CN109540986B - Preparation method of nano platinum-titanium electrode - Google Patents
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Abstract
The invention discloses a preparation method of a nano platinum-titanium electrode, which comprises the steps of firstly immersing a pure titanium electrode substrate subjected to surface treatment into a solution containing chloroplatinic acid radical ions with certain concentration, establishing a two-electrode system, applying micro-voltage, then adding a reducing agent into the solution, carrying out in-situ reduction deposition on the pure titanium electrode substrate to obtain platinum nano particles, and finally carrying out high-temperature treatment to obtain the nano platinum-titanium electrode. The preparation method has the characteristics of quick preparation, simple and convenient system composition, high platinum nanometer adsorption capacity and firm combination of the nanometer platinum and the electrode substrate, and the prepared nanometer platinum titanium electrode can resist the use of harsh environments such as strong acid and the like.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and relates to a preparation method of a nano platinum-titanium electrode.
Background
Platinum and platinum alloys have the characteristics of high catalytic performance, high corrosion resistance, high temperature resistance and the like when being used as catalysts of various reactions, and are widely applied to the fields of chemical industry, petrochemical industry, automobile exhaust treatment, chemical sensors, fuel cells, biology, medicine and the like. The platinum nano material has better application prospect than the conventional platinum material due to the unique physical and chemical properties, such as larger specific surface area, strong adsorption capacity, high surface reaction activity and catalytic capacity, good conductivity and the like.
The preparation method of the nano platinum comprises a chemical reduction method, a micro-emulsion method, a hydrogen absorption multiple reduction method, an electrochemical method, an immersion method, an ion exchange method, a photoreduction method, a vacuum evaporation method, a microwave-assisted method and the like, wherein the chemical reduction method and the electrochemical method are mainly used as the most studied and applied methods. The chemical reduction method is to add a reducing agent into metal salt or platinic acid of platinum to reduce platinum ions with high valence state to obtain simple substance of platinum. The electrochemical method is also called electrochemical deposition method, which utilizes electrochemical reaction to electrolyze, reduce and deposit high-price platinum salt or platinic acid on the surface of an electrode. The conventional chemical reduction method causes platinum nanoparticles generated by reaction in a solution to be adsorbed on an electrode substrate by virtue of adsorption, and has the problems of small platinum nanoparticle adsorption amount, long reaction time and the like, and the higher adsorption amount can be reached only by needing dozens of or even more time. The electrochemical method has the problems of relatively complex preparation system and higher requirement on preparation conditions. The preparation methods all have the problems that the combination of the nano platinum and the electrode substrate is not compact and the nano platinum is easy to fall off.
Disclosure of Invention
The invention aims to provide a method for preparing a nano platinum-titanium electrode, which is rapid, simple and convenient, has high nano platinum adsorption capacity and can firmly combine nano platinum with an electrode substrate.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for preparing a nano platinum-titanium electrode comprises the steps of firstly immersing a pure titanium electrode substrate subjected to surface treatment into a solution containing chloroplatinic acid radical ions with a certain concentration, establishing a two-electrode system, applying micro-voltage, then adding a reducing agent into the solution, carrying out in-situ reduction on the pure titanium electrode substrate to deposit platinum nano particles, and finally carrying out high-temperature treatment to obtain the nano platinum-titanium electrode.
Further, the surface treatment method of the pure titanium electrode substrate comprises the following steps: mechanically polishing pure titanium electrode substrate with metallographic abrasive paper, immersing in boiling ethanol for cleaning for 5-15 min, taking out, washing with water, and heating in NH with volume ratio of 7:33/H2O2Immersing in the aqueous solution for 5-15 min, then rinsing the substrate in pure water three times for 2 min each time, and drying in air or under nitrogen stream.
Further, the process of establishing a two-electrode system for applying micro-voltage comprises the following steps: the graphite rod is used as a cathode, the pure titanium electrode substrate subjected to surface treatment is used as an anode, and the applied micro-voltage is 10 mV-50 mV.
Further, the high-temperature treatment method of the nano platinum-titanium electrode comprises the following steps: the nano platinum-titanium electrode is placed in a muffle furnace, the heat treatment temperature is controlled to be 150-300 ℃, and the heat treatment time is 0.5-1.5 h.
