CN109133259A - A method of utilizing light anode activation sulfuric acid salt treatment waste water and by-product hydrogen - Google Patents

A method of utilizing light anode activation sulfuric acid salt treatment waste water and by-product hydrogen Download PDF

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Publication number
CN109133259A
CN109133259A CN201811126630.8A CN201811126630A CN109133259A CN 109133259 A CN109133259 A CN 109133259A CN 201811126630 A CN201811126630 A CN 201811126630A CN 109133259 A CN109133259 A CN 109133259A
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waste water
light anode
sulfuric acid
acid salt
salt treatment
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时鹏辉
严瑾
杨玲霞
岑菁
范金辰
闵宇霖
徐群杰
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Shanghai University of Electric Power
University of Shanghai for Science and Technology
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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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

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  • Environmental & Geological Engineering (AREA)
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  • Water Supply & Treatment (AREA)
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  • Health & Medical Sciences (AREA)
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  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The present invention relates to a kind of methods for activating sulfuric acid salt treatment waste water and by-product hydrogen using light anode, this method are as follows: using pucherite material as light anode, photoelectric catalysis degrading system is formed together with cathode material, xenon lamp, photoelectric catalysis degrading is carried out to the waste water in photo electrocatalysis reactor, contains sulfate in waste water.Compared with prior art, the present invention is using pucherite material as light anode, active oxidation substance is generated, is matched with cathode material, the sulfate contained in waste water is activated, generate potentiometric titrations, to strengthen the efficiency of photoelectric catalysis degrading Pollutants in Wastewater, while cathodic electrolytic water also originates in hydrogen, improves H2-producing capacity, it is easy to operate, it is high-efficient；Needn't additional PMS strong oxidizer and potentiometric titrations are directly generated from the waste water of containing sulfate, the concerted catalysis performance with hydroxyl radical free radical greatly improved.

Description

A method of utilizing light anode activation sulfuric acid salt treatment waste water and by-product hydrogen
Technical field
The invention belongs to technical field of waste water processing, it is related to a kind of utilizing light anode activation sulfuric acid salt treatment waste water and by-product The method of hydrogen.
Background technique
Pucherite (BiVO4) it is a kind of important P-type semiconductor material, because its band gap is narrow, wavelength response range is wide, can As photochemical catalyst, it is used in Photocatalyzed Hydrogen Production, toxic organic pollutant difficult to degrade etc. in removal waste water.But pucherite Light induced electron and hole to migration and separation it is more difficult, surface adsorption property is poor, cause its photocatalysis performance by by more Serious restriction.
In field of waste water treatment, traditional high-level oxidation technology is hydroxyl radical free radical of the generation as active material to drop Pollutant is solved, and the high-level oxidation technology based on potentiometric titrations also continues to develop in recent years.Currently, potentiometric titrations are Potentiometric titrations, but the higher cost of these persulfates are generated by persulfates such as additional peroxy-monosulfates (PMS), Limit further applying for the technology.
Summary of the invention
It is living using light anode that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of Change the method for sulfuric acid salt treatment waste water and by-product hydrogen.
The purpose of the present invention can be achieved through the following technical solutions:
A method of utilizing light anode activation sulfuric acid salt treatment waste water and by-product hydrogen, this method are as follows: with pucherite material Material is used as light anode, and photoelectric catalysis degrading system is formed together with cathode material, xenon lamp, to useless in photo electrocatalysis reactor Water carries out photoelectric catalysis degrading, contains sulfate in the waste water.Pucherite material is a kind of light with photocatalysis performance Catalyst.Sulfate includes potassium sulfate, sodium sulphate etc..
