CN109536986B - A kind of tantalum class compound elctro-catalyst and its preparation method and application based on oxidation platinum alloy - Google Patents

A kind of tantalum class compound elctro-catalyst and its preparation method and application based on oxidation platinum alloy Download PDF

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CN109536986B
CN109536986B CN201811447876.5A CN201811447876A CN109536986B CN 109536986 B CN109536986 B CN 109536986B CN 201811447876 A CN201811447876 A CN 201811447876A CN 109536986 B CN109536986 B CN 109536986B
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tantalum
class compound
catalyst
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platinum
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CN109536986A (en
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王建国
严逸珑
钟兴
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Zhejiang University of Technology ZJUT
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/13—Ozone
    • 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
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide

Abstract

The invention discloses a kind of tantalum class compound elctro-catalysts and its preparation method and application based on oxidation platinum alloy, platinum oxide-non-noble metal oxide that the tantalum class compound elctro-catalyst based on oxidation platinum alloy includes tantalum class compound and is supported on tantalum class compound, the tantalum class compound is one or more mixtures of tantalum oxide, tantalum nitride, nitrogen tantalum oxide, and base metal is at least one of iron, cobalt, nickel, copper, manganese, zinc metallic element；In the tantalum class compound elctro-catalyst, platinum oxide-non-noble metal oxide load capacity is 8% ~ 12%.The present invention synthesizes novel oxidation platinum alloy by easy and lower-cost method and loads tantalum class compound elctro-catalyst, in the linear sweep voltammetry test of electrolysis water production ozone, the current density of the tantalum class compound elctro-catalyst of the invention based on oxidation platinum alloy is better than traditional PbO2, there is good application prospect.

Description

A kind of tantalum class compound elctro-catalyst and preparation method thereof based on oxidation platinum alloy and Using
Technical field
The present invention relates to electro-catalysis technical fields, and in particular to a kind of tantalum class compound electro-catalysis based on oxidation platinum alloy Agent and its preparation method and application.
Background technique
Ozone has extremely strong oxidisability and sterilizing ability, and the product after reaction is the oxygen beneficial to human body, so It is widely used in the fields such as drinking water treatment, sewage treatment, chemical oxidation, health care, cultivation.Ozone is under field conditions (factors) With very high activity, so must be prepared in situ.Due to many factors, such as oxygen source (air or pure oxygen), environment temperature and sky The presence of magazine in gas will affect corona discharge method and produce ozoniferous efficiency, therefore the efficiency of ozone generation of air and pure oxygen is equal 5%(mass percent is not generated).
Traditional ozone electrolysis generation technology is a kind of method that oxygen-containing electrolyte is carried out electrolytic ozone generation gas, this Class electrolyte is generally oxyacid or salt, and advantage is that ozone concentration is higher, generally can reach 15%-20%, and without harmful NOxGas.Although can generate oxygen and ozone simultaneously by electrochemical method (EOP), the generation efficiency of ozone be may be up to 50%.And ozone generates in water, can directly use, and then eliminates ozone from gas phase to liquid phase (ozone problems of dissolution) Mass transfer problem.
Currently, the research that electrolysis water generates ozone technology focuses mostly in β-PbO2On anode electrode.Studies have shown that warp It crosses after being electrolysed for a long time, β-PbO2The partial size of particle sharply declines, and the recrystallization process under high condition leads to original Particle surface forms many nanoscale little particles, and electrolysis water is caused to generate the decline of ozone performance.And PtO2Electrode due to Its high electrochemical stability and higher oxygen evolution potential, receive significant attention in the research of electrochemistry formated ozone.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of tantalum class compound electro-catalysis based on oxidation platinum alloy Agent and its preparation method and application lives to the decomposition catalysis of water in neutral electrolyte its object is to improve noble metal catalyst Property and stability.
A kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy, it is characterised in that including tantalum class compound and load Platinum-non-noble metal composite oxide on tantalum class compound, the tantalum class compound are tantalum oxide, tantalum nitride, nitrogen tantalum oxide One or more mixtures of, base metal is at least one of iron, cobalt, nickel, copper, manganese, zinc metallic element；Platinum- The mass ratio of non-noble metal composite oxide and tantalum class compound is 0.08 ~ 0.12: 1.
A kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy, it is characterised in that the following steps are included:
1) it takes tantalum powder to be placed in Muffle furnace, is roasted under air atmosphere, obtain white powder, as tantalum oxide；
2) tantalum oxide obtained by step 1) and sodium chloride, sodium fluoride are mixed, a small amount of solvent are added in obtained solid mixture, Solid mixture moistened surface is fully ground by solvent, is subsequently placed in Muffle furnace the calcining 2-5 h at 450-650 DEG C；
3) the calcined product of step 2 is placed in tube furnace, is roasted under ammonia atmosphere, obtain tantalum class compound, so After be washed with deionized, it is dry, it is dry after solid and platinum salt, base metal salt and deionized water be added to hydro-thermal together In kettle, hydro-thermal reaction 4-24 h, is cooled to room temperature after reaction at 100-150 DEG C, then staticly settles, take out sediment according to It is secondary to be dried through water and ethanol washing, obtain platinum oxide load tantalum class compound elctro-catalyst crude product；
4) platinum oxide for obtaining step 3) loads tantalum class compound elctro-catalyst crude product, is placed in plasma reaction furnace In, it is passed through high-purity gas under vacuumized conditions and forms plasma atmosphere, vacuum degree is 30-100 Pa, in plasma electricity Pressure power is 100-300 W, and reaction temperature is 30-200 DEG C, after priming reaction 0.2-2 h, obtains described closing based on platinum oxide The tantalum class compound elctro-catalyst of gold.
A kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy, it is characterised in that in step 1), roasting Temperature is 400-700 DEG C, calcining time 5-15h.
A kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy, it is characterised in that in step 2, oxidation The molar ratio of tantalum, sodium chloride and sodium fluoride is 1-2: 1.5-3: 0-1.5；Calcination temperature is 450-650 DEG C, calcination time For 5-15 h.
A kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy, it is characterised in that in step 3), calcining Temperature is 850-950 DEG C, and calcination time is 2-10 hours, and ammonia flow is 50-400 mL/min, preferably 100-400mL/ min。
A kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy, it is characterised in that in step 3), platinum salt For chloroplatinic acid, potassium chloroplatinate, sub- potassium chloroplatinate, ammonium chloroplatinate or acetylacetone,2,4-pentanedione platinum, preferably chloroplatinic acid or sub- potassium chloroplatinate；It is non- Precious metal salt is ferric nitrate, iron chloride, ferric acetyl acetonade, cobalt nitrate, cobalt chloride, acetylacetone cobalt, nickel nitrate, nickel chloride, second Acyl acetone nickel, copper nitrate, copper chloride, acetylacetone copper, manganese nitrate, manganese acetate, zinc nitrate or zinc chloride, preferably nickel chloride or Cobalt nitrate.
A kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy, it is characterised in that high-purity in step 4) Gas is hydrogen, argon gas or the nitrogen of 99% or more purity；Vacuum degree is 50-70Pa, plasma potential 150-200W, instead Answering temperature is 60-100 DEG C, and the priming reaction time is 0.3-1h.
A kind of application of the tantalum class compound elctro-catalyst based on oxidation platinum alloy in electrolysis water production ozone.
A kind of application of the tantalum class compound elctro-catalyst based on oxidation platinum alloy in electrolysis water production ozone, It is characterized in that using two electrode system test devices, it is described to be based on platinum oxide using neutral inorganic salt solution as electrolyte The tantalum class compound elctro-catalyst of alloy is working electrode, and platinized platinum is to carry out electrolysis water reaction to electrode, generates ozone product.
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows:
The present invention synthesizes novel oxidation platinum alloy by easy and lower-cost method and loads tantalum class compound electricity Catalyst, current density are better than PbO2；And preparation method is simple, at low cost, is easy to regulate and control, the present invention mixes in platinum oxide Enter base metal, not only can be further improved the stability of electrode, moreover it is possible to enhance the activity of its electro-catalysis synthesis ozone, research Show either to generate O3Efficiency or electrode stability, oxidation platinum alloy electrode of the invention is better than traditional β- PbO2Electrode；It provides the foundation application study, has broad application prospects in electro-catalysis field for such material.
