CN112591856A - Electrocatalytic activity regulation and control method based on inert ion intercalation - Google Patents
Electrocatalytic activity regulation and control method based on inert ion intercalation Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000002687 intercalation Effects 0.000 title claims abstract description 34
- 238000009830 intercalation Methods 0.000 title claims abstract description 34
- 230000000694 effects Effects 0.000 title claims abstract description 23
- 230000007547 defect Effects 0.000 claims abstract description 34
- 150000001768 cations Chemical class 0.000 claims abstract description 15
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims abstract description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 17
- 239000010439 graphite Substances 0.000 claims description 17
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 12
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 10
- 239000011229 interlayer Substances 0.000 claims description 9
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- 235000003270 potassium fluoride Nutrition 0.000 claims description 9
- 239000011698 potassium fluoride Substances 0.000 claims description 9
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- 230000001276 controlling effect Effects 0.000 claims description 7
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
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- 239000005751 Copper oxide Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
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- 238000009472 formulation Methods 0.000 claims description 2
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- 238000003780 insertion Methods 0.000 claims description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 9
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 5
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 238000003933 environmental pollution control Methods 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 19
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- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 230000033558 biomineral tissue development Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
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- 238000006731 degradation reaction Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
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- -1 ammonium ions Chemical class 0.000 description 2
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YFSUTJLHUFNCNZ-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-M 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 0.000 description 1
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- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46152—Electrodes characterised by the shape or form
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
- C02F2201/4614—Current
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- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
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- C02F2201/4615—Time
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- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4616—Power supply
- C02F2201/46175—Electrical pulses
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- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
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Abstract
The invention relates to the field of environmental pollution control, in particular to an electrocatalytic activity regulation and control method based on inert ion intercalation. The invention comprises the following steps of processing the electrochemical electrode material with a defect state structure, and then passing Na+、K+、Ca2+、Mg2+And forming an ion atmosphere with extremely high concentration on the surface of the electrode by the inert metal ions, and enabling the ions to be inserted into the electrode defect state layer through strong interaction between the electrode and the ion atmosphere. The method takes the common cations in the traditional sewage as an electrode regulation and control means, and has outstanding treatment effect when controlling the high-salinity organic wastewater; in addition, the method omits the processes of coprecipitation doping roasting and the like which are usually adopted in the traditional electrode activity regulation, and has outstanding economic value and industrial benefit.
Description
Technical Field
The invention relates to the field of environmental pollution control, in particular to an electrocatalytic activity regulation and control method based on inert ion intercalation.
Background
The electrochemical method is a common advanced oxidation technology for treating organic pollutants in wastewater. The method is the current high-concentration organic sewage and secondary generationThe research focus of the effluent treatment. The basic mechanism of the electrochemical method for treating the wastewater is to generate strong oxidation substances (OH and H) in an electrolytic cell under the electrochemical action2O2、·O2Etc.) to perform direct oxidation and indirect oxidation reactions with organic pollutants in the sewage and wastewater, decompose high-concentration and nonbiodegradable macromolecular organic matters into easily biodegradable micromolecular organic matters, and even completely mineralize the micromolecular organic matters into CO2And H2And O and the like.
The electrochemical device is an electrolytic reaction tank consisting of positive and negative metal plates, wherein the electrodes are core components of the electrochemical technology, and generally metal oxides with catalytic activity are coated on the metal plates, and in the process of applying anode potential, the metal oxides can generate a large amount of strong oxidizing free radicals to degrade refractory and macromolecular organic pollutants in wastewater and finally realize the thorough mineralization of the organic pollutants. The common industrial electrodes at present mainly comprise noble metal electrodes, tin oxide electrodes, lead oxide electrodes and the like, and have the defects of small specific surface area, low space-time treatment capacity, low current efficiency, high energy consumption, high manufacturing cost and the like, and the effect of treating wastewater is not ideal.