Further, the pucherite material preparation method the following steps are included:
1) bismuth nitrate is added into liquor kalii iodide, the ethanol solution of 1,4-benzoquinone is added later, obtains electrolyte；
2) using FTO electro-conductive glass as working electrode, Ag/AgCl is reference electrode, and Pt is to electrode, to FTO electro-conductive glass Potentiostatic electrodeposition is carried out, electrode material is obtained；
3) vanadium precursor liquid is placed on electrode material, arrives the pucherite material after high annealing.It is prepared Pucherite material there is excellent photocatalysis performance and stability, in conjunction with cathode material, the common drop for strengthening organic pollutant Solution.
Further, in step 3), the vanadium precursor liquid includes vanadium acetylacetonate or vanadic anhydride.
Further, in step 3), in the high-temperature annealing process, annealing temperature is 300-550 DEG C.
Further, the cathode material includes one of Pt, FeNiP-NF or graphite.
Further, the FeNiP-NF preparation method the following steps are included:
1) nickel foam is placed in containing NH4F, in the mixture of urea, nickel nitrate and ferric nitrate, and at 100-140 DEG C 8-10h is reacted, NiFe-NF is obtained；
2) after mixing NiFe-NF with sodium hypophosphite, 2-4h is annealed at 290-310 DEG C to get the FeNiP- is arrived NF。
As a preferred technical solution, the FeNiP-NF preparation method the following steps are included:
1) nickel foam is placed in containing 4mmoLNH4F, 10mmoL urea, 2.8mmoL nickel nitrate and 1.2mmoL ferric nitrate In mixture, the hydro-thermal 9h at 120 DEG C of 45mL reaction kettle obtains NiFe-NF；
2) NiFe-NF the and 1.2g sodium hypophosphite for obtaining hydro-thermal 300 DEG C of annealing 3h in a nitrogen atmosphere, wherein will time Sodium phosphate is placed in above the air-flow of NiFe-NF.After annealing to get arrive the FeNiP-NF.
Further, the light intensity of the xenon lamp is 18-22mW/cm2, wavelength 380-760nm.
Further, in the waste water, the concentration of sulfate is 0.05-0.3mol/L.
Further, in the waste water, the concentration of pollutant is 5-50mg/L.By the pollutant concentration and sulphur in waste water Hydrochlorate concentration should control in a certain range, and excessively high concentration may make catalyst surface active site capped, reduce it Catalytic degradation and the effect for producing hydrogen.
Further, during carrying out photoelectric catalysis degrading to the waste water in photo electrocatalysis reactor, apply outer biasing Press 0-2.3V, degradation time 2-5h.
In the present invention, using pucherite material as light anode, conduction band positions are almost consistent with hydrogen reducing current potential, in light Excitation under, generate the hole of strong oxidizing property, by oxide sulfate be potentiometric titrations.The present invention uses the side of photoelectrocatalysis One step of method realizes the activation of sulfate, has the characteristics that simple process.
The method that the present invention uses photoelectrocatalysis makes sulfate activation for potentiometric titrations, carries out wastewater degradation, abandons It is traditional that the method that potentiometric titrations carry out wastewater degradation is generated using additional PMS, it can directly with common in industrial wastewater Sulfate be raw material, under conditions of bismuth vanadate photocatalyst and applied voltage, by sulfate conversion be potentiometric titrations, The degradation of waste water from dyestuff is carried out again, and potentiometric titrations play an important role in the oxidation process of hardly degraded organic substance, strong Oxidability, almost can be with mineralising major part pollutant, and this method condition is milder, and equipment is simple, can effectively solve difficult drop Solve the processing problem of organic wastewater.In addition, hydrogen can be generated simultaneously during wastewater degradation, be conducive to alleviate energy problem.
In the present invention, light anode uses photochemical catalyst BiVO4, hydroxyl radical free radical can be generated under light excitation, cathode is simultaneously It generates hydrogen peroxide and then is decomposed into hydroxyl radical free radical.Photochemical catalytic oxidation has stronger oxidability, and collaboration cathode material produces Raw active material improves the activation efficiency of sulfate.The synergistic effect of hydroxyl radical free radical and potentiometric titrations, significantly mentions The high degradation efficiency of Recalcitrant chemicals.
