CN109553160B - A kind of in-situ synthesis of spherical tin dioxide-supported platinum electrocatalyst preparation method and application thereof - Google Patents
A kind of in-situ synthesis of spherical tin dioxide-supported platinum electrocatalyst preparation method and application thereof Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 11
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract 14
- 238000003786 synthesis reaction Methods 0.000 title claims abstract 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000010936 titanium Substances 0.000 claims abstract description 79
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 78
- 239000010408 film Substances 0.000 claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 239000010409 thin film Substances 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 14
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
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- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 7
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
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- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
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- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims 12
- 238000001354 calcination Methods 0.000 claims 1
- JWKGXHRWEGHRSH-UHFFFAOYSA-J tetrachlorostannane tetrahydrate Chemical compound O.O.O.O.Cl[Sn](Cl)(Cl)Cl JWKGXHRWEGHRSH-UHFFFAOYSA-J 0.000 claims 1
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
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- YMOZVEUPTBUUNN-UHFFFAOYSA-N [Sn](=O)=O.[Pt] Chemical compound [Sn](=O)=O.[Pt] YMOZVEUPTBUUNN-UHFFFAOYSA-N 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 13
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- 238000001878 scanning electron micrograph Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
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- MMDJDBSEMBIJBB-UHFFFAOYSA-N [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] Chemical compound [O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[NH6+3] MMDJDBSEMBIJBB-UHFFFAOYSA-N 0.000 description 3
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- NFMHSPWHNQRFNR-UHFFFAOYSA-N hyponitrous acid Chemical compound ON=NO NFMHSPWHNQRFNR-UHFFFAOYSA-N 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 238000005272 metallurgy Methods 0.000 description 1
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- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
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- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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Abstract
本发明公开一种原位合成球形二氧化锡载铂电催化剂的制备方法及其应用，首先利用弱酸溶液将钛板表面蚀刻成麻面，再利用“浸渍‑提拉法”，将其钛基麻面浸渍在前驱体1中5min，于120‑160℃加热15‑30min，并重复N次直至钛板表面形成均匀的棕色膜，400‑650℃下焙烧3‑5h形成二氧化锡灰白色膜，最后利用“成膜法”，将酯类滴入所述前驱体2中形成薄膜，将此膜覆盖在二氧化锡灰白色膜表面，多次重复焙烧后可得球形二氧化锡载铂电催化剂，采用本发明所制备的电催化剂均匀、不脱落、不起泡，制备中不需要使用价格昂贵的nafion导电胶，避免了二次污染，降低了成本，克服了当前电极稳定性差、活性不高的问题。
The invention discloses a preparation method and application of an in-situ synthesis of spherical tin dioxide-supported platinum electrocatalyst. First, a weak acid solution is used to etch the surface of a titanium plate into a pockmarked surface, and then a "dipping-pulling method" is used to etch its titanium base The pockmarked surface was immersed in the precursor 1 for 5 min, heated at 120-160 ℃ for 15-30 min, and repeated N times until a uniform brown film was formed on the surface of the titanium plate, roasted at 400-650 ℃ for 3-5 h to form a gray-white tin dioxide film, Finally, using the "film-forming method", the esters are dropped into the precursor 2 to form a thin film, and the film is covered on the surface of the tin dioxide off-white film, and the spherical tin dioxide-supported platinum electrocatalyst can be obtained after repeated roasting. The electrocatalyst prepared by the invention is uniform, does not fall off, and does not foam, and does not need to use expensive nafion conductive adhesive in the preparation, avoids secondary pollution, reduces costs, and overcomes the current poor stability and low activity of electrodes. question.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a preparation method and application of a spherical tin dioxide platinum-loaded electrocatalyst synthesized in situ.
Background
In recent years, with the increase of environmental pollution, health problems have been receiving more and more attention. The nitrogen-containing compound is the most attractive pollutant in the wastewater due to the conversion of various inorganic/organic forms, and mainly comes from industries such as agriculture, animal husbandry, aquaculture, petrochemical industry, metallurgy, nonferrous metal processing, fertilizer production wastewater, landfill leachate and the like. The degradation of nitrogen in storage and land utilization is divided into two steps, firstly, organic nitrogen is converted into ammonia nitrogen, namely NH through bacteria3And NH4 +Secondly, when ammonia nitrogen flows into the surface/underground water, the ammonia nitrogen can be oxidized into NH2NH2、N2H5 +、NH2OH、H2N2O2、NO2 -、NO3 -And the like. Ammonia nitrogen is clearly a precursor for the formation of toxic nitrate nitrogen. Nitrate nitrogen causes eutrophication of water, algae reproduction, dissolved oxygen consumption, fish asphyxiation and water resource destruction. In the human body, nitrate nitrogen produces carcinogenic nitrosamines, resulting in digestive system cancers such as esophageal cancer, gastric cancer, etc. Therefore, the removal of ammonia nitrogen in wastewater is highly regarded by various countries in the world.