On the other hand, the ability of electrocatalysis to nondifferentially degrade pollutants is an advantage of an electrochemical technology, but at the same time, organic matters which are difficult to degrade or easy to degrade in water can indiscriminately consume oxidizing radicals generated by anode electrocatalysis, so that the faradaic efficiency of current is too low, and the energy consumption is high. In order to regulate the catalytic selectivity of the electrode so that it can be more efficiently used for the degradation of target pollutants, many researchers have provided solutions. Patent 201811551757.4 provides a boron-doped diamond film and a preparation method thereof, wherein a lotus leaf-shaped multi-level micro-nano structure is constructed on the surface of the boron-doped diamond film to form a bionic super-hydrophobic surface, the functions of filtering and electrocatalytic water purification are taken into consideration, and the oxidation performance of electrocatalysis can be effectively regulated and controlled, but the technology is developed based on the boron-doped diamond film, so that the cost is high, and the realization difficulty is high; patent 201810372477.0 discloses an electrolytic method for improving the treatment effect of organic waste water by adding a conditioning materialFilled into an electrolytic cell for foaming and forming, so that the electric field in the electrolytic cell is uniformly distributed, and the flocculation of the organic wastewater is realized with lower cost and better effect. The technology emphasizes flocculation treatment of pollutants in water, but has limited regulation and control degree on an electrocatalysis electrode; patent 200810103518.2 discloses an N-type TiO with P-N junction characteristics for treating organic pollutants in water with high efficiency2P-type boron-doped diamond film (BDD) BDD-TiO2The electrode can effectively regulate and control the degradation characteristics of pollutants in water by regulating and controlling the P-N junction characteristics and applying certain external voltage and ultraviolet irradiation, but the types of the pollutants in the water are too complex, complete degradation is difficult to realize by a photoelectric composite method, and the regulation and control method and means are limited.
Disclosure of Invention
The present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a method for effectively regulating electrocatalytic activity based on inert ion intercalation.
In order to achieve the purpose, the technical scheme of the invention is that an electrocatalytic activity regulating and controlling method based on inert ion intercalation is characterized by comprising the following steps of:
and 3, cation intercalation, namely exchanging the positions of a cathode and an anode, taking the defect state electrode as a cathode and the graphite electrode as an anode, applying a large cathode reduction current to insert different types of metal cations into the interlayer structure of the defect state electrode, continuously repeating the process steps to realize the continuous insertion of different types of ions with different concentrations, and accurately regulating and controlling the selectivity and the redox capability of the electrode.
On the basis of the above technical solution, further, the material of the metal oxide film in step 1 is limited to be one of cerium oxide, aluminum oxide, silicon oxide and copper oxide, and the cathode reduction current density of the dc pulse power supply is 0.5 to 10mA/cm2The pulse treatment time is 5-10 minutes;
on the basis of the above technical solution, further, the high-concentration inert metal salt in step 2 is limited to be one of sodium sulfate, potassium sulfate, calcium nitrate and magnesium nitrate, and the molar concentrations of the various formulations in the electrolyte are 1 mol/l of inert metal salt, 0.5 mol/l of sulfuric acid, 0.02 mol/l of potassium fluoride, 0.1 mol/l of triethylamine and 0.22 mol/l of potassium thiocyanate; the current density of the direct current pulse power supply for curing and oxidizing is 100mA/cm2The pulse processing time is 10-30 seconds.
On the basis of the technical scheme, further, in the step 3, the reduction current of the cathode is limited to be 0.2-1.0 mA/cm2The pulse treatment time is 12-24 hours.
The following explains the implementation of the technical solution, the defect state electrode is an emerging product in the traditional metal oxide electrode, and two common defects in the metal oxide film include surface and grain boundary defects, which have high regulation and control capability on the electrocatalytic activity. The research finds that the grain boundary defects have more influence on the electrochemical performance of the film and are the main reasons for influencing the carrier transport kinetics and causing the change of electrochemical activity.
The interlayer structure expansion refers to a special form of the surface of a defect state electrode, the surface of the electrode refers to the interaction of atoms on a layer plate through strong covalent bonds, and the interlayer is a layer-shaped or layer-column-shaped chemical substance acted by intermolecular force to form a larger interlayer cavity structure, the gaps are larger, more anions and cations can be accommodated and electrons can be captured, so that a strong electrostatic attraction effect is formed between the anions and cations of an electrolyte, an electron escape barrier is increased, the transmission resistance of current carriers is increased, the recombination probability of oxidative active centers is regulated, and the regulation and control of the selectivity and the activity of pollutant adsorption, electron transfer and electrochemical oxidation are realized.
