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CN114236249A - Functional device with electric field induction and light field sensing functions and application - Google Patents

Functional device with electric field induction and light field sensing functions and application Download PDF

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Publication number
CN114236249A
CN114236249A CN202111545378.6A CN202111545378A CN114236249A CN 114236249 A CN114236249 A CN 114236249A CN 202111545378 A CN202111545378 A CN 202111545378A CN 114236249 A CN114236249 A CN 114236249A
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module
processing module
bivo
electric field
field
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曾玮
肖仁旺
贺新雨
陈修宇
桂鹏彬
王思亮
陈志亮
黄志祥
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Anhui University
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Anhui University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R29/00—Arrangements for measuring or indicating electric quantities not covered by groups G01R19/00 - G01R27/00
    • G01R29/08—Measuring electromagnetic field characteristics
    • G01R29/0864—Measuring electromagnetic field characteristics characterised by constructional or functional features
    • G01R29/0878—Sensors; antennas; probes; detectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J1/00—Photometry, e.g. photographic exposure meter
    • G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R29/00—Arrangements for measuring or indicating electric quantities not covered by groups G01R19/00 - G01R27/00
    • G01R29/08—Measuring electromagnetic field characteristics
    • G01R29/0864—Measuring electromagnetic field characteristics characterised by constructional or functional features
    • G01R29/0871—Complete apparatus or systems; circuits, e.g. receivers or amplifiers

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Abstract

The invention discloses a functional device with electric field induction and light field perception and application, including WO3/BiVO4a/MXene working electrode, a counter electrode and a reference electrode; said WO3/BiVO4the/MXene working electrode comprises 100-110nm thick WO on FTO3Film of which WO is singly3Crystals having an area of (0.5-1.0) μm x (0.1-0.5) μm and a thickness of 0.2-0.3 μm, WO3BiVO with thickness of 0.1-0.2 μm on the film4Thin film, BiVO4MXene film with thickness of 20-30nm is coated on the film. The functional device has the characteristics of wide applicable environment, high detection sensitivity, small size, portability, convenience in movement and the like, realizes multiple functions, and has the functions of electric field sensing and light field sensing.

Description

Functional device with electric field induction and light field sensing functions and application
Technical Field
The invention relates to a functional device with electric field induction and light field sensing functions and application, and belongs to the field of electronic devices.
Background
The intelligent electronic product gradually develops towards the direction of small volume, high circuit integration level and high transmission speed. As an important component of an intelligent electronic product, a novel intelligent electronic component is developed in the direction of forward chip type, miniaturization, high frequency, broadband, high precision, integration and environmental protection. The optical field sensor can be used for detecting the change of the light intensity and is widely applied to daily life; the electric field sensor can measure the intensity of transient electric field in a high-voltage power system, and provides reliable means and basis for meteorological guarantee.
The prior patent, a composite electrode and preparation and application in electric field detection (CN 109884410 a), discloses that a device with the size of 2cm × 2.5cm is tested in a circuit to explore the performance of the sensor. From the current density-time (I-T) curve of the response of the tested current to the space electric field as a function of time, the device is formed by two poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate-reduced graphene oxide (P-rGO) aerogel electrodes are respectively and horizontally placed on PVA/H2SO4In the gel electrolyte, after being taken out, two P-rGO aerogel electrodes are placed in a face-to-face manner, a diaphragm is added in the middle, a parallel plate capacitor type electric field sensor is formed, a plasma sphere on the left side of the sensor serves as an electric field generator, the sensor is vertically placed on a radiation beam outwards from the center of the plasma sphere, and the plasma sphere is manually opened/closed at the frequency of 0.2Hz in the test process. The electric field intensity range is 1100--1Sensitivity of 1.3X 10-10mA m V-1The electric field response sensitivity is low, the test method does not consider background current, and the measured data is inaccurate.
Another patent is a ZnO modified WO3/BiVO4Preparation method of heterojunction and application thereof in photoelectrocatalysis (CN 109778223A), including WCl6Preparation of WO with PVP3A seed crystal layer; dissolving sodium tungstate in water, and sequentially adding hydrochloric acid and ammonium oxalate to obtain a transparent solution; adding the transparent solution with WO3Seed layer reaction to obtain WO3Array precursor, high-temperature annealing to obtain WO3An electrode; dissolving vanadium oxide bis (acetylacetone) and bismuth nitrate pentahydrate in glacial acetic acid, and adding ethyl cellulose to obtain BiVO4Precursor solution; BiVO (bismuth oxide) is added4Drop coating of precursor solution onto WO3Drying and annealing the electrode surface to obtain WO3/BiVO4A composite light anode; mixing WO3/BiVO4The composite photoanode is placed in an atomic layer deposition system, and the ZnO grows layer by layer after deposition circulation by using diethyl zinc and water, so that the ZnO modified WO with better high efficiency and stability in photoelectrocatalysis is obtained3/BiVO4A heterojunction. But WO modified by ZnO3/BiVO4The electrode of/ZnO was fitted with AM 1.5G (100mW cm) at a bias voltage of 0.8V with a 300W xenon lamp-2) When the optical filter is used as an analog light source, the response photocurrent density is lower than 0.8mA cm-2The photocurrent density was low.
The two schemes cannot realize functional compatibility when researching light field sensing and electric field sensing, and can only detect the electric field intensity and the light field intensity.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a functional device with both electric field induction and light field sensing and application thereof.
