CN111634944A - Preparation method of doped bismuth oxide particles, doped bismuth oxide composite material and preparation method thereof - Google Patents
Preparation method of doped bismuth oxide particles, doped bismuth oxide composite material and preparation method thereof Download PDFInfo
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- CN111634944A CN111634944A CN202010381159.8A CN202010381159A CN111634944A CN 111634944 A CN111634944 A CN 111634944A CN 202010381159 A CN202010381159 A CN 202010381159A CN 111634944 A CN111634944 A CN 111634944A
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- bismuth oxide
- doped bismuth
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- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 95
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000002245 particle Substances 0.000 title claims abstract description 94
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 150000001621 bismuth Chemical class 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
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- 238000001035 drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 5
- 150000003057 platinum Chemical class 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
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- 239000002041 carbon nanotube Substances 0.000 claims description 2
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- 239000010432 diamond Substances 0.000 claims description 2
- 229910003460 diamond Inorganic materials 0.000 claims description 2
- 229910003472 fullerene Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000002931 mesocarbon microbead Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 36
- 239000003054 catalyst Substances 0.000 description 11
- 239000011858 nanopowder Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
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- 238000002441 X-ray diffraction Methods 0.000 description 5
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- 150000002500 ions Chemical class 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- AHKZTVQIVOEVFO-UHFFFAOYSA-N oxide(2-) Chemical compound [O-2] AHKZTVQIVOEVFO-UHFFFAOYSA-N 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- -1 oxygen ion Chemical class 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/644—Arsenic, antimony or bismuth
- B01J23/6447—Bismuth
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/10—Preparation or treatment, e.g. separation or purification
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- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/218—Yttrium oxides or hydroxides
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- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract
The invention discloses a preparation method of doped bismuth oxide particles, which comprises the following steps: according to the molar ratio of Bi to A of 5: 1-2, dissolving soluble bismuth salt and soluble A salt in an acidic liquid with the pH value of 1-6 to obtain a mixed solution; stirring the mixed solution until the mixed solution forms a sol, and heating to dissolve the solThe preparation method of the doped bismuth oxide particles prepares the doped bismuth oxide particles doped with the rare earth oxide by a sol-gel method, and the prepared doped bismuth oxide particles have good consistency and α -Bi in the doped bismuth oxide particles can be seen by combining the specific embodiment part2O3Conversion to-Bi2O3Thereby having better electrical performance. The invention also discloses a bismuth oxide doped composite material and a preparation method thereof.
Description
Technical Field
The invention relates to the field of oxide ion conductors, in particular to a preparation method of doped bismuth oxide particles, a doped bismuth oxide composite material and a preparation method thereof.
Background
Recently, bismuth oxide (Bi) has been used2O3) The delta-centered cubic (FCC) phase of pure bismuth oxide has a high oxide ion conductivity at high temperatures, but is only stable between 730 ℃ to 825 ℃ (melting point)2O3) The obtained doped bismuth oxide can be stable at lower temperature. The application of the doped bismuth oxide can lead to the development of electrochemical devices, the working temperature of the electrochemical devices is greatly reduced, and the ionic conductivity can be obviously improved.
However, there is no optimized method for preparing doped bismuth oxide particles in the prior art.
Disclosure of Invention
Based on this, there is a need for a method for preparing doped bismuth oxide particles.
A preparation method of doped bismuth oxide particles comprises the following steps:
according to the molar ratio of Bi to A of 5: 1-2, dissolving soluble bismuth salt and soluble A salt in an acidic liquid with the pH value of 1-6 to obtain a mixed solution, wherein A is a rare earth element, and the total molar concentration of Bi and A in the mixed solution is 0.05-0.3 mol/L;
stirring the mixed solution until the mixed solution forms sol, then heating to convert the sol into gel, and drying the gel to obtain a precursor; and
and sintering the precursor at the temperature of 300-800 ℃ to obtain the required doped bismuth oxide particles.
The doped bismuth oxide composite material comprises, by mass, 10 parts of Pt, 60-80 parts of a carbon material and 10-30 parts of doped bismuth oxide particles prepared by the preparation method.
