CN108609695B - Fluorine-tin modified boron-doped diamond film electrode and preparation method and application thereof - Google Patents
Fluorine-tin modified boron-doped diamond film electrode and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorine-tin modified boron-doped diamond film electrode and a preparation method and application thereof. The preparation method comprises the following steps: firstly preparing a BDD electrode with tightly-packed crystal particles, and then adding styrene, phenol, polyoxyethylene ether and SnCl2Mixing with NaF, stirring, dissolving in water and ethanol, adding hexamethylene tetramine to obtain precursor turbid solution, and coating the precursor turbid solution on the surface of BDD electrode to obtain F and SnO2Coating, and calcining at certain temperature to obtain BDD/SnO2-an F electrode. The prepared fluorine-tin modified BDD film electrode has the advantages of uniform and compact surface, higher oxygen evolution potential, good corrosion resistance and strong electrooxidability; the composite material is used as an anode for treating organic wastewater difficult to degrade, and has good degradation effect.
Description
Technical Field
The invention belongs to the technical field of electrochemical electrode preparation, and particularly relates to a boron-doped diamond thin film electrode (BDD electrode) modified by fluorine tin, and a preparation method and application thereof.
Background
F-53B (Table 1) has been used as a chromium fog inhibitor for 30 years, has physicochemical properties such as stability, bioaccumulation and toxicity, and is a non-degradable pollutant.
TABLE 1 molecular Structure of chromium fog inhibitor F-53B
The electrochemical oxidation technology is convenient to operate, has strong oxidative degradation capability on persistent organic pollutants, and is widely applied to the treatment of organic dye and phenol wastewater which are difficult to degrade. Therefore, the method for treating the degradation-resistant pollutant F-53B by adopting the electrochemical oxidation method and developing and screening the anode material which is efficient, economical, simple and easy to obtain is a current research hotspot.
The boron-doped diamond film electrode (BDD electrode) has the advantages of high oxygen evolution potential, long electrode service life, stable chemical property, high degradation efficiency and the like. However, the BDD electrode on the market at present has large resistance and low electrocatalytic activity. The electrocatalytic properties can be further improved by surface modification methods. The surface of the BDD is modified by Co, Au and polymers, but the good properties of the BDD are covered by the modification methods. Therefore, it is required to develop a technique for improving conductivity and electrocatalytic performance while securing a high oxygen evolution potential of BDD itself.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a preparation method of a boron-doped diamond film electrode modified by fluorine tin (namely a BDD film electrode modified by fluorine tin).
The invention also aims to provide a fluorine tin modified BDD thin film electrode prepared by the preparation method.
The invention further aims to provide application of the fluorine tin modified BDD thin film electrode.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a fluorine tin modified BDD film electrode comprises the following steps:
(1) preparing a BDD electrode by a hot wire vapor deposition method;
(2) 5 parts by mass of styrene, 5 parts by mass of phenol, 5 parts by mass of polyoxyethylene ether and 1.8962 parts by mass of SnCl2Mixing with 0.8 part by mass of NaF, stirring uniformly, adding 9 parts by mass of water and 20 parts by mass of ethanol, dissolving the solid, adding 0.9 part by mass of hexamethylene tetramine into the solution, and fully mixing to obtain SnO with white precipitate2-F coating precursor haze;
(3) washing the surface of BDD electrode with aqua regia to form rough surface, and then adding SnO2Spin-coating the precursor turbid solution of the F coating on the surface of the BDD electrode, drying, naturally cooling to room temperature, and cleaning; then calcining (pyrolyzing and oxidizing) the electrode at 450 ℃ for 1 h; repeating the processes of spin coating and calcining for several times to obtain BDD/SnO2An F electrode, namely the fluorine tin modified BDD thin film electrode.
The specific steps of the step (1) are as follows: putting the pretreated silicon substrate into a 3KPa air pressure hot wire vapor deposition chamber, introducing hydrogen, methane and borane into the deposition chamber according to the volume ratio of 98:2:0.2, adopting a tungsten wire as a hot wire, wherein the distance between the hot wire and the silicon substrate is 8mm, and the temperature of the hot wire is 850 ℃; adjusting control voltage, increasing current passing through the hot wire, increasing the temperature of the hot wire to make the temperature of the silicon substrate reach above 850 ℃, starting to deposit a diamond film until the temperature of the silicon substrate is not increased any more, and cooling to room temperature at a cooling speed of 4 ℃/min after 8 hours of deposition to prepare the BDD electrode for later use.
