CN114457356B - Method for preparing chlorine by photoelectrocatalysis - Google Patents
Method for preparing chlorine by photoelectrocatalysis Download PDFInfo
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- CN114457356B CN114457356B CN202210092919.2A CN202210092919A CN114457356B CN 114457356 B CN114457356 B CN 114457356B CN 202210092919 A CN202210092919 A CN 202210092919A CN 114457356 B CN114457356 B CN 114457356B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
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Abstract
The invention relates to a method for preparing chlorine by photoelectrocatalysis, and belongs to the technical field of chlorine preparation. Firstly preparing a titanium dioxide film by adopting a hydrothermal method, and then placing the titanium dioxide film in a muffle furnace for calcination to obtain conductive glass loaded with the titanium dioxide film; and then assembling the prepared conductive glass loaded with the titanium dioxide film, a reaction device and a collection device, applying bias voltage, and giving illumination to obtain the device for preparing chlorine by photoelectrocatalysis. The invention introduces light energy into the reaction device for preparing chlorine, can fully utilize the light energy, realizes the environment-friendly production of the chlorine, and reduces the pollution to the environment by using the semiconductor material titanium dioxide as a photocatalyst.
Description
Technical Field
The invention belongs to the technical field of chlorine preparation, and particularly relates to a method for preparing chlorine by photoelectrocatalysis.
Background
In modern society, along with the increasingly consumed fossil energy and the problems of environmental pollution and the like which are increased day by day, renewable environmental protection energy sources become hot spots for researchers. At present, chlorine plays an important role in daily life, can be used for producing sodium hypochlorite, plastic and the like in industry, and can also be applied to a plurality of fields of sewage treatment, tap water disinfection, sterilization and pesticide, pharmacy and the like in a brewery. The current method for preparing chlorine mainly comprises the methods of electrolyzing saturated saline water, oxidizing concentrated hydrochloric acid and the like, but the methods have the defects of energy waste, strong pollution, unsafe and the like. Photoelectrocatalysis is a novel mode for preparing chlorine, and the method has the remarkable advantages that: (1) The solar energy is fully utilized, the introduction way of green energy sources such as solar energy is widened, the additional energy input is reduced, and the cost for producing chlorine is reduced; (2) The chlorine production mode is safe and environment-friendly, the raw materials are cheap and easy to obtain, and meanwhile, the inorganic solution (saturated potassium chloride solution) is used as the electrolyte, so that the potential safety hazard caused by using the concentrated hydrochloric acid as the reaction solution in the traditional method is avoided, and the method has a relatively wide application prospect; (3) The introduction of semiconductor materials into experiments for the photoelectrocatalysis of solar energy to produce chlorine has not been reported so far. Therefore, the photoelectrocatalysis is considered as a new method for preparing the chlorine with development prospect and innovation, and simultaneously, the method also provides important reference for further research on the preparation of the chlorine and expansion of the large-scale application field.
Disclosure of Invention
In order to solve the problems, the invention adopts the following technical scheme: a method for preparing chlorine by photoelectrocatalysis, comprising the following steps:
1) Preparing a titanium dioxide film by adopting a hydrothermal method, and then placing the titanium dioxide film in a muffle furnace for calcination to obtain conductive glass loaded with the titanium dioxide film;
2) And (3) assembling the conductive glass loaded with the titanium dioxide film prepared in the step (1), a reaction device and a collecting device to obtain the device for preparing chlorine by photoelectrocatalysis.
Further, in the method for preparing chlorine gas by photoelectrocatalysis, in the step 1), the preparation method of the conductive glass loaded with the titanium dioxide film comprises the following steps:
1) Sequentially adding concentrated hydrochloric acid and titanium tetrachloride into 15mL of water, and stirring for 15min to obtain a solution A;
2) Placing the washed conductive glass (FTO) into a reaction kettle, pouring the solution A prepared in the step 1) into the reaction kettle, immersing the conductive glass in the solution A, heating the solution A in an oven for reaction for 6 hours, taking out the conductive glass when the solution A is cooled to 50 ℃, washing the conductive glass with deionized water, naturally airing the conductive glass, and placing the conductive glass in a muffle furnace for calcination for 3 hours to obtain the conductive glass loaded with the titanium dioxide film.