The preparation method of the doped bismuth oxide composite material comprises the following steps:
doped bismuth oxide particles prepared according to the above-described method for preparing doped bismuth oxide particles;
dispersing soluble platinum salt, a carbon material and the doped bismuth oxide particles in alcohol to obtain a mixed liquid, wherein the mass ratio of Pt to the carbon material to the doped bismuth oxide particles is 10: 60-80: 10-30; and
and mixing a reducing agent with the mixed liquid, and fully reacting to obtain the doped bismuth oxide composite material.
According to the preparation method of the doped bismuth oxide particles, the doped bismuth oxide particles doped with the rare earth oxide are prepared by the sol-gel method, and the prepared doped bismuth oxide particles have good consistency and α -Bi in the doped bismuth oxide particles can be seen by combining the specific embodiment2O3Conversion to-Bi2O3Thereby having better electrical performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Wherein:
fig. 1 is an XRD pattern of yttrium-doped bismuth oxide particles prepared in example 1.
FIG. 2a is an SEM image (300 nm on a scale) of yttrium-doped bismuth oxide particles prepared in example 1.
FIG. 2b is an SEM image (500 nm on a scale) of yttrium-doped bismuth oxide particles prepared in example 1.
FIG. 3 is a graph of X-ray analysis (EDAX) of yttrium-doped bismuth oxide particles made in example 3.
FIG. 4 is an SEM image (20 nm on a scale) of yttrium-doped bismuth oxide particles prepared in example 3.
FIG. 5 is a Nyquist plot of the yttrium-doped bismuth oxide particles prepared in example 1 at 300 deg.C, 500 deg.C, and 600 deg.C.
Fig. 6 is an equivalent circuit modeling diagram of fig. 5.
FIG. 7 is a plot of conductivity (log σ) versus reciprocating temperature (1000/T) for yttrium-doped bismuth oxide particles made in example 1.
FIG. 8 is a graph showing the relationship between current density and potential during charge and discharge using the composite material obtained in example 8 as a catalyst.
FIG. 9 is a graph showing the relationship between current density and potential during charge and discharge using the composite material obtained in example 9 as a catalyst.
FIG. 10 is a graph showing the relationship between current density and potential during charge and discharge using the composite material obtained in example 10 as a catalyst.
Fig. 11 is a graph showing the relationship between current density and potential during charge and discharge using the composite material prepared in comparative example 1 as a catalyst.
FIG. 12 is a graph comparing electrochemical surface areas of composites made in example 8, example 9, example 10, and comparative example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention discloses a preparation method of doped bismuth oxide particles, which comprises the following steps:
s10, according to the molar ratio of Bi to A being 5: 1-2, dissolving soluble bismuth salt and soluble A salt in an acidic liquid with the pH value of 1-6 to obtain a mixed solution.
Wherein A is a rare earth element, and the total molar concentration of Bi and A in the mixed solution is 0.05 mol/L-0.3 mol/L.
Generally, rare earth elements include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), and scandium (Sc).
Preferably, in the mixed solution, the molar ratio of Bi to A is 3: 1, the total molar concentration of Bi and A is 0.1 mol/L.
Preferably, the rare earth element is Y.
In this embodiment, both the soluble bismuth salt and the soluble a salt are nitrates, and the acidic liquid is a nitric acid solution.
In order to prevent caking, a surfactant is also included in the mixed solution. In a specific embodiment, 3 wt% para-PEG 4000 (surfactant) is included in the mixed solution.
And S20, stirring the mixed solution obtained in the step S10 until the mixed solution forms a sol, then heating to convert the sol into gel, and drying the gel to obtain the precursor.
Preferably, the heating temperature is 75-100 ℃, and the drying temperature is 140-200 ℃.
Particularly preferably, the heating temperature is 90 ℃ and the drying temperature is 160 ℃.
The specific time for heating and drying is determined according to the amount of the sample actually prepared.
In a preferred embodiment, the heating time may be 0.5h to 2 h.
And S30, sintering the precursor obtained in the step S20 at the temperature of 300-800 ℃ to obtain the required doped bismuth oxide particles.
Preferably, the method further comprises the operation of pressing the precursor into the disk-shaped particles at a pressure of 50 to 200 mpa (preferably 100 mpa) after drying the gel to obtain the precursor and before sintering the precursor at a temperature of 300 to 800 ℃.
The specific time for sintering is determined according to the amount of the sample actually prepared.
