CN113620392A - Method for producing hydrogen synchronously by disinfecting water body through electroactive sulfite - Google Patents
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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Abstract
The invention discloses a method for producing hydrogen synchronously by disinfecting a water body through electroactive sulfite, and relates to the field of sewage electrochemical treatment technology and energy. According to the invention, sulfite is electrochemically activated to generate two strong oxidative active substances, namely sulfate radicals (oxidation-reduction potential (E0 is 2.5-3.1V)) and hydroxyl radicals), so that synchronous hydrogen production for water body disinfection is realized. The active substance of the self-made carbon electrode anode is C modified by alkaline glucose3N4The high-temperature carbonized nitrogen-doped carbon (NCN-OH) and the self-supporting cobalt nickel phosphide cathode material have low cost and do not cause secondary pollution. The method has no secondary pollution and no generation of disinfection by-products, and is a cleaning agentThe water treatment disinfection method with high efficiency and low cost has the logarithmic removal rate of 4.3 to escherichia coli by an electrochemical activation method and the hydrogen yield of 162.9 mu mol.
Description
Technical Field
The present invention relates to the fields of environment, disinfection and energy and electrochemistry. In particular to a method for producing hydrogen synchronously by electrically activating sulfite to disinfect water.
Background
The disinfection is used for inactivating microbial pathogens and preventing and controlling the spread of infectious diseases, thereby ensuring the water health of people. The electrochemical disinfection method has the advantages of environmental friendliness, safety, high efficiency, low treatment cost, easiness in control, no secondary pollution and the like, and is very effective in inactivation of various microorganisms in water, so that more and more attention is paid in recent years.
In the electrochemical disinfection system, the inactivation mechanism of microorganisms comprises direct action of electric field electrochemistry, action of free chlorine components generated in an electrochemical process and action of active groups. The electrochemical sterilization method can be classified into an electrochemical chlorine-containing method and an electrochemical chlorine-free method according to the electrolyte used. The electrochemical chlorine-containing process produces active chlorine in the process, which exhibits good disinfection capacity, but is prone to the presence of inorganic by-products (e.g., chlorates, perchlorates). In contrast, the electrochemical chlorine-free method can overcome the defect of chlorination disinfection, does not generate the disinfection byproducts in the electrolysis process, and is an effective and safe disinfection process. In the electrochemical disinfection process, hydroxyl free radicals generated by electrolysis are nonselective substances with strong oxidizing power, and have high disinfection efficiency.
Sulfate radical (SO)4 ·-) Selective degradation to electron rich contaminants is also of increasing interest due to their strong oxidative nature. Recently, SO has been reported4 ·-Is particularly effective in bacterial/viral inactivation. Obtaining SO4 ·-The common methods of (a) are heating, uv activation and chemical activation of Peroxymonosulfate (PMS) and Persulfate (PS); but all of these require the use of high cost oxidants and high energy consumption in large quantities. In addition, the use of chemical activators such as transition metal catalysts may constitute a secondary event to the water bodyAnd (4) pollution damage. There is therefore an increasing interest in developing SO4 ·-New generation methods, e.g. using low cost chemical Sulphite (SO)3 2-) Instead of PMS and PS. Sulfites are residual products of flue gas desulfurization. Over the past 50 years, oxygen has oxidized sulfites to SO catalyzed by metal ions4 ·-Or sulfates are of great interest. The oxidation of sulfite to SO has been investigated by a number of scholars4 ·-Or the kinetics and mechanism of the sulfate salt. Namely SO3 2-Oxidation to form sulfite anionic radicals (SO)3 ●-) It can further react rapidly with molecular oxygen to form more reactive species, for example as SO5 ●-，SO5 ●-And HO & free radical. However, these systems still suffer from a number of disadvantages, such as low catalytic efficiency, narrow pH range and secondary pollution. The structure of the trivalent arsenic ion oxidized by the latest electrochemically activated sulfite indicates that the electrochemical activation of sulfite is feasible in kinetics. However, to date, the use of electrically activated sulfites for aquatic bacterial disinfection has not been developed.
Disclosure of Invention
Aiming at the defects, the invention provides the method for synchronously producing hydrogen by using the electrically activated sulfite to disinfect the water body, which is simple and convenient to operate and can be used for synchronously producing hydrogen by inactivating the water body efficiently, stably, economically and environmentally.
