CN110964330A - UiO-66(NH2) -silver sulfide composite material and preparation process thereof - Google Patents
UiO-66(NH2) -silver sulfide composite material and preparation process thereof Download PDFInfo
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- CN110964330A CN110964330A CN201911121517.5A CN201911121517A CN110964330A CN 110964330 A CN110964330 A CN 110964330A CN 201911121517 A CN201911121517 A CN 201911121517A CN 110964330 A CN110964330 A CN 110964330A
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/3009—Sulfides
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Abstract
The invention relates to the field of composite materials, in particular to UiO-66 (NH)2) -silver sulphide composites and processes for their preparation. The preparation process of the UiO-66(NH2) -silver sulfide composite material is characterized by comprising the following steps: comprising the steps of S1: synthesis of UiO-66 (NH)2) (ii) a S2: a layer of UiO-66 (NH) is modified on the FTO glass2) (ii) a S3: in UiO-66 (NH)2) Growing Ag on the surface of compound2And S, obtaining the UiO-66(NH2) -silver sulfide composite material. The invention has the advantages of simple preparation process, low preparation cost, good chemical stability, lower detection limit and wider linear range.
Description
Technical Field
The invention relates to the field of composite materials, in particular to UiO-66 (NH)2) -silver sulphide composites and processes for their preparation.
Background
Metal Organic Frameworks (MOFs) represent a novel microporous material formed by a network of transition metal ions linked by organic ligands. MOFs are considered potential candidates for gas storage, absorption, microelectronics and catalysis due to their high surface area, high porosity and tunability characteristics.
In the MOFs group, Zr-based UIO-66-NH2As a common Zr-based MOF, the Zr-based MOF has good thermal stability, large surface area and good photocatalytic performance, and is widely researched and used for various occasions such as a photocatalyst, an organic pollutant remover, a tumor marker photoelectric detection and the like.
However, UIO-66-NH of the prior art2When applied to photoelectric detection, the compound has poor chemical stability, detection limit and linear range, and therefore needs to be further modified.
Disclosure of Invention
In order to solve the problems, the invention provides UiO-66 (NH) with simple preparation process, low preparation cost, good chemical stability, lower detection limit and wider linear range2) -silver sulphide composites and processes for their preparation.
The technical scheme adopted by the invention is as follows: UiO-66 (NH)2) -a process for the preparation of a silver sulfide composite material comprising the steps of S1: synthesis of UiO-66 (NH)2) (ii) a S2: a layer of UiO-66 (NH) is modified on the FTO glass2) (ii) a S3: in UiO-66 (NH)2) Growing Ag on the surface of compound2S, to obtain UiO-66 (NH)2) -silver sulfide composite.
The technical proposal is further improved in that in S1, UiO-66 (NH)2) The synthesis method comprises the following steps: a. ultrasonically dissolving zirconium tetrachloride and 2-amino terephthalic acid in a DMF solution by using a solvothermal reaction method, transferring the solution into a reaction kettle, and reacting for 12 to 36 hours at the temperature of between 10 and 200 ℃; b. centrifuging the light yellow product obtained after the reaction in the reaction kettle in the step a, washing the light yellow product for 1-5 times by using a washing solvent, wherein the washing solvent is 10-200 DEG CVacuum drying at room temperature, and standing to obtain UiO-66 (NH)2) And (3) solid powder.
The technical proposal is further improved in that in S2, UiO-66 (NH)2) The method for modifying the FTO glass comprises the following steps: a. cutting the FTO glass into sheets, ultrasonically cleaning for 1-5 min, b, drying the cleaned sheet FTO glass in the step a by using nitrogen, and taking 0.5mg mL-1-3.5 mg mL-1UiO-66 (NH)2) Uniformly dropwise adding the mixture on the surface of FTO glass, and naturally drying at room temperature.
The technical proposal is further improved in that in S3, in UiO-66 (NH)2) Growing Ag on the surface of compound2The method of S is as follows: a. taking AgNO3Mixing the ethanol and water to prepare a cation precursor solution; b. mixing ethanol containing thiourea with water to obtain an anion precursor solution; c. modification of UiO-66 (NH) in S22) The FTO glass is sequentially immersed into the cation precursor solution and the anion precursor solution, the circulation is carried out for 3 to 9 times, the immersion time is 3 to 7min each time, so that the Ag2S nano-particles grow on UiO-66 (NH)2) A surface; d. cleaning and blow-drying to obtain UiO-66 (NH)2) -silver sulfide composite.
The technical scheme is further improved in that in S1, the reaction temperature in the reaction kettle is 120 ℃, the reaction time is 24 hours, the washing solvent is methanol, the washing times are 3 times, and the vacuum drying temperature is 80 ℃.
