Nano-gold-loaded tungsten oxide-silver sulfide composite material and preparation method and application thereof
阅读说明：本技术 一种负载纳米金的氧化钨-硫化银复合材料及其制备方法和应用 (Nano-gold-loaded tungsten oxide-silver sulfide composite material and preparation method and application thereof ) 是由 张敏 刘超巧 程发良 谢世磊 谢东 柳鹏 王寿山 于 2021-09-26 设计创作，主要内容包括：本发明涉及复合材料技术领域,具体涉及一种负载纳米金的氧化钨-硫化银复合材料及其制备方法和应用,本发明通过溶液法在FTO玻璃上水热生长WO-(3)纳米方块片,再通过化学浴沉积法在WO-(3)纳米方块片表面生长Ag-(2)S,最后用恒电位沉积在Ag-(2)S/WO-(3)上,恒电位沉积Au纳米粒子,制成负载纳米金的氧化钨-硫化银复合材料,其工艺流程简单,制备方便,能够利用窄禁带的半导体材料在可见光区也有较好的吸光度,避免紫外光引起的生物分子失活,将该复合材料应用到肿瘤标记物CA15-3的光电化学检测,结果证明该光电传感器具备良好的光电化学稳定性、较低检出限和较宽的线性范围,应用前景好。(The invention relates to the technical field of composite materials, in particular to a tungsten oxide-silver sulfide composite material loaded with nanogold, and a preparation method and application thereof 3 Nano square sheets, then deposited on WO by chemical bath deposition 3 Ag grows on the surface of the nano square sheet 2 S, finally depositing on Ag by constant potential 2 S/WO 3 And Au nano particles are deposited at constant potential to prepare the tungsten oxide-silver sulfide composite material loaded with the nano gold, the process flow is simple, the preparation is convenient, and the nano gold can be utilizedThe semiconductor material with narrow forbidden band has better absorbance in a visible light region, so that the inactivation of biomolecules caused by ultraviolet light is avoided, and the result of applying the composite material to the photoelectrochemical detection of a tumor marker CA15-3 proves that the photoelectric sensor has good photoelectrochemical stability, lower detection limit and wider linear range, and has good application prospect.)
1. A preparation method of a tungsten oxide-silver sulfide composite material loaded with nano gold is characterized by comprising the following steps:
s1 preparation of WO3Nano square sheets;
s2 preparation of AgNO3Preparing thiourea ethanol solution as anion precursor solution by using ethanol solution as cation precursor solution;
s3, adding WO3The nano square piece is immersed into the anion precursor solution and the cation precursor solution in sequence, and is immersed for a plurality of times in a circulating way to ensure that the Ag is2S nanoparticles grown in WO3Cleaning the surface of the nano square sheet with ethanol and deionized water in sequence, and drying;
s4, loading Ag2WO of S3Placing the nano-square piece in sulfuric acid solution containing chloroauric acid, performing constant potential deposition, and then using deionized waterWashing with water and drying to obtain the tungsten oxide-silver sulfide composite material loaded with the nano-gold.
2. The method for preparing the tungsten oxide-silver sulfide composite material loaded with the nano-gold as claimed in claim 1, wherein the step S1 further comprises the following steps:
s10: cutting the FTO glass into sheets with the size of 1.5 multiplied by 2cm, ultrasonically cleaning the sheets in absolute ethyl alcohol for 3 to 5 minutes, and then ultrasonically cleaning the sheets in ionized water for 3 to 5 minutes;
s11: adding 30mL of solution containing 0.297g of sodium tungstate and 0.20g of ammonium oxalate into a polytetrafluoroethylene reaction kettle, adding cleaned FTO glass, and carrying out hydrothermal reaction for 1 hour at the constant temperature of 120 ℃;
s12: washing the FTO glass subjected to the hydrothermal reaction with ethanol and deionized water in sequence, drying, and annealing at the temperature of 450 ℃ for 1 hour in a muffle furnace to obtain WO3A nano-cube sheet.
3. The method for preparing the tungsten oxide-silver sulfide composite material loaded with the nano-gold as claimed in claim 1, wherein in step S2, AgNO in the cation precursor solution3At a concentration of 30mM, the ratio of ethanol to water being 4: 1; in the anionic precursor solution, the concentration of thiourea was 30mM and the ratio of ethanol to water was 4: 1.
4. The method for preparing a tungsten oxide-silver sulfide composite material loaded with nanogold according to claim 1, wherein in step S3, WO3The time for soaking the nano square sheets into the anion precursor solution and the cation precursor solution is 4-5 minutes, and the circulating soaking times are 4-6 times.
