CN114324984B - Anthracene-based molecular junction with photoelectric detection function and preparation method and application thereof - Google Patents
Anthracene-based molecular junction with photoelectric detection function and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of molecular electronics, and discloses an anthracene-based molecular junction with a photoelectric detection function, a preparation method and application thereof. In the preparation process, the rhodium acetate dimer complex [ Rh ] takes the axial coordination capacity into consideration 2 (O 2 CCR 3 ) 4 ](R＝H、F、CH 3 ) As strong Lewis acid, with a pyridyl bidentate organic ligand (L); at the same time introduce photosensitive organic molecules into Rh 2 -in the L molecular skeleton. Rhodium acetate dimer complex [ Rh ] 2 (O 2 CCR 3 ) 4 ]The complex and the organic ligand readily form a stable adduct [ Rh ] 2 (μ‑O 2 CCR 3 ) 4 L 2 ]With this advantage, supermolecular junctions with photoactive building blocks were successfully constructed on gold electrodes using stepwise preparation methods.
Description
Technical Field
The invention belongs to the technical field of molecular electronics, and particularly relates to an anthracene-based molecular junction (ABP-SM) with a photoelectric detection function, a preparation method and application thereof.
Background
The proposal of molecular electronics is a promising strategy to meet the technological demands of increasingly miniaturized conventional silicon-based electronic devices. Since the charge transport behavior of a molecular junction is closely related to the chemical structure of a molecule, the chemical structure determines the electron configuration of the molecule and the electrode-molecule interactions. Thus, the charge transport properties and function of the molecular junction can be controlled by adjusting the chemical structure of the supermolecule. Based on this strategy, various molecular electronics have been developed that utilize single or monolithic molecules to integrate the desired functions into the circuit, such as molecular wires, molecular rectifiers, molecular switches, etc. In addition to the basic electronic devices described above, a photodetector is also one of the basic electronic devices, which can convert an optical signal into an electrical signal. To our knowledge, there is very little research on molecular photodetectors. Therefore, research on molecular electronics as the function of a photoelectric detector is extended, and the method has important significance for meeting the requirements of high-performance electronic devices in the future.
Disclosure of Invention
To overcome the drawbacks and disadvantages of the prior art, a primary object of the present invention is to provide an anthracene-based molecular junction (ABP-SM) with a photodetection function, which is capable of recognizing light of different wavelengths with high sensitivity.
The invention also aims to provide a preparation method of the anthracene-based molecular junction with the photoelectric detection function; the invention takes the axial coordination ability into consideration, uses Lewis acid Rh 2 (O 2 CCR 3 ) 4 ](R＝H、F、CH 3 ) The pyridyl bidentate organic ligand and the photosensitive molecule are used as raw materials, the higher alcohol is used as a solvent, and under a milder condition, the reaction conditions such as the molar concentration ratio between the raw materials, the reaction time and the like are simultaneously regulated, and a self-assembled molecular film grows on a gold substrate by a layer-by-layer assembly method, so that a metal/molecule junction with an adjustable chemical structure is obtained.
The invention also provides an application of the anthracene-based molecular junction with the photoelectric detection function, wherein before detection, the anthracene-based molecular junction and a conductive atomic force microscope probe form a metal/molecule/metal junction, and finally the photoelectric property of the anthracene-based molecular junction is explored.
The aim of the invention is achieved by the following technical scheme:
an anthracene-based molecular junction with a photoelectric detection function, wherein the molecular junction has a structure shown as the following formula (I):
wherein R is H, F, CH 3 。
The molecular junction comprises a gold substrate electrode layer and a self-assembled molecular film layer, wherein the self-assembled molecular film layer is positioned on the gold substrate electrode layer.
The self-assembled molecular layer is a 4-mercaptoethylpyridine and rhodium acetate dimer complex [ Rh ] sequentially from bottom to top on the surface of the gold substrate electrode 2 (O 2 CCR 3 ) 4 ]Photosensitive molecule, rhodium acetate dimer complex [ Rh ] 2 (O 2 CCR 3 ) 4 ]A pyridyl bidentate organic ligand; the [ Rh ] 2 (O 2 CCR 3 ) 4 ]R in (B) is H, F or CH 3
The photoactive molecule is 9, 10-bis (4-pyridyl) anthracene; the pyridyl bidentate organic ligand is pyrazine.