In a preferred embodiment, the sintering time may be 1 to 4 hours.
Preferably, the sintering temperature is 500 ℃ or 650 ℃.
According to the preparation method of the doped bismuth oxide particles, the doped bismuth oxide particles doped with the rare earth oxide are prepared by the sol-gel method, and the prepared doped bismuth oxide particles have good consistency and α -Bi in the doped bismuth oxide particles can be seen by combining the specific embodiment2O3Conversion to-Bi2O3Thereby having better electrical performance.
The doped bismuth oxide particles prepared by the preparation method of the doped bismuth oxide particles can be applied to various fields, and particularly can be applied to the field of solid electrolytes.
The invention also discloses a doped bismuth oxide composite material which comprises, by mass, 10 parts of Pt, 60-80 parts of a carbon material and 10-30 parts of doped bismuth oxide particles prepared by the preparation method of the doped bismuth oxide particles.
The bismuth oxide doped composite material can be used as a catalyst or a solid electrolyte and applied to the fields of batteries, oxygen sensors, compact ceramic membranes for oxygen separation and the like.
The invention also discloses a preparation method of the doped bismuth oxide composite material, which comprises the following steps:
the doped bismuth oxide particles prepared according to the above-described method for preparing doped bismuth oxide particles.
Dispersing soluble platinum salt, a carbon material and doped bismuth oxide particles in alcohol to obtain a mixed liquid, wherein the mass ratio of Pt to the carbon material to the doped bismuth oxide particles is 10: 60-80: 10 to 30.
And mixing the reducing agent and the mixed liquid, and fully reacting to obtain the doped bismuth oxide composite material.
Preferably, the soluble platinum salt is H2PtCl6。
Preferably, the carbon material is selected from at least one of carbon black, carbon fiber, mesocarbon microbeads, natural graphite, glassy carbon, activated carbon, highly oriented graphite, carbon black, diamond, carbon nanotubes, fullerene, and graphene.
Preferably, the alcohol is methanol, ethanol, propanol or butanol.
The doped bismuth oxide composite material can be used as a fuel cell catalyst.
The following are specific examples.
Experimental reagent: bi (NO)3)3·5H2O (purity 98%), HNO3(purity 67.5%), Y (NO)3)3·6H2O, citric acid (AR grade) and PEG4000 were purchased from merck and used as received.
Experimental equipment XRD diffraction studies were carried out using a Philips (PW3710) diffractometer (CuK α radiation source (λ 0.151478nm) and the infrared transmittance and absorption spectra of two samples prepared using KBr particle technology were at 400-4000cm-1Was measured in the wave number range of (FTLA 2000-100). The field emission scanning electron microscope measurement research is carried out by using a Hitachi S4160 model. The ionic conductivity was measured by AC impedance analyzer technology with a Model4274A multi-frequency Hewlett packard LCR meter in the frequency range of 100 Hz-100 kHz. Sintered pellets the sintered pellets were placed between the two faces of the silver electrode and the experiment was carried out in 20 c steps with a stabilization time of 15 minutes for each step from 300 c to 800 c.
Example 1
Bi (NO) to be analytically pure3)3·5H2O and Y (NO)3)3·6H2O is obtained by mixing the following components in a molar ratio of 3: 1 in diluted nitric acid to prepare B3+And Y3+The sum of the concentrations was 0.1 mol/L. To prevent caking, 3% by weight of PEG4000 (polyethylene glycol having an average molecular weight equal to 4000) was added as surfactant.
The mixed solution was continuously stirred with a magnetic needle for 2 hours, and then a sol was formed. The sol was heated to 90 ℃ for 1h to form a pale yellow gel. The gel decomposed in an oven at 160 ℃, and the gel initially started to expand and fill the beaker, producing a foam-like precursor. This foam consists of a mixed oxide nanopowder of very small particle size in the form of homogeneous platelets.
The mixed oxide nanopowder was uniaxially compacted into disk-shaped particles having an outer diameter of 10 mm and a thickness of 1 mm at a relatively low pressure of 100 mpa.
Sintering the disc-shaped particles at the temperature of 500 ℃ for 2h to obtain the yttrium-doped bismuth oxide particles.