5. The method for preparing a tungsten oxide-silver sulfide composite material loaded with nanogold according to claim 1, wherein the concentration of the chloroauric acid in step S4 is 1 mM.
6. The method for preparing the tungsten oxide-silver sulfide composite material loaded with the nanogold according to claim 1, wherein in the step S4, the deposition potential is-0.2V, and the deposition time is 180-250 seconds.
7. A nanogold-loaded tungsten oxide-silver sulfide composite material, which is obtained by the production method according to any one of claims 1 to 6.
8. The tungsten oxide-silver sulfide composite material loaded with nanogold according to claim 7, wherein the particle size of the nanogold is 8-13 nm.
9. Use of the nanogold-loaded tungsten oxide-silver sulfide composite material according to claim 7 or 8 for the photodetection of tumor markers.
Technical Field
The invention relates to the technical field of composite materials, in particular to a tungsten oxide-silver sulfide composite material loaded with nanogold, and a preparation method and application thereof.
Background
The detection of the content of cancer markers and the like is an important index for cancer diagnosis and detection of therapeutic effects. The sugar chain antigen CA15-3 is a tumor marker of breast cancer, has an important auxiliary diagnosis effect on the breast cancer, and is also an optimal index for monitoring the postoperative condition of the breast cancer. At present, CA15-3 is detected by methods such as electrochemistry, electroluminescence, chemiluminescence and the like, but the methods have the defects of complex operation, high detection cost, low sensitivity and the like. Photoelectrochemical detection, in turn, is a method of Photoelectrochemical (PEC) analysis that combines the advantages of sensitivity and specificity of the biomolecule. But the difficulty of photoelectrochemical detection is to prepare a semiconductor composite material with excellent photoelectric activity and good stability.
Disclosure of Invention
In order to solve the problems, the invention provides a tungsten oxide-silver sulfide composite material loaded with nano-gold and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of a tungsten oxide-silver sulfide composite material loaded with nano-gold comprises the following steps:
s1 preparation of WO3Nano square sheets;
s2 preparation of AgNO3Preparing thiourea ethanol solution as anion precursor solution by using ethanol solution as cation precursor solution;
s3, adding WO3The nano square piece is immersed into the anion precursor solution and the cation precursor solution in sequence, and is circulated for many times to lead the Ag to be2S nanoparticles grown in WO3Cleaning the surface of the nano square sheet with ethanol and deionized water in sequence, and drying;
s4, loading Ag2WO of S3And (3) placing the nano square piece in a sulfuric acid solution containing chloroauric acid, depositing at a constant potential, washing with deionized water and drying to obtain the nano gold-loaded tungsten oxide-silver sulfide composite material.
Further, step S1 includes the following steps:
s10: cutting the FTO glass into sheets with the size of 1.5 multiplied by 2cm, ultrasonically cleaning the sheets in absolute ethyl alcohol for 3 to 5 minutes, and then ultrasonically cleaning the sheets in ionized water for 3 to 5 minutes;
s11: adding 30mL of solution containing 0.297g of sodium tungstate and 0.20g of ammonium oxalate into a polytetrafluoroethylene reaction kettle, adding cleaned FTO glass, and carrying out hydrothermal reaction for 1 hour at the constant temperature of 120 ℃;
s12: washing the FTO glass subjected to the hydrothermal reaction with ethanol and deionized water in sequence, drying, and annealing at the temperature of 450 ℃ for 1 hour in a muffle furnace to obtain WO3A nano-cube sheet.
Further, in step S2, AgNO in the cation precursor solution is added3At a concentration of 30mM, the ratio of ethanol to water being 4: 1; in the anionic precursor solution, the concentration of thiourea was 30mM and the ratio of ethanol to water was 4: 1.
Further, among them, in step S3, WO3The time for soaking the nano square sheets into the anion precursor solution and the cation precursor solution is 4-5 minutes, and the circulating soaking times are4-6 times.
Further, in step S4, the concentration of chloroauric acid is 1 mM.
Further, in step S4, the deposition potential is-0.2V and the deposition time is 180-250 seconds.
The invention also provides a composite material prepared by the preparation method of the tungsten oxide-silver sulfide composite material loaded with the nanogold.
Furthermore, the particle size of the nano-gold in the composite material is 8-13 nm.
The invention also provides application of the tungsten oxide-silver sulfide composite material loaded with the nano-gold in photoelectric detection of tumor markers.
