CN104192789A - Nanometer/micron gold film and preparing method thereof - Google Patents
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Abstract
The invention discloses a nanometer/micron gold film and a preparing method thereof. The nanometer/micron gold film comprises a matrix and a nanometer/micron gold layer. The nanometer/micron gold layer is formed by metal nanoparticles in a deposition mode. Amidogens are arranged on the surface of the matrix. The metal nanoparticles and the amidogens on the surface of the matrix form strong interaction. The preparing method comprises the steps that (1) the surface of the matrix is subjected to oxygen plasma treatment or ultraviolet irradiation; (2) the surface-activated matrix is soaked into an NH2(CH2)3Si(OC2H5)3 solution; and (3) a mixed solution of chloroauric acid and bicarbonate of a strong base and a glucose solution are evenly mixed and are arranged on the surface-amination matrix in a coating mode, and the nanometer/micron gold film is obtained through light-avoiding reaction. According to the nanometer/micron gold film, the types of matrixes are multiple, different mechanical property requirements can be met, combining is firm, breaking is not easy, according to the method, reaction is mild, and cost is low.
Description
Technical field
The invention belongs to field of nanometer material technology, more specifically, relate to a kind of nano/micron gold film and preparation method thereof.
Background technology
The nano/micron gold film of nano particle composition has obvious skin effect, bulk effect, small-size effect, quantum effect and good biocompatibility, and its optical characteristics, characteristic electron, sensing characteristics and biochemical characteristic are study hotspot always.
The preparation method of nano/micron gold layer mainly contains the methods such as electron beam evaporation, chemical vapour deposition (CVD) (CVD), physical vapour deposition (PVD) (PVD) at present, although these methods can obtain more uniform nano gold layer, its apparatus expensive, process complexity.In 2009, the human hairs such as Chen Hongyuan understood the method for chemical deposition nm of gold on PDMS, and the method is deposited gold on PDMS directly, and preparation is simple.But the method only can, taking PDMS as matrix, be of limited application.The nano gold layer uniformity simultaneously obtaining can not be guaranteed, gold be combined with PDMS insecure, in PDMS stretching, BENDING PROCESS golden easy fracture, come off.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of nano/micron gold film and preparation method thereof, its object is different stromal surface to adopt corresponding activation processing, then depositing nano/micron chickens layer, make nano/micron gold film, solve thus nano/micron gold film prepared by existing nano/micron gold film deposition method, in conjunction with insecure, easy fracture in stretching/BENDING PROCESS, the technical problem coming off.
For achieving the above object, according to one aspect of the present invention, a kind of nano/micron gold film is provided, comprise matrix and nano/micron gold layer, described Nano/micron metal layer is formed by metal nanoparticle deposition, described stromal surface has amino, and the amino strong interaction that forms of described metal nanoparticle and described stromal surface, makes described nano/micron gold layer firm attachment in described stromal surface.
Preferably, described Nano/micron metal film, its matrix is the dense film not absorbing water, and is preferably dimethyl silicone polymer, glass, indium tin oxide-coated glass, PETG film, polyimide film, polyethylene film or poly tetrafluoroethylene.
According to another aspect of the present invention, a kind of preparation method of Nano/micron metal film is provided, it is characterized in that, comprise the following steps:
(1) stromal surface processing: stromal surface is carried out to oxygen plasma treatment or UV-irradiation, make stromal surface produce the active group of oxidation, obtain the matrix of surface active;
(2) stromal surface amination: by the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, carry out amination processing, obtain the matrix of surface amination;
(3) depositing metallic films: the mixed solution of getting the bicarbonate of gold chloride and highly basic evenly mixes with glucose solution, and coating in the matrix of the surface amination obtaining in step (2), makes to be distributed with on every 1cm2 gold element 3.58 × 10
-5g to 2.87 × 10
-3g and glucose 7.5 × 10
-4g to 3 × 10
-3g, at 20 DEG C to 40 DEG C, lucifuge reaction after 2 hours to 4 hours washing dry, obtain described Nano/micron metal film.