Preferably, the solution containing chloroplatinic acid radical ions is one of a potassium hexachloroplatinate solution, a sodium hexachloroplatinate solution and a chloroplatinic acid solution, and the concentration of the solution containing chloroplatinic acid radical ions is 0.01 mM-0.07 mM.
More preferably, the platinum-containing solution is a potassium hexachloroplatinate solution.
Preferably, the reducing agent is one of ascorbic acid, sodium borohydride, sodium thiosulfate and citric acid, and the concentration of the reducing agent solution is 0.02M-0.15M.
More preferably, the reducing agent is ascorbic acid.
Preferably, the reaction time of the in-situ reduction deposition is 1-5 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention is based on a chemical reduction reaction system, combines a pure titanium electrode substrate with surface treatment as a positive electrode and a graphite rod as a negative electrode, applies weak constant voltage to form an electrostatic potential field in a solution, and promotes PtCl in the solution through an electrostatic field6 2-Ions are gathered near the anode, which is beneficial to the reaction in a short time to generate platinum nano particles and the platinum nano particles are quickly and massively adsorbed on the surface of the pure titanium electrode substrate.
(2) First, PtCl is prepared6 2-Ion solution, immersing the surface treated pure titanium electrode substrate and graphite rod in the solution to make PtCl6 2-Unlike conventional chemical reduction method, the method ensures PtCl near the pure titanium electrode substrate6 2-The ion increase also ensures that the platinum nano-particles are mainly generated near the pure titanium electrode substrate, is beneficial to the adsorption of the platinum nano-particles on the surface of the pure titanium electrode substrate, and improves the utilization rate of a reactant system.
(3) The preliminarily prepared nano platinum-titanium electrode is subjected to heat treatment by using a muffle furnace, so that the platinum nano particles and the pure titanium electrode substrate have good bonding strength.
(4) The preparation method has the characteristics of quick preparation, simple and convenient system composition, high platinum nanometer adsorption capacity and firm combination of the nanometer platinum and the electrode substrate, and the prepared nanometer platinum titanium electrode can resist the use of harsh environments such as strong acid and the like.
Drawings
FIG. 1 is an SEM photograph of an electrode obtained in example 1 of the present invention.
FIG. 2 is an SEM photograph of an electrode obtained in example 2 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
(1) Preparing a potassium hexachloroplatinate solution with the concentration of 0.02 mM;
(2) mechanically polishing pure titanium electrode substrate with metallographic abrasive paper, cleaning in boiling ethanol for 10 min, taking out, washing with water, and adding warm 7:3(v/v) NH3/H2O2Dipping in the aqueous solution for 10 minutes, then rinsing the substrate three times in pure water for 2 minutes each time, and drying in air;
(3) immersing the pure titanium electrode substrate subjected to surface treatment in the step (2) as an anode and a graphite rod as a cathode into the potassium hexachloroplatinate solution prepared in the step (1), applying a micro-voltage of 15mV, and standing for 20 min;
(4) adding a reducing agent ascorbic acid into the solution to ensure that the concentration of the ascorbic acid is 0.04M, and keeping the reaction time of the system for 2 hours;
(5) and placing the obtained nano platinum-titanium electrode in a muffle furnace, controlling the heat treatment temperature to be 200 ℃ and the heat treatment time to be 0.5h, and obtaining the final nano platinum-titanium electrode.
The nano platinum titanium electrode prepared in the embodiment is observed under a scanning electron microscope, and as shown in fig. 1, the prepared nano platinum particles are spherical with uniform size, the particle size is 100-200nm, and the distribution is relatively uniform.