Detailed description of the invention
Fig. 1 a is the PtNiO obtained of embodiment 12/Ta3N5Scanning electron microscope at 500 nm observes figure；
Fig. 1 b is the PtNiO obtained of embodiment 12/Ta3N5Scanning electron microscope at 250 nm observes figure；
Fig. 2 a is the PtNiO obtained of embodiment 12/Ta3N5Transmission electron microscope observation figure at 100 nm；
Fig. 2 b is the PtNiO obtained of embodiment 12/Ta3N5Transmission electron microscope observation figure at 20 nm；
Fig. 3 is 1 gained PtNiO of embodiment2/Ta3N5, 2 gained PtCoO of embodiment2/Ta3N5And PbO2Electrolysis water generate The linear sweep voltammetry figure of ozone；
Fig. 4 is 3 gained PtFeO of embodiment2/ TaON, 4 gained PtCuO of embodiment2/ TaON and PbO2Electrolysis water generate it is smelly The linear sweep voltammetry figure of oxygen；
Fig. 5 is 5 gained PtMnO of embodiment2/Ta2O5, 6 gained PtZnO of embodiment2/Ta2O5And PbO2Electrolysis water generate The linear sweep voltammetry figure of ozone.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1:PtNiO2/Ta3N5Synthesis
1) it taking tantalum powder to be placed in Muffle furnace, is roasted under air atmosphere, maturing temperature is 500 DEG C, and calcining time is 5 h, Obtain white powder, as tantalum oxide；
2) tantalum oxide, sodium chloride obtained by step 1) and sodium fluoride are mixed with the molar ratio of 4:9:1, obtained solid mixture It is middle a small amount of ethyl alcohol is added to be fully ground (ethyl alcohol by solid mixture moistened surface), it is subsequently placed in 550 DEG C of Muffle furnaces and calcines 4 h；
3) powder calcined in step 2 is placed in tube furnace, is roasted under ammonia atmosphere, maturing temperature 900 DEG C, calcining time is 7 hours, and ammonia flow is 200 mL/min, obtains tantalum nitride Nanorods Catalyst；
4) the resulting tantalum nitride Nanorods Catalyst of step 3) is washed with deionized 4 times, is then placed on 60 DEG C of vacuum Dry 12 h in drying box；
5) by step 4) it is dry after 100 mg of tantalum nitride Nanorods Catalyst, 13.3 mg of chloroplatinic acid, 11 mg of nickel chloride and 30 mL deionized waters be added water heating kettle in, 6 h of hydro-thermal reaction, is cooled to room temperature after reaction at 120 DEG C, then stand it is heavy It forms sediment, takes out sediment and be dried in vacuo successively through water and ethanol washing, then at 60 DEG C, obtain oxidation platinum-nickel alloy load nitridation Tantalum elctro-catalyst crude product；
6) the oxidation platinum-nickel alloy load tantalum nitride elctro-catalyst crude product that step 5) obtains is placed in plasma reaction In furnace, plasma potential power is 180 W, and reaction temperature is 170 DEG C, is passed through high-purity argon gas under vacuumized conditions and is formed Plasma atmosphere, vacuum degree are 50 Pa, are activated 2 hours under the plasma atmosphere, and the oxidation platinum-nickel alloy activated is negative Tantalum nitride elctro-catalyst (the referred to as PtNiO of load2/Ta3N5Catalyst), obtain the tantalum class compound based on oxidation platinum alloy Elctro-catalyst.
PtNiO obtained to the present embodiment2/Ta3N5It is scanned electron microscope respectively and transmission electron microscope is seen Characterization is examined, scanning electron microscope characterization result is shown in that Fig. 1 a and Fig. 1 b, transmission electron microscope characterization result are shown in Fig. 2 a and Fig. 2 b. It can be seen that the present embodiment PtNiO obtained from Fig. 1 a, Fig. 1 b, Fig. 2 a and Fig. 2 b2/Ta3N5For nanorod structure, nanometer Stick structure can expose special crystal face { 010 } and { 001 } of tantalum nitride, the two crystal faces and platinum-non-noble metal composite oxide Combination it is more stable, and compared to the tantalum nitride without special crystal face, have { 010 } and { 001 } special crystal face tantalum nitride and Has special electron transmission effect between platinum-non-noble metal composite oxide, in PtNiO2/Ta3N5Under catalyst action, make Electrolysis water reaction is obtained to be more easier to carry out.
The PtNiO that embodiment 1 is prepared2/Ta3N5The catalytic performance of catalyst is tested, and the specific method is as follows:
Electrocatalysis characteristic test is to be carried out at room temperature using the CHI760E three-electrode cell system of Shanghai Chen Hua , reference solution is 3M KCl aqueous solution in Ag/AgCl(, and the reference electrode and embodiment 1 of following embodiment be identical) electrode is Reference electrode, platinized platinum are used as the PtNiO prepared to electrode, embodiment 12/Ta3N5Catalyst is made into dispersion liquid, and (catalyst quality is 4 mg, 900 100 μ L of μ L, Nafion of ethyl alcohol) uniformly drop is on the carbon cloth of 1 × 1 cm, after drying at room temperature, directly as Working electrode；To be saturated K2SO4Aqueous solution carries out generation ozone reaction (EOP) test experiments, linear scan volt as electrolyte The sweep speed of peace method is 5mV/s, and test result is shown in Fig. 3.