The invention provides the following technical scheme: a method for producing hydrogen synchronously by disinfecting a water body by using electroactive sulfite comprises the following steps of using an electrochemical method to inactivate bacteria in a water sample in an electrochemical water treatment device to produce hydrogen synchronously without secondary pollution: adding a water sample containing escherichia coli into an electrochemical reactor under the condition of an external direct current electric field, and efficiently inactivating and synchronously producing hydrogen; the electrochemical reactor adopts a modified carbon fiber anode and adopts a material prepared by a hypophosphite reduction method as a self-supporting cobalt nickel phosphide cathode.
Further, the preparation method of the modified carbon fiber anode comprises the following steps:
s1: calcining 1.0-3.0 g of melamine in a tubular furnace in a nitrogen atmosphere at 5-10 ℃ for min-1Heating at 550 ℃ for 4h to form C3N4(ii) a C is to be3N4Mixing the glucose with ammonia water in a ratio of 2:1, adding 1-5 mL of ammonia water and 10-20 mL of aqueous solution, uniformly mixing, carrying out hydrothermal reaction at 120 ℃ for 2 hours, collecting the mixture after the reaction, transferring the mixture into a tubular furnace for calcination, and carrying out calcination at 5-10 ℃ for min in a nitrogen atmosphere-1Heating at a heating rate, keeping the mixture at 800-1000 ℃ for 1-4 hours, cooling to room temperature under the protection of nitrogen, taking out and grinding to obtain the alkaline glucose modified C3N4High temperature carbonized nitrogen-doped activated carbon, basic glucose-modified C3N4High-temperature carbonized nitrogen-doped activated carbon is used as an active substance NCN-OH;
s2: pretreatment: cutting carbon fiber cloth into a plurality of carbon fiber cloth blocks with the area of 2cm multiplied by 2cm, treating for 2h by adopting 30 percent nitric acid, washing by ultrasonic oscillation, washing by using distilled water and absolute ethyl alcohol in sequence, drying, washing for later use and drying, wherein active sites can be increased in the acid etching process;
s3: assembling an anode: taking the carbon fiber cloth obtained in the step S2 as a base material, carrying out ultrasonic dispersion on 4-8 mg of the active substance obtained in the step S1 in a mixed solution of 2-5 mL of ethanol and water for 20-30 min, then dripping 100-200 mu L of a binder Nafion, and continuing to carry out ultrasonic dispersion for 10-20 min to obtain uniform slurry; and uniformly spraying the slurry on carbon fiber cloth by using a high-pressure spray gun, drying under an infrared lamp, and weighing to calculate the mass of the active substance.
Further, the concentration of the binder Nafion used in the S3 step was 5 wt.%.
Further, the mixed solution of ethanol and water in the step S3 is prepared by using ethanol and water in a volume ratio of 3: 1.
Further, the preparation method of the self-supporting cobalt nickel phosphide cathode material comprises the following steps:
m1: pretreatment: cutting foamed cobalt and nickel into 2cm multiplied by 1mm in number; soaking the raw materials in 20% hydrochloric acid solution, washing the raw materials by ultrasonic oscillation, sequentially washing the raw materials by distilled water and absolute ethyl alcohol, and drying the raw materials for later use to obtain clean foamed cobalt nickel A;
m2: respectively placing 5.0-10.0 g of sodium hypophosphite and foamed cobalt nickel A in a ratio of 5:1 in a corundum crucible, placing the crucible filled with the sodium hypophosphite at the upstream of the flow of the tubular furnace gas, and placing the crucible carrying the foamed cobalt nickel at the downstream of the flow; under the protection of inert gas at 5 deg.C for min-1The temperature is raised to the highest temperature of 300 ℃ at the temperature raising rate, and the temperature is kept for 2 hours at the highest temperature in the calcining process;
m3: cooling to room temperature under the protection of inert gas, collecting, centrifuging and cleaning the obtained product with ethanol and deionized water for several times, and drying for later use.
Further, the cobalt content of the foamed cobalt nickel in the M1 was 5 wt.%.
Further, the inert gas in the M2 is nitrogen or argon.
Further, the electrolyte solution used is sodium sulfate or phosphate and sodium sulfite.