At present, secondary pollution is caused by ammonia nitrogen removal through processes such as steam stripping, chemical precipitation, membrane absorption, ion exchange, breakpoint chlorination and the like. The biological nitrification and denitrification method has low cost and good effect, but has long time consumption, large floor area and large influence of temperature. Considering that electricity is a clean energy source, the technology for catalyzing and oxidizing ammonia nitrogen attracts great attention in recent years. The electrocatalytic oxidation technology utilizes an electrocatalyst to directly or indirectly convert ammonia nitrogen into nitrogen gas selectively, and the electrocatalytic oxidation technology is more energy-saving than a simple electrochemical oxidation technology because the electricity is used for enriching ions and exciting the catalyst. The core technology of electrocatalytic oxidation is to prepare an electrocatalytic electrode with high activity and high stability. By direct loss of electrons at the anode surface, or generation of strongly oxidizing hydroxyl radicals (HO.), or oxidation of Cl-Generation of ClO-And realizing an oxidation technology.
The spherical tin dioxide platinum-loaded electrocatalyst can be used as a high-activity anode for electrocatalytic oxidation of ammonia nitrogen. The preparation method of the spherical tin dioxide mainly comprises a sol-gel method (ZL200610016171.9 and CN105800741A), hydrothermal synthesis (CN106129344A and ZL201510010763.9), a dry-heat oxidation annealing method (CN102923826A) and the like. The preparation method of the hollow spherical grade structure tin dioxide mainly comprises the solvothermal reaction (CN106430291A, CN106391038A) and the like. The preparation method of the tin dioxide supported platinum mainly comprises thermal decomposition-catalytic reduction (CN105628748A) and the like.
Most of the spherical tin dioxide is prepared into powder material, and then the powder material is adhered to the surface of an electrode substrate by conductive adhesive for electrocatalytic activity test. The method has two defects, if the consumption of the conductive adhesive is small, the surface of the electrode is powdery, easy to fall off, easy to foam and uneven; if the consumption of the conductive adhesive is too much, the pores of the spherical tin dioxide are easily blocked, so that the specific surface area is reduced, and the electrocatalytic activity is reduced. In addition, a titanium-based platinum-tin dioxide electrode can also be prepared by a magnetron sputtering coating-pyrolysis method (CN 106906472A). The technology for directly preparing the spherical tin dioxide platinum-carrying material on the surface of the electrode in situ is not researched.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of an in-situ synthesized spherical tin dioxide platinum-loaded electrocatalyst.
The technical scheme is as follows: the preparation method of the in-situ synthesized spherical tin dioxide platinum-loaded electrocatalyst is characterized by comprising the following steps of:
s1: placing the titanium plate in a saturated weak acid solution, and etching the titanium plate until the surface of the titanium plate forms a pitted surface;
s2: ethanol, n-butanol, isobutanol and ethylene glycol are mixed according to the volume ratio of (20-70): (10-30): (10-35): (0-10) fully mixing to obtain a mixed alcohol solution 1;
s3: polyethylene glycol 800 and ethanol are mixed according to the mass ratio of (30-60): (40-80) fully mixing to obtain a mixed alcohol solution 2;
s4: mixing (0-2) g SbxOyOr SbxClyDissolving in 1-1.5mL of concentrated acid, and adding (0-20) g of SnxCly·mH2Dissolving O in 49mL of the mixed alcohol solution 1, mixing the O and the mixed alcohol solution to form a precursor 1, and dissolving Sn in the precursor 1xClyOr SbxClyAnd SbxOyWherein Sn is Sb (50-80): (1-5);
s5: mixing (0.03-0.17) g H2PtCl6·6H2Dissolving O in 0-0.5mL of concentrated hydrochloric acid, and dissolving in 0.5-1mL of mixed alcohol solution 2 to form a precursor 2;
s6: in a water bath at 30-50 ℃, the titanium plate pretreated in S1 is placed in the precursor 1 to be soaked for 5min, then the precursor is heated for 15-30min at 120-160 ℃, the heating is repeated for N times until a uniform brown film is formed on the surface of the titanium plate, and then the titanium plate is roasted for 3-5h to form a tin dioxide gray film;
s7: and (3) dropping esters into the precursor 2 to form a layer of film on the surface of the solution, covering the film on the surface of the grey-white tin dioxide film on the surface of the titanium plate in S6, heating at the temperature of 120-160 ℃ for 10-30min to form a brown film, and roasting for 1h after repeating M times to form the spherical tin dioxide platinum-loaded electrocatalyst. Wherein the value of N can be 2-5, and the value of M can be 3-5.
