CN115445619A - Preparation method of iron-doped cobaltosic oxide electrode and arsenic-polluted water body treatment method - Google Patents
Preparation method of iron-doped cobaltosic oxide electrode and arsenic-polluted water body treatment method Download PDFInfo
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- CN115445619A CN115445619A CN202211054655.8A CN202211054655A CN115445619A CN 115445619 A CN115445619 A CN 115445619A CN 202211054655 A CN202211054655 A CN 202211054655A CN 115445619 A CN115445619 A CN 115445619A
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 46
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000011065 in-situ storage Methods 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 42
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 239000006260 foam Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 17
- 229910020599 Co 3 O 4 Inorganic materials 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 231100000419 toxicity Toxicity 0.000 abstract description 7
- 230000001988 toxicity Effects 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- 229910017061 Fe Co Inorganic materials 0.000 description 34
- 238000001179 sorption measurement Methods 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 22
- 238000006056 electrooxidation reaction Methods 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 6
- AQLMHYSWFMLWBS-UHFFFAOYSA-N arsenite(1-) Chemical compound O[As](O)[O-] AQLMHYSWFMLWBS-UHFFFAOYSA-N 0.000 description 6
- 230000002860 competitive effect Effects 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229910017855 NH 4 F Inorganic materials 0.000 description 3
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/33—
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
-
- 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
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
Abstract
The invention provides a preparation method of an iron-doped cobaltosic oxide electrode and a method for treating arsenic-polluted water body, wherein the preparation method of the iron-doped cobaltosic oxide electrode comprises the following steps: mixing Fe source, co source and NH 4 Dissolving F and urea in water, and stirring and mixing uniformly to obtain a mixed solution; transferring the mixed solution to a reaction kettle with a substrate, heating the reaction kettle to 80-180 ℃ for reaction, and cleaning and drying after the reaction is finished to obtain a hydroxide precursor growing on the substrate in situ; hydroxide to be grown in situ on a substrateAnd calcining the precursor to obtain the iron-doped cobaltosic oxide electrode. By adopting the technical scheme of the invention, fe-Co 3 O 4 The arsenic removing solution grows in situ on a substrate, is firmly combined with the substrate and uniformly grows, has high efficient removal rate on trivalent arsenic in water when being used as an anode, can be deeply removed, and can effectively reduce the toxicity of the arsenic in the water through the oxidation effect of the trivalent arsenic removing solution.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a preparation method of an iron-doped cobaltosic oxide electrode and a method for treating arsenic-polluted water.
Background
The highly toxic heavy metal arsenic mainly exists in natural water in two inorganic forms of electroneutral arsenite As (III) and electronegative arsenite As (V) oxyanions, wherein the toxicity of the electroneutral arsenite As (III) is 25 to 60 times higher than that of the electroneutral arsenite As (V) oxyanions, and the electroneutral arsenite As (V) oxyanions are more difficult to remove. The nano powder metal oxide adsorbent has excellent purification performance on As (III) in water, but the process needs to add an oxidant, so that the operation cost and the risk of secondary pollution are increased. In addition, the nano powder adsorbent is easy to agglomerate to influence the adsorption efficiency, and the powder catalyst is troublesome to separate from the water phase, so that the powder adsorbent is difficult to apply to the actual treatment process.
Electrochemical processes are a green, controlled option due to their low maintenance requirements and no risk of secondary contamination. In essence, the anode has the potential to continuously oxidize As (III) to As (V), while a positively charged anode should favor the adsorption of negatively charged As (V) anions. However, the conventional electrochemical oxidation adsorption process usually needs to generate the oxidation active species by continuous aeration to improve the oxidation efficiency, and the adsorption efficiency is low, so that the purpose of deep removal is difficult to achieve.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a preparation method of an iron-doped cobaltosic oxide electrode and a method for treating arsenic-polluted water body, wherein Fe-Co 3 O 4 The trivalent arsenic is converted into pentavalent arsenic with lower toxicity by anode catalytic oxidation and simultaneously used as an adsorbent to capture the arsenic in the solution, thereby realizing the complete removal of the arsenic in water, solving the problem that the trivalent arsenic is difficult to be efficiently and deeply removed by the traditional electrochemical oxidation technology, and realizing the arsenic pollution in the field of water body treatmentAnd (4) breaking through.