In order to achieve the above object, the present invention adopts a sensing module including a WO3/BiVO4a/MXene working electrode, a counter electrode and a reference electrode;
said WO3/BiVO4the/MXene working electrode comprises 100-110nm thick WO on FTO3Film of which WO is singly3Crystals having an area of (0.5-1.0) μm x (0.1-0.5) μm and a thickness of 0.2-0.3 μm, WO3BiVO with thickness of 0.1-0.2 μm on the film4Thin film, BiVO4MXene film with thickness of 20-30nm is coated on the film.
As an improvement, the WO3/BiVO4the/MXene working electrode is prepared by the following method:
1) preparation of WO3An electrode: adding 1.21-1.25mmol of Na2WO4·2H2O and 1.06-1.16mmol (NH)4)2C2O4·H2Dissolving O in 33-36mL deionized water, adding 9-12mL HCl while stirring, and adding 8-10mL H2O2Stirring the solution for 10-15min, adding 30-35mL of anhydrous C2H6O, stirring for 10-15min, and synthesizing WO on FTO by water bath heating method3The film is annealed at the temperature of 500-550 ℃ for 2-3 h;
2) preparation of WO3/BiVO4Pole: adding 0.25-0.30mmol of Bi (NO)4)2·5H2O and 0.30-0.35mmol C10H14O5V dissolved in 5-10mL of CH3COOH and C5H8O2Stirring the mixture solution at room temperature until no precipitate is formed in a volume ratio of 20:1, and adding 20-30 mu L of BiVO4Precursor solution coating on WO3Drying the surface at room temperature, then carrying out heat treatment in air at 150-200 ℃ for 15-20min, and finally carrying out annealing at 550-600 ℃ for 2-2.5 h;
3) preparation of WO3/BiVO4The electrode of/MXene: adding 0.5-1.5g LiF, 10-30mL HCl solution, 0.5-1.5g Ti3AlC2Stirring at 30-40 deg.C for 23-24h, repeatedly washing with deionized water, and washing with 3000-3500r min-1Centrifuging, ultrasonic pulverizing for 40-50min, and finally 3500r min at 3000--1Centrifuging for 25-35min to obtain 1-3mg mL-1MXene precursor solution with the speed of 2000--1Spin coating for 30-35s, in WO3/BiVO4Depositing 1-3mg mL of the solution on the substrate-1MXene solution to form WO3/BiVO4a/MXene working electrode.
In addition, the invention also provides a functional device with both electric field induction and light field perception, which comprises a mechanical module, a processing module, a display module, a power management module and a sensing module;
the power management module is respectively connected with the mechanical module, the processing module and the display module and supplies power to the mechanical module, the processing module and the display module, and the processing module is respectively connected with the mechanical module, the sensing module and the display module.
As a refinement, the mechanical module comprises an electric field blocking plate and a light blocking field plate; the light blocking field plate is used for controlling whether an optical field acts on a working electrode of the sensing module or not; the electric field baffle plate is used for controlling whether an electrostatic field acts on the working electrode or not.
As an improvement, the counter electrode, the reference electrode and WO in the sensing module3/BiVO4the/MXene working electrode is respectively connected with the counter electrode port, the reference electrode port and the working electrode port of the processing module; the power supply management module is respectively connected with different voltage supply power ports of the processing module, the mechanical module and the display module; the display module is connected with the data transmission port of the processing module; the mechanical module is connected with the control port of the processing module.
Finally, the invention also provides the application of the functional device, the electric field blocking plate and the light blocking field plate in the mechanical module are controlled to be opened and closed in sequence by the processing module, the data collected by the sensing module is output to the processing module, and the data output by the sensing module is fed back by the display module.
As a further improvement, the method specifically comprises the following steps:
s1, the processing module controls the mechanical module to close the light blocking field plate and the electric blocking field plate, and the processing module detects and records the background current I of the sensing moduleS1；
S2, the processing module only controls the electric field baffle plate of the mechanical module to be opened, the electrostatic field to be detected penetrates through the light blocking field plate to act on the working electrode of the sensing module, the opening and closing frequency of the electric field baffle plate is controlled to be 0.20-0.25Hz, the period of completely closing the baffle plate is controlled to be 0.50-0.67ms, and a current value I is obtainedS2Lasting for 4-5 test periods to obtain a group of current values, and calculating the average value of the current values by a processing module
Figure BDA0003415698110000031
S3, the processing module controls the mechanical module to open the light blocking field plate and the electric field blocking plate simultaneously to enable the light source to be detected and the electrostatic field to be detected to directly act on the working electrode of the sensing module, the processing module controls the electric field blocking plate of the mechanical module to be in a normally open state, controls the light blocking field plate to be opened and closed according to the frequency of 0.2-0.25Hz, the period of completely closing the blocking plate is 0.50-0.67ms, and obtains a current value IS3Lasting for 4-5 test periods to obtain a group of current values, and calculating the average value of the current values by a processing module
Figure BDA0003415698110000041
S4, obtaining the electric field induction current value by the steps S1-S2:
Figure BDA0003415698110000042
the processing module is toeCarrying out distortion-free amplification, filtering and conversion output to obtain the electric field intensity E, and finally outputting data to a display of a display module by a processing module;
s5, obtaining the light field sensing current value through the steps S1-S4:
Figure BDA0003415698110000043
the processing module is tolAnd carrying out distortion-free amplification, filtering and conversion output to obtain light intensity, and finally outputting the data to a display of the display module by the processing module.