At present, most of spherical tin dioxide and the hierarchical structure thereof are prepared into nano particles and then coated on the surface of an electrode by conductive adhesive for testing, which is not beneficial to the dispersion of tin dioxide and platinum materials. The invention designs a preparation method and application of an in-situ synthesized spherical tin dioxide platinum-loaded electrocatalyst, and the prepared novel titanium-based electrode has low cost, long service life, high strength and high catalytic activity, wherein mixed alcohol is used as a solvent to greatly enhance the mechanical strength of a tin dioxide coating, and ester organic matters are used to greatly enhance the dispersibility of platinum on the surface of tin dioxide, and the main advantages are as follows:
1. the price is low, the acid resistance and the corrosion resistance are realized, the mechanical property is stable, and the dissolution is not easy to realize;
2. due to TiO and SnO2The lattice parameters are similar, a Ti-O-Sn-O conductive chain can be formed by sintering, the conductive chain is very stable and is not easy to fall off, and after Sb is doped in Sn, the conductivity of tin dioxide is greatly improved, and a film forming method is used for directly synthesizing spherical tin dioxide platinum-carrying electrode on a tin dioxide surface layer in situThe conductive adhesive is not used, so that the condition that the electrocatalysis performance of the surface of the electrode is unstable due to uneven adhesion is avoided;
3、SnO2(111) crystal face to NH3The spherical nano particles have the function of selective adsorption, and have the auxiliary function of activating broken bonds of ammonia, and are accompanied with the transfer of hydrogen along-Sn-OH bonds and Pt-SnO on an electrocatalystxThe hydrogen adsorption can realize the selective N-H bond rupture under mild conditions to generate nitrogen;
4. the electrode prepared by the invention is used for the anodic electrocatalytic oxidation of ammonia nitrogen wastewater, and the method is simple and efficient and has good industrial application prospect.
Preferably, the method comprises the following steps:
in S1, before the titanium plate is etched, the titanium plate is placed in an alkaline solution to be boiled to remove oil stains on the surface of the titanium plate.
Sb as described abovexOyIs Sb3O5Or Sb2O3Said SbxClyIs SbCl3Or SbCl5Sn ofxCly·mH2O is stannous chloride dihydrate, anhydrous stannic chloride, stannic chloride tetrahydrate or stannic chloride pentahydrate.
The concentrated acid is mineral acid such as hydrochloric acid, nitric acid or sulfuric acid.
The weak acid is a weak acid capable of coordinating with Ti, such as oxalic acid or hydrofluoric acid.
In S7, the volume ratio of the esters to the precursor 2 is 2: 15.
The above esters are one or more of methyl acrylate, ethyl acrylate, and modified acrylate.
In S7, the roasting temperature is 400-650 ℃.
The application of the preparation method of the in-situ synthesized spherical tin dioxide platinum-supported electrocatalyst is characterized in that: the titanium plate loaded with the tin dioxide platinum-supported electrocatalyst prepared by the preparation method for synthesizing the spherical tin dioxide platinum-supported electrocatalyst in situ is used as an anode, and the pure titanium plate is used as a cathode to treat domestic wastewater, industrial wastewater or landfill leachate.
The appearance of a commercially available titanium plate is shown as 1a in figure 1, the appearance of the titanium plate with a tin dioxide grey-white film formed after roasting is shown as 1b in figure 1, the appearance of the titanium plate with a spherical tin dioxide platinum-loaded electrocatalyst formed finally is shown as 1c in figure 1, and the appearance change of the titanium plate preliminarily shows that the spherical tin dioxide platinum-loaded electrocatalyst formed on the surface of the titanium plate is successfully prepared preliminarily.
The Scanning Electron Microscope (SEM) image of the titanium plate etched by weak acid in S1 is shown in FIG. 2, wherein the ruler at 2a is 10 μm, the ruler at 2b is 1 μm, and the SEM image of the titanium plate is changed, which indicates that the etching on the surface of the pure titanium plate is successful and is beneficial to the stability of the coating.