The preparation method of the anthracene-based molecular junction with the photoelectric detection function comprises the following operation steps:
(1) Preparing a gold substrate electrode by utilizing a vacuum evaporation method;
(2) And self-assembling an anthracene-based molecular junction on the surface of the gold substrate electrode.
The preparation of the gold substrate electrode by the vacuum evaporation method in the step (1) specifically comprises the following steps: fixing the newly cut mica sheet on an evaporation base of a high vacuum resistance evaporation coating machine, and setting the evaporation rateEvaporating high purity gold onto mica sheet at 2×10 -5 ～7×10 -6 And the thickness of 100-150 nm is reached under the Torr pressure, and the gold substrate electrode is obtained.
The self-assembled anthracene-based molecular junction on the surface of the gold substrate electrode in the step (1) specifically comprises the following steps: sequentially soaking the gold substrate electrode in the following soaking solutions: 4-mercaptoethylpyridine, rhodium acetate dimer complex [ Rh ] 2 (O 2 CCR 3 ) 4 ]Photosensitive molecule, rhodium acetate dimer complex [ Rh ] 2 (O 2 CCR 3 ) 4 ]And a pyridyl bidentate organic ligand, wherein the gold substrate electrode is washed by ethanol and purged by nitrogen for drying before the soaking liquid is replaced each time; the [ Rh ] 2 (O 2 CCR 3 ) 4 ]R in (B) is H, F or CH 3 ；
The 4-mercaptoethyl groupThe concentration of pyridine is 0.01-0.5 mmol/L, and the rhodium acetate dimer complex [ Rh ] 2 (O 2 CCR 3 ) 4 ]The concentration of the pyridine bidentate organic ligand is 0.05-1 mmol/L, the concentration of the photosensitive molecule is 0.05-1 mmol/L, and the concentration of the pyridine bidentate organic ligand is 0.05-1 mmol/L. The photoactive molecule is 9, 10-bis (4-pyridyl) anthracene; the pyridyl bidentate organic ligand is pyrazine.
The gold substrate electrode is sequentially arranged on 4-mercaptoethylpyridine, rhodium acetate dimer complex [ Rh ] 2 (O 2 CCR 3 ) 4 ]Photosensitive molecule, rhodium acetate dimer complex [ Rh ] 2 (O 2 CCR 3 ) 4 ]Soaking in the pyridyl bidentate organic ligand for 1-3 h, 2-30 min and 2-30 min; the temperature of the gold substrate electrode soaked in 4-mercaptoethylpyridine, photosensitive molecules and pyridyl bidentate organic ligands is room temperature, and the gold substrate electrode is a rhodium acetate dimer complex [ Rh ] 2 (O 2 CCR 3 ) 4 ]The soaking temperature is less than 0 ℃.
Rh with photoelectric detection function 2 (O 2 CCR 3 ) 4 ]The application of the base molecular junction in molecular photoelectric detection is that before the anthracene base molecular junction is applied to molecular photoelectric detection, the anthracene base molecular junction and the conductive atomic force probe form a metal/molecule/metal junction.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The present invention successfully adds a photosensitive molecule to Rh 2 (O 2 CCR 3 ) 4 On the main chain of pyridine oligomer ABP-SM, a photosensitive supermolecule is constructed on the gold electrode by a layer-by-layer preparation method. Experimental results show that the molecular junction based on ABP-SM has good optical switch response. Specifically, the current was found to be near 20nA without UV radiation when measured with a conductive probe atomic force microscope at a bias of.+ -. 1V, whereas the current was negligible (< 0.1 nA) when irradiated with 365nm UV light. And the switching times may last 50 cycles. Further mechanism studies have shown that the HOMO of the supramolecules can be used as charge transport in the absence of lightA channel. In contrast, charge transport is hindered after photon excitation, which may be due to an energy mismatch between the natural transition orbitals (ntus) of the supramolecules and the fermi levels of the electrodes. The research shows that supermolecule with proper chemical structure has optical switch conductivity and may be used as molecular photoelectric detector.