The principle of the functional device of the invention is as follows:
WO in the sensor module, as shown in fig. 1a, when the electric field blocking plate and the light blocking field plate of the mechanical module are in a closed state, i.e. in the absence of a spatial electrostatic field and an optical field3/BiVO4the/MXene (WBM) working electrode region does not excite any carriers, and the anion SO4 2-Or a cation Na+Na randomly distributed around WBM working electrode2SO4In the electrolyte.
When the processing module controls the electric field baffle plate and the light blocking field plate of the mechanical module to be orderly opened and closed, namely when the space electrostatic field and/or the light acts on the working electrode,induced electrons of the electrostatic field in space (E)-) And sensing holes (E)+) In MXene and BiVO4Region formation, as shown by the black solid line circle in FIG. 1b, and then excitation of E+E excited by migration along the direction of the electrostatic field in space to the left surface of the electrode-To adjacent WO3The layer migrates. Simultaneously, electrons (L) excited by light-) And a cavity (L)+) In WO3And BiVO4The region is generated. In BiVO4In the region of L+(or L)-) To adjoining MXene (or WO)3) The layer migrates. In WO3In the region of L+(or L)-) To BiVO4The (or FTO) layer migrates as indicated by the black dashed circle in FIG. 1 b. Here, the double arrow denotes WO3And BiVO4Charge transfer between, single arrow representing MXene and BiVO4With hollow, unidirectional arrows indicating the migration of cations and anions in the electrolyte. In addition, in the electrostatic field of the space, cations and anions in the electrolyte are also excited and then migrate to the counter electrode and the working electrode, respectively. The increase of the intensity of the space electrostatic field is equivalent to the increase of the hard line bias voltage and the acceleration L-And L+Is being migrated.
When the electric field blocking plate and the light blocking field plate of the mechanical module are completely closed, as shown in fig. 1c, the electrolyte and the excited carriers (holes or electrons) and the anions and cations in the electrolyte will diffuse to the region with relatively low concentration, and when the electrostatic field in space and light no longer act on the working electrode, the excited carriers (L) will diffuse to the region with relatively low concentration+、L-、E+、E-) And anions, cations and diffusion into regions of relatively low carrier concentration in the electrolyte. It can be observed that the influence of the light field includes WO3And BiVO4The space electrostatic field influences carriers in the semiconductor region including MXene and BiVO4Carriers in the region of (a). MXene and BiVO when the space electrostatic field is not acted on the working electrode any more4The carriers in the dielectric layer are recombined, so that the built-in electric field disappears gradually, and the induced bias voltage is attenuated continuously until the induced bias voltage is zero.
Compared with the prior art, the invention has the beneficial effects that:
1) the functional device has the characteristics of wide applicable environment, high detection sensitivity, small size, portability, convenience in movement and the like. The response range of the WBM working electrode in the functional device to the electric field is 700-1100Vm-1The sensitivity is 1.12X 10- 4mA mV-1. The WBM working electrode has a corresponding visible light response wavelength range of 300-800nm in optical field response, wherein the WBM working electrode is more sensitive to the visible light wavelength range of 400-500nm, and the average photocurrent density of the WBM working electrode is 1.15mA cm under the bias voltage of 0.8V-2。
2) The functional device realizes multiple functions and simultaneously has the functions of electric field induction and light field sensing.
Drawings
FIG. 1 is a schematic diagram of the working principle of the functional device of the present invention; a is a WBM working electrode and electrolyte internal anion and cation distribution diagram without space electrostatic field and optical field; b is a distribution diagram of the carrier migration inside the WBM working electrode and the movement of anions and cations in the electrolyte when a space electrostatic field and an optical field act on the working electrode; c is a migration distribution diagram of carriers in the WBM working electrode and anions and cations in the electrolyte when an electric field blocking plate and a light blocking field plate of the mechanical module are in a closed state, namely a space electrostatic field and an optical field are simultaneously shielded, and d is an energy band diagram of the WBM working electrode;
FIG. 2 is a schematic flow chart of the preparation of the WBM working electrode of the present invention;
FIG. 3 is a schematic structural diagram of a functional device according to the present invention;
FIG. 4 is a front view of a mechanical module of the functional device of the present invention;
FIG. 5 is a front view of a display module in the functional device of the present invention;
FIG. 6 is a schematic view of the connection of the functional device of the present invention;
fig. 7 is a graph showing the response of the WBM working electrode in example 1 of the present invention at different external electric field strengths;
FIG. 8 shows the light passing/shielding pair WO of the present invention at 0.2Hz frequency with an external bias voltage of 0.8V3、BiVO4Four electrodes of WB and WBM working electrode are used for measuring electrochemical photocurrent-time(I-T) diagram;
FIG. 9 is a flow chart of a test application of the functional device of the present invention;
FIG. 10 is a waveform diagram illustrating the operations of steps S1, S2 and S3 in the test application of the present invention;
FIG. 11 is an I-T diagram of different fields of the present invention, wherein a is the I-T diagram of S1 and S2 of the test flow chart, b) is the I-T diagram of S3 of the test flow chart;
FIG. 12 is an impedance plot of a WBM working electrode of the present invention;
in the figure: 1. mechanical module, 11, electric field blocking plate, 12, light blocking field plate, 13, through hole, 2, sensing module, 21, counter electrode, 22, reference electrode, 23, WO3/BiVO4The device comprises a/MXene working electrode, a processing module, a display module, a light button, a power button, a test button, a power management module and a power button, wherein the display module is 41, and the light button is 42, 43.