Further, the external electric field is direct current, and the voltage is set to be 1-4V.
Further, the concentration of the sodium sulfite is controlled to be 0.1-3 mM.
The invention has the beneficial effects that:
(1) the method provided by the application can be used for generating strong oxidative active substances (sulfate radicals and hydroxyl radicals) in situ through electrochemical activation of sulfite to sterilize water and synchronously generate hydrogen. The method has the characteristics and advantages of no secondary pollution and no generation of disinfection byproducts, and is a clean and efficient water treatment disinfection method.
(2) The method provided by the application has the advantages that the voltage and the voltage of the external electric field are low, potential safety hazards do not exist, the method is easy to be applied to practical application, and is particularly suitable for the treatment of small non-concentrated water bodies, the operation cost is low, the installation is easy, and the method is suitable for the practical application of small waste water.
(3) The method provided by the application has a good effect of removing bacteria and viruses, is low in cost, economical and applicable, is a high-efficiency synchronous sterilization and hydrogen production method, has the characteristics of economy and environmental protection, and is strong in adaptability and wide in application prospect.
Drawings
The invention will be described in more detail hereinafter on the basis of embodiments and with reference to the accompanying drawings. Wherein:
FIG. 1 is a reaction schematic diagram of the present invention for producing hydrogen by using electrically activated sulfite to disinfect water body;
FIG. 2 is a transmission electron micrograph of an active material (NCN-OH) from a carbon anode;
FIG. 3 is a scanning electron microscope image of a self-made self-supporting cobalt nickel phosphide cathode material;
FIG. 4 is a graph demonstrating the log E.coli removal rate in the quenching experiment of the oxidative actives of example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Firstly, adding a certain amount of escherichia coli water sample with a certain concentration into a reactor, then adding a sodium sulfate solution with a concentration of 50mM and a sodium sulfite solution with a concentration of 2mM into the reactor, wherein the total volume of the system is 100mL, and the adopted electrode materials are a modified carbon fiber electrode anode and a self-supporting cobalt nickel phosphide cathode material. The distance between the anode and the cathode is controlled to be 2cm, the reaction is carried out at room temperature, the direct current is started, the reaction is started, the voltage is controlled to be 2.5V, the concentration of escherichia coli in the system under different reaction time is detected, respective inactivation curves are drawn, and experimental results show that the removal rate of the electrochemical activated water to the escherichia coli in hospital wastewater is high, and the logarithmic removal rate of the escherichia coli is 4.3 in 90 min. FIG. 4 shows the logarithmic removal rate of E.coli in the quenching experiment of the oxidative active substance of this example.
The invention discloses a preparation method of a modified carbon fiber anode for synchronous hydrogen production by electrically activated sulfite for water disinfection, which comprises the following steps:
s1: calcining 1.0-3.0 g of melamine in a tubular furnace in a nitrogen atmosphere at 5-10 ℃ for min-1Heating at 550 ℃ for 4 h. Form C3N4(ii) a C is to be3N4Mixing the glucose with ammonia water in a ratio of 2:1, adding 1-5 mL of ammonia water and 10-20 mL of aqueous solution, uniformly mixing, carrying out hydrothermal reaction at 120 ℃ for 2 hours, collecting the mixture after the reaction, transferring the mixture into a tubular furnace for calcination, and carrying out calcination at 5-10 ℃ for min in a nitrogen atmosphere-1Heating at a heating rate, keeping the mixture at 800-1000 ℃ for 1-4 hours, cooling to room temperature under the protection of nitrogen, taking out and grinding to obtain the alkaline glucose modified C3N4High temperature carbonized nitrogen-doped activated carbon, basic glucose-modified C3N4High-temperature carbonized nitrogen-doped activated carbon is used as an active substance NCN-OH;
s2: pretreatment: cutting carbon fiber cloth into a plurality of carbon fiber cloth blocks with the area of 2cm multiplied by 2cm, treating for 2h by adopting 30 percent nitric acid, washing by ultrasonic oscillation, washing by using distilled water and absolute ethyl alcohol in sequence, drying, washing for later use and drying, wherein active sites can be increased in the acid etching process;
s3: assembling an anode: taking the carbon fiber cloth obtained in the step S2 as a base material, carrying out ultrasonic dispersion on 4-8 mg of the active substance obtained in the step S1 in a mixed solution of 2-5 mL of ethanol and water for 20-30 min, then dripping 100-200 mu L of a binder Nafion, and continuing to carry out ultrasonic dispersion for 10-20 min to obtain uniform slurry; and uniformly spraying the slurry on carbon fiber cloth by using a high-pressure spray gun, drying under an infrared lamp, and weighing to calculate the mass of the active substance.