The technical proposal is further improved in that in S2, the FTO glass is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 3 minutes in sequence, and 2.5mg mL of the FTO glass is taken-1UiO-66 (NH)2) Dropwise addition was carried out.
The technical proposal is further improved in that in S3, the cation precursor solution contains AgNO3The volume ratio of the ethanol to the water is 4:1, and the volume ratio of the ethanol containing thiourea in the anion precursor solution to the water is 4: 1; circulating for 7 times, and soaking for 5min each time.
UiO-66(NH2) -a silver sulfide composite material, obtained by the method of preparation according to any one of claims 1 to 7.
The technical proposal is further improved that Ag in the composite material2The S quantum dots are 8-12 nm.
The invention has the beneficial effects that:
1. in one aspect, the UiO-66 (NH) of the invention2) The silver sulfide composite material has a narrow forbidden band, can utilize the good absorbance of a semiconductor material of the narrow forbidden band in a visible light region, and avoids the inactivation of biomolecules caused by ultraviolet light, so that the silver sulfide composite material has good chemical stability, lower detection limit, wider linear range and excellent physical and chemical properties, and can be applied to the field of detection of cancer blank antigens. In the second aspect, the synthesis process disclosed by the invention is simple in flow, easy in obtaining of synthesis raw materials, easy in realization of synthesis conditions, and suitable for large-scale popularization.
2. In S1, UiO-66 (NH) was synthesized2) When the method is used, the methanol is adopted to clean a light yellow product in the reaction kettle, and the boiling point of the methanol is 64 ℃, so that the volatility is good, the methanol is ensured to be completely volatilized in the washing process, the purity of the product is improved, and the chemical stability of the product is further improved. After cleaning, vacuum drying is carried out at the temperature of 80 ℃ to ensure that the UiO powder is completely dried, thereby further improving the UiO-66 (NH)2) Is favorable for improving the finally obtained UiO-66 (NH)2) Chemical stability of silver sulfide, ensuring the stability and reliability of the detection results.
3. A layer of UiO-66 (NH) is modified on the FTO glass2) In the process, the FTO glass is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 3 minutes in sequence, and 2.5mg mL of the FTO glass is taken-1UiO-66 (NH)2) Dropwise adding; ensuring the cleanness of the conductive surface of the glass, avoiding the contamination of foreign matters and preventing the foreign matters from blocking the active substance UiO-66 (NH)2) The load on the FTO is improved, and the finally obtained UiO-66 (NH)2) The purity of the silver sulfide ensures the stability and reliability of the chemical property of the silver sulfide and the reliability of the detection result.
4. In S3, the selected anion precursor solution and cation precursor solution have low material cost, no pollution and suitability for batch synthesis, and meanwhile, the anion precursor solution and the cation precursor solution sequentially carry UiO-66 (NH)2) The FTO glass is soaked to ensure Ag2S nano-particles can be completely grown on UiO-66 (NH)2) Superficially, prepared UiO-66 (NH)2) The silver sulfide has high purity, the chemical property is stable and reliable, and the reliability of a detection result is ensured.
5、UiO-66(NH2) The material band gap width of the quantum dots of Ag2S in the silver sulfide composite material is small, about 1eV is easy to absorb light and excite, photoelectrons are generated, therefore, the photoelectric reaction is better carried out to obtain the CEA level, and the stability and reliability of the detection result are further ensured.
Drawings
FIG. 1 shows the prepared UiO-66 (NH)2) SEM picture of silver sulfide.
Detailed Description
The invention will be further described with reference to the following examples and the accompanying drawings.
Example 1: synthesis of UiO-66 (NH)2) A preparation process of the silver sulfide composite material, which comprises the following specific steps,
s1: synthesis of UiO-66 (NH)2) Specifically, a, ultrasonically dissolving zirconium tetrachloride and 2-amino terephthalic acid in a DMF (dimethyl formamide) solution by using a solvothermal reaction method, transferring the solution to a reaction kettle, and reacting for 24 hours at 120 ℃; b. centrifuging a light yellow product obtained after the reaction in the reaction kettle in the step a, washing the light yellow product for 3 times by using a washing solvent, drying the light yellow product in vacuum at 80 ℃, and standing the dried product to obtain UiO-66 (NH)2) And (3) solid powder.
S2: a layer of UiO-66 (NH) is modified on the FTO glass2) Cutting the FTO glass into sheets, sequentially ultrasonically cleaning the sheets in absolute ethyl alcohol and deionized water for 3 minutes, and b, drying the cleaned sheets of the FTO glass in the step a by using nitrogen, and taking 2.5mg mL-1UiO-66 (NH)2) Uniformly dropwise adding the mixture on the surface of FTO glass, and naturally drying at room temperature.