Example 2
Bi (NO) to be analytically pure3)3·5H2O and Y (NO)3)3·6H2O is obtained by mixing the following components in a molar ratio of 3: 1 in diluted nitric acid to prepare B3+And Y3+The sum of the concentrations was 0.1 mol/L. To prevent caking, 3% by weight of PEG4000 (polyethylene glycol having an average molecular weight equal to 4000) was added as surfactant.
The mixed solution was continuously stirred with a magnetic needle for 2 hours, and then a sol was formed. The sol was heated to 90 ℃ for 1h to form a pale yellow gel. The gel decomposed in an oven at 160 ℃, and the gel initially started to expand and fill the beaker, producing a foam-like precursor. This foam consists of a mixed oxide nanopowder of very small particle size in the form of homogeneous platelets.
The mixed oxide nanopowder was uniaxially compacted into disk-shaped particles having an outer diameter of 10 mm and a thickness of 1 mm at a relatively low pressure of 100 mpa.
Sintering the disc-shaped particles at the temperature of 600 ℃ for 2h to obtain the yttrium-doped bismuth oxide particles.
Example 3
Bi (NO) to be analytically pure3)3·5H2O and Y (NO)3)3·6H2O is obtained by mixing the following components in a molar ratio of 3: 1 in diluted nitric acid to prepare B3+And Y3+The sum of the concentrations being 0.1mol/LAnd (4) mixing the solution. To prevent caking, 3% by weight of PEG4000 (polyethylene glycol having an average molecular weight equal to 4000) was added as surfactant.
The mixed solution was continuously stirred with a magnetic needle for 2 hours, and then a sol was formed. The sol was heated to 90 ℃ for 1h to form a pale yellow gel. The gel decomposed in an oven at 160 ℃, and the gel initially started to expand and fill the beaker, producing a foam-like precursor. This foam consists of a mixed oxide nanopowder of very small particle size in the form of homogeneous platelets.
The mixed oxide nanopowder was uniaxially compacted into disk-shaped particles having an outer diameter of 10 mm and a thickness of 1 mm at a relatively low pressure of 100 mpa.
Sintering the disc-shaped particles at 650 ℃ for 2h to obtain the yttrium-doped bismuth oxide particles.
Example 4
Bi (NO) to be analytically pure3)3·5H2O and Y (NO)3)3·6H2O is obtained by mixing the following components in a molar ratio of 3: 1 in diluted nitric acid to prepare B3+And Y3+The sum of the concentrations was 0.1 mol/L. To prevent caking, 3% by weight of PEG4000 (polyethylene glycol having an average molecular weight equal to 4000) was added as surfactant.
The mixed solution was continuously stirred with a magnetic needle for 2 hours, and then a sol was formed. The sol was heated to 90 ℃ for 1h to form a pale yellow gel. The gel decomposed in an oven at 160 ℃, and the gel initially started to expand and fill the beaker, producing a foam-like precursor. This foam consists of a mixed oxide nanopowder of very small particle size in the form of homogeneous platelets.
The mixed oxide nanopowder was uniaxially compacted into disk-shaped particles having an outer diameter of 10 mm and a thickness of 1 mm at a relatively low pressure of 100 mpa.
Sintering the disc-shaped particles at the temperature of 300 ℃ for 2h to obtain the yttrium-doped bismuth oxide particles.
Example 5
Bi (NO) to be analytically pure3)3·5H2O and Y (NO)3)3·6H2O is obtained by mixing the following components in a molar ratio of 3: 1 in diluted nitric acid to prepare B3+And Y3+The sum of the concentrations was 0.1 mol/L. To prevent caking, 3% by weight of PEG4000 (polyethylene glycol having an average molecular weight equal to 4000) was added as surfactant.
The mixed solution was continuously stirred with a magnetic needle for 2 hours, and then a sol was formed. The sol was heated to 90 ℃ for 1h to form a pale yellow gel. The gel decomposed in an oven at 160 ℃, and the gel initially started to expand and fill the beaker, producing a foam-like precursor. This foam consists of a mixed oxide nanopowder of very small particle size in the form of homogeneous platelets.
The mixed oxide nanopowder was uniaxially compacted into disk-shaped particles having an outer diameter of 10 mm and a thickness of 1 mm at a relatively low pressure of 100 mpa.
Sintering the disc-shaped particles at the temperature of 800 ℃ for 2h to obtain the yttrium-doped bismuth oxide particles.