Example 2
(1) Preparing a potassium hexachloroplatinate solution with the concentration of 0.06 mM;
(2) mechanically polishing pure titanium electrode substrate with metallographic abrasive paper, cleaning in boiling ethanol for 10 min, taking out, washing with water, and adding warm 7:3(v/v) NH3/H2O2Dipping in the aqueous solution for 10 minutes, then rinsing the substrate three times in pure water for 2 minutes each, and drying in a nitrogen stream;
(3) immersing the pure titanium electrode substrate subjected to surface treatment in the step (2) as an anode and a graphite rod as a cathode into the potassium hexachloroplatinate solution prepared in the step (1), applying a micro-voltage of 40mV, and standing for 30 min;
(4) adding a reducing agent ascorbic acid into the solution to ensure that the concentration of the ascorbic acid is 0.12M, and keeping the reaction time of the system for 4.5 hours;
(5) and placing the obtained nano platinum-titanium electrode in a muffle furnace, controlling the heat treatment temperature to be 250 ℃ and the heat treatment time to be 1h, and obtaining the final nano platinum-titanium electrode.
The nano platinum titanium electrode prepared in the embodiment is observed under a scanning electron microscope, and as shown in fig. 2, the prepared nano platinum particles are spherical with uniform size, the particle size is 150-500nm, and the distribution is relatively uniform. The nano platinum particles of this example are larger in size and larger in number than those of example 1.
Example 3
(1) Preparing a sodium hexachloroplatinate solution with the concentration of 0.01 mM;
(2) mechanically polishing pure titanium electrode substrate with metallographic abrasive paper, cleaning by soaking in boiling ethanol for 5min, taking out, washing with water, and adding warm 7:3(v/v) NH3/H2O2Immersion in the aqueous solution for 15 minutes, and then rinsing the substrate three times in pure water for 2 minutes each, and drying in a stream of nitrogen;
(3) immersing the pure titanium electrode substrate subjected to surface treatment in the step (2) as an anode and a graphite rod as a cathode into the sodium hexachloroplatinate solution prepared in the step (1), applying a micro-voltage of 10mV, and standing for 30 min;
(4) adding a reducing agent citric acid into the solution to ensure that the concentration of the citric acid is 0.02M, and keeping the reaction time of the system for 1 hour;
(5) and placing the obtained nano platinum-titanium electrode in a muffle furnace, controlling the heat treatment temperature to be 150 ℃ and the heat treatment time to be 0.5h, and obtaining the final nano platinum-titanium electrode.
Example 4
(1) Preparing a chloroplatinic acid solution with the concentration of 0.07 mM;
(2) mechanically polishing pure titanium electrode substrate with metallographic abrasive paper, soaking in boiling ethanol for cleaning for 15min, taking outWashed with water and warmed 7:3(v/v) NH3/H2O2Dipping in the aqueous solution for 5 minutes, then rinsing the substrate three times in pure water for 2 minutes each, and drying in a nitrogen stream;
(3) immersing the pure titanium electrode substrate subjected to surface treatment in the step (2) as an anode and a graphite rod as a cathode into the chloroplatinic acid solution prepared in the step (1), applying a micro-voltage of 50mV, and standing for 30 min;
(4) adding reducing agent sodium borohydride into the solution to enable the concentration of the sodium borohydride to be 0.15M, and keeping the reaction time of the system for 5 hours;
(5) and placing the obtained nano platinum-titanium electrode in a muffle furnace, controlling the heat treatment temperature to be 300 ℃ and the heat treatment time to be 1.5h, and obtaining the final nano platinum-titanium electrode.
Example 5
(1) Preparing a potassium hexachloroplatinate solution with the concentration of 0.04 mM;
(2) mechanically polishing pure titanium electrode substrate with metallographic abrasive paper, cleaning in boiling ethanol for 10 min, taking out, washing with water, and adding warm 7:3(v/v) NH3/H2O2Immersion in the aqueous solution for 15 minutes, and then rinsing the substrate three times in pure water for 2 minutes each, and drying in a stream of nitrogen;
(3) immersing the pure titanium electrode substrate subjected to surface treatment in the step (2) as an anode and a graphite rod as a cathode into the potassium hexachloroplatinate solution prepared in the step (1), applying a micro-voltage of 20mV, and standing for 30 min;
(4) adding reducing agent sodium thiosulfate into the solution to enable the concentration of the sodium thiosulfate to be 0.1M, and keeping the reaction time of the system for 3.5 hours;
(5) and placing the obtained nano platinum-titanium electrode in a muffle furnace, controlling the heat treatment temperature to be 200 ℃ and the heat treatment time to be 1h, and obtaining the final nano platinum-titanium electrode.