Further, in the preparation method of the conductive glass loaded with the titanium dioxide film, in the step 1), concentrated hydrochloric acid is used according to the mass ratio: titanium tetrachloride=27-30:1.
In the further preparation method of the conductive glass loaded with the titanium dioxide film, in the step 2), the heating temperature in the oven is 165 ℃.
In the further preparation method of the conductive glass loaded with the titanium dioxide film, in the step 2), the calcination temperature in the muffle furnace is 550 ℃.
Further, in the method for preparing chlorine by photoelectrocatalysis, in the step 2), the preparation method of the device for preparing chlorine by photoelectrocatalysis is as follows: the method comprises the steps of taking conductive glass loaded with a titanium dioxide film as a working electrode, ag/AgCl as a reference electrode, pt wires as a counter electrode, taking potassium chloride solution as electrolyte, taking sodium hydroxide solution as absorption liquid and collection liquid under the condition of a three-electrode system, applying bias voltage, and giving illumination to complete the assembly of the device for preparing chlorine by photoelectrocatalysis.
Furthermore, the preparation method of the device for preparing chlorine by photoelectrocatalysis comprises the following steps of: 34.5g of potassium chloride crystal is taken and dissolved in 100mL of water, stirred for 15min and sonicated for 15min to fully dissolve the potassium chloride crystal.
Furthermore, the preparation method of the device for preparing chlorine by photoelectrocatalysis, wherein the sodium hydroxide solution is 0.01M sodium hydroxide solution, and the preparation method comprises the following steps: 0.04g of sodium hydroxide crystals were dissolved in 100mL of water and sonicated for 15min to allow for adequate dissolution.
Further, in the preparation method of the device for preparing chlorine by photoelectrocatalysis, the applied bias voltage is 1.13V.
The beneficial effects of the invention are as follows:
1. the invention introduces light energy into the equipment for producing chlorine, realizes the conversion from solar energy to electric energy, realizes the cooperative conversion of solar energy, electric energy and chemical energy, and achieves the utilization effect of solar energy.
2. The invention introduces the traditional semiconductor material titanium dioxide, reduces energy consumption, uses inorganic solution (saturated potassium chloride solution) as the reaction solution, and avoids the potential safety hazard caused by using concentrated hydrochloric acid as the reaction solution in the traditional method.
3. The titanium dioxide film is used as a photocatalyst, has excellent photocatalytic performance, obviously reduces the chlorine production voltage under illumination, improves the yield of chlorine, saves electric energy and widens the application range of green energy.
4. According to the invention, solar energy is introduced into a system for producing chlorine, so that existing renewable energy sources are further utilized, and the chlorine is prepared under the condition of not consuming non-renewable energy sources such as fossil energy sources and the like, so that the utilization space of the renewable energy sources is widened, and the green and environment-friendly production of the chlorine is realized.
Drawings
FIG. 1 is a schematic structural diagram of a device for preparing chlorine by photoelectrocatalysis.
FIG. 2 is a schematic diagram of a device for preparing chlorine by photoelectrocatalysis.
Fig. 3 is an X-ray diffraction (XRD) pattern of the titanium oxide film.
Fig. 4 is a Linear Sweep Voltammetry (LSV) test chart of a titania film (with water as the electrolyte).
Fig. 5 is a Linear Sweep Voltammetry (LSV) test pattern of a titanium dioxide film (saturated potassium chloride solution as electrolyte).
FIG. 6 is a graph of a Linear Sweep Voltammetry (LSV) test of a titanium dioxide film with a potassium chloride solution containing 0.1M hydrochloric acid as the electrolyte.
FIG. 7 is a graph of current-time (i-t) test of titanium oxide films.
FIG. 8 is an ion chromatogram of a 1000-fold diluted potassium chloride solution (prior to electrolysis).
FIG. 9 is an ion chromatogram of a 1000-fold diluted potassium chloride solution (after an electrolytic reaction).
FIG. 10 is a graph showing the results of a chloridiometer test on sodium hydroxide solution (prior to the electrolytic reaction).
FIG. 11 is a graph showing the results of a chloridiometer test on sodium hydroxide solution (after the electrolytic reaction).