For the present invention when handling the pollutant in waste water, pollutant provides a large amount of matter in by free-radical oxidation degradation process Son, while light induced electron, hydrogen ion obtain electronics and generate hydrogen, make photoelectrocatalysis cathodic electrolytic water in the condition for being not necessarily to sacrifice agent Lower highly effective hydrogen yield.It mutually acts synergistically between pollutant and photochemical catalyst, is conducive to the enhancing of photoelectrocatalysis H2-producing capacity.
Compared with prior art, the invention has the characteristics that:
1) present invention is generated active oxidation substance, is matched with cathode material using pucherite material as light anode, to useless The sulfate contained in water is activated, and potentiometric titrations is generated, to strengthen the effect of photoelectric catalysis degrading Pollutants in Wastewater Rate, while cathodic electrolytic water also originates in hydrogen, improves H2-producing capacity, it is easy to operate, it is high-efficient；
2) needn't additional PMS strong oxidizer and potentiometric titrations are directly generated from the waste water of containing sulfate, substantially mention The high concerted catalysis performance with hydroxyl radical free radical.
Detailed description of the invention
Fig. 1 is the BiVO being prepared in embodiment 14The X-ray diffractogram of light anode；
Fig. 2 is the BiVO being prepared in embodiment 14The scanning electron microscope (SEM) photograph of light anode；
Fig. 3 is the BiVO being prepared in embodiment 14The photoelectricity flow graph of light anode；
Fig. 4 is the test chart of photoelectric catalysis degrading rhdamine B under different photocathodes in embodiment 1 and embodiment 2；
Fig. 5 is BiVO4In light anode and comparative example under the conditions of natural daylight catalytic degradation rhdamine B test chart.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention Premised on implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to Following embodiments.
Embodiment 1:
Pucherite material is prepared as follows:
By 0.9g Bi (NO3)3·H2O is dissolved into the KI solution of 100mL 0.4M, and with dust technology adjust pH value of solution to 1.7, obtain solution A.It will be added in solution A with vigorous stirring dissolved with the 20mL dehydrated alcohol of 0.23M 1,4-benzoquinone, obtain palm fibre Brown solution.Potentiostatic electrodeposition is carried out using occasion China CHI660 electrochemical workstation, using above-mentioned solution as electrolyte, FTO is conductive Glass is working electrode, and Ag/AgCl is reference electrode, Pt be to electrode, using the three-electrode system, to FTO electro-conductive glass into Row potentiostatic electrodeposition.Vanadium precursor liquid is placed on the electrode, high annealing, obtains pucherite material.The pucherite material that will be obtained Expect to impregnate in NaOH solution, removes the oxide of excess surface, obtain BiVO4Light anode.
Using X-ray diffractometer (the model D/Max-2550PC of Japanese RIGAKU production) to above-mentioned BiVO4Light anode It is measured, X-ray diffractogram is as shown in Figure 1.Occurs SnO in Fig. 12、BiVO4Characteristic peak, SnO2It is led from FTO Electric glass shows to have prepared nanometer pucherite light anode BiVO4Crystal.
Using scanning electron microscope (the model ESCALAB of Thermo-VG Scientific company of U.S. production 250) to above-mentioned BiVO4Light anode is scanned, and scanning electron microscope (SEM) photograph is as shown in Figure 2.As seen from Figure 2, for preparing receives Rice pucherite light anode BiVO4Crystalline material is in peanut shape, and structure is uniform.
Fig. 3 is above-mentioned BiVO4The photoelectricity flow graph of light anode.As seen from Figure 3, pucherite current density can achieve 2mA/cm2Left and right has good photoresponse.