Embodiment 2:PtCoO2/Ta3N5Synthesis
1) it taking tantalum powder to be placed in Muffle furnace, is roasted under air atmosphere, maturing temperature is 500 DEG C, and calcining time is 5 h, Obtain white powder, as tantalum oxide；
2) tantalum oxide, sodium chloride obtained by step 1) and sodium fluoride are mixed with the molar ratio of 4:9:1, obtained solid mixture It is middle a small amount of ethyl alcohol is added to be fully ground (ethyl alcohol by solid mixture moistened surface), it is subsequently placed in 550 DEG C of Muffle furnaces and calcines 4 h；
3) powder calcined in step 2 is placed in tube furnace, is roasted under ammonia atmosphere, maturing temperature 900 DEG C, calcining time is 7 hours, and ammonia flow is 200 mL/min, obtains tantalum nitride Nanorods Catalyst；
4) the resulting tantalum nitride Nanorods Catalyst of step 3) is washed with deionized 4 times, is then placed on 60 DEG C of vacuum Dry 12 h in drying box；
5) 100 mg of tantalum nitride Nanorods Catalyst, 13.3 mg of chloroplatinic acid, cobalt nitrate 24.7 by step 4) after dry Mg and 30 mL deionized waters are added in water heating kettle, and 6 h of hydro-thermal reaction, is cooled to room temperature after reaction at 120 DEG C, then quiet Precipitating is set, sediment is taken out and is dried in vacuo successively through water and ethanol washing, then at 60 DEG C, obtains oxidation platinum-nickel alloy load Tantalum nitride elctro-catalyst crude product；
6) the oxidation platinum-nickel alloy load tantalum nitride elctro-catalyst crude product that step 5) obtains is placed in plasma reaction In furnace, plasma potential power is 180 W, and reaction temperature is 170 DEG C, is passed through high-purity argon gas under vacuumized conditions and is formed Plasma atmosphere, vacuum degree are 50 Pa, are activated 2 hours under the plasma atmosphere, and the platinum oxide cobalt alloy activated is negative Tantalum nitride elctro-catalyst (the abbreviation PtCoO of load2/Ta3N5), obtain the tantalum class compound elctro-catalyst based on oxidation platinum alloy.
The PtCoO that embodiment 2 is prepared2/Ta3N5The catalytic performance of catalyst is tested, and the specific method is as follows:
Electrocatalysis characteristic test is to be carried out at room temperature using the CHI760E three-electrode cell system of Shanghai Chen Hua , Ag/AgCl(3M KCl) electrode is reference electrode, platinized platinum is used as to electrode, PtCoO prepared by embodiment 22/Ta3N5Catalysis Agent is made into dispersion liquid (catalyst quality is 4 mg, 900 100 μ L of μ L, Nafion of ethyl alcohol) uniformly carbon cloth of the drop in 1 × 1 cm On, after drying at room temperature, directly as working electrode；To be saturated K2SO4Aqueous solution carries out generation ozone reaction as electrolyte (EOP) sweep speed of test experiments, linear sweep voltammetry is 5 mV/s, and test result is shown in Fig. 3.
Embodiment 3:PtFeO2The synthesis of/TaON
1) it takes tantalum powder to be placed in Muffle furnace, is roasted under air atmosphere, maturing temperature is 500 DEG C, and calcining time is 5 h, is obtained To white powder, as tantalum oxide；
2) tantalum oxide, sodium chloride obtained by step 1) and sodium fluoride are mixed with the molar ratio of 4:9:1, obtained solid mixture It is middle a small amount of ethyl alcohol is added to be fully ground (ethyl alcohol by solid mixture moistened surface), it is subsequently placed in 550 DEG C of Muffle furnaces and calcines 4 h；
3) powder calcined in step 2 is placed in tube furnace, is roasted under ammonia atmosphere, maturing temperature 850 DEG C, calcining time is 5 hours, and ammonia flow is 50 mL/min, obtains granular nitrogen tantalum oxide catalyst；
4) granular nitrogen tantalum oxide catalyst obtained by step 3) is washed with deionized 4 times, is then placed on 60 DEG C very Dry 12 h in empty drying box；
5) 100 mg of nitrogen tantalum oxide catalyst by step 4) after dry, 13.3 mg of chloroplatinic acid, 15.6 mg of ferric acetate and 30 mL deionized waters be added water heating kettle in, 6 h of hydro-thermal reaction, is cooled to room temperature after reaction at 120 DEG C, then stand it is heavy It forms sediment, takes out sediment and be dried in vacuo successively through water and ethanol washing, then at 60 DEG C, obtain oxidation pt-fe alloy load nitridation Tantalum elctro-catalyst；
6) the oxidation pt-fe alloy load tantalum nitride elctro-catalyst that step 5) obtains is placed in plasma reaction furnace, Plasma potential power is 180 W, and reaction temperature is 170 DEG C, is passed through high-purity argon gas under vacuumized conditions and forms plasma Body atmosphere, vacuum degree are 50 Pa, are activated 2 hours under the plasma atmosphere, the nitrogen of the oxidation pt-fe alloy load activated Change tantalum elctro-catalyst (abbreviation PtFeO2/ TaON), obtain the tantalum class compound elctro-catalyst based on oxidation platinum alloy.