Preferably, described preparation method, described in it, matrix is the dense film not absorbing water, and is preferably dimethyl silicone polymer, glass, indium tin oxide-coated glass, PETG film, polyimide film, polyethylene film or poly tetrafluoroethylene.
Preferably, described preparation method, in the time that described matrix is polyethylene film or poly tetrafluoroethylene, stromal surface is processed and is adopted UV-irradiation.
Preferably, described preparation method, the described oxygen plasma treatment time of its step (1) is 3 minutes to 5 minutes, described UV-irradiation, its ultraviolet ray intensity is 90uW/cm to 180uW/cm, irradiation time is 40 minutes to 90 minutes.
Preferably, described preparation method, the concrete operations of its step (2) are:
By the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, react 30 minutes to 120 minutes, with dry after deionized water washing.
Preferably, described preparation method, the concrete grammar of its step (3) coating is, the middle reeded dimethyl silicone polymer of tool (PDMS) piece of reversible keying in the matrix of the surface amination obtaining in step (2), described groove is in order to hold deposit solution.
Preferably, described preparation method, the mixed solution of the bicarbonate of the described gold chloride of its step (3) and highly basic, wherein gold chloride concentration is 10
-3g/ml to 2 × 10
-2between g/ml, the concentration of bicarbonate radical is at 0.15mol/L to 0.5mol/L.
In general, the above technical scheme of conceiving by the present invention compared with prior art, can obtain following beneficial effect:
(1) nano/micron gold film provided by the invention, matrix can be multiple, different matrix has different mechanical properties, as category of glass matrix has higher mechanical strength, and dimethyl silicone polymer (PDMS) matrix has good tensile property, therefore described nano/micron gold film can meet different application demands.
(2) nano/micron gold film provided by the invention, applying nano gold grain and amino strong interaction, the nano/micron gold layer of formation evenly with matrix energy strong bonded, in stretching, BENDING PROCESS gold not easy fracture, come off.
(3) nano/micron gold membrane preparation method provided by the invention, adopts chemical deposition, does not need expensive equipment, and preparation method is simple, and reaction condition gentleness, can be applicable to large-scale industrial production, significantly reduces the production cost of nano/micron gold film.
(4) nano/micron gold membrane preparation method provided by the invention, can be directly proportional by the content of gold and the thickness of the amount of deposit solution and the nano gold layer of deposition in the mixed solution of the bicarbonate of control gold chloride and highly basic, can regulate by controlling the amount of deposit solution the thickness of nano gold layer, can deposit the gold layer that repeatedly obtains different-thickness, meet different process demand simultaneously.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.In addition,, in each embodiment of described the present invention, involved technical characterictic just can combine mutually as long as do not form each other conflict.
Nano/micron gold film provided by the invention, comprise matrix and nano/micron gold layer, described Nano/micron metal layer is formed by metal nanoparticle deposition, described stromal surface has amino, the amino strong interaction that forms of described metal nanoparticle and described stromal surface, makes described nano/micron gold layer firm attachment in described stromal surface.Described matrix is the dense film not absorbing water, and is preferably dimethyl silicone polymer, glass, indium tin oxide-coated glass, PETG film, polyimide film, polyethylene film or poly tetrafluoroethylene.
Described nano/micron gold film, its preparation method, comprises the following steps:
(1) stromal surface processing: stromal surface is carried out to oxygen plasma treatment or UV-irradiation, make stromal surface produce the active group of oxidation, obtain the matrix of surface active; Described matrix is the dense film not absorbing water, and is preferably dimethyl silicone polymer, glass, indium tin oxide-coated glass, PETG film, polyimide film, polyethylene film or poly tetrafluoroethylene.The described oxygen plasma treatment time of step (1) is 3 minutes to 5 minutes, and ultraviolet ray intensity is 90uW/cm to 180uW/cm, and irradiation time is 40 minutes to 90 minutes.