The pretreatment comprises cutting, grinding and polishing, boiling, grinding, cleaning and drying, and specifically comprises the following steps of cutting a Si sheet into small blocks with the thickness of 15mm and × 15mm as a substrate, polishing by using sand paper, boiling for 15min, grinding the silicon substrate by using diamond grinding paste with the thickness of 0.5 mu m for 10min, then ultrasonically cleaning by using acetone, absolute ethyl alcohol and deionized water for 5min in sequence, and finally drying.
In the step (2), the number average molecular weight Mn of the polyoxyethylene ether is 1622, and the molecular weight distribution index D is 1.10.
And (3) washing the surface of the BDD electrode for 3min by using aqua regia.
The spin coating speed in the step (3) is 3000 r/min; the drying is carried out for 20min at 300 ℃; the cleaning is performed by using absolute ethyl alcohol and distilled water.
And (4) repeating the processes of spin coating and calcining for three times in the step (3) to obtain the fluorine-tin modified BDD film electrode.
BDD/SnO prepared by the invention2The surface particles of the F electrode are uniform and compact; the oxygen evolution potential is 2.37V (vs. SCE, saturated calomel) obtained by adopting a linear sweep voltammetry testElectrodes). The BDD/SnO2the-F electrode can be used for electrocatalytic degradation of pollutant F-53B at initial pH of 3 and current density of 30mA/cm2And the degradation rate of F-53B can reach 95.6% under the condition that the electrolyte is 1.0mol/L NaCl.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) BDD/SnO prepared by the invention2-F electrode particle tight bond, SnO2The F coating increases the conductivity of the electrode without affecting the BDD electrocatalytic performance.
(2) The electrode coating prepared by the preparation method is not easy to fall off, and the oxygen evolution potential is improved from 2.15V of BDD to BDD/SnO22.37V of-F, the electrocatalytic capacity is greatly improved.
Drawings
Fig. 1 is the surface topography of the BDD electrode prepared in example 1;
FIG. 2 is a BDD/SnO prepared in comparative example 12The surface appearance of the electrode;
FIG. 3 is BDD/SnO prepared in example 12-F electrode surface topography;
FIG. 4 shows BDD, BDD/SnO prepared in example 1 and comparative example 12、BDD/SnO2-linear sweep voltammogram comparison of F electrode, (a) BDD electrode; (b) is BDD/SnO2(ii) a (c) Is BDD/SnO2-F；
FIG. 5 shows BDD, BDD/SnO prepared in example 1 and comparative example 12、BDD/SnO2Comparison of the removal rates of F-53B for F electrodes, a BDD electrode; b is BDD/SnO2(ii) a c is BDD/SnO2-F。
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1:
the embodiment provides a fluorine tin modified BDD film electrode and a preparation method thereof. The preparation method comprises the following steps:
(1) cutting a Si sheet into small blocks with the thickness of 15mm × 15mm as a substrate, polishing by using sand paper, boiling for 15min, grinding the silicon substrate by using diamond grinding paste with the thickness of 0.5 mu m for 10min, then ultrasonically cleaning by using acetone, absolute ethyl alcohol and deionized water for 5min in sequence, and finally drying to obtain the pretreated silicon substrate;
putting the pretreated silicon substrate into a 3KPa air pressure hot wire vapor deposition chamber, introducing hydrogen, methane and borane into the deposition chamber according to the volume ratio of 98:2:0.2, adopting a tungsten wire as a hot wire, wherein the distance between the hot wire and the silicon substrate is 8mm, and the temperature of the hot wire is 850 ℃; adjusting control voltage, increasing current passing through the hot wire, increasing the temperature of the hot wire to make the temperature of the silicon substrate reach above 850 ℃, starting to deposit a diamond film until the temperature of the silicon substrate is not increased any more, and cooling to room temperature at a cooling speed of 4 ℃/min after 8 hours of deposition to prepare the BDD electrode for later use.