The PtFeO that embodiment 3 is prepared2The catalytic performance of/TaON catalyst is tested, and the specific method is as follows:
Electrocatalysis characteristic test is to be carried out at room temperature using the CHI760E three-electrode cell system of Shanghai Chen Hua , Ag/AgCl(3M KCl) electrode is reference electrode, platinized platinum is used as to electrode, PtFeO prepared by embodiment 32/ TaON is made into Uniformly drop is on the carbon cloth of 1 × 1 cm, room for dispersion liquid (catalyst quality is 4 mg, 900 100 μ L of μ L, Nafion of ethyl alcohol) After being dried under temperature, directly as working electrode；To be saturated K2SO4Aqueous solution carries out generation ozone reaction (EOP) as electrolyte The sweep speed of test experiments, linear sweep voltammetry is 5 mV/s, and test result is shown in Fig. 4.
Embodiment 4:PtCuO2The synthesis of/TaON
1) it taking tantalum powder to be placed in Muffle furnace, is roasted under air atmosphere, maturing temperature is 500 DEG C, and calcining time is 5 h, Obtain white powder, as tantalum oxide；
2) tantalum oxide, sodium chloride obtained by step 1) and sodium fluoride are mixed with the molar ratio of 4:9:1, obtained solid mixture It is middle a small amount of ethyl alcohol is added to be fully ground (ethyl alcohol by solid mixture moistened surface), it is subsequently placed in 550 DEG C of Muffle furnaces and calcines 4 h；
3) powder calcined in step 2 is placed in tube furnace, is roasted under ammonia atmosphere, maturing temperature 850 DEG C, calcining time is 5 hours, and ammonia flow is 50 mL/min, obtains granular nitrogen tantalum oxide catalyst；
4) granular nitrogen tantalum oxide catalyst obtained by step 3) is washed with deionized 4 times, is then placed on 60 DEG C very Dry 12 h in empty drying box；
5) 100 mg of nitrogen tantalum oxide catalyst by step 4) after dry, 13.3 mg of chloroplatinic acid, 15.7 mg of copper acetate and 30 mL deionized waters be added water heating kettle in, 6 h of hydro-thermal reaction, is cooled to room temperature after reaction at 120 DEG C, then stand it is heavy It forms sediment, takes out sediment and be dried in vacuo successively through water and ethanol washing, then at 60 DEG C, obtain oxidation Mock gold load nitridation Tantalum elctro-catalyst crude product；
6) the oxidation Mock gold load tantalum nitride elctro-catalyst crude product that step 5) obtains is placed in plasma reaction In furnace, plasma potential power is 180 W, and reaction temperature is 170 DEG C, is passed through high-purity argon gas under vacuumized conditions and is formed Plasma atmosphere, vacuum degree are 50 Pa, are activated 2 hours under the plasma atmosphere, and the oxidation Mock gold activated is negative Tantalum nitride elctro-catalyst (the abbreviation PtCuO of load2/ TaON), obtain the tantalum class compound elctro-catalyst based on oxidation platinum alloy.
The PtCuO that embodiment 4 is prepared2The catalytic performance of/TaON catalyst is tested, and the specific method is as follows:
Electrocatalysis characteristic test is to be carried out at room temperature using the CHI760E three-electrode cell system of Shanghai Chen Hua , Ag/AgCl(3M KCl) electrode is reference electrode, platinized platinum is used as to electrode, PtCuO prepared by embodiment 42/ TaON is made into Uniformly drop is on the carbon cloth of 1 × 1 cm, room for dispersion liquid (catalyst quality is 4 mg, 900 100 μ L of μ L, Nafion of ethyl alcohol) After being dried under temperature, directly as working electrode；To be saturated K2SO4Aqueous solution carries out generation ozone reaction (EOP) as electrolyte The sweep speed of test experiments, linear sweep voltammetry is 5mV/s, and test result is shown in Fig. 4.