The method takes the common cations in the traditional sewage and wastewater as an electrode regulation and control means, has outstanding treatment effect when controlling the high-salinity organic wastewater, and has the main advantages that:
1. the method has the advantages that the object of regulation and control is the metal oxide electrocatalysis electrode which is low in cost and simple in processing method, and the feasibility is high;
2. the method omits the processes of coprecipitation doping roasting and the like which are usually adopted in the traditional electrode activity regulation and control, and has simple operation;
3. the method can realize the doping of various different inert metal ions, and the doping concentration and the doping degree are controllable and adjustable;
4. the electrode regulated and controlled by the method can tolerate higher salinity and pollutant concentration, and has strong adaptability and wide range;
5. the method can realize the treatment of high-salinity wastewater, and can regulate and control the catalytic capacity and selectivity of the electrode by means of anions and cations rich in the high-salinity wastewater.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings used in the description of the embodiments section below are briefly described.
FIG. 1 is a scanning electron microscope image of a surface intercalation structure in a defective electrode;
FIG. 2 is a schematic diagram illustrating the principle of inserting inert metal ions into a defect state electrode surface intercalation structure;
wherein 1 is a pulse direct current power supply; 2 is a base electrode; 3 is a layered structure formed by a metal oxide film; 4 is an electrolyte; 5 is an electrolyte solution to neutralize inert metal cations inserted into the layered structure;
FIG. 3 shows the selectivity of electrode to nitrate reduction process after different types of inert metal ion regulation.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.
Example 1
Firstly, placing a stainless steel electrode with a cerium oxide film on the surface in an electrolytic cell as a cathode, a graphite electrode as an anode, respectively connecting the anode and the cathode of a direct current pulse power supply with the anode and the cathode, and setting the pulse current density to be 0.5mA/cm2Starting a power supply to process the metal electrode, and continuously processing for 5 minutes to enable the oxide film to properly form holes and form a layered defect state structure to form a defect state electrode; and performing expansion treatment on the defective electrode, namely taking the defective electrode as an anode and a graphite electrode as a cathode, adding 1 mol/L of sodium sulfate, 0.5 mol/L of sulfuric acid, 0.02 mol/L of potassium fluoride, 0.1 mol/L of triethylamine and 0.22 mol/L of potassium thiocyanate into an electrolytic cell to serve as electrolytes, respectively connecting the anode and the cathode of a direct-current pulse power supply to the anode and the cathode, and setting the pulse current density to be 100mA/cm2Starting a power supply for continuous treatment for 10 seconds, activating the intercalation effect of potassium thiocyanate by anode oxidation of a direct-current pulse power supply to expand the interlayer structure of the defective electrode to create conditions for subsequent cation intercalation, realizing cation intercalation on the defective electrode, exchanging the positions of a cathode and an anode, respectively connecting a graphite electrode and the defective electrode with the anode and the cathode of the direct-current pulse power supply, and setting the current density to be 0.2mA/cm2The pulse treatment time was 12 hours, so that different types of metal cations were inserted into the interior of the interlayer structure of the defect-state electrode.
The treatment process can realize accurate intercalation of sodium ions to the cerium oxide thin film electrode, the doping rate can reach 5%, the sodium ion intercalation structure realized by the method is stable, and the electrode has high selectivity on the reaction of reducing nitrate radicals into nitrogen, as shown in figure 3, the current density of the electrode is 5mA/cm2Under the condition of (1), the nitrate with the concentration as high as 500mg/L can be removed, 95.2 percent of nitrate can be reduced into nitrogen in 30min, and simultaneously, a very small amount of nitrite and ammonium ions are generated.