Detailed Description
The following examples are further illustrative of the present invention as to the technical content of the present invention, but the essence of the present invention is not limited to the following examples, and one of ordinary skill in the art can and should understand that any simple changes or substitutions based on the essence of the present invention should fall within the protection scope of the present invention.
Example 1
As shown in FIG. 2, a WO3/BiVO4The preparation method of the/MXene working electrode comprises the following steps:
1) preparation of WO3An electrode: adding 1.21mmol of Na2WO4·2H2O and 1.06mmol (NH)4)2C2O4·H2O was dissolved in 33mL deionized water, 9mL HCl was added with stirring, and 8mL H was added2O2Stirring the solution for 10min, adding 30mL of anhydrous C2H6O, stirring for 10min, heating by water bath (80 deg.C, 200min, FTO placed vertically in 40mL WO)3In solution) Synthesis of WO on FTO (1 cm. times.3 cm)3Carrying out annealing treatment on the film at 500 ℃ for 2 h;
2) preparation of WO3/BiVO4(WB) electrode: 0.25mmol of Bi (NO)4)2·5H2O and 0.30mmol C10H14O5V dissolved in 5mL of CH3COOH and C5H8O2Stirring the mixture at room temperature in a mixed solution with the volume ratio of 20:1 until no precipitate exists, and adding 20 mu L of BiVO4Precursor solution coating on WO3Drying on the surface at room temperature, then carrying out heat treatment at 150 ℃ for 15min in air, and finally carrying out annealing at 550 ℃ for 2 h;
3) preparation of WO3/BiVO4/MXene (WBM) electrode: 0.5g LiF, 10mL HCl solution, 0.5g Ti3AlC2Stirring at 30 deg.C for 23h, repeatedly washing with deionized water and 3500r min-1Centrifuging, ultrasonic pulverizing for 40min, and finally 3500r min-1Centrifuging for 25min to obtain a concentration of 1mg mL-1MXene precursor solution with a rate of 2000r s-1Spin coating for 30s, in WO3/BiVO4Deposit 1mg mL on the substrate-1MXene solution to form WO3/BiVO4a/MXene (WBM) working electrode.
In combination with the graph shown in fig. 1, the chemical bonding state and the grafting degree of the WBM working electrode are analyzed, and the existence of a Ti-O covalent bond (the Ti element of MXene forms a covalent bond with the O element of BiVO 4) indicates that MXene nanosheets have been successfully bonded to the surface of the composite electrode, and the formation of a schottky junction between BiVO4 and MXene is also proved.
Analyzing the band diagram of the WBM working electrode and knowing the working principle: as shown in fig. 1 d, the fermi level of MXene is 1.64eV (vs. sce), WO3Has a Conduction Band (CB) and a Valence Band (VB) of 0.95 and 3.71eV (vs. SCE), respectively, and a band gap of 2.76 eV. And BiVO4Has a bandgap of 2.40eV, and has a CB and VB of 0.58 and 2.98eV (vs. SCE), respectively. L is+Or L-In WO3And BiVO4In the layer. Due to the Fermi level and BiVO of MXene4Has a very small gap between the CB's, effectively reducing the potential barrier for electron transfer, L-Is easy to migrate to BiVO4Of (2) is provided. In MXene and BiVO4Induced E in the layer+From MXene to WO3The direction of one side is shifted.BiVO4And WO3L in (1)-And L+Will be influenced by the electric field, L-And L+Will move in the opposite direction to the electric field. Electric field energy promotes L-From BiVO4Migration to WO3Region, and L+The migration direction of (2) is opposite. In addition, MXene has excellent metal conductivity, its Fermi level and BiVO4There is a gap between CB or VB. To balance the potential difference, BiVO4Has a bent CB or VB band and is in MXene/BiVO4Forming a Schottky barrier at the interface to suppress L-From BiVO4Flow to MXene, further promoting L-From BiVO4To WO3The CB of (1). When metal is in contact with semiconductor, L-From BiVO4Flowing MXene into BiVO4A space charge region composed of positively charged and immovable impurity ions is formed on the surface layer of (a). In this region, from BiVO4A built-in electric field is formed to the MXene layer to prevent BiVO4The electrons in (1) flow into MXene to promote the electrons to flow from BiVO4Migration to WO3。WO3Is just opposite to BiVO4VB (or CB), then L-From BiVO4Transfer of CB of layer to WO3The CB of (1). At the same time, WO3L in layer VB+Is injected into BiVO4In layer VB.