Embodiment 5:PtMnO2/Ta2O5Synthesis
1) it taking tantalum powder to be placed in Muffle furnace, is roasted under air atmosphere, maturing temperature is 500 DEG C, and calcining time is 5 h, Obtain white powder, as tantalum oxide；
2) tantalum oxide, sodium chloride obtained by step 1) and sodium fluoride are mixed with the molar ratio of 4:9:1, obtained solid mixture It is middle a small amount of ethyl alcohol is added to be fully ground (ethyl alcohol by solid mixture moistened surface), it is subsequently placed in 550 DEG C of Muffle furnaces and calcines 4 h；
3) powder calcined in step 2 is washed with deionized 4 times, is then placed in 60 DEG C of vacuum ovens and does Dry 12 h；
4) 100 mg of solid, 13.3 mg of chloroplatinic acid, 16.3 mg of manganese nitrate and the 30 mL deionizations by step 3) after dry Water is added in water heating kettle, and 6 h of hydro-thermal reaction, is cooled to room temperature after reaction at 120 DEG C, then staticly settles, and takes out precipitating Object is dried in vacuo successively through water and ethanol washing, then at 60 DEG C, and it is thick to obtain platinum oxide manganese alloy load tantalum oxide elctro-catalyst Product；
5) the platinum oxide manganese alloy load tantalum oxide elctro-catalyst crude product that step 4) obtains is placed in plasma reaction In furnace, plasma potential power is 180 W, and reaction temperature is 170 DEG C, is passed through high-purity argon gas under vacuumized conditions and is formed Plasma atmosphere, vacuum degree are 50 Pa, are activated 2 hours under the plasma atmosphere, and the platinum oxide manganese alloy activated is negative Tantalum oxide elctro-catalyst (the abbreviation PtMnO of load2/Ta2O5).
The PtMnO that embodiment 5 is prepared2/Ta2O5The catalytic performance of catalyst is tested, and the specific method is as follows:
Electrocatalysis characteristic test is to be carried out at room temperature using the CHI760E three-electrode cell system of Shanghai Chen Hua , Ag/AgCl(3M KCl) electrode is reference electrode, platinized platinum is used as to electrode, PtMnO prepared by embodiment 52/Ta2O5It is made into Uniformly drop is on the carbon cloth of 1 × 1 cm for dispersion liquid (catalyst quality is 4 mg, 900 100 μ L of μ L, Nafion of ethyl alcohol), directly It connects as working electrode；To be saturated K2SO4Aqueous solution carries out generation ozone reaction (EOP) test experiments, linearly as electrolyte The sweep speed for scanning voltammetry is 5mV/s, and test result is shown in Fig. 5.
Embodiment 6:PtZnO2/Ta2O5Synthesis
1) it taking tantalum powder to be placed in Muffle furnace, is roasted under air atmosphere, maturing temperature is 500 DEG C, and calcining time is 5 h, Obtain white powder, as tantalum oxide；
2) tantalum oxide, sodium chloride obtained by step 1) and sodium fluoride are mixed with the molar ratio of 4:9:1, obtained solid mixture It is middle a small amount of ethyl alcohol is added to be fully ground (ethyl alcohol by solid mixture moistened surface), it is subsequently placed in 550 DEG C of Muffle furnaces and calcines 4 h；
3) powder obtained after calcining step 2 is washed with deionized 4 times, is then placed in 60 DEG C of vacuum ovens Dry 12 h；
4) 100 mg of solid, 13.3 mg of chloroplatinic acid, 22.7 mg of zinc nitrate and the 30 mL deionizations by step 3) after dry Water is added in water heating kettle, and 6 h of hydro-thermal reaction, is cooled to room temperature after reaction at 120 DEG C, then staticly settles, and takes out precipitating Object is dried in vacuo successively through water and ethanol washing, then at 60 DEG C, and it is thick to obtain platinum oxide kirsite load tantalum oxide elctro-catalyst Product；
5) the platinum oxide kirsite load tantalum oxide elctro-catalyst crude product that step 4) obtains is placed in plasma reaction In furnace, plasma potential power is 180 W, and reaction temperature is 170 DEG C, is passed through high-purity argon gas under vacuumized conditions and is formed Plasma atmosphere, vacuum degree are 50 Pa, are activated 2 hours under the plasma atmosphere, and the platinum oxide kirsite activated is negative Tantalum oxide elctro-catalyst (the abbreviation PtZnO of load2/Ta2O5).