Using pucherite material obtained as light anode, sulfate is activated to the rhdamine B in industrial wastewater Carry out photoelectric catalysis degrading processing, and by-product hydrogen.Detailed process is as follows for it:
Take that 100mL contains 5-50mg/L rhodamine B and the solution of 0.05-0.3mol/L sodium sulphate is placed in 250mL bilayer light In electric catalysis reactor, external recirculated water makes temperature of reactor maintain room temperature, is reacted with 750r/min magnetic agitation.With Occasion China CHI660 electrochemical workstation, setting i-t constant voltage are tested.By the BiVO of preparation4Material as light anode, using Pt as Photocathode, Ag/AgCl are reference electrode, in simulated solar irradiation AM1.5G (100mW/cm2) under irradiation condition, bias 1- 2.3V starts to take sample at regular intervals for zero point with chrono-amperometric, measures solution absorbance with ultraviolet specrophotometer.
Embodiment 2:
Pt in embodiment 1 is replaced with into FeNiP-NF as photocathode, the rhdamine B in industrial wastewater is carried out Photoelectric catalysis degrading processing.
Fig. 4 is the test chart of photoelectric catalysis degrading rhdamine B under different photocathodes in embodiment 1 and embodiment 2.By Fig. 4 can be seen that rhdamine B under conditions of Pt and FeNiP-NF is respectively as electric cathode, direct photolysis efficiency only phase Poor 5%, and since the cost of FeNiP-NF is lower, preferably FeNiP-NF.
By embodiment 1 and embodiment 2 it is found that using pucherite material as light anode, it is with sulfate common in waste water The presoma of potentiometric titrations reacts item to the significant effect of wastewater degradation using the method for photoelectrocatalysis activation sulfate Part is mild, is not required to additional strong oxidizer PMS, just can reach excellent catalytic degradation performance, reduce costs.
Comparative example:
Degradation process under the conditions of simulation natural daylight is carried out according to traditional photocatalytic degradation method, to sieve in industrial wastewater Red bright B dyestuff carries out catalytic degradation reaction, and process is as follows:
Take that 100mL contains 5-50mg/L rhodamine B and the solution of 0.05-0.3mol/L sodium sulphate is placed in 250mL bilayer light In electric catalysis reactor, external recirculated water makes temperature of reactor maintain room temperature, is reacted with 750r/min magnetic agitation.? Simulated solar irradiation AM1.5G (100mW/cm2) under irradiation condition, take sample at regular intervals, measured with ultraviolet specrophotometer Solution absorbance.
Fig. 5 is BiVO4In light anode and comparative example under the conditions of natural daylight catalytic degradation rhdamine B test chart. As seen from Figure 5, rhdamine B is in BiVO4The efficiency of photoelectric catalysis degrading rhdamine B under light anode is than direct Photodissociation is high by 57%.
Embodiment 3:
A method of utilizing light anode activation sulfuric acid salt treatment waste water and by-product hydrogen, this method are as follows: with pucherite material Material is used as light anode, and photoelectric catalysis degrading system is formed together with cathode material, xenon lamp, to useless in photo electrocatalysis reactor Water carries out photoelectric catalysis degrading.Contain sulfate in waste water, the concentration of sulfate is 0.05mol/L；The concentration of pollutant is 50mg/L。
Wherein, pucherite material preparation method the following steps are included:
1) bismuth nitrate is added into liquor kalii iodide, the ethanol solution of 1,4-benzoquinone is added later, obtains electrolyte；
2) using FTO electro-conductive glass as working electrode, Ag/AgCl is reference electrode, and Pt is to electrode, to FTO electro-conductive glass Potentiostatic electrodeposition is carried out, electrode material is obtained；
3) vanadium precursor liquid (vanadium acetylacetonate) is placed on electrode material, arrives pucherite after 300 DEG C of high annealings Material.
Cathode material is graphite.The light intensity of xenon lamp is 22mW/cm2, wavelength 380nm.
During carrying out photoelectric catalysis degrading to the waste water in photo electrocatalysis reactor, apply applying bias 2.3V, drop The solution time is 2h.