In contrast, the technical scheme adopted by the invention is as follows:
a preparation method of an iron-doped cobaltosic oxide electrode comprises the following steps:
step S1, fe source, co source and NH 4 Dissolving F and urea in water, and stirring and mixing uniformly to obtain a mixed solution;
s2, transferring the mixed solution to a reaction kettle with a substrate, heating the reaction kettle to 80-180 ℃ for reaction, and cleaning and drying after the reaction is finished to obtain a hydroxide precursor growing on the substrate in situ;
s3, calcining the hydroxide precursor growing on the substrate in situ to obtain the iron-doped cobaltosic oxide electrode, namely the iron-doped cobaltosic oxide nano array electrode, referred to as Fe-Co for short 3 O 4 An electrode ".
The iron-doped cobaltosic oxide electrode, fe-Co, prepared by the technical scheme 3 O 4 In-situ growth is carried out on a substrate to form a nano brush array, the nano brush array is a monolithic integrated nano array catalyst, a stable structure is kept without sacrificing catalytic activity, the specific surface area is large, more active sites are easy to expose, and when the electrode is used as an anode for electrocatalytic reaction treatment of arsenic-polluted water, fe-Co on the electrode 3 O 4 Can catalyze and oxidize trivalent arsenic to be converted into pentavalent arsenic with lower toxicity, and Co 3 O 4 On the surface of Co 3+ /Co 2+ The conversion between the two is easy to absorb and activate the gaseous oxygen, thereby generating hydroxyl oxygen which is an important active site for absorbing and oxidizing As on the surface of the metal oxide, absorbing and capturing the arsenic in the solution and realizing the complete removal of the arsenic in the water.
As a further improvement of the present invention, the molar ratio of Fe in the Fe source to Co in the Co source is 1:40 to 60. Further, the molar ratio of Fe in the Fe source to Co in the Co source is 1:45 to 55. Further, the molar ratio of Fe in the Fe source to Co in the Co source is 1:48 to 50. More preferably, the molar ratio of Fe in the Fe source to Co in the Co source is 1:49.
as a hair brushIn a further development, in step S1, the Fe source is Fe (NO) 3 ) 3 The Co source is Co (NO) 3 ) 2 。
As a further improvement of the invention, in the step S2, the heating reaction time is 5 to 10 hours.
As a further improvement of the invention, in the step S3, the calcining temperature is 300-600 ℃, and the time is 1-5h.
As a further improvement of the invention, the substrate is carbon cloth, carbon felt, titanium sheet, titanium mesh, stainless steel sheet, stainless steel mesh, foamed nickel or foamed copper. Further, the substrate is foamed nickel. Further, the thickness of the substrate is 0.1 to 2mm. Further, the thickness of the substrate is 0.5 to 1.5mm. Further preferably, the thickness of the substrate is 1mm.
The invention also discloses a method for treating the arsenic-polluted water body, which comprises the following steps:
taking an iron-doped cobaltosic oxide electrode as an anode and a counter electrode as a cathode, placing the anode and the counter electrode in an arsenic polluted water body to be treated, and applying a constant potential to form an electrocatalytic reaction system for treatment;
the iron-doped cobaltosic oxide electrode is prepared by the preparation method of the iron-doped cobaltosic oxide electrode.
Wherein the arsenic in the arsenic polluted water body to be treated is arsenite. The concentration of the treated arsenic is 50 to 50000ppb.
As a further improvement of the invention, the counter electrode is a titanium mesh, a copper mesh, a stainless steel mesh or a platinum mesh.
As a further improvement of the invention, in the iron-doped cobaltosic oxide electrode, the load capacity of the iron-doped cobaltosic oxide is 0.1 to 5mg/cm 2 。
As a further improvement of the invention, the voltage of the constant potential is +0.6 to +3.0V. Further, the voltage of the constant potential is +1.0 to +3.0V.
As a further development of the invention, the electrocatalytic reaction system is a three-electrode system comprising a reference electrode.