Example 6
According to YB (yttrium-doped bismuth oxide particles): pt: c is 10: 10: 80, 0.113g of YB prepared in example 1 was dispersed in 5cc of ethanol, followed by addition of H2PtCl6·6H2O (0.305 g dissolved in 5cc of ethanol) (0.113 g of Pt obtained by reduction of ethylene glycol) and 0.345g of carbon black were added to obtain a mixed solution.
0.96g of ethylene glycol is dissolved in 10cc of ethanol, mixed and mixed in the mixed solution, and the YB composite material is obtained after full reaction.
Example 7
According to YB (yttrium-doped bismuth oxide particles): pt: and C is 30: 10: 60, 0.339g of YB prepared in example 1 was dispersed in 5cc of ethanol, followed by addition of H2PtCl6·6H2O (0.305 g dissolved in 5cc of ethanol) (0.113 g of Pt obtained by reduction of ethylene glycol) and 0.259g of carbon black were added to obtain a mixed liquid.
0.96g of ethylene glycol is dissolved in 10cc of ethanol, mixed and mixed in the mixed solution, and the YB composite material is obtained after full reaction.
Example 8
According to YB (yttrium-doped bismuth oxide particles): pt: c is 20: 10: 70, 0.226g of YB prepared in example 1 was dispersed in 5cc of ethanol, followed by addition of H2PtCl6·6H2O (0.305 g dissolved in 5cc of ethanol) (0.113 g of Pt obtained by reduction of ethylene glycol) and 0.301g of carbon black were added to obtain a mixed solution.
0.96g of ethylene glycol is dissolved in 10cc of ethanol, mixed and mixed in the mixed solution, and the YB composite material is obtained after full reaction.
Example 9
According to YB (yttrium-doped bismuth oxide particles): pt: c is 20: 10: 70, 0.226g of YB prepared in example 2 was dispersed in 5cc of ethanol, followed by addition of H2PtCl6·6H2O (0.305 g dissolved in 5cc of ethanol) (0.113 g of Pt obtained by reduction of ethylene glycol) and 0.301g of carbon black were added to obtain a mixed solution.
0.96g of ethylene glycol is dissolved in 10cc of ethanol, mixed and mixed in the mixed solution, and the YB composite material is obtained after full reaction.
Example 10
According to YB (yttrium-doped bismuth oxide particles): pt: c is 20: 10: 70, 0.226g of YB prepared in example 4 was dispersed in 5cc of ethanol, followed by addition of H2PtCl6·6H2O (0.305 g dissolved in 5cc of ethanol) (0.113 g of Pt obtained by reduction of ethylene glycol) and 0.301g of carbon black were added to obtain a mixed solution.
0.96g of ethylene glycol is dissolved in 10cc of ethanol, mixed and mixed in the mixed solution, and the YB composite material is obtained after full reaction.
Comparative example 1
According to the Pt: c is 10: 70, mixing H with2PtCl6·6H2O (0.305 g dissolved in 5cc of ethanol) (0.113 g of Pt obtained by reduction of ethylene glycol) and 0.301g of carbon black were mixed to obtain a mixed solution.
0.96g of ethylene glycol was dissolved in 10cc of ethanol, and mixed with the above mixed solution to obtain a composite material after sufficient reaction.
Test example 1
The yttrium-doped bismuth oxide particles prepared in example 1 were scanned in step scan mode at 4 ° -60 ° in the 2 θ range for 5s, yielding figure 1.
The corresponding peaks of the reflection planes of the cubic structure of metallic bismuth are shown in fig. 1, and a small fraction of unidentified phases is observed.
Average crystallite size determined by Debe-Scherer formula.
Where L is the coherence length, related to the spherical particle diameter D4/3L, λ is the wavelength of the X-rays (nm), k is a constant (0.9 assuming the particle is spherical), β is the full width at half maximum radius (FWHM) of the highest peak (rad), and θ is the bragg angle of the highest peak.
With reference to FIG. 1, the particle size obtained from the XRD data was 18.14nm, and the parameters of the lattice parameter thus calculated by least squares fitting were
The yttrium-doped bismuth oxide particles obtained in example 1 were observed by means of a scanning electron microscope (sem), and sem images at different magnifications were obtained: fig. 2a, 2 b.