The structure of the WBM working electrode prepared in example 1 was: attaching WO with thickness of 100nm to FTO3Film of which WO is singly3The area of the crystal was 1.0. mu. m.times.0.4. mu.m, the thickness was 0.2. mu.m, WO3BiVO with the thickness of 0.1 μm is formed on the surface of the film4Film, finally in BiVO4An MXene transparent square film with the thickness of 20nm is deposited on the film. Wherein the Ti element and BiVO of the WBM working electrode MXene4The interface generated by Ti-O covalent bond formed by the element O increases the conductivity and enhances the light absorption, so that the corresponding visible light response wavelength range of the WBM working electrode in the optical field response is 300-800nm, wherein the response is more sensitive to the visible light wavelength range of 400-500nm, and the average photocurrent density of the WBM working electrode is 1.15mA cm under the bias voltage of 0.8V-2。
Example 2
As shown in FIG. 2, a WO3/BiVO4The preparation method of the/MXene working electrode comprises the following steps:
1) preparation of WO3An electrode: adding 1.25mmol of Na2WO4·2H2O and 1.16mmol (NH)4)2C2O4·H2O was dissolved in 36mL of deionized water, 12mL of HCl was added with stirring, and 10mL of H was added2O2Stirring the solution for 15min, adding 35mL of anhydrous C2H6O, stirring for 15min, heating by water bath (85 deg.C, 250min, FTO placed vertically in 50mL WO)3In solution) Synthesis of WO on FTO (1 cm. times.3 cm)3Carrying out annealing treatment on the film at 550 ℃ for 3 h;
2) preparation of WO3/BiVO4Pole: 0.30mmol of Bi (NO)4)2·5H2O and 0.35mmol C10H14O5V dissolved in 10mL of CH3COOH and C5H8O2Stirring the mixture at room temperature in a mixed solution with the volume ratio of 20:1 until no precipitate is formed, and adding 30 mu L of BiVO4Precursor solution coating on WO3Drying on the surface at room temperature, then carrying out heat treatment in air at 150 ℃ for 20min, and finally carrying out annealing at 600 ℃ for 2.5 h;
3) preparation of WO3/BiVO4The electrode of/MXene: 1.5g LiF, 30mL HCl solution, 1.5g Ti3AlC2Stirring at 40 deg.C for 24h, repeatedly washing with deionized water and 3500r min-1Centrifuging, ultrasonic pulverizing for 50min, and finally 3500r min-1Centrifuging for 35min to obtain a concentration of 3mg mL-1MXene precursor solution with rate of 2500r s-1Spin coating for 35s, in WO3/BiVO43mg mL of deposit on the substrate-1MXene solution to form WO3/BiVO4a/MXene working electrode.
The structure of the WBM working electrode prepared in example 2 was: attaching WO with thickness of 100nm to FTO3Film of which WO is singly3The area of the crystal was 1.0. mu. m.times.0.4. mu.m, and the thickness was 0.25μm，WO3BiVO with a thickness of 0.15 μm is formed on the surface4Film, finally in BiVO4An MXene transparent square film with a thickness of 25nm is deposited on the film, so that the response range of the WBM working electrode to the electric field is 700--1The sensitivity is 1.12X 10-4mA m V-1。
Example 3
As shown in fig. 3-5, a device with both electric field sensing and light field sensing functions includes a mechanical module 1, a processing module 3, a display module 4, a power management module 5, and a sensing module 2;
the power management module 5 is respectively connected with the mechanical module 1, the processing module 3 and the display module 4 and supplies power to the mechanical module 1, the processing module 3 and the display module 4, and the processing module 3 is respectively connected with the mechanical module 1, the sensing module 2 and the display module 4. The processing module 3 is used for detecting, recording and processing data output by the sensing module 2, and controlling the electric field blocking plate 11 and the light blocking field plate 12 of the mechanical module 1 to be sequentially opened and closed; the power management module 5 is used for supplying power to the processing module 3, the mechanical module 1 and the display module 4; the display module 4 is used for displaying the data output by the processing module 3, and a light button 41, a power button 42 and a test button 43 are arranged in the display module 4; the sensing module 2 is used for converting the influence of the electric field and the optical field into an electric signal, and comprises a working electrode, a reference electrode 22 (such as a calomel electrode), and a counter electrode 23 (such as a platinum electrode); the mechanical module 1 is used for orderly controlling the penetration or shielding of the electrostatic field and the optical field to be detected.
The light-blocking field plate 12 is a black plastic plate, which can block light from penetrating through, and whether the light field acts on the working electrode of the sensing module 2 is controlled by controlling the opening and closing of the light-blocking field plate 12; the electric field baffle plate 11 is a metal baffle plate, can shield the influence of an electrostatic field on the working electrode of the sensing module 2, and controls the electric field baffle plate 11 so as to control whether the electrostatic field acts on the working electrode.
Specifically, the counter electrode 21 (platinum electrode), the reference electrode 22 (calomel electrode) and the WO in the sensing module 23/BiVO4the/MXene working electrode 23 is respectively connected with the counter electrode port and the reference electrode port of the processing module 3A port, a working electrode port; the power management module 5 is respectively connected with different voltage supply power ports of the processing module 3, the mechanical module 1 and the display module 4; the display module 4 is connected with the data transmission port of the processing module 3; the machine module 1 is connected to a control port of the process module 3.
Example 4
As shown in fig. 6, the connection relationship of the functional device is: the power management module 5 is a 3.7V direct current voltage supply circuit and provides a stable voltage source for the mechanical module 1, the processing module 3 and the display module 4;
the mechanical module 1 controls the orderly opening and closing electric field blocking plate or the light blocking field plate by the processing module 3, and has the function of orderly controlling a field to be tested to act on the working electrode so as to meet the requirement of a test program;
the processing module 3 consists of three parts: the circuit comprises a chip circuit, an I/V and operational amplification circuit and a filter circuit; STM32 is the core chip, and sensing module 2 will gather weak current signal output to the I/V converting circuit and become corresponding voltage signal, and rethread process control amplifier circuit standardizes voltage signal, then eliminates useless background noise through the filtering circuit that makes an uproar and obtains useful signal, and useful signal gathers through STM 32's A/D converting module and obtains corresponding digital signal, uses the STM32 treater to export the display of display module 4 after handling the signal.
Example 5
The WBM working electrode prepared in example 1 was assembled into a sensing module 1, and a functional device was constructed by combining a power management module 5, a processing module 3, a display module 4, and a mechanical module 1, for detecting the electrostatic field in the space.