Described matrix is Plastic matrix, and during as polyethylene film or poly tetrafluoroethylene, yielding during due to employing oxygen plasma treatment, stromal surface is processed should adopt UV-irradiation.
(2) stromal surface amination: by the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, carry out amination processing, obtain the matrix of surface amination; Concrete operations are:
By the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, react 30 minutes to 120 minutes, with dry after deionized water washing.
(3) depositing metallic films: the mixed solution of getting the bicarbonate of gold chloride and highly basic evenly mixes with glucose solution, and coat in the matrix of the surface amination obtaining in step (2), make every 1cm
2on be distributed with gold element 3.58 × 10
-5g to 2.87 × 10
-3g and glucose 7.5 × 10
-4g to 3 × 10
-3g, at 20 DEG C to 40 DEG C, lucifuge reaction after 2 hours to 4 hours washing dry, obtain described Nano/micron metal film.The mixed solution of the bicarbonate of described gold chloride and highly basic, wherein gold chloride concentration is 10
-3g/ml to 2 × 10
-2between g/ml, the concentration of bicarbonate radical is at 0.15mol/L to 0.5mol/L.
The concrete grammar of coating is, the centre reeded dimethyl silicone polymer of tool (PDMS) piece of reversible keying in the matrix of surface amination obtaining in step (2), and described groove is in order to hold deposit solution.
Prepared gold nano/the micron membranes of this method can be applicable to obtaining of electrochemical sensing, bio-sensing, cell pattern, can further be applied to the fields such as medicine diagnosis, organizational project.
Be below embodiment:
Embodiment 1
Nano/micron gold film provided by the invention, comprise matrix and nano/micron gold layer, described Nano/micron metal layer is formed by metal nanoparticle deposition, described stromal surface has amino, the amino strong interaction that forms of described metal nanoparticle and described stromal surface, makes described nano/micron gold layer firm attachment in described stromal surface.Described matrix is the dense film not absorbing water, and is dimethyl silicone polymer.
Described nano/micron gold film, its preparation method, comprises the following steps:
(1) stromal surface processing: dimethyl silicone polymer stromal surface is carried out to oxygen plasma treatment, make stromal surface produce the active group of oxidation, obtain the matrix of surface active.The oxygen plasma treatment time is 3 minutes.
(2) stromal surface amination: by the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, carry out amination processing, obtain the matrix of surface amination; Concrete operations are:
By the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, react 120 minutes, with dry after deionized water washing.
(3) depositing metallic films: the mixed solution of getting the bicarbonate of gold chloride and highly basic evenly mixes with glucose solution, and coat in the matrix of the surface amination obtaining in step (2), make every 1cm
2on be distributed with gold element 3.58 × 10
-5g and glucose 7.5 × 10
-4g, at 25 DEG C, lucifuge reaction after 4 hours washing dry, obtain described Nano/micron metal film.The mixed solution of the bicarbonate of described gold chloride and highly basic, wherein gold chloride concentration is 10
-3between g/ml, the concentration of bicarbonate radical is at 0.15mol/L.
The concrete grammar of coating is, the centre reeded dimethyl silicone polymer of tool (PDMS) piece of reversible keying in the matrix of surface amination obtaining in step (2), and described groove is in order to hold deposit solution.
Can repeating step (3) Multiple depositions gold film, thereby control golden film thickness.
Embodiment 2
Nano/micron gold film provided by the invention, comprise matrix and nano/micron gold layer, described Nano/micron metal layer is formed by metal nanoparticle deposition, described stromal surface has amino, the amino strong interaction that forms of described metal nanoparticle and described stromal surface, makes described nano/micron gold layer firm attachment in described stromal surface.Described matrix is the dense film not absorbing water, and is glass.
Described nano/micron gold film, its preparation method, comprises the following steps:
(1) stromal surface processing: oxygen plasma treatment is carried out in glass matrix surface, make stromal surface produce the active group of oxidation, obtain the matrix of surface active.The oxygen plasma treatment time is 4 minutes.