In conjunction with FIGS. 1, 2a and 2b, it can be seen that when the ionic radius is small
Y of (A) is3+The radius of the substituted ion is larger
Of Bi3+In time, the size of a unit cell may be reduced. After a sintering time of 2h, except for a small amount of free Y2O3Almost all α -Bi still can be identified on the XRD pattern2O3Has been completely converted into-Bi2O3。
Dispersed elemental analysis x-ray analysis (EDAX) was used to analyze the yttrium-doped bismuth oxide particles obtained in example 3, yielding figure 3.
As can be seen from fig. 2a and 2b, the yttrium-doped bismuth oxide particles are a continuous, homogeneous material without voids. In connection with fig. 3, the elements in the yttrium-doped bismuth oxide particles are confirmed.
The yttrium-doped bismuth oxide particles from example 3 were dispersed in acetone and placed on a carbon-coated TEM copper grid and then observed using a scanning electron microscope (sem), yielding figure 4.
As can be seen from fig. 4, the yttrium-doped bismuth oxide particles prepared in example 3 are spherical, and the particle size of the yttrium-doped bismuth oxide particles is less than 40nm, which is better in conformity with the XRD result.
Test example 2
Impedance spectra of the yttrium-doped bismuth oxide particles obtained in example 1 were recorded at temperatures of 300 ℃, 500 ℃ and 600 ℃, and experimental impedance data at the given temperatures are presented in the form of Nyquist plots for the nanopowders at the temperatures indicated above, as shown in fig. 5.
The observed complex impedance plot can be modeled with an equivalent circuit as shown in fig. 6.
Referring to fig. 5, a partially resolved half-arc was observed between 1MHz and 100Hz, the half-arc in the high frequency region being due to the parallel combination of bulk resistance (Rg) and bulk capacitance (Cg), representing the grain response of the yttrium-doped bismuth oxide particles, and the low frequency arc likely being due to the electrode response.
The conductivity (log σ) of the yttrium-doped bismuth oxide particles is plotted against the reciprocation temperature (1000/T) in FIG. 7 and Table 1 below.
Table 1: conductivity and activation energy at different temperatures
And after least square fitting is carried out on the impedance data, obtaining the resistance related to the high and medium frequency arcs according to a formula: and (2) deducing the conductivities of the constitutional region and the crystal boundary region according to the geometric shape of the sample.
Where L is the sample thickness and A is its cross-sectional area.
The temperature dependence of the conductivity can be expressed by the Arrhenius equation.
σ＝σ0exp(-Ea/KT) (3)
Where σ 0 is a pre-exponential constant, Ea is the activation energy of ion migration (eV), K is the Boltzmann constant, and T is the temperature (K). According to the above relationship, the activation energy can be calculated by giving the slope Ea/k of a straight line to the graph of the logarithm of σ 1000/T.
The ionic conductivity is calculated by using the value at which the imaginary part (Z "") of the real part (Z ") of the impedance is minimum.
Referring to fig. 7 and table 1, the ion conductivity, which is caused by the oxygen ion hopping from lattice site to lattice site under the influence of the electric field, increases with increasing temperature.
The decrease in the fitted semi-circle diameter indicates that the bulk resistance decreases with increasing temperature. It was found that the ionic conductivity increased with increasing temperature. Conductivity change at 500 ℃ and Bi doped with various lanthanides2O3The conductivity change at the same temperature is similar, especially at low dopant concentrations. However, the graph of the internal conductivity of the crystal grain as a function of the reciprocating temperature shows two cases of bismuth-based oxides which are generally observed, in which a step-order transition is involved. This transformation appears to affect O as a charge carrier2-The ordering of the ions.
In conclusion, the homogeneous doped bismuth oxide nanoparticles are prepared by a sol-gel method. A single phase obtained at a temperature lower than that of the conventional solid state process. The grain diameter of the doped bismuth oxide nano-particles is less than 40nm, and the doped bismuth oxide nano-particles have equiaxial morphology and better mechanical properties, such as high fracture toughness and high ion conductivity.
At a lower sintering temperature, Bi is found2O3The phases act as wetting agents for the grain boundaries. Due to this behavior, most of Bi2O3Isolated at the grain boundaries, and no camber lines were observed in connection with the grain boundary reaction.