The PtZnO that embodiment 6 is prepared2/Ta2O5The catalytic performance of catalyst is tested, and the specific method is as follows:
Electrocatalysis characteristic test is to be carried out at room temperature using the CHI760E three-electrode cell system of Shanghai Chen Hua , Ag/AgCl(3M KCl) electrode is reference electrode, platinized platinum is used as to electrode, PtZnO prepared by embodiment 62/Ta2O5It is made into Uniformly drop is on the carbon cloth of 1 × 1 cm for dispersion liquid (catalyst quality is 4 mg, 900 100 μ L of μ L, Nafion of ethyl alcohol), directly It connects as working electrode；To be saturated K2SO4Aqueous solution carries out generation ozone reaction (EOP) test experiments, linearly as electrolyte The sweep speed for scanning voltammetry is 5mV/s, and test result is shown in Fig. 5.
Embodiment 7:PbO2The preparation of catalyst
With PbO2(99.90%) as the contrast sample for generating ozone reaction, performance test methods are as follows: weighing 4 mg PbO2Solid is added in the centrifuge tube of 4 mL, and the Nafion solution of 100 μ L and the nothing of 900 μ L are successively measured with liquid-transfering gun Water-ethanol is added in centrifuge tube, is subsequently placed in ultrasound 30 minutes in Ultrasound Instrument, forms it into evenly dispersed PbO2Slurries.With shifting Liquid rifle is by the PbO of 1 mL2Slurries equably apply on the carbon cloth of 1 × 1 cm, dry at room temperature, and as working electrode, Using Ag/AgCl(3M KCl) electrode is reference electrode, with platinized platinum to electrode, carry out generation ozone reaction (EOP) test, electro-catalysis Performance test is to be carried out at room temperature using the CHI760E three-electrode cell system of Shanghai Chen Hua.Carry out generation ozone Reacting (EOP) to test electrolyte used is saturation K2SO4Aqueous solution, the sweep speed of linear sweep voltammetry are 5 mV/s.
Fig. 3 is the PtNiO of embodiment 12/Ta3N5The PtCoO of catalyst, embodiment 22/Ta3N5Catalyst and embodiment 7 PbO2The EOP linear sweep voltammetry figure of catalyst, as seen from Figure 3, PtNiO2-Ta3N5Catalyst has in EOP reaction Preferable overpotential (for current density at 10 mA/cm2, EOP overpotential is 153 mV), performance are better than business PbO2(electric current For density at 10 mA/cm2, EOP overpotential is 126 mV).These excellent performances are attributed to tantalum nitride and oxidation platinum alloy is received The synergistic effect of rice grain nanoparticle.
Fig. 4 is the PtFeO of embodiment 32The PtCuO of/TaON catalyst, embodiment 42/ TaON catalyst and embodiment 7 PbO2The EOP linear sweep voltammetry figure of catalyst, finds out PtFeO by Fig. 42/ TaON catalyst, PtCuO2The property of/TaON catalyst It can be better than business PbO2。
Fig. 5 is the PtMnO of embodiment 52/Ta2O5The PtZnO of catalyst, embodiment 62/Ta2O5Catalyst and embodiment 7 PbO2The EOP linear sweep voltammetry figure of catalyst, as seen from Figure 5 PtMnO2/Ta2O5Catalyst, PtZnO2/Ta2O5Catalyst Slightly inferior properties in business PbO2。
Comparison diagram 3 and Fig. 4 can be seen that the PtFeO in Fig. 42/ TaON catalyst, PtCuO2The catalysis of/TaON catalyst Performance is compared with PtNiO2/Ta3N5Catalyst, PtCoO2/Ta3N5The catalytic performance difference of catalyst, this may be because of PtNiO2/ Ta3N5Catalyst, PtCoO2/Ta3N5The tantalum nitride of nano bar-shape of the formation with special crystal face in catalyst, and PtFeO2/ TaON catalyst, PtCuO2The nitrogen tantalum oxide that rule particle shape is formd in/TaON catalyst, it is sudden and violent due to no special crystal face Dew, so catalytic performance is poor.