The functional device is placed in a dark box body, an electrostatic field generator is arranged in the box body and used for generating electrostatic fields with different electric field intensities, and the through holes 13 of the functional device are opposite to the electrostatic field generator. The processing module 3 of the functional device sets the electric field blocking plate 11 and the light blocking field plate 12 of the mechanical module 1 to be in a normally open state, the electric field to be tested can directly act on the working electrode of the sensing module 2, and the functional device tests 4 sample points at different time periods (black square points from left to right in fig. 7 are sample points 1, 2, 3 and 4 respectively). In connection with the functional device shown in fig. 7The current value I of the sensing module 2 when the processing module 3 detects the sample point 1e1The current value detected at sample point 1 is 0Vm as the electric field intensity-1Background current of time; the processing module 3 of the functional device detects the current value I of the sensing module 2 when the sample point 2 is detectede2After I/V conversion, operational amplifier and filtering, the chip processes data and transmits the data to the display module 4, and the electric field intensity is 700V m-1(ii) a The processing module 3 of the functional device detects the current value I of the sensing module 2 when the sample point 3 is detectede30.123mA, an electric field strength of 900V m was obtained-1(ii) a When the processing module 3 of the functional device detects the sample point 4, the current value of the sensing module 2 is Ie40.135mA, an electric field strength of 1100V m was obtained-1(ii) a The long straight line in the figure is a fitting straight line, and the fitting degree is 0.96627.
Example 6
WO obtained in example 13、BiVO4WB, WBM electrodes are designated as samples 1, 2, 3,4, respectively.
Referring to fig. 8, the through hole 13 of the functional device is aligned to the optical field to be measured, the processing module 3 controls the electric field blocking plate 11 of the mechanical module 1 to be in an open state, the light blocking field plate 12 is opened and closed at a frequency of 0.2Hz, and meanwhile, the processing module 3 applies a 0.8V hard line bias voltage to the working electrode to obtain a measured electrochemical I-T diagram of the samples 1, 2, 3 and 4. The processing module 3 of the functional device detects the photocurrent values of the samples 1, 2, 3 and 4, the photocurrent values are subjected to I/V conversion, operational amplification and filtering, and finally the data are processed by the chip and transmitted to the display module 4, and the comparison of the data shows that the photocurrent I of the sample 1l10.75mA, photocurrent I of sample 2l21.5mA, photocurrent I of sample 3l32.64mA, photocurrent I of sample 4l4Analysis shows that the working electrode of sample 4 responds better to light than other samples, so the WBM electrode is the most suitable working electrode for the sensing module.
Example 7
The functional device test procedure of the present invention is shown in fig. 9, and the WBM electrode prepared in example 1 was used as a test working electrode. Wherein, the testing steps are as follows:
s1 control machine for processing module 3The mechanical module 1 closes the light blocking field plate 12 and the electric field blocking plate 11, and the processing module 3 detects and records the background current I of the sensing module 2S1＝0.01mA；
S2, the processing module 3 only controls the electric field blocking plate 11 of the mechanical module 1 to be opened, the light blocking field plate 12 is in a closed state, an electric field to be measured penetrates through the light blocking field plate 12 to act on the working electrode of the sensing module 2, the opening and closing frequency of the light blocking field plate 11 is controlled to be 0.20Hz, the complete closing baffle period is controlled to be 0.50ms, and a current value I is obtainedS2Lasting for 5 test periods to obtain a set of current values, and calculating the average value of the current by the processing module 3
Figure BDA0003415698110000101
S3, the processing module 3 controls the mechanical module 1 to open the light blocking field plate 12 and the electric field blocking plate 11 at the same time, the light source to be detected and the electric field to be detected directly act on the working electrode of the sensing module 2, the processing module 3 controls the electric field blocking plate 11 of the mechanical module 1 to be in a normally open state, the light blocking field plate 12 is controlled to be opened and closed according to the frequency of 0.2Hz, the period of completely closing the blocking plate is 0.50ms, and the current value I is obtainedS3Lasting for 5 test periods to obtain a set of current values, and calculating the average value of the current by the processing module 3
Figure BDA0003415698110000111
S4, obtaining the electric field induction current value by the steps S1-S2:
Figure BDA0003415698110000112
the processing module 3 willePerforming distortion-free amplification, filtering and conversion output to obtain an electric field strength E of 1000Vm-1The final data is output to the display of the display module 4 by the processing module 3;
s5, obtaining the light field sensing current value through the steps S1-S4:
Figure BDA0003415698110000113
the processing module 3 willlPerforming distortion-free amplification, filtering and conversion to obtain light intensity I of 100mW cm-2The final data is output by the processing module 3To the display of the display module 4.