The concentration of the binder Nafion used in the S3 step was 5 wt.%.
The mixed solution of ethanol and water in the step S3 is prepared by ethanol and water according to the volume ratio of 3: 1. As shown in fig. 2, it is a transmission electron microscope image of the active material (NCN-OH) of the self-made carbon anode prepared by the present invention.
The invention discloses a preparation method of a self-supporting cobalt nickel phosphide cathode material used for synchronous hydrogen production by electrically activated sulfite to disinfect water, which comprises the following steps:
m1: pretreatment: cutting foamed cobalt and nickel into 2cm multiplied by 1mm in number; soaking the raw materials in 20% hydrochloric acid solution, washing the raw materials by ultrasonic oscillation, sequentially washing the raw materials by distilled water and absolute ethyl alcohol, and drying the raw materials for later use to obtain clean foamed cobalt nickel A;
m2: respectively placing 5.0-10.0 g of sodium hypophosphite and foamed cobalt nickel A in a ratio of 5:1 in a corundum crucible, placing the crucible filled with the sodium hypophosphite at the upstream of the flow of the tubular furnace gas, and placing the crucible carrying the foamed cobalt nickel at the downstream of the flow; under the protection of inert gas at 5 deg.C for min-1The temperature is raised to the highest temperature of 300 ℃ at the temperature raising rate, and the temperature is kept for 2 hours at the highest temperature in the calcining process;
m3: cooling to room temperature under the protection of inert gas, collecting, centrifuging and cleaning the obtained product with ethanol and deionized water for several times, and drying for later use.
Cobalt content of foamed cobalt nickel in M1 was 5 wt.%.
The inert gas in M2 is nitrogen or argon.
FIG. 3 shows a scanning electron microscope image of the self-supporting cobalt nickel phosphide cathode material prepared by the present invention.
As shown in figure 1, is a schematic diagram of the application of the self-prepared self-supporting cobalt nickel phosphide cathode material and the modified carbon fiber anode for electro-activation of sulfite in sodium sulfite solution to disinfect water body and synchronously produce hydrogen,
example 2
Firstly, adding a certain amount of escherichia coli water sample with a certain concentration into a reactor, then adding a sodium sulfate solution with a concentration of 50mM and a sodium sulfite solution with a concentration of 2mM into the reactor, wherein the total volume of the system is 100mL, and the adopted electrode materials are a modified carbon fiber electrode anode and a self-supporting cobalt nickel phosphide cathode material. The distance between the cathode and the anode is controlled to be 2cm, the reaction is carried out at room temperature, the direct current is started, the reaction is started, the voltage is controlled to be 1V, 2V, 2.5V, 3V and 4V respectively, the concentration of escherichia coli in different voltage systems is detected, and the logarithmic removal rate of the escherichia coli is calculated respectively, as shown in table 1, the experimental result shows that the logarithmic removal rate of the escherichia coli is increased and then decreased along with the increase of the voltage at 90min, and the optimal voltage is 2.5V. However, the larger the hydrogen production amount, the better, and the optimum voltage is 4V.
TABLE 1 Log removal of E.coli in example two
| Different voltages (V) | 1 | 2 | 2.5 | 3 | 4 |
| Log removal rate of E.coli | 3.1 | 3.9 | 4.3 | 4.9 | 5.2 |
| Hydrogen production (. mu. mol) | 23.1 | 43.1 | 162.9 | 183.6 | 203.1 |
Example 3
Firstly, a certain amount of escherichia coli water sample with a certain concentration is added into a reactor, then sodium sulfate with a concentration of 50mM and a certain amount of sodium sulfite solution (0.1, 0.5, 1, 1.5, 2, 3mM) are added into the reactor, the total volume of the system is 100mL, and the adopted electrode materials are used for modifying a carbon fiber electrode anode and a self-supporting cobalt nickel phosphide cathode material. The distance between the anode and the cathode is controlled to be 2cm, the reaction is carried out at room temperature, the direct current is started, the reaction is started, the voltage is controlled to be 2.5V, the concentration of escherichia coli in different sodium sulfite solution systems is detected, and the logarithmic removal rate of each escherichia coli is calculated, as shown in table 2, the experimental result shows that the logarithmic removal rate of the escherichia coli is increased and then reduced along with the increase of the voltage at 90min, and the optimal sodium sulfite concentration is 2 mM.