(2) stromal surface amination: by the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, carry out amination processing, obtain the matrix of surface amination; Concrete operations are:
By the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, react 90 minutes, with dry after deionized water washing.
(3) depositing metallic films: the mixed solution of getting the bicarbonate of gold chloride and highly basic evenly mixes with glucose solution, and coat in the matrix of the surface amination obtaining in step (2), make every 1cm
2on be distributed with gold element 3.5 × 10
-4g and glucose 1.2 × 10
-3g, at 20 DEG C, lucifuge reaction after 3 hours washing dry, obtain described Nano/micron metal film.The mixed solution of the bicarbonate of described gold chloride and highly basic, wherein gold chloride concentration is 10
-2between g/ml, the concentration of bicarbonate radical is at 0.3mol/L.
The concrete grammar of coating is, the centre reeded dimethyl silicone polymer of tool (PDMS) piece of reversible keying in the matrix of surface amination obtaining in step (2), and described groove is in order to hold deposit solution.
Embodiment 3
Nano/micron gold film provided by the invention, comprise matrix and nano/micron gold layer, described Nano/micron metal layer is formed by metal nanoparticle deposition, described stromal surface has amino, the amino strong interaction that forms of described metal nanoparticle and described stromal surface, makes described nano/micron gold layer firm attachment in described stromal surface.Described matrix is the dense film not absorbing water, and is indium tin oxide-coated glass.
Described nano/micron gold film, its preparation method, comprises the following steps:
(1) stromal surface processing: indium tin oxide-coated glass stromal surface is carried out to oxygen plasma treatment, make stromal surface produce the active group of oxidation, obtain the matrix of surface active.The oxygen plasma treatment time is 5 minutes.
(2) stromal surface amination: by the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, carry out amination processing, obtain the matrix of surface amination; Concrete operations are:
By the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, react 30 minutes, with dry after deionized water washing.
(3) depositing metallic films: the mixed solution of getting the bicarbonate of gold chloride and highly basic evenly mixes with glucose solution, and coat in the matrix of the surface amination obtaining in step (2), make every 1cm
2on be distributed with gold element 2.87 × 10
-3g and glucose 3 × 10
-3g, at 40 DEG C, lucifuge reaction after 2 hours washing dry, obtain described Nano/micron metal film.The mixed solution of the bicarbonate of described gold chloride and highly basic, wherein gold chloride concentration is 2 × 10
-2between g/ml, the concentration of bicarbonate radical is at 0.5mol/L.
The concrete grammar of coating is, the centre reeded dimethyl silicone polymer of tool (PDMS) piece of reversible keying in the matrix of surface amination obtaining in step (2), and described groove is in order to hold deposit solution.
Embodiment 4
Nano/micron gold film provided by the invention, comprise matrix and nano/micron gold layer, described Nano/micron metal layer is formed by metal nanoparticle deposition, described stromal surface has amino, the amino strong interaction that forms of described metal nanoparticle and described stromal surface, makes described nano/micron gold layer firm attachment in described stromal surface.Described matrix is the dense film not absorbing water, and is PETG film.
Described nano/micron gold film, its preparation method, comprises the following steps:
(1) stromal surface processing: UV-irradiation is carried out in PETG membrane matrix surface, make stromal surface produce the active group of oxidation, obtain the matrix of surface active.Ultraviolet ray intensity is 90uW/cm, and irradiation time is 90 minutes.
(2) stromal surface amination: by the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, carry out amination processing, obtain the matrix of surface amination; Concrete operations are:
By the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, react 120 minutes, with dry after deionized water washing.
(3) depositing metallic films: the mixed solution of getting the bicarbonate of gold chloride and highly basic evenly mixes with glucose solution, and coat in the matrix of the surface amination obtaining in step (2), make every 1cm
2on be distributed with gold element 3.58 × 10
-5g and glucose 7.5 × 10
-4g, at 25 DEG C, lucifuge reaction after 3 hours washing dry, obtain described Nano/micron metal film.The mixed solution of the bicarbonate of described gold chloride and highly basic, wherein gold chloride concentration is 10
-3between g/ml, the concentration of bicarbonate radical is at 0.15mol/L.