Embodiment 4:
A method of utilizing light anode activation sulfuric acid salt treatment waste water and by-product hydrogen, this method are as follows: with pucherite material Material is used as light anode, and photoelectric catalysis degrading system is formed together with cathode material, xenon lamp, to useless in photo electrocatalysis reactor Water carries out photoelectric catalysis degrading.Contain sulfate in waste water, the concentration of sulfate is 0.3mol/L；The concentration of pollutant is 5mg/ L。
Wherein, pucherite material preparation method the following steps are included:
1) bismuth nitrate is added into liquor kalii iodide, the ethanol solution of 1,4-benzoquinone is added later, obtains electrolyte；
2) using FTO electro-conductive glass as working electrode, Ag/AgCl is reference electrode, and Pt is to electrode, to FTO electro-conductive glass Potentiostatic electrodeposition is carried out, electrode material is obtained；
3) vanadium precursor liquid (vanadic anhydride) is placed on electrode material, arrives pucherite after 550 DEG C of high annealings Material.
Cathode material is FeNiP-NF.The light intensity of xenon lamp is 18mW/cm2, wavelength 760nm.
During carrying out photoelectric catalysis degrading to the waste water in photo electrocatalysis reactor, apply applying bias 0V, degradation Time is 5h.
Embodiment 5:
A method of utilizing light anode activation sulfuric acid salt treatment waste water and by-product hydrogen, this method are as follows: with pucherite material Material is used as light anode, and photoelectric catalysis degrading system is formed together with cathode material, xenon lamp, to useless in photo electrocatalysis reactor Water carries out photoelectric catalysis degrading.Contain sulfate in waste water, the concentration of sulfate is 0.1mol/L；The concentration of pollutant is 25mg/L。
Wherein, pucherite material preparation method the following steps are included:
1) bismuth nitrate is added into liquor kalii iodide, the ethanol solution of 1,4-benzoquinone is added later, obtains electrolyte；
2) using FTO electro-conductive glass as working electrode, Ag/AgCl is reference electrode, and Pt is to electrode, to FTO electro-conductive glass Potentiostatic electrodeposition is carried out, electrode material is obtained；
3) vanadium precursor liquid (vanadium acetylacetonate) is placed on electrode material, arrives pucherite after 420 DEG C of high annealings Material.
Cathode material is Pt.The light intensity of xenon lamp is 20mW/cm2, wavelength 570nm.
During carrying out photoelectric catalysis degrading to the waste water in photo electrocatalysis reactor, apply applying bias 1V, degradation Time is 4h.
Embodiment 6:
In the present embodiment, the preparation method of cathode material FeNiP-NF, the FeNiP-NF the following steps are included:
1) nickel foam is placed in containing NH4F, it in the mixture of urea, nickel nitrate and ferric nitrate, and is reacted at 100 DEG C 10h obtains NiFe-NF；
2) after mixing NiFe-NF with sodium hypophosphite, 4h is annealed at 290 DEG C to get FeNiP-NF is arrived.
Remaining is the same as embodiment 4.
Embodiment 7:
In the present embodiment, the preparation method of cathode material FeNiP-NF, the FeNiP-NF the following steps are included:
1) nickel foam is placed in containing NH4F, it in the mixture of urea, nickel nitrate and ferric nitrate, and is reacted at 140 DEG C 8h obtains NiFe-NF；
2) after mixing NiFe-NF with sodium hypophosphite, 2h is annealed at 310 DEG C to get FeNiP-NF is arrived.
Remaining is the same as embodiment 4.
Embodiment 8:
In the present embodiment, the preparation method of cathode material FeNiP-NF, the FeNiP-NF the following steps are included:
1) nickel foam is placed in containing NH4F, it in the mixture of urea, nickel nitrate and ferric nitrate, and is reacted at 120 DEG C 9h obtains NiFe-NF；
2) after mixing NiFe-NF with sodium hypophosphite, 3h is annealed at 300 DEG C to get FeNiP-NF is arrived.