(2) 5g of styrene, 5g of phenol, 5g of polyoxyethylene ether (number average molecular weight Mn: 1622, molecular weight distribution index D: 1.10), 1.8962g of SnCl2And 0.8g of NaF, uniformly mixing and stirring, adding 9mL of water and 20mL of ethanol, slowly adding 0.9g of hexamethylene tetramine into the solution after the solid is dissolved, and fully mixing to obtain SnO2-F coating precursor haze;
(3) washing BDD electrode surface with aqua regia for 3min to form rough surface, and adding SnO2Spin-coating precursor turbid solution of the-F coating on the surface of the BDD electrode at the rotating speed of 3000r/min, then placing the prepared electrode in an oven at 300 ℃ for drying for 20min, naturally cooling to room temperature (25 ℃), cleaning with absolute ethyl alcohol and distilled water, slowly heating to 450 ℃ for pyrolysis and oxidation for 1h, and repeating the processes from spin coating to calcination for three times to obtain BDD/SnO2An F electrode (i.e. the fluorine tin modified BDD thin film electrode).
Comparative example 1: SnO2Modified BDD/SnO2Preparation of the electrodes
(1) Preparing a BDD electrode with reference to step (1) of example 1 above;
(2) 5g of styrene, 5g of phenol, 5g of polyoxyethylene ether (number average molecular weight Mn: 1622, molecular weight distribution index D: 1.10), 1.8962g of SnCl2Mixing and stirring uniformly, adding 9mL of water and 20mL of ethanol, slowly adding 0.9g of hexamethylene tetramine into the solution after the solid is dissolvedFully mixing to obtain precursor turbid liquid;
(3) washing the surface of a BDD electrode for 3min by aqua regia to form a rough surface, spin-coating a precursor turbid solution on the surface of the BDD electrode at the rotating speed of 3000r/min, placing the prepared electrode in a 300 ℃ oven to be dried for 20min, naturally cooling to 25 ℃, washing by absolute ethyl alcohol and distilled water, slowly heating to 450 ℃ for pyrolysis and oxidation for 1h, and repeating the processes from spin coating to calcination for three times to obtain SnO2Modified BDD/SnO2And an electrode.
Fig. 1 is an SEM image of the BDD prepared in example 1, and it can be seen from fig. 1 that the diamond polycrystalline thin film crystal particles on the BDD electrode surface are closely packed and grown in a step form, the crystallite size of the particles is micron-sized, the surface is smooth and the edges are clear, and the high crystallinity of the BDD electrode is represented. FIG. 2 is BDD/SnO prepared in comparative example 12The scanning electron microscope atlas of the electrode can be seen from the figure, it is SnO2After modification, the original morphology of the BDD electrode is still visible. FIG. 3 is BDD/SnO prepared in example 12SEM image of-F electrode, from which SnO can be seen2The F particles already mask the original morphology of BDD.
FIG. 4 is a linear sweep voltammogram of a BDD modified electrode, showing BDD/SnO according to the linear sweep voltammogram2The oxygen evolution overpotential of the F electrode is 2.37(vs. SCE), which is obviously higher than that of BDD and BDD/SnO2The oxygen evolution overpotential of the electrode was 2.15V, 2.19V (vs. sce). The linear sweep voltammetry adopts an electrochemical three-electrode system to prepare electrodes (BDD, BDD/SnO)2Electrode, BDD/SnO2-F electrode) as working electrode, platinum electrode as counter electrode, saturated calomel electrode as reference electrode, electrolyte solution 0.5mol/L H2SO4The analysis parameters of the solution are that the initial potential is-0.5V, the termination potential is 3V, the scanning speed is 0.05V/s, the sampling interval is 0.001V, the rest time is 2s, and the sensitivity is 1 × e-0.001Analyzing the oxygen evolution potential of the electrode under the A/V condition.