Example 2
Firstly, a stainless steel electrode with an alumina film on the surface is placed in an electrolytic cell as a cathode, a graphite electrode is used as an anode, and the pulse current density is set to be 10mA/cm2Starting a power supply to treat the metal electrode for 10 minutes continuously, taking the defect state electrode as an anode and the graphite electrode as a cathode, adding potassium sulfate 1 mol/L, sulfuric acid 0.5 mol/L, potassium fluoride 0.02 mol/L, triethylamine 0.1 mol/L and potassium thiocyanate 0.22 mol/L as electrolytes into an electrolytic cell, and setting the pulse current density at 100mA/cm2Starting the power supply for 30 seconds, changing the positions of the cathode and the anode, and setting the current density to be 1.0mA/cm2The pulse treatment time is 24 hours, other treatment conditions are similar to those of the example 1 and are not repeated, and the potassium ion intercalation defect state electrode is obtained.
The process can realize the precise intercalation of potassium ion to alumina film electrode with doping rate up to 1.7%, and the intercalation structure is stable and has high selectivity to the reduction of nitrate radical into nitrogen gas, and the electrode has current density of 2mA/cm2Under the condition of (1), the nitrate with the concentration of 100mg/L can be removed, 98.7 percent of nitrate can be reduced into nitrogen gas within 20min, and simultaneously, a very small amount of nitrite and ammonium ions are generated.
Example 3
Firstly, a stainless steel electrode with a silicon oxide film on the surface is placed in an electrolytic cell as a cathode, a graphite electrode is used as an anode, and the pulse current density is set to be 2.5mA/cm2Starting a power supply to treat the metal electrode for 7 minutes continuously, taking the defect state electrode as an anode and the graphite electrode as a cathode, adding 1 mol/L of calcium nitrate, 0.5 mol/L of sulfuric acid, 0.02 mol/L of potassium fluoride, 0.1 mol/L of triethylamine and 0.22 mol/L of potassium thiocyanate as electrolyte into an electrolytic cell, and setting the pulse current density at 100mA/cm2Starting the power supply for continuous treatment for 15 seconds, changing the positions of the cathode and the anode, and setting the current density to be 0.5mA/cm2The pulse treatment time was 18 hours, and other treatment conditions were similar to those in example 1 and were not described again, and a calcium ion intercalation defective electrode was obtained.
The treatment process can realize accurate intercalation of calcium ions to the silicon oxide film electrode, the doping rate can reach 2.7%, the calcium ion intercalation structure realized by the method is stable, the selectivity to atrazine oxidation reaction is high, the selective mineralization of atrazine (30mg/L) in complex high-salt organic sewage can be realized, and the mineralization rate is as high as 80.5%.
Example 4
Firstly, a stainless steel electrode with a copper oxide film on the surface is placed in an electrolytic cell as a cathode, a graphite electrode is used as an anode, and the pulse current density is set to be 7.5mA/cm2Starting a power supply to treat the metal electrode for 6 minutes continuously, taking the defect state electrode as an anode and the graphite electrode as a cathode, adding 1 mol/L of magnesium nitrate, 0.5 mol/L of sulfuric acid, 0.02 mol/L of potassium fluoride, 0.1 mol/L of triethylamine and 0.22 mol/L of potassium thiocyanate as electrolyte into an electrolytic cell, and setting the pulse current density to be 100mA/cm2Starting the power supply for continuous treatment for 22 seconds, changing the positions of the cathode and the anode, and setting the current density to be 0.85mA/cm2The pulse treatment time was 20 hours, and other treatment conditions were similar to those in example 1 and were not described again, and a magnesium ion intercalation defect state electrode was obtained.
The treatment process can realize the accurate intercalation of magnesium ions to the copper oxide film electrode, the doping rate can reach 3.4 percent, the magnesium ion intercalation structure realized by the method is stable, the high-efficiency selective reduction of noble metal platinum (120mg/L) in high-salt wastewater can be realized, and the purity of the reduced platinum is as high as 95 percent.
Example 5
Firstly, a stainless steel electrode with an alumina film on the surface is placed in an electrolytic cell as a cathode, a graphite electrode is used as an anode, and the pulse current density is set to be 2.2mA/cm2Starting a power supply to treat the metal electrode for 9.5 minutes continuously, taking the defect state electrode as an anode and the graphite electrode as a cathode, adding 1 mol/L magnesium sulfate, 0.5 mol/L sulfuric acid, 0.02 mol/L potassium fluoride, 0.1 mol/L triethylamine and 0.22 mol/L potassium thiocyanate as electrolytes into an electrolytic cell, and setting the pulse current density at 100mA/cm2Starting the power supply for 14 seconds, changing the positions of the cathode and the anode, and setting the current density to be0.2mA/cm2The pulse treatment time was 14 hours, and other treatment conditions were similar to those in example 1 and were not described again, and a magnesium ion intercalation defect state electrode was obtained.