The concrete grammar of coating is, the centre reeded dimethyl silicone polymer of tool (PDMS) piece of reversible keying in the matrix of surface amination obtaining in step (2), and described groove is in order to hold deposit solution.
Embodiment 5
Nano/micron gold film provided by the invention, comprise matrix and nano/micron gold layer, described Nano/micron metal layer is formed by metal nanoparticle deposition, described stromal surface has amino, the amino strong interaction that forms of described metal nanoparticle and described stromal surface, makes described nano/micron gold layer firm attachment in described stromal surface.Described matrix is the dense film not absorbing water, and is polyimide film.
Described nano/micron gold film, its preparation method, comprises the following steps:
(1) stromal surface processing: polyimide film stromal surface is carried out to UV-irradiation, make stromal surface produce the active group of oxidation, obtain the matrix of surface active.Ultraviolet ray intensity is 120uW/cm, and irradiation time is 60 minutes.
(2) stromal surface amination: by the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, carry out amination processing, obtain the matrix of surface amination; Concrete operations are:
By the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, react 60 minutes, with dry after deionized water washing.
(3) depositing metallic films: the mixed solution of getting the bicarbonate of gold chloride and highly basic evenly mixes with glucose solution, and coat in the matrix of the surface amination obtaining in step (2), make every 1cm
2on be distributed with gold element 3.7 × 10
-4g and glucose 1.3 × 10
-3g, at 20 DEG C, lucifuge reaction after 4 hours washing dry, obtain described Nano/micron metal film.The mixed solution of the bicarbonate of described gold chloride and highly basic, wherein gold chloride concentration is 10
-2between g/ml, the concentration of bicarbonate radical is at 0.3mol/L.
The concrete grammar of coating is, the centre reeded dimethyl silicone polymer of tool (PDMS) piece of reversible keying in the matrix of surface amination obtaining in step (2), and described groove is in order to hold deposit solution.
Can repeating step (3) Multiple depositions gold film, thereby control golden film thickness.
Embodiment 6
Nano/micron gold film provided by the invention, comprise matrix and nano/micron gold layer, described Nano/micron metal layer is formed by metal nanoparticle deposition, described stromal surface has amino, the amino strong interaction that forms of described metal nanoparticle and described stromal surface, makes described nano/micron gold layer firm attachment in described stromal surface.Described matrix is the dense film not absorbing water, and is poly tetrafluoroethylene.
Described nano/micron gold film, its preparation method, comprises the following steps:
(1) stromal surface processing: poly tetrafluoroethylene stromal surface is carried out to UV-irradiation, make stromal surface produce the active group of oxidation, obtain the matrix of surface active.Ultraviolet ray intensity is 180uW/cm, and irradiation time is 40 minutes.
(2) stromal surface amination: by the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, carry out amination processing, obtain the matrix of surface amination; Concrete operations are:
By the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, react 30 minutes, with dry after deionized water washing.
(3) depositing metallic films: the mixed solution of getting the bicarbonate of gold chloride and highly basic evenly mixes with glucose solution, and coat in the matrix of the surface amination obtaining in step (2), make every 1cm
2on be distributed with gold element 2.87 × 10
-3g and glucose 3 × 10
-3g, at 40 DEG C, lucifuge reaction after 2 hours washing dry, obtain described Nano/micron metal film.The mixed solution of the bicarbonate of described gold chloride and highly basic, wherein gold chloride concentration is 2 × 10
-2between g/ml, the concentration of bicarbonate radical is at 0.5mol/L.
The concrete grammar of coating is, the centre reeded dimethyl silicone polymer of tool (PDMS) piece of reversible keying in the matrix of surface amination obtaining in step (2), and described groove is in order to hold deposit solution.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a nano/micron gold film, it is characterized in that, comprise matrix and nano/micron gold layer, described Nano/micron metal layer is formed by metal nanoparticle deposition, described stromal surface has amino, the amino strong interaction that forms of described metal nanoparticle and described stromal surface, makes described nano/micron gold layer firm attachment in described stromal surface.