The invention also discloses a device for treating the arsenic-polluted water body, which comprises a reaction container, wherein an iron-doped cobaltosic oxide electrode, a counter electrode and a reference electrode are arranged in the reaction container, the iron-doped cobaltosic oxide electrode and the counter electrode are electrically connected with an electrochemical workstation, and the reference electrode is electrically connected with the counter electrode.
Compared with the prior art, the invention has the following beneficial effects:
firstly, with the technical scheme of the invention, fe-Co 3 O 4 The nano array has the advantages of stable in-situ growth on the substrate, firm combination with the substrate, uniform growth, strong washing resistance, good mechanical property and full exposure of active sites.
Secondly, the technical scheme of the invention utilizes Fe-Co during water treatment 3 O 4 Anodic oxidation with adsorption, fe-Co 3 O 4 When the nano-array anode is used for electrocatalytic oxidation of trivalent arsenic, the arsenic in the water is Fe-Co 3 O 4 The anode adsorbs and captures, the oxidation effectively reduces the toxicity of trivalent arsenic, reduces the toxicity of arsenic in water, and realizes the complete removal of arsenic in water (the effluent concentration is lower than the highest arsenic content of drinking water specified by WHO: 10 mug/L); wherein, the applied electric field can not only accelerate the oxidation of As (III) to As (V) with less toxicity, but also improve the adsorption efficiency of the catalyst to arsenic compared with Fe-Co 3 O 4 Adsorption system, fe-Co 3 O 4 The anodic electrochemical oxidation adsorption rate is greatly improved, and meanwhile, the influences of the solution environmental pH and competitive anions can be effectively resisted.
Thirdly, the technical scheme of the invention has the application potential of being developed into portable arsenic-polluted water body remediation equipment, namely Fe-Co 3 O 4 The anodic electrochemical oxidation synergistic adsorption system has great application value in the experimental arsenic polluted water treatment process.
Drawings
FIG. 1 is a schematic view showing the treatment of arsenic-contaminated water by the electrocatalytic reaction apparatus of the present invention, wherein (a) is before treatment and (b) is after treatment.
FIG. 2 shows Fe-Co of examples of the present invention 3 O 4 Comparison of adsorptionA line graph of the effect of electrochemical oxidation adsorption on removing trivalent arsenic; in the figure, niF adsorption is comparative example 1, co 3 O 4 Adsorption was comparative example 2, fe-Co 3 O 4 Adsorption was comparative example 3, fe 2 -Co 3 O 4 Adsorption was comparative example 4, niF electrooxidation adsorption was comparative example 5, co 3 O 4 Electrooxidation adsorption of comparative example 6, fe-Co 3 O 4 Electrooxidative adsorption to example 4 2 -Co 3 O 4 Electrooxidative adsorption was comparative example 7.
FIG. 3 shows the monolithic integration of Fe-Co obtained in example 1 of the present invention 3 O 4 SEM image of the electrode.
FIG. 4 shows Fe-Co of example 1 of the present invention 3 O 4 The anode cycling performance map.
FIG. 5 shows Fe-Co of example 4 of the present invention 3 O 4 The processing capacity of the anode to arsenic under different pH value environments is compared.
FIG. 6 is Fe-Co of example 4 of the present invention 3 O 4 Comparing the processing capacity of the anode to arsenic under different competitive anion environments with and without applied potential; wherein (a) is no potential applied and (b) is a potential 2V applied.
The reference numerals include:
1-reaction vessel, 2-Fe-Co 3 O 4 Anode, 3-counter electrode, 4-reference electrode, 5-electrochemical workstation.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
By using Fe-Co 3 O 4 The method for treating the arsenic polluted water body by using anodic oxidation and adsorption, which comprises the following steps:
(1) Mixing Fe-Co 3 O 4 The anode is arranged in a single-chamber electrocatalytic reaction treatment device injected with arsenic polluted water body;
the electrocatalytic reaction treatment device comprises a three-electrode system adopting a working electrode, a counter electrode and a reference electrode. As shown in FIG. 1, the electrocatalytic reaction treatment apparatus includes a reactor containing an arsenic-contaminated water body to be treatedA reactor 1, wherein Fe-Co is arranged in the reactor 1 3 O 4 An anode 2, a counter electrode 3 and a reference electrode 4, the Fe-Co 3 O 4 The anode 2 is electrically connected to the counter electrode 3 via an electrochemical workstation 5, and the reference electrode 4 is electrically connected to the counter electrode 3. The counter electrode 3 is any one of a titanium mesh, a copper mesh, a stainless steel mesh and a platinum mesh, and preferably a platinum mesh. The electrochemical workstation 5 provides a regulated dc voltage supply.