An SEM image of the titanium plate after the tin dioxide off-white film was formed on the surface thereof in S6 is shown in fig. 3.
The SEM image after forming the platinum electrocatalyst on spherical tin dioxide on the surface of the titanium plate in S7 is shown in FIG. 4, in which 4a is 90000 times and 4b is 5000000 times. The X-ray diffraction (XRD) pattern after forming the platinum electrocatalyst supported on spherical tin dioxide on the surface of the titanium plate is shown in FIG. 5, wherein curve a is the XRD pattern of the electrode before reaction, which shows that the prepared electrode has Pt and SnO on the surface2And Pt mainly has crystal faces such as Pt (111), (200), (220) and (311), SnO2Mainly of SnO2(110) Crystal planes of (101), (211), and (301) prove that the tin dioxide platinum-supported electrocatalyst is successfully prepared. And a curve b is an XRD (X-ray diffraction) pattern of the electrode after ammonia nitrogen in the alkaline wastewater is degraded, and the change of the crystal form of the spherical tin dioxide platinum-loaded electrocatalyst before and after reaction is small, so that the stability of the prepared titanium plate electrode is proved to be very good.
Has the advantages that: the invention adopts a mixed alcohol leaching-thermal decomposition method similar to temperature programming to ensure that Ti-O-Sn-O conductive chains are uniform and not easy to crack, and uses an organic film-thermal decomposition method to prepare spherical SnO2Preparing in-situ on the specific surface of the electrode, and under the action of an organic film, preparing SnO of a Ti-O-Sn-O conductive chain2Becomes spherical due to H6PtCl6Is dispersed on organic film and can be uniformly dispersed on SnO after thermal decomposition2The prepared electrocatalyst is uniform, does not fall off or foam, does not need expensive nafion conductive adhesive in preparation, avoids secondary pollution, reduces cost, and overcomes the defect of stability of the current electrodeBad and low activity.
Drawings
FIG. 1 is a schematic external view of a titanium plate;
FIG. 2 is an SEM image of a titanium plate after weak acid treatment;
FIG. 3 is an SEM image (30000 times) of a titanium plate after a tin dioxide gray film is formed on the surface of the titanium plate;
FIG. 4 is an SEM image of a titanium plate after forming a spherical tin dioxide platinum-supported electrocatalyst on the surface;
FIG. 5 is an XRD diagram of a titanium plate after a spherical tin dioxide platinum-loaded electrocatalyst is formed on the surface of the titanium plate;
FIG. 6 is a cyclic voltammogram of the titanium plate electrode prepared in examples 1 and 2 in alkaline ammonia nitrogen wastewater.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1, a method for preparing an in situ synthesized spherical tin dioxide platinum-supported electrocatalyst, comprising the following steps:
s1: placing the titanium plate in 0.1mol/L sodium hydroxide solution to boil to slightly boil so as to remove oil stains on the surface of the titanium plate substrate, and then placing the titanium plate without the oil stains in saturated oxalic acid solution to etch for 2 hours until the surface forms a pitted surface;
s2: ethanol, n-butanol, isobutanol and ethylene glycol are mixed according to the volume ratio of 50: 20: 25: 3 to obtain a mixed alcohol solution 1;
s3: polyethylene glycol 800 and ethanol are mixed according to the mass ratio of 35: 56 to obtain a mixed alcohol solution 2;
s4: in a 50ml beaker, 0.07g of Sb3O5Dissolved in 1mL of concentrated hydrochloric acid and then 10g of SnCl4·5H2Dissolving O in 49mL of the mixed alcohol solution 1, and mixing the O and the mixed alcohol solution to form a precursor 1;
s5: 0.08g H2PtCl6·6H2Dissolving O in 0.5mL of concentrated hydrochloric acid, and dissolving in 1mL of mixed alcohol solution 2 to form a precursor 2;
s6: placing the titanium plate pretreated in the S1 in a water bath at 40 ℃ into the precursor 1 to be soaked for 5min, then heating the titanium plate in an oven at 145 ℃ for 30min, repeating the heating for 5 times until a uniform brown film is formed on the surface of the titanium plate, and then placing the titanium plate in a muffle furnace to be roasted for 5h at 500 ℃ to form a tin dioxide grey-white film;
s7: and (2) dropping methyl acrylate into the precursor 2, wherein the volume ratio of the methyl acrylate to the precursor 2 is 2:15, forming a layer of film on the surface of the solution, covering the film on the surface of the tin dioxide grey-white film on the surface of the titanium plate in S6, heating for 10min in an oven at 145 ℃ to form a brown film, repeating for 3 times, and then placing the film in a muffle furnace at 500 ℃ for roasting for 1h to form the spherical tin dioxide platinum-loaded electrocatalyst.