(2) The preparation method disclosed by the invention is simple to operate, short in preparation time and relatively stable in growing the self-assembled molecular film.
Drawings
FIG. 1 is a schematic diagram of the structure of a synthetic ABP-SM junction according to example 1 of the present invention;
FIG. 2 is an ultraviolet-visible absorption spectrum of an ABP-SM junction synthesized in example 1 of the invention, wherein FIG. 2- (A) is an ultraviolet-visible absorption spectrum of the ABP-SM junction, a dotted line represents a self-assembled molecular layer of rhodium trifluoroacetate and 9, 10-bis (4-pyridyl) anthracene, a solid line represents a self-assembled molecular layer of rhodium trifluoroacetate and pyrazine, an illustration is a partial enlarged view of 350nm to 410nm, FIG. 2- (B) is an ultraviolet-visible absorption spectrum of rhodium trifluoroacetate dimer and 9, 10-bis (4-pyridyl) anthracene oligomer, and FIG. 2- (C) is an ultraviolet-visible absorption spectrum of rhodium trifluoroacetate dimer and pyrazine oligomer;
FIG. 3 is a differential voltammogram for the synthesis of ABP-SM junctions and corresponding oligomers according to example 1 of the present invention, wherein FIG. 3- (A) is the differential voltammogram for the ABP-SM junctions, wherein FIG. 3- (B) is the differential voltammogram for rhodium trifluoroacetate dimer and 9, 10-bis (4-pyridyl) anthracene oligomer, and wherein FIG. 3- (C) is the differential voltammogram for rhodium trifluoroacetate dimer and pyrazine;
FIG. 4 is a graph showing the analysis of the thickness and image cross section of the synthetic ABP-SM junction according to example 1 of the present invention, wherein FIG. 4- (A) is the thickness of the ABP-SM junction and FIG. 4- (B) is the analysis of the cross section of FIG. 4- (A) of the ABP-SM junction;
FIG. 5 is a graph of current (I) -voltage (V) characteristics of a synthetic ABP-SM junction according to example 1 of the present invention, wherein FIG. 5- (A) is a graph of current (I) -voltage (V) characteristics of an ABP-SM junction when irradiated with 365nm ultraviolet light; FIG. 5- (B) is a graph of current (I) -voltage (V) characteristics of an ABP-SM junction without ultraviolet light irradiation;
FIG. 6 is a graph of current (I) -time (t) for the synthetic ABP-SM junctions of example 1 of the invention under different wavelength light irradiation.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1: anthracene-based molecular junction (ABP-SM) with photoelectric detection function of the embodiment
By [ Rh ] 2 (O 2 CCF 3 ) 4 ]Is Lewis acid, 9, 10-di (4-pyridyl) anthracene is photosensitive molecule, and pyrazine is used as pyridyl bidentate organic ligand.
The method comprises the following steps: SAMs of 4-mercaptoethylpyridine was prepared by immersing the gold substrate electrode in a 0.1mmol/L solution of 4-mercaptoethylpyridine in ethanol at room temperature for 1 hour. SAMs is washed with ethanol and treated with N 2 Purging and drying; transfer it to 0.2mmol/L rhodium trifluoroacetate dimer [ Rh ] 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution at low temperature (< 0deg.C) for 1hour; then soaking in 9, 10-di (4-pyridyl) anthracene at room temperature for 10min, and performing rhodium trifluoroacetate dimer [ Rh ] at low temperature (< 0℃) 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution for 5min, soaking in pyrazine at room temperature for 5min, washing with ethanol and adding N 2 Drying to obtain anthracene-based molecular junction (ABP-SM) with structure shown in figure 1.
The structure of the self-assembled molecular film of the example was characterized by using an Shimadzu ultraviolet spectrophotometer UV-2600, and the obtained ultraviolet absorption spectrum found that the peak positions of ABP-SM and the peak positions of rhodium trifluoroacetate dimer and 9, 10-di (4-pyridyl) anthracene oligomer, rhodium trifluoroacetate dimer and pyrazine oligomer respectively remain highly consistent (see figure 2), thus proving that the self-assembled molecular film successfully grows on the surface of a gold substrate.