(2) Applying a constant potential to the reaction system by using an electrochemical workstation to perform electrochemical oxidation and adsorption removal on arsenic in the solution; the constant voltage applied may be +1.0 to +3.0V, and the potential applied is preferably +1.5V.
(3) And (3) detecting the solution treated in the step (1) by using ICP-MS.
In the step (1), the Fe-Co 3 O 4 The anode is a monolithic integrated nano-array catalyst and comprises a substrate and a functional layer; the functional layer is Fe-Co grown in situ 3 O 4 The load capacity of the nano brush array is about 0.1 to 5mg/cm 2 ；
The substrate material can be any one of carbon cloth, carbon felt, titanium sheet, titanium net, stainless steel sheet, stainless steel net and foam nickel, preferably foam nickel material is used as the substrate, and preferably foam nickel thickness is 1mm. The following description will be made with foamed nickel as a substrate.
Fe-Co described in step (1) 3 O 4 The preparation method of the anode comprises the following steps:
(a) The total amount of Fe (NO) is 1 to 10mmolFe 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O，5~20mmolNH 4 Dissolving F and 10 to 30mmol of urea in 50 to 200mL of ionized water, and stirring to form a transparent solution;
(b) Transferring the solution obtained in the step (a) to a high-pressure reaction kettle with a polytetrafluoroethylene inner container containing foamed nickel, wherein the area of the foamed nickel is 1-15cm 2 ；
(c) Placing the reaction system described in the step (b) in an oven for heating reaction, taking out the precursor from the reaction kettle after the reaction is finished, washing, and drying in vacuum at the heating temperature of 80-180 ℃ for 5-10 h;
(d) Calcining the hydroxide precursor growing in situ on the foam nickel obtained in the step (c) in a muffle furnace to obtain monolithic integrated Fe-Co 3 O 4 The calcining temperature of the electrode is 300 to 600 ℃, and the calcining time is 1 to 5 hours.
Preferably, said Fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1;
a monolithic integrated Fe-Co produced by the above method 3 O 4 The anode and the substrate are firmly combined, grow uniformly, have strong washing resistance and good mechanical property and recycling performance.
The following examples are further described below.
Example 1
Fe-Co 3 O 4 The preparation method of the anode comprises the following steps:
(a) The total amount of Fe (NO) is 1mmol 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O，5mmol NH 4 F and 30mmol of urea are dissolved in 50mL of ionized water and stirred to form a transparent solution; wherein, fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1.
(b) Transferring the solution obtained in the step (a) to a high-pressure reaction kettle with a polytetrafluoroethylene liner containing foamed nickel, wherein the area of the foamed nickel is 1cm 2 ；
(c) Placing the reaction system described in the step (b) in a drying oven for heating reaction, taking out the precursor from the reaction kettle after the reaction is finished, washing, and carrying out vacuum drying at the heating temperature of 80 ℃ for 10 hours;
(d) Putting the hydroxide precursor growing in situ on the foam nickel obtained in the step (c) into a muffle furnace to be calcined to obtain monolithic integrated Fe-Co 3 O 4 The calcining temperature of the electrode is 300 ℃, and the calcining time is 5h.
Monolithic integration of Fe-Co obtained in example 1 3 O 4 SEM image of the electrode is shown in FIG. 3, and Fe-Co is seen 3 O 4 The anode is firmly combined with the substrate and grows uniformly.
Example 2
Fe-Co 3 O 4 The preparation method of the anode comprises the following steps:
(a) The total amount of 10mmol Fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O， 20mmol NH 4 F and 30mmol of urea are dissolved in 200mL of ionized water and stirred to form a transparent solution; wherein, fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1.