TABLE 2 logarithmic removal rate of E.coli in example III
| Different sodium sulfite concentration (mM) | 0.1 | 0.5 | 1 | 1.5 | 2 | 3 |
| Log removal rate of E.coli | 4.5 | 4.7 | 5.2 | 5.1 | 4.3 | 4.6 |
| Hydrogen production (. mu. mol) | 119.3 | 133.7 | 141.9 | 169.1 | 162.9 | 168.2 |
The above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (10)
1. A method for producing hydrogen synchronously by disinfecting a water body by using electroactive sulfite is characterized in that an electrochemical method is used for performing bacterial inactivation and hydrogen production synchronously in an electrochemical water treatment device on a water sample, and secondary pollution is not generated, and the method comprises the following steps: adding a water sample containing escherichia coli into an electrochemical reactor under the condition of an external direct current electric field, and efficiently inactivating and synchronously producing hydrogen; the electrochemical reactor adopts a modified carbon fiber anode and adopts a material prepared by a hypophosphite reduction method as a self-supporting cobalt nickel phosphide cathode.
2. The method for producing hydrogen synchronously by using electroactive sulfite to disinfect water body according to claim 1, wherein the preparation method of the modified carbon fiber anode comprises the following steps:
s1: calcining 1.0-3.0 g of melamine in a tubular furnace in a nitrogen atmosphere at 5-10 ℃ for min-1Heating at 550 ℃ for 4h to form C3N4(ii) a C is to be3N4Mixing the glucose with ammonia water in a ratio of 2:1, adding 1-5 mL of ammonia water and 10-20 mL of aqueous solution, uniformly mixing, carrying out hydrothermal reaction at 120 ℃ for 2 hours, collecting the mixture after the reaction, transferring the mixture into a tubular furnace for calcination, and carrying out calcination at 5-10 ℃ for min in a nitrogen atmosphere-1Heating at a heating rate, keeping the mixture at 800-1000 ℃ for 1-4 hours, cooling to room temperature under the protection of nitrogen, taking out and grinding to obtain the alkaline glucose modified C3N4High temperature carbonized nitrogen-doped activated carbon, basic glucose-modified C3N4High-temperature carbonized nitrogen-doped activated carbon as an active substance;
s2: pretreatment: cutting carbon fiber cloth into a plurality of carbon fiber cloth blocks with the area of 2cm multiplied by 2cm, treating for 2h by adopting 30 percent nitric acid, washing by ultrasonic oscillation, washing by using distilled water and absolute ethyl alcohol in sequence, drying, washing for later use and drying, wherein active sites can be increased in the acid etching process;
s3: assembling an anode: taking the carbon fiber cloth obtained in the step S2 as a base material, carrying out ultrasonic dispersion on 4-8 mg of the active substance obtained in the step S1 in a mixed solution of 2-5 mL of ethanol and water for 20-30 min, then dripping 100-200 mu L of a binder Nafion, and continuing to carry out ultrasonic dispersion for 10-20 min to obtain uniform slurry; and uniformly spraying the slurry on carbon fiber cloth by using a high-pressure spray gun, drying under an infrared lamp, and weighing to calculate the mass of the active substance.
3. The method for synchronously producing hydrogen by electrically activated sulfite to disinfect water body as claimed in claim 2, wherein the concentration of the adhesive Nafion adopted in the step S3 is 5 wt.%.
4. The method for synchronously producing hydrogen by electrically activated sulfite to disinfect water body according to claim 2, wherein the mixed solution of ethanol and water in the step S3 is prepared by ethanol and water according to the volume ratio of 3: 1.