The structure of the self-assembled molecular film of this example was characterized by the Chenhua electrochemical workstation CH1760E, and the resulting differential voltammogram revealed that the peak position of ABP-SM was between rhodium trifluoroacetate dimer and 9, 10-bis (4-pyridyl) anthracene oligomer and rhodium trifluoroacetate dimer and pyrazine oligomer (see FIG. 3), further demonstrating that the self-assembled molecular film successfully grew on the gold substrate surface.
The self-assembled molecular film thickness of this example was characterized by a bruk Multimode 8 atomic force microscope, and the obtained results were consistent with the theoretical calculated molecular length (see fig. 4), further demonstrating that the self-assembled molecular film was successfully grown on the gold substrate surface.
Example 2: self-assembly of molecular junctions (ABP-SM) at different molar ratios
The anthracene-based molecular junction (ABP-SM) with photoelectric detection function of the embodiment. By [ Rh ] 2 (O 2 CCF 3 ) 4 ]Is Lewis acid, 9, 10-di (4-pyridyl) anthracene is photosensitive molecule, and pyrazine is used as pyridyl bidentate organic ligand. The method comprises the following steps:
SAMs of 4-mercaptoethylpyridine was prepared by immersing the gold substrate electrode in a 0.2mmol/L solution of 4-mercaptoethylpyridine in ethanol at room temperature for 1 hour. SAMs is washed with ethanol and treated with N 2 Purging and drying; transfer it to 0.6mmol/L rhodium trifluoroacetate dimer [ Rh ] 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution at low temperature (< 0deg.C) for 1hour; then soaking in 9, 10-di (4-pyridyl) anthracene for 10min at room temperature, and performing rhodium trifluoroacetate dimer complex [ Rh ] at low temperature (less than 0℃) 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution for 5min, soaking in pyrazine at room temperature for 5min, washing with ethanol and adding N 2 Drying to obtain the anthracene-based molecular junction (ABP-SM).
Example 3: self-assembly of molecular junctions (ABP-SM) at different molar ratios
The anthracene-based molecular junction (ABP-SM) with photoelectric detection function of the embodiment. By [ Rh ] 2 (O 2 CCF 3 ) 4 ]Is Lewis acid, 9, 10-di (4-pyridyl) anthracene is photosensitive molecule, and pyrazine is used as pyridyl bidentate organic ligand. The method comprises the following steps:
SAMs of 4-mercaptoethylpyridine was prepared by immersing the gold substrate electrode in a 0.2mmol/L solution of 4-mercaptoethylpyridine in ethanol at room temperature for 1 hour. SAMs is washed with ethanol and treated with N 2 Purging and drying; transfer to 1mmol/L rhodium trifluoroacetate dimer [ Rh ] 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution at low temperature (< 0deg.C) for 1hour; then soaking in 9, 10-di (4-pyridyl) anthracene for 10min at room temperature, and performing rhodium trifluoroacetate dimer complex [ Rh ] at low temperature (less than 0℃) 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution for 5min, soaking in pyrazine at room temperature for 5min, washing with ethanol and adding N 2 Drying to obtain the anthracene-based molecular junction (ABP-SM).
Example 4: self-assembly of molecular junctions (ABP-SM) at different molar ratios
The anthracene-based molecular junction (ABP-SM) with photoelectric detection function of the embodiment uses [ Rh ] 2 (O 2 CCF 3 ) 4 ]Is Lewis acid, 9, 10-di (4-pyridyl) anthracene is photosensitive molecule, and pyrazine is used as pyridyl bidentate organic ligand. The method comprises the following steps:
SAMs of 4-mercaptoethylpyridine was prepared by immersing the gold substrate electrode in a 0.1mmol/L solution of 4-mercaptoethylpyridine in ethanol at room temperature for 1 hour. SAMs is washed with ethanol and treated with N 2 Purging and drying; transfer to 1mmol/L rhodium trifluoroacetate dimer [ Rh ] 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution at low temperature (< 0deg.C) for 1hour; then soaking in 9, 10-di (4-pyridyl) anthracene for 10min at room temperature, and performing rhodium trifluoroacetate dimer complex [ Rh ] at low temperature (less than 0℃) 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution for 5min, soaking in pyrazine at room temperature for 5min, washing with ethanol and adding N 2 Drying to obtain the anthracene-based molecular junction (ABP-SM).