S3: in UiO-66 (NH)2) Growing Ag2S on the surface of the compound to obtain UiO-66 (NH)2) -silver sulfide composite. The method specifically comprises the following steps: a. taking AgNO3Mixing the ethanol and water to prepare a cation precursor solution; b. mixing ethanol containing thiourea with water to obtain an anion precursor solution; c. modification of UiO-66 (NH) in S22) The FTO glass is sequentially immersed into a cation precursor solution and an anion precursor solution,circulating for 7 times, soaking for 5min each time to make Ag2S nano-particles grow on UiO-66 (NH)2) A surface; d. cleaning and blow-drying to obtain UiO-66 (NH)2) -silver sulfide composite. In S3, the cation precursor solution contains AgNO3The volume ratio of the ethanol to the water is 4:1, and the volume ratio of the ethanol containing thiourea in the anion precursor solution to the water is 4: 1; circulating for 7 times, and soaking for 5min each time; UiO-66 (NH)2) Ag in silver sulfide composite2The quantum dots of S are 10 nm.
Example 2: UiO-66 (NH)2) -silver sulfide composite
Using the procedure in example 1, UiO-66 (NH) was prepared2) -silver sulfide composite.
For the prepared UiO-66 (NH)2) Silver sulfide test SEM images of them, the results are shown in figure 1. As can be seen from FIG. 1, UiO-66 (NH) synthesized in this example2) Silver sulfide, which has a narrow bandgap, can prevent the deactivation of biomolecules caused by ultraviolet light by using the good absorbance of the semiconductor material with the narrow bandgap in the visible region.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1.UiO-66(NH2) -a process for the preparation of silver sulphide composites, characterized in that: comprising the steps of S1: synthesis of UiO-66 (NH)2) (ii) a S2: a layer of UiO-66 (NH) is modified on the FTO glass2) (ii) a S3: in UiO-66 (NH)2) Growing Ag on the surface of compound2And S, obtaining the UiO-66(NH2) -silver sulfide composite material.
2. The UiO-66 (NH) of claim 12) Preparation process of silver sulfide composite materialThe method is characterized in that: in S1, UiO-66 (NH)2) The synthesis method comprises the following steps: a. ultrasonically dissolving zirconium tetrachloride and 2-amino terephthalic acid in a DMF solution by using a solvothermal reaction method, transferring the solution into a reaction kettle, and reacting for 12 to 36 hours at the temperature of between 10 and 200 ℃; b. centrifuging a light yellow product obtained after the reaction in the reaction kettle in the step a, washing the light yellow product for 1-5 times by using a washing solvent, drying the product in vacuum at 10-200 ℃, and standing the dried product to obtain UiO-66 (NH)2) And (3) solid powder.
3. The UiO-66 (NH) of claim 22) -a process for the preparation of silver sulphide composites, characterized in that: in S2, UiO-66 (NH)2) The method for modifying the FTO glass comprises the following steps: a. cutting the FTO glass into sheets, ultrasonically cleaning for 1-5 min, b, drying the cleaned sheet FTO glass in the step a by using nitrogen, and taking 0.5mg mL-1~3.5mg mL-1UiO-66 (NH)2) Uniformly dropwise adding the mixture on the surface of FTO glass, and naturally drying at room temperature.
4. The UiO-66 (NH) of claim 32) -a process for the preparation of silver sulphide composites, characterized in that: at S3, in UiO-66 (NH)2) Growing Ag on the surface of compound2The method of S is as follows: a. taking AgNO3Mixing the ethanol and water to prepare a cation precursor solution; b. mixing ethanol containing thiourea with water to obtain an anion precursor solution; c. modification of UiO-66 (NH) in S22) The FTO glass is sequentially immersed into the cation precursor solution and the anion precursor solution, the circulation is carried out for 3 to 9 times, the immersion time is 3 to 7min each time, so that the Ag2S nano-particles grow on UiO-66 (NH)2) A surface; d. cleaning and blow-drying to obtain the UiO-66(NH2) -silver sulfide composite material.
5. The UiO-66 (NH) of claim 42) -a process for the preparation of silver sulphide composites, characterized in that: in S1, the reaction temperature in the reaction kettle is 120 ℃, the reaction time is 24h, the washing solvent is methanol, the washing times are 3 times, and the vacuum drying temperature is 80 ℃.