(b) Transferring the solution obtained in the step (a) to a high-pressure reaction kettle with a polytetrafluoroethylene liner containing foamed nickel, wherein the area of the foamed nickel is 15cm 2 ；
(c) Placing the reaction system described in the step (b) in a drying oven for heating reaction, taking out the precursor from the reaction kettle after the reaction is finished, washing, and drying in vacuum at the heating temperature of 180 ℃ for 5 hours;
(d) Putting the hydroxide precursor growing in situ on the foam nickel obtained in the step (c) into a muffle furnace to be calcined to obtain monolithic integrated Fe-Co 3 O 4 The electrode is calcined at the temperature of 600 ℃ for 1h.
Example 3
Fe-Co 3 O 4 The preparation method of the anode comprises the following steps:
(a) The total amount of Fe (NO) is 5mmol 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 O，12mmol NH 4 F and 20mmol of urea are dissolved in 100mL of ionized water and stirred to form a transparent solution; wherein, fe (NO) 3 ) 3 ·9H 2 O and Co (NO) 3 ) 2 ·6H 2 The molar ratio of O is 1.
(b) Transferring the solution obtained in the step (a) to a high-pressure reaction kettle with a polytetrafluoroethylene liner containing foamed nickel, wherein the area of the foamed nickel is 10cm 2 ；
(c) Placing the reaction system described in the step (b) in a drying oven for heating reaction, taking out the precursor from the reaction kettle after the reaction is finished, washing, and carrying out vacuum drying at the heating temperature of 130 ℃ for 8h;
(d) Putting the hydroxide precursor growing in situ on the foam nickel obtained in the step (c) into a muffle furnace to be calcined to obtain monolithic integrated Fe-Co 3 O 4 The electrode is calcined at the temperature of 500 ℃ for 3h.
Fe-Co obtained in examples 1 to 3 3 O 4 The anode and the substrate are firmly combined, grow uniformly, are washed by water with larger flow velocity, are still more stable, have strong washing resistance and have good mechanical property.
Example 4
As shown in FIG. 1, using Fe-Co prepared in example 1 3 O 4 The electrode is used as an anode, a platinum net is used as a counter electrode, and a single-chamber reactor is adopted to oxidize trivalent arsenic in water to be treated and capture and remove the trivalent arsenic. The +1.5V potential was applied by potentiostatic method through the electrochemical workstation and the treated sample was collected and the concentration of arsenic in the solution was measured using ICP-MS. The recycling performance is shown in fig. 4, and it can be seen that the electrode of the present embodiment still has good arsenic removal capability and good stability after multiple cycles.
Comparative example 1
On the basis of example 4, in this comparative example, no potential was applied, and the adsorption treatment was directly performed on the arsenic-contaminated water body using a nickel foam (NiF) substrate.
Comparative example 2 based on example 4, in this comparative example, pure Co supported without potential application was used 3 O 4 The electrode of the catalyst directly adsorbs the arsenic polluted water body.
Comparative example 3
On the basis of example 4, in this comparative example, without applying a potential, fe — Co supporting Fe: co molar ratio of 1 3 O 4 The catalyst directly carries out adsorption treatment on the water body to be treated.
Comparative example 4
Radical in example 4In addition, in this comparative example, without applying a potential, fe supporting Fe to Co in a molar ratio of 1 2 -Co 3 O 4 The catalyst directly carries out adsorption treatment on the water body to be treated.
Comparative example 5
On the basis of example 4, in this comparative example, a potential was applied, and an electrooxidation adsorption treatment was performed on the water body to be treated by using a NiF base electrode.
Comparative example 6
On the basis of example 4, in this comparative example, a potential was applied, and pure Co-supported was used 3 O 4 The electrode of the catalyst is used for carrying out electrooxidation adsorption treatment on the water body to be treated.
Comparative example 7
In this comparative example, on the basis of example 4, a potential was applied using Fe supporting a Fe: co molar ratio of 1 2 -Co 3 O 4 The electrode carries out electrooxidation adsorption treatment on the water body to be treated.