Example 5: self-assembly of molecular junctions (ABP-SM) at different times
The anthracene-based molecular junction (ABP-SM) with photoelectric detection function of the embodiment uses [ Rh ] 2 (O 2 CCF 3 ) 4 ]Is Lewis acid, 9, 10-di (4-pyridyl) anthracene is photosensitive molecule, and pyrazine is used as pyridyl bidentate organic ligand. The method comprises the following steps:
the gold substrate electrode was placed in 0.1mM 4-mercaptoethylpyridine ethanol solution at room temperature to soak 2 hrs to prepare SAM of 4-mercaptoethylpyridines. SAMs is washed with ethanol and treated with N 2 Purging and drying; transfer to 0.2mM rhodium trifluoroacetate dimer [ Rh ] 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution at low temperature (< 0deg.C) for 1hour; then soaking in 9, 10-di (4-pyridyl) anthracene for 10min at room temperature, and performing rhodium trifluoroacetate dimer complex [ Rh ] at low temperature (less than 0℃) 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution for 5min, soaking in pyrazine at room temperature for 5min, washing with ethanol and adding N 2 Drying to obtain the anthracene-based molecular junction (ABP-SM).
Example 6: self-assembly of molecular junctions (ABP-SM) at different times
The anthracene-based molecular junction (ABP-SM) with photoelectric detection function of the embodiment uses [ Rh ] 2 (O 2 CCF 3 ) 4 ]Is Lewis acid, 9, 10-di (4-pyridyl) anthracene is photosensitive molecule, and pyrazine is used as pyridyl bidentate organic ligand. The method comprises the following steps:
SAMs of 4-mercaptoethylpyridine was prepared by immersing the gold substrate electrode in 0.1mM 4-mercaptoethylpyridine ethanol solution at room temperature for 3 hours. SAMs is washed with ethanol and treated with N 2 Purging and drying; transfer to 0.2mM rhodium trifluoroacetate dimer [ Rh ] 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution at low temperature (< 0deg.C) for 1hour; then soaking in 9, 10-di (4-pyridyl) anthracene for 10min at room temperature, and performing rhodium trifluoroacetate dimer complex [ Rh ] at low temperature (less than 0℃) 2 (O 2 CCF 3 ) 4 ]Soaking in ethanol solution for 5min, soaking in pyrazine at room temperature for 5min, washing with ethanol and adding N 2 Drying to obtain the anthracene-based molecular junction (ABP-SM).
Performance data:
the present invention is an anthracene-based molecular junction (ABP-SM) with photodetection function prepared according to the synthetic method of example 1, whose properties were measured by a bruk multisode 8 atomic force microscope. The specific method comprises the following steps: a bias voltage is applied between the conductive probe and the sample and the current through the sample can be measured by a current amplifier. The current (I) -voltage (V) characteristic curve is obtained, and the current (I) -time (t) characteristic curve is also obtained, and the obtained data are shown in fig. 5 and 6. In addition, we have visualized it, and the data obtained are shown in FIG. 6, which shows that the device has a switching response under 365nm ultraviolet light stimulation, but does not have a switching response under 520nm green light irradiation. These properties of ABP-SM have broad application prospects in photosensitive molecular electronics.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (8)
1. A metal/molecule junction with photodetection function, characterized in that: the metal/molecule junction has a structure shown in the following formula (I):
(I)
Wherein R is H, F, CH 3 ；
The metal/molecule junction comprises a gold substrate electrode layer and a self-assembled molecule film layer, wherein the self-assembled molecule film layer is positioned on the gold substrate electrode layer.
2. A metal/molecule junction with photodetection function according to claim 1, wherein: the self-assembled molecular film layer is a 4-mercaptoethylpyridine and rhodium acetate dimer complex Rh sequentially from bottom to top on the surface of the gold substrate electrode 2 (O 2 CCR 3 ) 4 Photosensitive molecule, rhodium acetate dimer complex Rh 2 (O 2 CCR 3 ) 4 A pyridyl bidentate organic ligand; the Rh 2 (O 2 CCR 3 ) 4 R in (B) is H, F or CH 3 。
3. A metal/molecule junction with photodetection function according to claim 2, wherein: the photoactive molecule is 9, 10-bis (4-pyridyl) anthracene; the pyridyl bidentate organic ligand is pyrazine.