The thus prepared titanium plate loaded with the tin dioxide platinum-supported electrocatalyst was used as an anode, Pt was used as a cathode, Hg/HgO was used as a reference electrode, and 3600ppm ammonia nitrogen was selectively oxidized at-0.3V (vs. Hg/HgO) under a strong alkaline condition with pH 14, with the result as shown in cyclic voltammogram a of fig. 6; 7200ppm ammonia nitrogen can be selectively oxidized, and the result is shown as a cyclic voltammogram b in FIG. 6. The oxidation effect is best around-0.28V. The curve o in figure 6 indicates that no ammonia nitrogen concentration is equal to zero.
s1: placing the titanium plate in 0.3mol/L sodium hydroxide solution to boil to slightly boil so as to remove oil stains on the surface of the titanium plate substrate, and then placing the titanium plate without the oil stains in saturated oxalic acid solution to etch for 2 hours until the surface forms a pitted surface;
s2: ethanol, isobutanol and ethylene glycol are mixed according to the volume ratio of 60: 17: 23: 5 to obtain a mixed alcohol solution 1;
s3: polyethylene glycol 800 and ethanol are mixed according to a mass ratio of 30: 70 to obtain mixed alcohol solution 2;
s4: in a 50ml beaker, 0.07g of Sb2O3Dissolved in 1mL of concentrated hydrochloric acid, and 7g of SnCl4Dissolving the mixture in 49mL of the mixed alcohol solution 1, and mixing the solution and the mixed alcohol solution to form a precursor 1;
s5: 0.1g H2PtCl6·6H2Dissolving O in 0.5mL of concentrated hydrochloric acid, and dissolving in 1mL of mixed alcohol solution 2 to form a precursor 2;
s6: placing the titanium plate pretreated in the S1 into the precursor 1 in a water bath at 40 ℃ for soaking for 5min, then heating in an oven at 145 ℃ for 30min, repeating the heating for 5 times until a uniform brown film is formed on the surface of the titanium plate, and then placing the titanium plate in a muffle furnace for roasting at 450 ℃ for 5h to form a tin dioxide gray film;
s7: and dropping ethyl acrylate into the precursor 2, wherein the volume ratio of the ethyl acrylate to the precursor 2 is 2:15, forming a layer of film on the surface of the solution, covering the film on the surface of the tin dioxide grey-white film on the surface of the titanium plate in S6, heating for 10min in an oven at 145 ℃ to form a brown film, repeating for 3 times, and then placing the film in a 600 ℃ muffle furnace for roasting for 1h to form the spherical tin dioxide platinum-supported electrocatalyst.
The thus prepared titanium plate loaded with the tin dioxide platinum-supported electrocatalyst was used as an anode, Pt was used as a cathode, and Hg/HgO was used as a reference electrode, and selective oxidation of 10800ppm ammonia nitrogen was started at-0.3V (vs. Hg/HgO) under a strong alkaline condition with pH 14, with the results shown in fig. 6, cyclic voltammogram c; 14400ppm ammonia nitrogen can be selectively oxidized, and the result is shown as a cyclic voltammogram d in FIG. 6. The oxidation effect is best at about-0.25V.