The invention has the following beneficial effects:
the invention hydrothermally grows WO on FTO glass by a solution method3Nano square sheets, then deposited on WO by chemical bath deposition3Ag grows on the surface of the nano square sheet2S, finally depositing on Ag by constant potential2S/WO3The method has the advantages that Au nano particles are deposited at constant potential to prepare the tungsten oxide-silver sulfide composite material loaded with the nano gold, the process flow is simple, the preparation is convenient, the semiconductor material with narrow forbidden band can be utilized to have better absorbance in a visible light region, the inactivation of biomolecules caused by ultraviolet light is avoided, the composite material is applied to the photoelectrochemical detection of the tumor marker CA15-3, and the result proves that the photoelectric sensor has good photoelectrochemical stability, lower detection limit and wider linear range, and the application prospect is good.
Drawings
FIG. 1 is an SEM image of a composite material according to a first embodiment of the invention;
FIG. 2 is a diagram illustrating a test of photoelectrochemical stability of the composite material according to the first embodiment of the present invention.
Detailed Description
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete. The various starting materials used in the examples are, unless otherwise indicated, conventional commercial products.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The numerical values set forth in the examples of the present invention are approximations, not necessarily values. All values within the error range may be included without limiting to the specific values disclosed in the embodiments of the present invention, where the error or experimental conditions allow.
The numerical ranges disclosed in the examples of the present invention are intended to indicate the relative amounts of the components in the mixture and the ranges of temperatures or other parameters recited in the other method examples.
The preparation method of the nano-gold-loaded tungsten oxide-silver sulfide composite material comprises the following steps:
s1 preparation of WO3Nano square sheets;
s2 preparation of AgNO3Preparing thiourea ethanol solution as anion precursor solution by using ethanol solution as cation precursor solution;
s3, adding WO3The nano square piece is immersed into the anion precursor solution and the cation precursor solution in sequence, and is circulated for many times to lead the Ag to be2S nanoparticles grown in WO3Cleaning the surface of the nano square sheet with ethanol and deionized water in sequence, and drying;
s4, loading Ag2WO of S3And (3) placing the nano square piece in a sulfuric acid solution containing chloroauric acid, depositing at a constant potential, washing with deionized water and drying to obtain the nano gold-loaded tungsten oxide-silver sulfide composite material.
Further, step S1 includes the following steps:
s10: cutting the FTO glass into sheets with the size of 1.5 multiplied by 2cm, ultrasonically cleaning the sheets in absolute ethyl alcohol for 3 to 5 minutes, and then ultrasonically cleaning the sheets in ionized water for 3 to 5 minutes;
s11: adding 30mL of solution containing 0.297g of sodium tungstate and 0.20g of ammonium oxalate into a polytetrafluoroethylene reaction kettle, adding cleaned FTO glass, and carrying out hydrothermal reaction for 1 hour at the constant temperature of 120 ℃;
s12: washing the FTO glass subjected to the hydrothermal reaction with ethanol and deionized water in sequence, drying, and annealing at the temperature of 450 ℃ for 1 hour in a muffle furnace to obtain WO3A nano-cube sheet.
Further, in step S2, AgNO in the cation precursor solution is added3At a concentration of 30mM, the ratio of ethanol to water being 4: 1; in the anionic precursor solution, the concentration of thiourea was 30mM and the ratio of ethanol to water was 4: 1.
Further, among them, in step S3, WO3The time for soaking the nano square sheets into the anion precursor solution and the cation precursor solution is 4-5 minutes, and the circulating soaking times are 4-6 times.
Further, in step S4, the concentration of chloroauric acid is 1 mM.
Further, in step S4, the deposition potential is-0.2V and the deposition time is 180-250 seconds.
The invention hydrothermally grows WO on FTO glass by a solution method3Nano square sheets, then deposited on WO by chemical bath deposition3Ag grows on the surface of the nano square sheet2S, finally depositing on Ag by constant potential2S/WO3The method has the advantages that Au nano particles are deposited at constant potential to prepare the tungsten oxide-silver sulfide composite material loaded with the nano gold, the process flow is simple, the preparation is convenient, the semiconductor material with narrow forbidden band can be utilized to have better absorbance in a visible light region, the inactivation of biomolecules caused by ultraviolet light is avoided, the composite material is applied to the photoelectrochemical detection of the tumor marker CA15-3, and the result proves that the photoelectric sensor has good photoelectrochemical stability, lower detection limit and wider linear range, and the application prospect is good.