2. Nano/micron metal film as claimed in claim 1, it is characterized in that, described matrix is the dense film not absorbing water, and is preferably dimethyl silicone polymer, glass, indium tin oxide-coated glass, PETG film, polyimide film, polyethylene film or poly tetrafluoroethylene.
3. the preparation method of Nano/micron metal film as claimed in claim 1 or 2, is characterized in that, comprises the following steps:
(1) stromal surface processing: stromal surface is carried out to oxygen plasma treatment or UV-irradiation, make stromal surface produce the active group of oxidation, obtain the matrix of surface active;
(2) stromal surface amination: by the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, carry out amination processing, obtain the matrix of surface amination;
(3) depositing metallic films: the mixed solution of getting the bicarbonate of gold chloride and highly basic evenly mixes with glucose solution, and coating in the matrix of the surface amination obtaining in step (2), makes to be distributed with on every 1cm2 gold element 3.58 × 10
-5g to 2.87 × 10
-3g and glucose 7.5 × 10
-4g to 3 × 10
-3g, at 20 DEG C to 40 DEG C, lucifuge reaction after 2 hours to 4 hours washing dry, obtain described Nano/micron metal film.
4. preparation method as claimed in claim 3, it is characterized in that, described matrix is the dense film not absorbing water, and is preferably dimethyl silicone polymer, glass, indium tin oxide-coated glass, PETG film, polyimide film, polyethylene film or poly tetrafluoroethylene.
5. preparation method as claimed in claim 4, is characterized in that, in the time that described matrix is polyethylene film or poly tetrafluoroethylene, stromal surface is processed and adopted UV-irradiation.
6. the preparation method as described in claim 3 to 5 any one, it is characterized in that, the described oxygen plasma treatment time of step (1) is 3 minutes to 5 minutes, described UV-irradiation, its ultraviolet ray intensity is 90uW/cm to 180uW/cm, and irradiation time is 40 minutes to 90 minutes.
7. preparation method as claimed in claim 3, is characterized in that, the concrete operations of described step (2) are:
By the matrix of the surface active obtaining in step (1), immerse in 3-aminopropyl triethoxysilane solution, react 30 minutes to 120 minutes, with dry after deionized water washing.
8. preparation method as claimed in claim 3, it is characterized in that, the concrete grammar of described step (3) coating is, the middle reeded dimethyl silicone polymer of tool (PDMS) piece of reversible keying in the matrix of the surface amination obtaining in step (2), described groove is in order to hold deposit solution.
9. preparation method as claimed in claim 3, is characterized in that, the mixed solution of the bicarbonate of the described gold chloride of step (3) and highly basic, and wherein gold chloride concentration is 10
-3g/ml to 2 × 10
-2between g/ml, the concentration of bicarbonate radical is at 0.15mol/L to 0.5mol/L.
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| WO2016178043A1 (en) * | 2015-05-01 | 2016-11-10 | Noxtak Technologies Vba. | Unit for neutralizing electrosmog |
| CN107383413A (en) * | 2017-09-13 | 2017-11-24 | 哈尔滨工业大学 | A kind of preparation method of surface modified PET food package film |
| CN107383413B (en) * | 2017-09-13 | 2020-03-13 | 哈尔滨工业大学 | Preparation method of surface-modified PET food packaging film |
| CN112316936A (en) * | 2020-11-23 | 2021-02-05 | 华中科技大学 | BiVO4Interface photocatalyst, preparation method and application thereof |
| CN112316936B (en) * | 2020-11-23 | 2022-03-29 | 华中科技大学 | BiVO4Interface photocatalyst, preparation method and application thereof |
| CN113295667A (en) * | 2021-04-30 | 2021-08-24 | 华东师范大学 | Detect Cu simultaneously+And Cu2+Surface-enhanced Raman spectrum probe and preparation method and application thereof |
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