4. The method for preparing a metal/molecule junction with a photoelectric detection function according to claim 1, wherein the method comprises the following steps:
(1) Preparing a gold substrate electrode by utilizing a vacuum evaporation method;
(2) And self-assembling an anthracene-based molecular junction on the surface of the gold substrate electrode.
5. The method for preparing a metal/molecule junction with a photoelectric detection function according to claim 4, wherein the method comprises the following steps: the preparation of the gold substrate electrode by the vacuum evaporation method in the step (1) specifically comprises the following steps: fixing the newly cut mica sheet on an evaporation base of a high vacuum resistance evaporation coating machine, setting the evaporation rate to be 0.5-3A/s, evaporating high-purity gold on the mica sheet, and performing 2X 10 evaporation on the mica sheet -5 ~7×10 −6 And (5) reaching the thickness of 100-150 nm under the condition of Torr to obtain the gold substrate electrode.
6. The method for preparing a metal/molecule junction with a photoelectric detection function according to claim 4, wherein the method comprises the following steps: the self-assembled anthracene-based molecular junction on the surface of the gold substrate electrode in the step (2) specifically comprises the following steps: sequentially soaking the gold substrate electrode in the following soaking solutions: 4-mercaptoethylpyridine, rhodium acetate dimer complex Rh 2 (O 2 CCR 3 ) 4 Photosensitive molecule, rhodium acetate dimer complex Rh 2 (O 2 CCR 3 ) 4 And a pyridyl bidentate organic ligand, wherein the gold substrate electrode is washed by ethanol and purged by nitrogen for drying before the soaking liquid is replaced each time; the Rh 2 (O 2 CCR 3 ) 4 R in (B) is H, F or CH 3 ；
Concentration of the 4-mercaptoethylpyridine0.01-0.5 mmol/L of rhodium acetate dimer complex Rh 2 (O 2 CCR 3 ) 4 The concentration of the pyridine bidentate organic ligand is 0.05-1 mmol/L, the concentration of the photosensitive molecule is 0.05-1 mmol/L, and the concentration of the pyridine bidentate organic ligand is 0.05-1 mmol/L.
7. The method for preparing a metal/molecule junction with a photoelectric detection function according to claim 6, wherein: the gold substrate electrode is sequentially arranged on 4-mercaptoethylpyridine, rhodium acetate dimer complex Rh 2 (O 2 CCR 3 ) 4 Photosensitive molecule, rhodium acetate dimer complex Rh 2 (O 2 CCR 3 ) 4 Soaking in the pyridyl bidentate organic ligand for 1-3 hours, 2-30 minutes and 2-30 minutes; the temperature of the gold substrate electrode soaked in 4-mercaptoethylpyridine, photosensitive molecules and pyridyl bidentate organic ligands is room temperature, and the gold substrate electrode is prepared into rhodium acetate dimer complex Rh 2 (O 2 CCR 3 ) 4 The soaking temperature is less than 0 ℃.
8. Use of a metal/molecule junction according to claim 1 in molecular photodetection, characterized in that: before the metal/molecule junction is applied to molecular photoelectric detection, the metal/molecule junction and the conductive atomic force probe form a metal/molecule/metal junction.
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| CN108956736A (en) * | 2018-05-11 | 2018-12-07 | 河北科技大学 | Method and its application based on electropolymerization p-Mercaptoaniline film preparation diethylstilbestrol molecular imprinting electrochemical sensor |
| CN110044987A (en) * | 2019-04-25 | 2019-07-23 | 闽南师范大学 | The method of the preparation method and its Electrochemical Detection troponin of the covalent organic frame modified electrode of ferrocenyl |
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Inventor after: Bu Donglei Inventor after: Huang Changgeng Inventor after: Du Yaqi Inventor after: Huang Shaoming Inventor before: Huang Changgeng Inventor before: Du Yaqi Inventor before: Bu Donglei Inventor before: Huang Shaoming |
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