6. The UiO-66 (NH) of claim 42) -a process for the preparation of silver sulphide composites, characterized in that: in S2, the FTO glass is ultrasonically cleaned in absolute ethyl alcohol and deionized water for 3 minutes in sequence, and 2.5mg mL of the FTO glass is taken-1UiO-66 (NH)2) Dropwise addition was carried out.
7. The UiO-66 (NH) of claim 42) -a process for the preparation of silver sulphide composites, characterized in that: in S3, the cation precursor solution contains AgNO3The volume ratio of the ethanol to the water is 4:1, and the volume ratio of the ethanol containing thiourea in the anion precursor solution to the water is 4: 1; circulating for 7 times, and soaking for 5min each time.
8.UiO-66(NH2) -a silver sulfide composite characterized in that: prepared by the preparation method of any one of claims 1 to 7.
9. The UiO-66 (NH) of claim 82) -a silver sulfide composite characterized in that: ag in composite material2The S quantum dots are 8-12 nm.
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Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5703885A (en) * | 1995-03-06 | 1997-12-30 | Motorola, Inc. | Method and apparatus for constructing verification test sequences by merging and touring hierarchical unique input/output sequence (UIO) based test subsequence graphs |
CN106492638A (en) * | 2017-01-17 | 2017-03-15 | 哈尔滨工业大学 | A kind of preparation method of nanometer silver organic frame ultrafilter membrane and the method using its water purification |
CN107236538A (en) * | 2017-05-10 | 2017-10-10 | 东南大学 | A kind of noble metal nano particles metal organic frame fluorescent probe molecule and its preparation method and application |
CN107880876A (en) * | 2017-11-21 | 2018-04-06 | 苏州影睿光学科技有限公司 | A kind of preparation method using MOFs as the silver sulfide quantum dot of carrier |
CN108445057A (en) * | 2018-01-31 | 2018-08-24 | 大丰跃龙化学有限公司 | A kind of preparation and analysis method for detecting the electrochemical sensor of heavy metal ion |
CN108636454A (en) * | 2018-04-12 | 2018-10-12 | 常州大学 | One kind being based on metal-organic framework materials UIO-66 (NH2) composite photo-catalyst preparation method |
CN108993604A (en) * | 2018-08-10 | 2018-12-14 | 淮阴师范学院 | High visible-light activity AgIn5S8/UIO-66-NH2Composite material and preparation method and application |
CN109746001A (en) * | 2018-12-13 | 2019-05-14 | 广东工业大学 | A kind of tin oxide photonic crystal load tungsten oxide and vulcanization silver composite membrane and its preparation method and application |
CN110779976A (en) * | 2019-11-15 | 2020-02-11 | 东莞理工学院 | Cancer blank antigen detection method based on UiO-66(NH2) -silver sulfide composite material |
-
2019
- 2019-11-15 CN CN201911121517.5A patent/CN110964330B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5703885A (en) * | 1995-03-06 | 1997-12-30 | Motorola, Inc. | Method and apparatus for constructing verification test sequences by merging and touring hierarchical unique input/output sequence (UIO) based test subsequence graphs |
CN106492638A (en) * | 2017-01-17 | 2017-03-15 | 哈尔滨工业大学 | A kind of preparation method of nanometer silver organic frame ultrafilter membrane and the method using its water purification |
CN107236538A (en) * | 2017-05-10 | 2017-10-10 | 东南大学 | A kind of noble metal nano particles metal organic frame fluorescent probe molecule and its preparation method and application |
CN107880876A (en) * | 2017-11-21 | 2018-04-06 | 苏州影睿光学科技有限公司 | A kind of preparation method using MOFs as the silver sulfide quantum dot of carrier |
CN108445057A (en) * | 2018-01-31 | 2018-08-24 | 大丰跃龙化学有限公司 | A kind of preparation and analysis method for detecting the electrochemical sensor of heavy metal ion |
CN108636454A (en) * | 2018-04-12 | 2018-10-12 | 常州大学 | One kind being based on metal-organic framework materials UIO-66 (NH2) composite photo-catalyst preparation method |
CN108993604A (en) * | 2018-08-10 | 2018-12-14 | 淮阴师范学院 | High visible-light activity AgIn5S8/UIO-66-NH2Composite material and preparation method and application |
CN109746001A (en) * | 2018-12-13 | 2019-05-14 | 广东工业大学 | A kind of tin oxide photonic crystal load tungsten oxide and vulcanization silver composite membrane and its preparation method and application |
CN110779976A (en) * | 2019-11-15 | 2020-02-11 | 东莞理工学院 | Cancer blank antigen detection method based on UiO-66(NH2) -silver sulfide composite material |
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