Claims (6)
1. A preparation method of a nanometer platinum-titanium electrode is characterized in that firstly, a pure titanium electrode substrate subjected to surface treatment is immersed into a solution containing chloroplatinic acid radical ions with certain concentration, a two-electrode system is established to apply micro-voltage, a graphite rod is used as a cathode, the pure titanium electrode substrate subjected to surface treatment is used as an anode, and the applied micro-voltage is 10 mV-50 mV; and then adding a reducing agent into the solution, carrying out in-situ reduction deposition on the pure titanium electrode substrate for 1-5 h, and finally placing the obtained nano platinum-titanium electrode in a muffle furnace, wherein the heat treatment temperature is controlled to be 150-300 ℃, and the heat treatment time is 0.5-1.5 h, so as to obtain the nano platinum-titanium electrode.
2. The method for preparing the nano platinum-titanium electrode according to claim 1, wherein the surface treatment method of the pure titanium electrode substrate comprises the following steps: mechanically polishing pure titanium electrode substrate with metallographic abrasive paper, immersing in boiling ethanol for 5-15 min after polishing, taking out, washing with water, and heating in NH with volume ratio of 7:33 / H2O2Immersing in the aqueous solution for 5-15 min, then rinsing the substrate in pure water three times for 2 min each time, and drying in air or under nitrogen stream.
3. The method for preparing a nano platinum-titanium electrode according to any one of claims 1 or 2, wherein the solution containing chloroplatinic acid ions is one of a potassium hexachloroplatinate solution, a sodium hexachloroplatinate solution and a chloroplatinic acid solution, and the concentration of the solution containing chloroplatinic acid ions is 0.01 mM-0.07 mM.
4. The method for preparing the nano platinum-titanium electrode according to claim 3, wherein the solution containing chloroplatinic acid radical ions is a potassium hexachloroplatinate solution.
5. The method for preparing a nano platinum-titanium electrode according to any one of claims 1 or 2, wherein the reducing agent is one of ascorbic acid, sodium borohydride, sodium thiosulfate and citric acid, and the concentration of the reducing agent is 0.02M to 0.15M.
6. The method for preparing a nano platinum-titanium electrode according to claim 5, wherein the reducing agent is ascorbic acid.
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Citations (4)
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|---|---|---|---|---|
| JPH0493650A (en) * | 1990-08-03 | 1992-03-26 | Hitachi Ltd | Ion selective electrode and utilization thereof |
| CN103613171A (en) * | 2013-11-26 | 2014-03-05 | 三峡大学 | Preparation method of stainless steel wire mesh electrode loading single-walled carbon nanotubes |
| CN105870399A (en) * | 2016-04-15 | 2016-08-17 | 厦门大学 | Preparation method of transition metal oxide@ linear carbon negative electrode with porous mesh structure |
| CN107462621A (en) * | 2016-06-03 | 2017-12-12 | 张家港万众芯生物科技有限公司 | A kind of electrophoresis system and method suitable for ion-sensitive field-effect sensor |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0493650A (en) * | 1990-08-03 | 1992-03-26 | Hitachi Ltd | Ion selective electrode and utilization thereof |
| CN103613171A (en) * | 2013-11-26 | 2014-03-05 | 三峡大学 | Preparation method of stainless steel wire mesh electrode loading single-walled carbon nanotubes |
| CN105870399A (en) * | 2016-04-15 | 2016-08-17 | 厦门大学 | Preparation method of transition metal oxide@ linear carbon negative electrode with porous mesh structure |
| CN107462621A (en) * | 2016-06-03 | 2017-12-12 | 张家港万众芯生物科技有限公司 | A kind of electrophoresis system and method suitable for ion-sensitive field-effect sensor |
Non-Patent Citations (1)
| Title |
|---|
| The Preparation of Platinum Nanoparticles on Titanium Using Chemical Reductive Growth Procedures;Li Guo et al;《Advanced Materials Research》;20120315;第490-495卷;3811-3815 * |
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