5. The method for producing hydrogen synchronously by using electroactive sulfite to disinfect water body according to claim 1, wherein the preparation method of the self-supporting cobalt nickel phosphide cathode material comprises the following steps:
m1: pretreatment: cutting foamed cobalt and nickel into 2cm multiplied by 1mm in number; soaking the raw materials in 20% hydrochloric acid solution, washing the raw materials by ultrasonic oscillation, sequentially washing the raw materials by distilled water and absolute ethyl alcohol, and drying the raw materials for later use to obtain clean foamed cobalt nickel A;
m2: respectively placing 5.0-10.0 g of sodium hypophosphite and foamed cobalt nickel A in a ratio of 5:1 in a corundum crucible, placing the crucible filled with the sodium hypophosphite at the upstream of the flow of the tubular furnace gas, and placing the crucible carrying the foamed cobalt nickel at the downstream of the flow; under the protection of inert gas at 5 deg.C for min-1The temperature is raised to the highest temperature of 300 ℃ at the temperature raising rate, and the temperature is kept for 2 hours at the highest temperature in the calcining process;
m3: cooling to room temperature under the protection of inert gas, collecting, centrifuging and cleaning the obtained product with ethanol and deionized water for several times, and drying for later use.
6. The method for synchronously producing hydrogen by electrically activated sulfite to disinfect water body as claimed in claim 5, wherein cobalt content of foamed cobalt nickel in M1 is 5 wt.%.
7. The method for synchronously producing hydrogen by electrically activated sulfite to disinfect water body as claimed in claim 5, wherein the inert gas in M2 is nitrogen or argon.
8. The method for synchronously producing hydrogen by electrically activated sulfite to disinfect water body according to claim 1, wherein the electrolyte solution is sodium sulfate or phosphate and sodium sulfite.
9. The method for synchronously producing hydrogen by electrically activated sulfite to disinfect a water body according to claim 1, wherein the external electric field is direct current, and the voltage is set to be 1-4V.
10. The method for synchronously producing hydrogen by electrically activated sulfite to disinfect a water body according to claim 1, wherein the concentration of sodium sulfite is controlled to be 0.1-3 mM.
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|---|---|---|---|---|
| WO2008049179A1 (en) * | 2006-10-24 | 2008-05-02 | Cirne Silva Andre Luiz | Treatment system of ships ballast water, offshore petroleum platforms and vessels, in general, through a process in an electrochemical reactor |
| CN104630822A (en) * | 2015-01-14 | 2015-05-20 | 太原理工大学 | Foam transition-metal solid (gas) phosphated self-support hydrogen evolution electrode and preparation method thereof |
| CN111074290A (en) * | 2019-11-29 | 2020-04-28 | 华南师范大学 | Graphite-phase carbon nitride-based titanium dioxide composite modified electrode and preparation method thereof, and method for preparing hydrogen by photocatalytic oxidation of sodium sulfite |
| CN111957335A (en) * | 2020-07-30 | 2020-11-20 | 太原理工大学 | Graphite phase carbon nitride composite material and preparation method and application thereof |
| WO2021031967A1 (en) * | 2019-08-16 | 2021-02-25 | 江南大学 | Preparation method and application for non-precious metal monoatomic catalyst |
-
2021
- 2021-07-20 CN CN202110816248.5A patent/CN113620392B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008049179A1 (en) * | 2006-10-24 | 2008-05-02 | Cirne Silva Andre Luiz | Treatment system of ships ballast water, offshore petroleum platforms and vessels, in general, through a process in an electrochemical reactor |
| CN104630822A (en) * | 2015-01-14 | 2015-05-20 | 太原理工大学 | Foam transition-metal solid (gas) phosphated self-support hydrogen evolution electrode and preparation method thereof |
| WO2021031967A1 (en) * | 2019-08-16 | 2021-02-25 | 江南大学 | Preparation method and application for non-precious metal monoatomic catalyst |
| CN111074290A (en) * | 2019-11-29 | 2020-04-28 | 华南师范大学 | Graphite-phase carbon nitride-based titanium dioxide composite modified electrode and preparation method thereof, and method for preparing hydrogen by photocatalytic oxidation of sodium sulfite |
| CN111957335A (en) * | 2020-07-30 | 2020-11-20 | 太原理工大学 | Graphite phase carbon nitride composite material and preparation method and application thereof |
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