FIG. 5 shows BDD, BDD/SnO prepared in example 1 and comparative example 12、BDD/SnO2Comparison of the removal rates of F-53B by F electrode. Can be seen from the figureTo that, after electrochemical oxidation for 30min, BDD/SnO2And BDD/SnO2The degradation rates of the F electrode to the F-53B are respectively 80.54%, 90.4% and 95.6%, and therefore, the electrochemical oxidation capacity of the modified BDD electrode is greatly improved.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of a fluorine tin modified BDD film electrode is characterized by comprising the following steps:
(1) preparing a BDD electrode for later use by a hot wire vapor deposition method; the method comprises the following specific steps: putting the pretreated silicon substrate into a 3kPa air pressure hot wire vapor deposition chamber, introducing hydrogen, methane and borane into the deposition chamber according to the volume ratio of 98:2:0.2, adopting a tungsten wire as a hot wire, wherein the distance between the hot wire and the silicon substrate is 8mm, and the temperature of the hot wire is 850 ℃; adjusting control voltage, increasing current passing through a hot wire, increasing the temperature of the hot wire to enable the temperature of the silicon substrate to reach above 850 ℃, starting to deposit a diamond film until the temperature of the silicon substrate is not increased any more, and cooling to room temperature at a cooling speed of 4 ℃/min after 8 hours of deposition to prepare a BDD electrode for later use;
(2) 5 parts by mass of styrene, 5 parts by mass of phenol, 5 parts by mass of polyoxyethylene ether and 1.8962 parts by mass of SnCl2Mixing with 0.8 part by mass of NaF, stirring uniformly, adding 9 parts by mass of water and 20 parts by mass of ethanol, dissolving the solid, adding 0.9 part by mass of hexamethylene tetramine into the solution, and fully mixing to obtain SnO with white precipitate2-F coating precursor haze; 1 part by mass is 1g, and 1 part by volume is 1 mL;
(3) washing the surface of BDD electrode with aqua regia to form rough surface, and then adding SnO2Spin-coating the precursor turbid solution of the F coating on the surface of the BDD electrode, drying, naturally cooling to room temperature, and cleaning; then calcining the electrode at 450 ℃ for 1 h; process for spin coating and calciningRepeating the steps for several times to obtain the fluorine tin modified BDD film electrode.
2. The preparation method of the fluorine tin modified BDD thin film electrode, as claimed in claim 1, wherein the pretreatment comprises cutting, polishing, boiling, grinding, cleaning and drying, and comprises the steps of cutting a Si sheet into pieces of 15mm × 15mm as a substrate, polishing with sand paper, boiling for 15min, grinding the silicon substrate with diamond grinding paste with a particle diameter of 0.5 μm for 10min, sequentially ultrasonically cleaning with acetone, absolute ethyl alcohol and deionized water for 5min, and finally drying.
3. The preparation method of the fluorine tin modified BDD thin film electrode as claimed in claim 1, wherein the number average molecular weight Mn of the polyoxyethylene ether in the step (2) is 1622, and the molecular weight distribution index D is 1.10.
4. The preparation method of the fluorine tin modified BDD film electrode as claimed in claim 1, wherein in the step (3), the surface of the BDD electrode is washed with aqua regia for 3 min.
5. The preparation method of the fluorine tin modified BDD thin film electrode as claimed in claim 1, wherein the spin coating rotation speed of the step (3) is 3000 r/min; the drying is carried out for 20min at 300 ℃; the cleaning is performed by using absolute ethyl alcohol and distilled water.
6. The preparation method of the fluorine tin modified BDD thin film electrode according to claim 1, wherein the spin coating and calcining process in the step (3) is repeated three times to obtain the fluorine tin modified BDD thin film electrode.
7. A fluorine tin modified BDD thin film electrode, which is prepared by the preparation method of the fluorine tin modified BDD thin film electrode as claimed in any one of claims 1 to 6.
8. The use of the fluorotin modified BDD thin film electrode of claim 7 in the electrocatalytic degradation of contaminant F-53B.
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| CN103193217A (en) * | 2013-03-12 | 2013-07-10 | 南京理工大学 | Method for preparing boron-doped diamond and carbon nanotube composite nanocone |
| CN105688971A (en) * | 2016-02-29 | 2016-06-22 | 大连理工大学 | Electrochemical reduction CO2 catalyst based on boron and nitrogen co-doped nano-diamond and preparation method and application of catalyst |
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| CN103193217A (en) * | 2013-03-12 | 2013-07-10 | 南京理工大学 | Method for preparing boron-doped diamond and carbon nanotube composite nanocone |
| CN105688971A (en) * | 2016-02-29 | 2016-06-22 | 大连理工大学 | Electrochemical reduction CO2 catalyst based on boron and nitrogen co-doped nano-diamond and preparation method and application of catalyst |
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| Highly efficient electrochemical degradation of perfluorooctanoic acid(PFOA) by F-doped Ti/SnO2 electrode;Bo Yang等;《Journal of Hazardous Materials》;20151231;第417-424页 * |
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