The treatment process can realize the accurate intercalation of magnesium ions to the alumina membrane electrode, the doping rate can reach 5.5%, the magnesium ion intercalation structure realized by the method is stable, the accurate oxidation to perfluorooctane sulfonate pollutants in water can be realized, and the 120-minute removal rate can reach 65%.
The above-described embodiments are only intended to specifically illustrate the spirit of the present invention, and the scope of the present invention is not limited thereto, and it is obvious to those skilled in the art that other embodiments can be easily made by changes, substitutions or alterations according to the technical contents disclosed in the present specification, and these other embodiments should be covered within the scope of the present invention.
Claims (4)
1. An electrocatalytic activity regulation and control method based on inert ion intercalation is characterized by comprising the following steps:
step 1, preparing a defect state electrode by an in-situ reduction method, namely placing a metal electrode with a metal oxide film on the surface in an electrolytic cell as a cathode, using a graphite electrode as an anode, and treating the metal electrode by direct current pulse power supply cathode reduction to form an oxide film pore-forming and layered defect state structure to form the defect state electrode;
step 2, carrying out expansion treatment on the defect state electrode, namely taking the defect state electrode as an anode and a graphite electrode as a cathode, adding high-concentration inert metal salt, sulfuric acid, potassium fluoride, triethylamine and potassium thiocyanate into an electrolytic cell to serve as electrolyte, and activating the intercalation effect of the potassium thiocyanate by anodic oxidation of a direct-current pulse power supply to expand the interlayer structure of the defect state electrode to create conditions for subsequent cation intercalation;
and 3, cation intercalation, namely exchanging the positions of a cathode and an anode, taking the defect state electrode as a cathode and the graphite electrode as an anode, applying a large cathode reduction current to insert different types of metal cations into the interlayer structure of the defect state electrode, continuously repeating the process steps to realize the continuous insertion of different types of ions with different concentrations, and accurately regulating and controlling the selectivity and the redox capability of the electrode.
2. The method of claim 1, wherein the metal oxide film in step 1 is made of one of cerium oxide, aluminum oxide, silicon oxide and copper oxide, and the cathode reduction current density of the DC pulse power supply is 0.5-10 mA/cm2The pulse treatment time is 5-10 minutes.
3. The method for controlling electrocatalytic activity based on inert ion intercalation as claimed in claim 1, wherein said high concentration inert metal salt in step 2 can be one of sodium sulfate, potassium sulfate, calcium nitrate, magnesium nitrate, and the molar concentration of various formulations in the electrolyte is inert metal salt 1 mol/l, sulfuric acid 0.5 mol/l, potassium fluoride 0.02 mol/l, triethylamine 0.1 mol/l, potassium thiocyanate 0.22 mol/l; the current density of anodic oxidation of the direct current pulse power supply is 100mA/cm2The pulse processing time is 10-30 seconds.