Detailed Description
Example 1A method for preparing chlorine gas by photoelectrocatalysis (one) supporting titanium dioxide film on FTO conductive glass
The preparation method comprises the following steps:
preparing a titanium dioxide film by a hydrothermal method, sequentially adding 16.5g of concentrated hydrochloric acid and 0.6g of titanium tetrachloride into 15mL of water, and stirring for 15min to uniformly mix the concentrated hydrochloric acid and the 0.6g of titanium tetrachloride to obtain a solution A; placing the washed conductive glass (FTO) into a reaction kettle, pouring the prepared solution A into the reaction kettle, immersing the conductive glass in the solution A, heating in an oven at 165 ℃ for reaction for 6 hours, taking out the conductive glass when the conductive glass is cooled to 50 ℃, washing the conductive glass with deionized water, naturally airing the conductive glass, and placing the conductive glass into a muffle furnace for calcination for 3 hours at 550 ℃ to obtain the conductive glass loaded with the titanium dioxide film.
(II) photoelectrocatalysis for preparing chlorine
The preparation method comprises the following steps:
the electrochemical workstation is utilized, conductive glass loaded with a titanium dioxide film is used as a working electrode, ag/AgCl is used as a reference electrode, pt wires are used as a counter electrode, saturated potassium chloride solution is used as electrolyte and respectively inserted into rubber plugs with proper apertures, the rubber plugs are placed on quartz beakers of the saturated potassium chloride solution, 100mL of 0.01M sodium hydroxide solution is prepared, the solution is averagely placed into two glass bottles, one bottle is used as a collecting liquid, the other bottle is used as an absorbing liquid, a reaction device and a collecting device are communicated through a conduit, a ventilation part is sealed through plasticine, 1.13V bias voltage is applied, and the irradiation is carried out under simulated sunlight (a xenon lamp is used as a light source) for 1.5 hours, so that the titanium dioxide film can be fully irradiated by the simulated sunlight (AM 1.5), and the generated chlorine can be absorbed and collected in the sodium hydroxide solution. The structure schematic diagram of the device for preparing chlorine by photoelectrocatalysis is shown in fig. 1, and the physical diagram is shown in fig. 2.
(III) testing and computing
1) XRD testing
XRD test is carried out on the titanium dioxide film, the characteristic spectrum is shown in figure 3, and as can be seen from figure 3, the sample shows obvious characteristic diffraction peaks of titanium dioxide, the peaks are sharp, and the obtained product is the titanium dioxide semiconductor film with higher crystallinity.
2) Linear Sweep Voltammetry (LSV) test
The photocatalytic activity of the titanium dioxide film is verified by respectively selecting water, saturated potassium chloride solution and potassium chloride solution containing 0.1M hydrochloric acid as electrolyte, and Linear Sweep Voltammetry (LSV) tests are respectively carried out on different reaction systems, and as can be seen from figures 4 to 6, the titanium dioxide film is used as a photocatalyst in three different electrolytes, the oxygen production voltage under the illumination condition is lower than that under the dark condition, and the chlorine production voltage under the illumination condition is also lower than that under the dark condition; as shown in FIG. 5, the chlorine generating voltage under illumination was reduced by 0.2V, which was reduced by 1.8V compared with about 2V under dark conditions, demonstrating that the titanium dioxide film has excellent photocatalytic activity.
3) Current-time (i-t) test
From the results of the i-t test in FIG. 7, the total amount of charge involved in the reaction in the circuit was 10.45C.
4) Ion chromatography for measuring chloride ions
The potassium chloride solutions before and after the electrolysis reaction were diluted 1000-fold and subjected to ion chromatography detection, respectively, and as is clear from the data of fig. 8 and 9, the peak area of chloride ions in the potassium chloride electrolyte was decreased from 167.269 before electrolysis to 164.279 after electrolysis, indicating that a part of chloride ions had undergone oxidation reaction and was decreased.