Comparing the treatment results of example 4 and comparative examples 1 to 7, the results are shown in FIG. 2, and it can be seen that in the electrochemical oxidation process, the trivalent arsenic concentration of example 4 with the initial concentration of 1000. Mu.g/L can be reduced to less than 10. Mu.g/L within 20 minutes, and the treatment efficiency is highest.
In addition, compared with Fe-Co 3 O 4 Adsorption system, fe-Co 3 O 4 The anodic electrochemical oxidation adsorption rate is greatly improved.
Example 5
As shown in FIG. 5, the arsenic-containing water to be treated was treated at different pH values (3, 5, 7, 9, and 11, respectively) based on example 4, and it can be seen that Fe-Co was used in this example 3 O 4 The anode still has good arsenic removal capacity in different pH environments, and can effectively resist the influence of the solution environment pH.
Example 6
On the basis of example 4, arsenic-containing water to be treated containing different competitive anions is treated, the removal of arsenic under the conditions of applying a potential of 2V and not applying the potential is shown in FIG. 6, and it can be seen that Fe-Co of the example 3 O 4 The anode still has good arsenic removal capacity under different competitive anion environments, and can effectively resist the influence of competitive anions.
The foregoing is a further detailed description of the invention in connection with specific preferred embodiments and it is not intended to limit the invention to the specific embodiments described. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. A preparation method of an iron-doped cobaltosic oxide electrode is characterized by comprising the following steps: the method comprises the following steps:
step S1, a Fe source, a Co source and NH 4 Dissolving F and urea in water, and stirring and mixing uniformly to obtain a mixed solution;
s2, transferring the mixed solution to a reaction kettle with a substrate, heating the reaction kettle to 80-180 ℃ for reaction, and cleaning and drying after the reaction is finished to obtain a hydroxide precursor growing on the substrate in situ;
and S3, calcining the hydroxide precursor growing on the substrate in situ to obtain the iron-doped cobaltosic oxide electrode.
2. The method of preparing an iron-doped cobaltosic oxide electrode according to claim 1, wherein: the molar ratio of Fe in the Fe source to Co in the Co source is 1:40 to 60.
3. The method for preparing an iron-doped cobaltosic oxide electrode according to claim 2, wherein the method comprises the following steps: in step S1, the Fe source is Fe (NO) 3 ) 3 The Co source is Co (NO) 3 ) 2 ；
In the step S2, the heating reaction time is 5 to 10 hours;
in the step S3, the calcining temperature is 300-600 ℃, and the time is 1-5h.
4. The method for preparing an iron-doped cobaltosic oxide electrode according to any one of claims 1 to 3, wherein the method comprises the following steps: the substrate is carbon cloth, carbon felt, titanium sheet, titanium net, stainless steel sheet, stainless steel net, foam nickel or foam copper.
5. The method for preparing an iron-doped cobaltosic oxide electrode according to claim 4, wherein: the substrate is foamed nickel, and the thickness of the substrate is 0.1-2mm.
6. A method for treating arsenic-polluted water, which is characterized by comprising the following steps:
taking an iron-doped cobaltosic oxide electrode as an anode and a counter electrode as a cathode, placing the anode and the counter electrode in an arsenic polluted water body to be treated, and applying a constant potential to form an electrocatalytic reaction system for treatment;
the iron-doped cobaltosic oxide electrode is prepared by the preparation method of the iron-doped cobaltosic oxide electrode as claimed in any one of claims 1 to 5.
7. The method of treating arsenic-contaminated water as claimed in claim 6, wherein: the counter electrode is a titanium mesh, a copper mesh, a stainless steel mesh or a platinum mesh.
8. The method of treating arsenic-contaminated water according to claim 6, characterized in that: in the iron-doped cobaltosic oxide electrode, the load capacity of the iron-doped cobaltosic oxide is 0.1 to 5mg/cm 2 。
9. The method of treating arsenic-contaminated water as claimed in claim 6, wherein: the voltage of the constant potential is +0.6 to +3.0V.
10. A treatment device for arsenic polluted water is characterized in that: the device comprises a reaction vessel, wherein an iron-doped cobaltosic oxide electrode, a counter electrode and a reference electrode are arranged in the reaction vessel.
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