4. The method for regulating and controlling the electrocatalytic activity based on the inert ion intercalation as claimed in claim 1, wherein in the step 3, the cathodic reduction current is 0.2 to 1.0mA/cm2The pulse treatment time is 12-24 hours.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0537526A1 (en) * | 1991-10-11 | 1993-04-21 | MIZ Co., Ltd. | Controlling apparatus for continuous electrolytic ion water producing apparatus |
| US5443601A (en) * | 1993-05-03 | 1995-08-22 | Regents, University Of California | Method for intercalating alkali metal ions into carbon electrodes |
| EP1011162A1 (en) * | 1998-06-08 | 2000-06-21 | Toshiba Battery Co., Ltd. | Nickel-hydrogen secondary cell |
| US7024338B2 (en) * | 2003-01-31 | 2006-04-04 | Yieldboost Tech, Inc. | System and method for improving TFT-array manufacturing yields |
| CN1789497A (en) * | 2004-12-15 | 2006-06-21 | 中国科学院生态环境研究中心 | Electrode for removing nitrate from water and preparation method thereof |
| CN1950970A (en) * | 2004-05-10 | 2007-04-18 | 株式会社日本触媒 | Material for electrolytic solution, ionic material-containing composition and use thereof |
| CN101704595A (en) * | 2009-11-30 | 2010-05-12 | 重庆大学 | Method for removing nitrates from water |
| CN105154913A (en) * | 2015-07-02 | 2015-12-16 | 北京师范大学 | Preparation method of electrocatalysis electrode middle layer for water treatment |
| CN107919477A (en) * | 2017-12-22 | 2018-04-17 | 湖南工业大学 | A kind of application of mixed expanded graphite as lithium ion battery negative material |
| EP3486989A1 (en) * | 2017-11-15 | 2019-05-22 | Lee, Sora | Manufacturing method for laminated secondary battery |
| CN110729462A (en) * | 2019-10-22 | 2020-01-24 | 湖北大学 | Manganese oxide electrode material with metal cation intercalation structure and preparation method and application thereof |
| CN110803743A (en) * | 2019-11-15 | 2020-02-18 | 中国地质大学（北京） | Preparation method of defect-state titanium oxide-aluminum oxide-graphene ceramic electrode |
-
2020
- 2020-12-04 CN CN202011414310.XA patent/CN112591856B/en not_active Expired - Fee Related
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0537526A1 (en) * | 1991-10-11 | 1993-04-21 | MIZ Co., Ltd. | Controlling apparatus for continuous electrolytic ion water producing apparatus |
| US5443601A (en) * | 1993-05-03 | 1995-08-22 | Regents, University Of California | Method for intercalating alkali metal ions into carbon electrodes |
| EP1011162A1 (en) * | 1998-06-08 | 2000-06-21 | Toshiba Battery Co., Ltd. | Nickel-hydrogen secondary cell |
| US7024338B2 (en) * | 2003-01-31 | 2006-04-04 | Yieldboost Tech, Inc. | System and method for improving TFT-array manufacturing yields |
| CN1950970A (en) * | 2004-05-10 | 2007-04-18 | 株式会社日本触媒 | Material for electrolytic solution, ionic material-containing composition and use thereof |
| CN1789497A (en) * | 2004-12-15 | 2006-06-21 | 中国科学院生态环境研究中心 | Electrode for removing nitrate from water and preparation method thereof |
| CN101704595A (en) * | 2009-11-30 | 2010-05-12 | 重庆大学 | Method for removing nitrates from water |
| CN105154913A (en) * | 2015-07-02 | 2015-12-16 | 北京师范大学 | Preparation method of electrocatalysis electrode middle layer for water treatment |
| EP3486989A1 (en) * | 2017-11-15 | 2019-05-22 | Lee, Sora | Manufacturing method for laminated secondary battery |
| CN107919477A (en) * | 2017-12-22 | 2018-04-17 | 湖南工业大学 | A kind of application of mixed expanded graphite as lithium ion battery negative material |
| CN110729462A (en) * | 2019-10-22 | 2020-01-24 | 湖北大学 | Manganese oxide electrode material with metal cation intercalation structure and preparation method and application thereof |
| CN110803743A (en) * | 2019-11-15 | 2020-02-18 | 中国地质大学（北京） | Preparation method of defect-state titanium oxide-aluminum oxide-graphene ceramic electrode |
Non-Patent Citations (4)
| Title |
|---|
| DONG XU ET AL.: "Electrochemical removal of nitrate in industrial wastewater", 《FRONTIERS OF ENVIRONMENTAL SCIENCE & ENGINEERING》 * |
| YIQIONG ZHANG ET AL.: "Defect Engineering on Electrode Materials for Rechargeable", 《ADVANCED NATERLALS》 * |
| 卞克平等: "论纳米材料修饰电极在重金属离子检测中应用 ", 《科技展望》 * |
| 孟凡宁等: "界面修饰策略在钙钛矿太阳能电池中的应用", 《化学进展》 * |
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