5) Determination of chloride ions by a chloride ion meter
As can be seen from the data in FIGS. 10 and 11, the concentration of chloride ions in the sodium hydroxide solution before and after the electrolytic reaction was measured by using the chloride ion meter, respectively, and the concentration of chloride ions before the reaction was 10 because the measured value of the chloride ion meter before the reaction was 5.62 and the measured value after the reaction was 5.26 in the sodium hydroxide solution -5.62 ＝2.3988×10 -6 mol/L, chloride ion concentration after reaction is 10 -5.26 ＝5.495×10 -6 The total volume of the sodium hydroxide solution is 0.1L in mol/L, so that the concentration of chloride ions in the sodium hydroxide solution is increased, and the number of electrons participating in the reaction is as follows: (5.495X 10) -6 -2.3988×10 -6 )×2×0.1＝6.1924×10 -7 mol. Indicating that a part of chloride ions in the potassium chloride electrolyte are oxidized to generate chlorine, and the chlorine is then introduced into sodium hydroxide solution through a conduit and reacts with the sodium hydroxide solutionThe reaction results in an increase in its chloride ion concentration.
6) Calculation of chlorine production efficiency
As can be seen from the data in fig. 7, the total charge amount involved in the reaction in the circuit is 10.45C, which is obtained by conversion: the total electron quantity in the circuit is 1.085 ×10 -4 mol, from 5), it is found that the concentration of chloride ions in the sodium hydroxide solution is increased, and the number of electrons participating in the reaction is 6.1924 ×10 -7 mol. The calculation process of chlorine production efficiency is thus as follows:i.e. the chlorine production efficiency in the total system is 0.57%.
Claims (4)
1. A method for preparing chlorine by photoelectrocatalysis, which is characterized by comprising the following steps:
1) Sequentially adding concentrated hydrochloric acid and titanium tetrachloride into 15mL water, and stirring for 15min to obtain a solution A;
2) Placing the washed conductive glass (FTO) into a reaction kettle, pouring the solution A prepared in the step 1) into the reaction kettle, immersing the conductive glass in the solution A, placing the solution A into an oven for heating reaction 6h, taking out the conductive glass when the solution A is cooled to 50 ℃, washing the conductive glass with deionized water, naturally airing the conductive glass, and placing the conductive glass into a muffle furnace for calcining 3h to obtain the conductive glass loaded with the titanium dioxide film;
3) Under the condition of a three-electrode system, a potassium chloride solution is used as an electrolyte, a sodium hydroxide solution is used as an absorption liquid and a collection liquid, bias voltage is applied, illumination is given, and the assembly of the device for preparing chlorine by photoelectrocatalysis is completed;
in the step 1), the mass ratio of the concentrated hydrochloric acid is as follows: titanium tetrachloride = 27-30:1;
the potassium chloride solution is saturated potassium chloride solution, and the preparation method comprises the following steps: dissolving 34.5. 34.5g potassium chloride crystal in 100mL water, stirring for 15min, and ultrasonic treating for 15min to dissolve completely;
the sodium hydroxide solution is 0.01M sodium hydroxide solution, and the preparation method comprises the following steps: 0.04g sodium hydroxide crystal is dissolved in 100mL water and is sonicated for 15min to make it fully dissolved.
2. The method for preparing chlorine by photoelectrocatalysis according to claim 1, wherein in step 2), the heating temperature in the oven is 165 ℃.
3. The method for preparing chlorine by photoelectrocatalysis according to claim 1, wherein in step 2), the calcination temperature in the muffle furnace is 550 ℃.
4. The method of claim 1, wherein in step 3) the applied bias voltage is 1.13. 1.13V.
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| KR101198215B1 (en) * | 2011-04-21 | 2012-11-07 | 한국에너지기술연구원 | Apparatus and method for photoelectrochemical hydrogen production using by preparation of electrodeposited Pt on TiO2 natubular electrode as cathode, natural seawater and concentrated seawater electrolytes obtained from membrane process |
| CN102254697B (en) * | 2011-04-25 | 2012-11-21 | 宁波大学 | Titanium dioxide light anode, and preparation method and use thereof |
| CN104658761B (en) * | 2015-02-26 | 2017-07-25 | 江汉大学 | A kind of method that film reaction method prepares dye sensibilization solar cell nanometer titanium dioxide thin film photo-anode |
| CN105931848B (en) * | 2016-05-23 | 2018-04-06 | 吉林大学 | One kind Situ Hydrothermal on FTO grows Cu3BiS3The TiO of sensitization2Sull, preparation method and applications |
| CN112536032A (en) * | 2020-12-04 | 2021-03-23 | 浙江师范大学 | High-temperature-resistant sintering catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof |
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