Remaining is the same as embodiment 4.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention. Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention Within protection scope.

Claims (10)

1. a kind of method for activating sulfuric acid salt treatment waste water and by-product hydrogen using light anode, which is characterized in that this method are as follows: with Pucherite material forms photoelectric catalysis degrading system as light anode together with cathode material, xenon lamp, reacts photoelectrocatalysis Waste water in device carries out photoelectric catalysis degrading, contains sulfate in the waste water.
2. a kind of method for activating sulfuric acid salt treatment waste water and by-product hydrogen using light anode according to claim 1, Be characterized in that, the preparation method of the pucherite material the following steps are included:
1) bismuth nitrate is added into liquor kalii iodide, the ethanol solution of 1,4-benzoquinone is added later, obtains electrolyte；
2) using FTO electro-conductive glass as working electrode, Ag/AgCl is reference electrode, and Pt is to carry out to electrode to FTO electro-conductive glass Potentiostatic electrodeposition obtains electrode material；
3) vanadium precursor liquid is placed on electrode material, arrives the pucherite material after high annealing.
3. a kind of method for activating sulfuric acid salt treatment waste water and by-product hydrogen using light anode according to claim 2, It is characterized in that, in step 3), the vanadium precursor liquid includes vanadium acetylacetonate or vanadic anhydride.
4. a kind of method for activating sulfuric acid salt treatment waste water and by-product hydrogen using light anode according to claim 2, It is characterized in that, in step 3), in the high-temperature annealing process, annealing temperature is 300-550 DEG C.
5. a kind of method for activating sulfuric acid salt treatment waste water and by-product hydrogen using light anode according to claim 1, It is characterized in that, the cathode material includes one of Pt, FeNiP-NF or graphite.
6. a kind of method for activating sulfuric acid salt treatment waste water and by-product hydrogen using light anode according to claim 5, Be characterized in that, the preparation method of the FeNiP-NF the following steps are included:
1) nickel foam is placed in containing NH4F, in the mixture of urea, nickel nitrate and ferric nitrate, and 8- is reacted at 100-140 DEG C 10h obtains NiFe-NF；
2) after mixing NiFe-NF with sodium hypophosphite, 2-4h is annealed at 290-310 DEG C to get the FeNiP-NF is arrived.
7. a kind of method for activating sulfuric acid salt treatment waste water and by-product hydrogen using light anode according to claim 1, It is characterized in that, the light intensity of the xenon lamp is 18-22mW/cm2, wavelength 380-760nm.
8. a kind of method for activating sulfuric acid salt treatment waste water and by-product hydrogen using light anode according to claim 1, It is characterized in that, in the waste water, the concentration of sulfate is 0.05-0.3mol/L.
9. a kind of method for activating sulfuric acid salt treatment waste water and by-product hydrogen using light anode according to claim 1, It is characterized in that, in the waste water, the concentration of pollutant is 5-50mg/L.
10. a kind of method for activating sulfuric acid salt treatment waste water and by-product hydrogen using light anode according to claim 1, It is characterized in that, during carrying out photoelectric catalysis degrading to the waste water in photo electrocatalysis reactor, applies applying bias 0-2.3V, Degradation time is 2-5h.
CN201811126630.8A 2018-09-26 2018-09-26 A method of utilizing light anode activation sulfuric acid salt treatment waste water and by-product hydrogen Pending CN109133259A (en)

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CN113023842A (en) * 2021-03-19 2021-06-25 西安建筑科技大学 Method for treating antibiotic wastewater by electrochemically strengthening and catalyzing persulfate
CN113087088A (en) * 2021-04-20 2021-07-09 合肥工业大学 Method for synchronously degrading pollutants in water through photoelectrocatalysis hydrogen evolution
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CN114132999A (en) * 2021-11-26 2022-03-04 宁波职业技术学院 Method for treating printing and dyeing wastewater by activating persulfate through anode electrochemistry
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