The following are specific examples of the preparation of the above composite material:
example one
The preparation method of the tungsten oxide-silver sulfide composite material loaded with the nano-gold comprises the following steps:
s1: preparation of WO3Nano square sheets;
s10: cutting the FTO glass into sheets with the size of 1.5 multiplied by 2cm, firstly ultrasonically cleaning in absolute ethyl alcohol for 3 minutes, and then ultrasonically cleaning in deionized water for 3 minutes;
s11: placing the cleaned FTO glass in the step S10 in a 30mL polytetrafluoroethylene reaction kettle containing 0.297g of sodium tungstate and 0.20g of ammonium oxalate solution, and carrying out hydrothermal reaction for 1h at a constant temperature of 120 ℃;
s12: washing the FTO glass subjected to the hydrothermal reaction in the step S11 with ethanol and water for 5 times in sequence, drying, and annealing at the temperature of 450 ℃ in a muffle furnace for 1h to obtain WO3Nano square sheets;
s2, preparation containing 30mM AgNO3Preparing an ethanol solution containing 30mM thiourea as an anion precursor solution, wherein the ratio of ethanol to water in the cation precursor solution and the anion precursor solution is 4: 1;
s3, adding WO3The nano square piece is immersed into the anion precursor solution and the cation precursor solution in sequence for 4 minutes and circulated for 5 times to ensure that the Ag is2S nanoparticles grown in WO3Cleaning the surface of the nano square sheet with ethanol and deionized water in sequence, and drying;
s4, loading Ag2WO of S3And (3) placing the nano square piece in a sulfuric acid solution containing chloroauric acid with the concentration of 0.2mM, depositing for 200s at a constant potential under a potential of-0.2V, and then washing and drying by using deionized water to obtain the tungsten oxide-silver sulfide composite material loaded with the nano gold.
Example two
In the preparation method of the tungsten oxide-silver sulfide composite material loaded with nanogold in this embodiment, on the basis of the first embodiment, the solution in the polytetrafluoroethylene reaction kettle in the step S11 is 25mL, and the temperature rise rate of the muffle furnace in the step S12 is 5 ℃/min.
EXAMPLE III
In the preparation method of the tungsten oxide-silver sulfide composite material loaded with nanogold in this embodiment, on the basis of the first embodiment, the volume of the anion precursor solution and the cation precursor solution in step S3 is 30mL, the immersion time is 5 minutes, and the cycle number is 5 times.
Example four
In the preparation method of the tungsten oxide-silver sulfide composite material loaded with nano-gold in this embodiment, on the basis of the first embodiment, in step S4, the concentration of chloroauric acid is 1mM, the deposition potential is-0.2V, and the deposition time is 200S.
Referring to FIG. 1, the present invention hydrothermally grows WO on FTO glass by a solution method3Nano square sheets, then deposited on WO by chemical bath deposition3Ag grows on the surface of the nano square sheet2S, finally depositing on Ag by constant potential2S/WO3And depositing Au nano particles at constant potential to prepare the tungsten oxide-silver sulfide composite material loaded with the nano gold. As shown in figure 1, a compact Ag2S film grows on the WO3 nano square sheet, the WO3 nano square sheet is completely wrapped, Au nano-particles are uniformly deposited on the Ag2S film, and the particle size distribution of the Au nano-particles is about 10-20 nm. The method has simple process flow and convenient preparation, and can utilize the semiconductor material with narrow forbidden band to have better absorbance in a visible light region so as to avoid the inactivation of biomolecules caused by ultraviolet light.
Referring to fig. 2, FTO glass loaded with the nano-gold-loaded tungsten oxide-silver sulfide composite material prepared in the first embodiment is mounted on a platinum electrode holder as a working electrode, a platinum sheet as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode are placed in 0.2M PBS buffer solution containing 0.1M ascorbic acid, a detection light source is a 500W xenon lamp, a detection potential is-0.3V, and an electrochemical stability test is performed, as can be seen from the test results in fig. 2, compared with a conventional wide band gap semiconductor material, the nano-gold-loaded tungsten oxide-silver sulfide composite material prepared by the preparation method of the present invention combines the light absorption frequencies of tungsten oxide and silver sulfide, and at the same time, AuNPs have a plasma resonance effect in a visible light region, and the visible light region has a better absorbance and a good photoelectrochemical stability. The composite material is applied to the photoelectrochemical detection of a tumor marker CA15-3, and the result proves that the photoelectric sensor has a lower detection limit and a wider linear range.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.