Embodiment 3, a method for preparing an in situ synthesized spherical tin dioxide platinum-supported electrocatalyst, comprising the following steps:
s1: placing the titanium plate in 0.4mol/L sodium hydroxide solution to boil to slightly boil so as to remove oil stains on the surface of the titanium plate substrate, and then placing the titanium plate without the oil stains in saturated hydrofluoric acid solution to etch for 2 hours until the surface forms a pitted surface;
s2: fully mixing ethanol, n-butanol, isobutanol and ethylene glycol according to the volume ratio of 70:30:35:10 to obtain a mixed alcohol solution 1;
s3: fully mixing polyethylene glycol 800 and ethanol according to the mass ratio of 60:40 to obtain a mixed alcohol solution 2;
s4: in a 50ml beaker, 2g of SbCl were added3Dissolved in 1.5mL of concentrated nitric acid, and 20g of SnCl2·2H2O is dissolved in 49In mL of the mixed alcohol solution 1, mixing the two solutions to form a precursor 1;
s5: 0.17g H2PtCl6·6H2Dissolving O in 0.5mL of concentrated hydrochloric acid, and dissolving in 1mL of mixed alcohol solution 2 to form a precursor 2;
s6: placing the titanium plate pretreated in the S1 into the precursor 1 in a water bath at 50 ℃ for soaking for 5min, then heating in an oven at 120 ℃ for 15min, repeating the heating for 2 times until a uniform brown film is formed on the surface of the titanium plate, then placing the titanium plate in a muffle furnace, and roasting at 650 ℃ for 3h to form a tin dioxide gray film;
s7: and dropping modified acrylate into the precursor 2, wherein the volume ratio of the modified acrylate to the precursor 2 is 2:15, forming a layer of film on the surface of the solution, covering the film on the surface of the tin dioxide grey-white film on the surface of the titanium plate in S6, heating for 15min in an oven at 120 ℃ to form a brown film, repeating for 3 times, and then placing the film in a muffle furnace at 650 ℃ for roasting for 1h to form the spherical tin dioxide platinum-loaded electrocatalyst.
Embodiment 4, a method for preparing an in situ synthesized spherical tin dioxide platinum-supported electrocatalyst, comprising the following steps:
s1: placing the titanium plate in 0.5mol/L sodium hydroxide solution to boil to slightly boil so as to remove oil stains on the surface of the titanium plate substrate, and then placing the titanium plate without the oil stains in saturated hydrofluoric acid solution to etch for 2 hours until the surface forms a pitted surface;
s2: ethanol, n-butanol and isobutanol are mixed according to the volume ratio of 20: 10: 10 to obtain a mixed alcohol solution 1;
s3: fully mixing polyethylene glycol 800 and ethanol according to the mass ratio of 50:80 to obtain a mixed alcohol solution 2;
s4: in a 50ml beaker, 1g of SbCl was added5Dissolved in 1mL of concentrated sulfuric acid, and 5g of SnCl4·4H2Dissolving O in 49mL of the mixed alcohol solution 1, and mixing the O and the mixed alcohol solution to form a precursor 1;
s5: 0.03g H2PtCl6·6H2Dissolving O in 0.1mL of concentrated hydrochloric acid, and dissolving in 0.7mL of mixed alcohol solution 2 to form a precursor 2;
s6: placing the titanium plate pretreated in the S1 into the precursor 1 in a water bath at the temperature of 30 ℃, soaking for 5min, then heating in an oven at the temperature of 160 ℃ for 20min, repeating for 4 times until a uniform brown film is formed on the surface of the titanium plate, and then placing the titanium plate in a muffle furnace to bake for 4h at the temperature of 400 ℃ to form a tin dioxide grey-white film;
s7: dropping a mixed solution of methyl acrylate and ethyl acrylate (the volume ratio of the methyl acrylate to the ethyl acrylate is 1:1) into the precursor 2, wherein the volume ratio of the mixed solution of methyl acrylate and ethyl acrylate to the precursor 2 is 2:15, forming a layer of film on the surface of the solution, covering the film on the surface of the tin dioxide grey-white film on the surface of the titanium plate in S6, heating the film in an oven at 160 ℃ for 30min to form a brown film, repeating the steps for 5 times, and then placing the film in a 400 ℃ muffle furnace for roasting for 1h to form the spherical tin dioxide platinum-loaded electrocatalyst.
The effect of oxidizing ammonia nitrogen of the titanium plate loaded with the spherical tin dioxide platinum-loaded electrocatalyst prepared in the embodiments 3 and 4 under the strong alkaline condition is not much different from that of the embodiment 1, and the description is omitted.
Finally, it should be noted that the above-mentioned description is only a preferred embodiment of the present invention, and those skilled in the art can make various similar representations without departing from the spirit and scope of the present invention.
Claims (8)
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| CN102205239A (en) * | 2011-04-03 | 2011-10-05 | 长安大学 | Tin dioxide electro-catalyst modified by graphene and preparation method thereof |
| CN102509630A (en) * | 2011-10-26 | 2012-06-20 | 中国科学院化学研究所 | Flexible platinized counter electrode, and preparation method and application thereof |
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| CN102205239A (en) * | 2011-04-03 | 2011-10-05 | 长安大学 | Tin dioxide electro-catalyst modified by graphene and preparation method thereof |
| CN102509630A (en) * | 2011-10-26 | 2012-06-20 | 中国科学院化学研究所 | Flexible platinized counter electrode, and preparation method and application thereof |
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