Example 8
The functional device test procedure of the present invention is shown in fig. 9, and the WBM electrode prepared in example 2 was used as a test working electrode. Wherein, the testing steps are as follows:
s1, the processing module 3 controls the mechanical module 1 to close the light blocking field plate 12 and the electric blocking field plate 11, and the processing module 3 detects and records the background current I of the sensing module 2S1＝0.011mA；
S2, the processing module 3 only controls the electric field blocking plate 11 of the mechanical module 1 to be opened, the light blocking field plate 12 is in a closed state, an electric field to be measured penetrates through the light blocking field plate 12 to act on the working electrode of the sensing module 2, the opening and closing frequency of the light blocking field plate 11 is controlled to be 0.20Hz, the complete closing baffle period is controlled to be 0.50ms, and a current value I is obtainedS2Lasting for 5 test periods to obtain a set of current values, and calculating the average value of the current by the processing module 3
Figure BDA0003415698110000114
S3, the processing module 3 controls the mechanical module 1 to open the light blocking field plate 12 and the electric field blocking plate 11 at the same time, the light source to be detected and the electric field to be detected directly act on the working electrode of the sensing module 2, the processing module 3 controls the electric field blocking plate 11 of the mechanical module 1 to be in a normally open state, the light blocking field plate 12 is controlled to be opened and closed according to the frequency of 0.2Hz, the period of completely closing the blocking plate is 0.50ms, and the current value I is obtainedS3Lasting for 5 test periods to obtain a set of current values, and calculating the average value of the current by the processing module 3
Figure BDA0003415698110000115
S4, obtaining the electric field induction current value by the steps S1-S2:
Figure BDA0003415698110000116
the processing module 3 willeThe electric field intensity E is 1100Vm obtained by performing distortion-free amplification, filtering and conversion output-1The final data is output to the display of the display module 4 by the processing module 3;
s5, S1-S4, obtaining a light field sensing current value:
Figure BDA0003415698110000121
the processing module 3 willlPerforming distortion-free amplification, filtering and conversion to obtain light intensity I of 100mW cm-2The final data is output by the processing module 3 to the display of the display module 4.
Example 9
Waveforms of steps S2 and S3 in examples 7 and 8 are shown in fig. 10.
When the step S1 is executed, the STM32 chip output waveform is as shown by the S1 waveform in fig. 10, in which the electric field blocking plate 11 and the light blocking field plate 12 simultaneously receive a low-level instruction of the STM32 chip, both of which are in the off state.
When the step S2 is executed, the output waveform of the STM32 chip is shown as the waveform S2 in fig. 10, in which the input end of the light blocking field plate 12 receives a low level command of the chip and is in a closed state, the electric field blocking plate 11 receives a control command of the chip, a high level indicates that the electric field blocking plate 11 is opened, and a low level indicates that the electric field blocking plate 11 is closed.
When the step S3 is executed, the output waveform of the STM32 chip is shown as the waveform S3 in fig. 10, in which the input terminal of the electric field baffle 11 is in the normally open state when receiving a chip high level command, the light blocking field plate 12 receives a control command of the chip, the high level represents that the electric field baffle 12 is open, and the low level represents that the electric field baffle 12 is closed.
Example 10
As shown in steps S1, S2, S3 of embodiments 7 and 8, the sensor device assembled by the WBM working electrodes is a sensor module.
When the electric field blocking plate 11 and the light blocking field plate 12 of the mechanical module 1 are all closed, the data output by the sensing module 2 and measured by the processing module 3 is background noise, the electric field blocking plate 11 is opened after collection and is opened and closed according to the frequency of 0.2Hz, and the electric field intensity is 1100V m at the moment-1The electric field to be detected acts on the working electrode through the light blocking field plate 12, the processing module 3 collects and records data of the sensing module 2, fig. 11a is a partial data diagram of steps S1 and S2, and the processing module 3 detects the sensing module 1S before the electric field blocking plate 11 is closedThe data output by the block 2 is averaged to finally detect the background current I of the sensing module 2S10.01mA, electric field current value IS2＝0.134mA。Ie＝IS2-IS1The data is further processed, after I/V conversion, operational amplification and filtering processing by the processing module, the final conversion result is output to the display of the display module 4 by the chip, and the display electric field intensity is 1100V m-1；
After the step S2, step S3 is performed, the electric field blocking plate 11 is in a normally open state, the light blocking field plate 12 is opened and closed at 0.2Hz, and the electric field strength is 1100V m-1The electric field to be measured and the light intensity are 100mW cm-2The mixed field composed of the light field acts on the working electrode, the processing module 3 collects and records data of the sensing module 2, fig. 11b is a partial data diagram of the step S3, the processing module 3 detects data output by the sensing module 2 1S before the light blocking field plate 12 is closed, the average value of multiple groups of data is taken, and finally the mixed field current value I of the sensing module 2 is detectedS3＝0.424mA，Il＝IS3-Ie. After I/V conversion, operational amplification and filtering processing by the processing module, the final conversion result is output to a display of the display module 4 by a chip, and the intensity of a display light field is 100mW cm-2. The data show that the functional device has high stability and repeatability in detecting the electric field, the optical field and the mixed field.
Example 11
When the functional device is started, the working electrode needs to be self-checked, the processing module 3 sends an instruction to the mechanical module 1, the electric field blocking plate 11 and the light blocking field plate 12 of the mechanical module 1 are in a closed state, meanwhile, 0.8V hard line bias voltage is applied to the sensing module 2, and at the moment, the processing module 3 detects an impedance value of the WBM working electrode of the sensing module 2.
As shown in fig. 12, when the processing module 3 detects that the impedance value of the WBM working electrode of the sensing module 2 is below 10 Ω or above 6.1K Ω, the processing module 3 sends an ERROR report ERROR to the display of the display module 4 to complete self-test. When the impedance value of the WBM working electrode is 10-6.1K omega, the functional device detects that the sensing module 2 is in a non-failure state, and continues to execute the test program.
The invention establishes a multifunctional electrochemical device based on the requirements of realizing electric field induction and optical field sensing, can measure the change of electric field intensity and detect the change of optical intensity, and has wide application in the technical fields of aviation, aerospace and intelligent robot sensing and industrial production.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (7)

1. A sensing module, characterized in that it comprises a WO3/BiVO4a/MXene working electrode, a counter electrode and a reference electrode;
said WO3/BiVO4the/MXene working electrode comprises 100-110nm thick WO on FTO3Film of which WO is singly3Crystals having an area of (0.5-1.0) μm x (0.1-0.5) μm and a thickness of 0.2-0.3 μm, WO3BiVO with thickness of 0.1-0.2 μm on the film4Thin film, BiVO4MXene film with thickness of 20-30nm is coated on the film.
