metal ions and Au (III) (10 mg/L). The residual amount of the solution was analyzed by Atomic Absorption Spectrophotometry (AAS). The amount of adsorption was calculated from the difference in Au (III) concentration before and after adsorption.
In order to explore the selectivity of UiO-66-BTU in practical application, a selective adsorption experiment was performed in a laboratory simulation gold mine exploitation wastewater. In this study, the concentration of Au (III) was 50mg/L, and the concentration of other coexisting metal ions was 50 mg/L. As shown in FIG. 3, UiO-66-BTU preferentially captures Au (III) and Cu2+、Zn2+And Mn2+The capture capability of (a) is negligible. Impressively, even the concentration of Au (III) was reduced to one fifth (10mg/L) of the interfering metal, and the affinity (III) and selectivity for Au were evaluated by measuring the distribution coefficient value (Kd) of UiO-66-BTU, as shown in Table 1, and the distribution coefficient value (K) of UiO-66-BTU to Au (III) was foundd) Reach 9998mL/g, which is much higher than the original UiO-66-NH2Partition coefficient value of (183.18 mL/g). Thus, these results indicate that UiO-66-BTU has good selectivity for Au (III) and other co-existing interfering metals. In addition, the high K value of the coexisting ions further demonstrates the superior affinity between au (iii) and the adsorbent. In a word, the UiO-66-BTU has good prospect in the recovery application of gold.
TABLE 1UiO-66-NH2Selective adsorption of Au (III) by UiO-66-BTU
Figure BDA0002997397140000061
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (9)

1. The preparation method of the dual-thiourea modified Zr-MOF adsorption material is characterized in that UiO-66-NH is used2Is a metal organic framework, glyoxal is a cross-linking agent, and a bithiourea molecule is grafted on UiO-66-NH through an amine-aldehyde condensation reaction2Thus, UiO-66-BTU was obtained.
2. The preparation method of the bisthiourea modified Zr-MOF adsorption material according to claim 1, characterized by comprising the following specific operations:
mixing UiO-66-NH2And dispersing the dithiourea into deionized water, adding glyoxal, heating in a water bath, reacting under stirring, washing after the reaction is finished, and drying to obtain UiO-66-BTU.
3. The preparation method of the bisthiourea modified Zr-MOF adsorption material according to claim 2, characterized in that 3g of UiO-66-NH is added2And 3g of dithiourea are uniformly dispersed in 100mL of deionized water, heated and stirred at 60 ℃ for 20min, then 16mL of glyoxal is added dropwise, and the mixture reacts for 6h under the condition of heating and stirring in a water bath at 60 ℃.
4. The method for preparing the bisthiourea-modified Zr-MOF adsorption material according to claim 1, wherein the UiO-66-NH is2The preparation method comprises the following steps:
reacting ZrCl4And NH2-BDC in DMF, after which hydrochloric acid is addedAnd acetic acid to obtain a reaction solution, transferring the reaction solution into a polytetrafluoroethylene high-pressure tank, heating in a microwave extraction instrument, and obtaining a reactant after the reaction is finished; then washing and drying to obtain UiO-66-NH2。
5. The method for preparing the dual-thiourea modified Zr-MOF adsorbing material according to claim 4, wherein in the reaction solution, 699mg ZrCl is added to 70mL DMF4、543mg NH2-BDC, 0.5mL hydrochloric acid and 3mL acetic acid;
wherein, the concentration of the hydrochloric acid is concentrated hydrochloric acid, and the concentration of the acetic acid is 36%.
6. The preparation method of the bisthiourea modified Zr-MOF adsorption material according to claim 4, characterized in that the reaction conditions are as follows: heating with microwave at 120 deg.C for 45 min.
7. The preparation method of the bisthiourea-modified Zr-MOF adsorption material according to claim 4, characterized in that the washing operation is: washed with DMF, methanol and dichloromethane.
8. A bis-thiourea modified Zr-MOF adsorbing material, characterized in that it is prepared according to the preparation method of any one of claims 1 to 7.
9. Use of the bisthiourea-modified Zr-MOF adsorbing material according to claim 8 for selective adsorption of gold ions and reduction to elemental gold.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105289552A (en) * 2015-12-02 2016-02-03 天津工业大学 Method for rapidly adsorbing mercury ion in water based on bis-thiourea functionalized superfine fibers
CN110813244A (en) * 2019-11-17 2020-02-21 中山大学 Modified zirconium-based organic metal framework adsorbent for adsorbing lead ions and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105289552A (en) * 2015-12-02 2016-02-03 天津工业大学 Method for rapidly adsorbing mercury ion in water based on bis-thiourea functionalized superfine fibers
CN110813244A (en) * 2019-11-17 2020-02-21 中山大学 Modified zirconium-based organic metal framework adsorbent for adsorbing lead ions and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JUNKANG GUO，ET AL: ""Highly efficient and selective recovery of Au(III) from aqueous solution by bisthiourea immobilized UiO-66-NH2: Performance and mechanisms"" *

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