Comparison diagram 3, Fig. 4 and Fig. 5 can be seen that PtMnO2/Ta2O5Catalyst, PtZnO2/Ta2O5The catalytic of catalyst Can be poor, this may be because the step of roasting under ammonia, foring unformed oxidation in catalyst preparation process Tantalum, the catalytic performance for electrolysis water production ozone are poor.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered When the concrete form for being seen as limited by embodiment and being stated.

Claims (10)

1. a kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy, it is characterised in that including tantalum class compound and be supported on Platinum-non-noble metal composite oxide on tantalum class compound, the tantalum class compound be one of tantalum nitride, nitrogen tantalum oxide or Two kinds of mixtures, base metal are at least one of iron, cobalt, nickel, copper, manganese, zinc metallic element；Platinum-base metal composite oxygen The mass ratio of compound and tantalum class compound is 0.08 ~ 0.12: 1；The preparation method of the catalyst, comprising the following steps:
1) it takes tantalum powder to be placed in Muffle furnace, is roasted under air atmosphere, obtain white powder, as tantalum oxide；
2) tantalum oxide obtained by step 1) and sodium chloride, sodium fluoride are mixed, a small amount of alcohol solvent are added in obtained solid mixture, Solid mixture moistened surface is fully ground by alcohol solvent, is subsequently placed in Muffle furnace and is calcined 2- at 450-650 DEG C 5 h；
3) the calcined product of step 2 is placed in tube furnace, is roasted under ammonia atmosphere, obtained tantalum class compound, then use Deionized water washing, dry, solid and platinum salt, base metal salt and deionized water after drying are added to water heating kettle together In, hydro-thermal reaction 4-24 h, is cooled to room temperature after reaction at 100-150 DEG C, then staticly settles, and takes out sediment successively It is dry through water and ethanol washing, obtain platinum oxide load tantalum class compound elctro-catalyst crude product；
4) platinum oxide for obtaining step 3) loads tantalum class compound elctro-catalyst crude product, is placed in plasma reaction furnace, takes out It is passed through high-purity gas under vacuum condition and forms plasma atmosphere, vacuum degree is 30-100 Pa, in plasma potential power For 100-300 W, reaction temperature is 30-200 DEG C, after priming reaction 0.2-2 h, obtains the tantalum based on oxidation platinum alloy Class compound elctro-catalyst；Wherein, high-purity gas is the argon gas or nitrogen of 99% or more purity.
2. a kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy according to claim 1, it is characterised in that step It is rapid 1) in, maturing temperature be 400-700 DEG C, calcining time 5-15h.
3. a kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy according to claim 2, it is characterised in that step It is rapid 2) in, the molar ratio of tantalum oxide, sodium chloride and sodium fluoride is 1-2: 1.5-3: 0-1.5, and the mole of sodium fluoride is not 0；Calcination temperature is 450-650 DEG C, and calcination time is 5-15 h.
4. a kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy according to claim 1, it is characterised in that step It is rapid 3) in, maturing temperature be 850-950 DEG C, calcining time be 2-10 hour, ammonia flow be 50-400 mL/min.
5. a kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy according to claim 4, it is characterised in that ammonia Throughput is 100-400mL/min.
6. a kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy according to claim 1, it is characterised in that step It is rapid 3) in, platinum salt is chloroplatinic acid, potassium chloroplatinate, sub- potassium chloroplatinate, ammonium chloroplatinate or acetylacetone,2,4-pentanedione platinum；Base metal salt is nitric acid Iron, iron chloride, ferric acetyl acetonade, cobalt nitrate, cobalt chloride, acetylacetone cobalt, nickel nitrate, nickel chloride, nickel acetylacetonate, nitric acid Copper, copper chloride, acetylacetone copper, manganese nitrate, manganese acetate, zinc nitrate or zinc chloride.
7. a kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy according to claim 6, it is characterised in that platinum Salt is chloroplatinic acid or sub- potassium chloroplatinate；Base metal salt is nickel chloride or cobalt nitrate.
8. a kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy according to claim 1, it is characterised in that step It is rapid 4) in vacuum degree be 50-70Pa, plasma potential 150-200W, reaction temperature be 60-100 DEG C, the priming reaction time For 0.3-1h.
9. a kind of tantalum class compound elctro-catalyst based on oxidation platinum alloy according to claim 1 produces smelly in electrolysis water Application in oxygen.
10. application according to claim 9, it is characterised in that two electrode system test devices are used, with the inorganic of neutrality Saline solution is electrolyte, and the tantalum class compound elctro-catalyst based on oxidation platinum alloy is working electrode, and platinized platinum is to electricity Pole carries out electrolysis water reaction, generates ozone product.
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