2. A sensing module according to claim 1, wherein the WO is3/BiVO4the/MXene working electrode is prepared by the following method:
1) preparation of WO3An electrode: adding 1.21-1.25mmol of Na2WO4·2H2O and 1.06-1.16mmol (NH)4)2C2O4·H2Dissolving O in 33-36mL deionized water, adding 9-12mL HCl while stirring, and adding 8-10mL H2O2Stirring the solution for 10-15min, adding 30-35mL of anhydrous C2H6O, stirring for 10-15min, and synthesizing WO on FTO by water bath heating method3The film is annealed at the temperature of 500-550 ℃ for 2-3 h;
2) preparation of WO3/BiVO4Pole: adding 0.25-0.30mmol of Bi (NO)4)2·5H2O and 0.30-0.35mmol C10H14O5V dissolved in 5-10mL of CH3COOH and C5H8O2Stirring the mixture solution at room temperature until no precipitate is formed in a volume ratio of 20:1, and adding 20-30 mu L of BiVO4Precursor solution coating on WO3Drying the surface at room temperature, then carrying out heat treatment in air at 150-200 ℃ for 15-20min, and finally carrying out annealing at 550-600 ℃ for 2-2.5 h;
3) preparation of WO3/BiVO4The electrode of/MXene: 0.5-1.5g LiF, 10-30mL HCl solution, 0.5-1.5g Ti3AlC2Stirring at 30-40 deg.C for 23-24h, repeatedly washing with deionized water, and washing with 3000-3500r min-1Centrifuging, ultrasonic pulverizing for 40-50min, and finally 3500r min at 3000--1Centrifuging for 25-35min to obtain 1-3mg mL-1MXene precursor solution with the speed of 2000--1Spin coating for 30-35s, in WO3/BiVO4Depositing 1-3mg mL of the solution on the substrate- 1MXene solution to form WO3/BiVO4a/MXene working electrode.
3. A functional device with both electric field induction and light field sensing is characterized by comprising a mechanical module, a processing module, a display module, a power management module and a sensing module according to any one of claims 1-2;
the power management module is respectively connected with the mechanical module, the processing module and the display module and supplies power to the mechanical module, the processing module and the display module, and the processing module is respectively connected with the mechanical module, the sensing module and the display module.
4. The device of claim 3, wherein the mechanical module comprises an electric field blocking plate and a light blocking field plate;
the light blocking field plate is used for controlling whether an optical field acts on a working electrode of the sensing module or not; the electric field baffle plate is used for controlling whether an electrostatic field acts on the working electrode or not.
5. The device with electric field sensing and optical field sensing functions as claimed in claim 3, wherein the counter electrode, the reference electrode and the WO in the sensing module3/BiVO4the/MXene working electrode is respectively connected with the counter electrode port, the reference electrode port and the working electrode port of the processing module; the power supply management module is respectively connected with different voltage supply power ports of the processing module, the mechanical module and the display module; the display module is connected with the data transmission port of the processing module; the mechanical module is connected with the control port of the processing module.
6. The application of the functional device as claimed in any one of claims 3 to 5, wherein the electric field baffle plate and the light blocking field plate in the mechanical module are controlled to be opened and closed in sequence by the processing module, the data collected by the sensing module is output to the processing module, and finally the data output by the sensing module is fed back by the display module.
7. The use according to claim 6, characterized in that it comprises in particular the following steps:
s1, the processing module controls the mechanical module to close the light blocking field plate and the electric blocking field plate, and the processing module detects and records the background current I of the sensing moduleS1；
S2, the processing module only controls the electric field baffle plate of the mechanical module to be opened, the electrostatic field to be detected penetrates through the light blocking field plate to act on the working electrode of the sensing module, the opening and closing frequency of the electric field baffle plate is controlled to be 0.20-0.25Hz, the period of completely closing the baffle plate is controlled to be 0.50-0.67ms, and a current value I is obtainedS2Lasting for 4-5 test periods to obtain a group of current values, and calculating the average value of the current values by a processing module
Figure FDA0003415698100000021
S3, the processing module controls the mechanical module to open the light blocking field plate and the electric field blocking plate at the same time, so that the light source to be detected and the electrostatic field to be detected directly act on the working electrode of the sensing module, and the processing module controls the electric field blocking plate of the mechanical module to be in a normally open stateControlling the light blocking field plate to open and close according to the frequency of 0.2-0.25Hz, and completely closing the baffle plate for 0.50-0.67ms to obtain the current value IS3Lasting for 4-5 test periods to obtain a group of current values, and calculating the average value of the current values by a processing module
Figure FDA0003415698100000031
S4, obtaining the electric field induction current value by the steps S1-S2:
Figure FDA0003415698100000032
the processing module is toeCarrying out distortion-free amplification, filtering and conversion output to obtain the electric field intensity E, and finally outputting data to a display of a display module by a processing module;
s5, obtaining the light field sensing current value through the steps S1-S4:
Figure FDA0003415698100000033
the processing module is tolAnd carrying out distortion-free amplification, filtering and conversion output to obtain light intensity, and finally outputting the data to a display of the display module by the processing module.
CN202111545378.6A 2021-12-16 2021-12-16 Functional device with electric field induction and light field sensing functions and application Pending CN114236249A (en)

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