Test example 3
Electrochemical characteristics and degradation behavior of the composite materials prepared in example 8, example 9, example 10 and comparative example 1 as catalysts were measured by VersaSTAT3 cyclic voltammetry to obtain fig. 8, fig. 9, fig. 10 and fig. 11.
The electrochemical characterization of the composite material for electrochemical characteristic determination is carried out at room temperature, the working electrode is a Glassy Carbon (GC) disk, the reference electrode is Ag/AgCl, the counter electrode is a platinum wire, and the electrolyte is 0.1M HClO4。
Catalyst powder was as follows (30. mu.g Pt cm)-2At 0.196cm2Upper) 80 μ L calculated amount of deionized water.
800 μ L of isopropanol (analytical grade, 99.7% by weight of the national drug control) and 20 μ L of Nafion (DuPont 5 wt%) solution were sequentially added to a sample tube, and the sample was placed in an ultrasonic cell under ice-cold conditions for 20min to obtain a uniformly dispersed catalyst ink. The amount of platinum on a 5mm GC working electrode per diameter was adjusted to 28. mu.g Pt cm-2And dried in air overnight. Before the experiment, nitric acid gas was fed for 30 minutes to purge dissolved oxygen in the electrolyte. The working electrode was then immersed in the electrolyte for 30 minutes at 50mVs between-0.28 and 0.92V-1The scanning rate of (2) to obtain CV data.
ECSA for 4 different catalysts can be calculated from figures 8, 9, 10, 11. As can be seen from FIG. 12, the ECSA loss is the smallest for sample YB/Pt/C700, higher for sample YB/Pt/C500 and sample YB/Pt/C300, and the largest for Pt/C.
ECSA＝QH/0.21LPt
Wherein L isPtThe mass loading of platinum (28. mu.g/cm in this test example), Q (mC cm)-2) Is the coulombic charge of the hydrogen dehydrogenation.
Next, the electrochemical surface area (ECSA) of the composite material was measured to obtain fig. 12.
Referring to fig. 8 to 12, it can be seen that the current density and the potential of the battery are maintained in a better state when the composite materials prepared in examples 8, 9 and 10 are used as catalysts, and the electrochemical surface area of the YB composite materials prepared in examples 8, 9 and 10 is significantly higher than that of the composite material prepared in comparative example 1.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the claims. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A preparation method of doped bismuth oxide particles is characterized by comprising the following steps:
according to the molar ratio of Bi to A of 5: 1-2, dissolving soluble bismuth salt and soluble A salt in an acidic liquid with the pH value of 1-6 to obtain a mixed solution, wherein A is a rare earth element, and the total molar concentration of Bi and A in the mixed solution is 0.05-0.3 mol/L;
stirring the mixed solution until the mixed solution forms sol, then heating to convert the sol into gel, and drying the gel to obtain a precursor; and
and sintering the precursor at the temperature of 300-800 ℃ to obtain the required doped bismuth oxide particles.
2. The method for preparing doped bismuth oxide particles according to claim 1, wherein the molar ratio of Bi to A in the mixed solution is 3: 1, the total molar concentration of Bi and A is 0.1 mol/L.
3. The method of claim 1, wherein the rare earth element is Y.
4. The method of preparing doped bismuth oxide particles of claim 1 wherein the soluble bismuth salt and the soluble A salt are both nitrates and the acidic liquid is a nitric acid solution;
the mixed solution also comprises a surfactant.
5. The method of claim 1, further comprising pressing the precursor into disk-shaped particles at a pressure of 50 mpa to 200 mpa after drying the gel to obtain the precursor and before sintering the precursor at a temperature of 300 ℃ to 800 ℃.
6. The method for preparing doped bismuth oxide particles according to claim 1, wherein the heating is performed at 75-100 ℃ to convert the sol into gel, and the drying is performed at 140-200 ℃ to obtain the precursor.
7. The method of claim 6, wherein the heating temperature is 90 ℃ and the drying temperature is 160 ℃;
and in the operation of sintering the precursor at the temperature of 300-800 ℃, the sintering temperature is 500 ℃ or 650 ℃.
8. A doped bismuth oxide composite material is characterized by comprising 10 parts by mass of Pt, 60-80 parts by mass of carbon material and 10-30 parts by mass of doped bismuth oxide particles prepared by the preparation method of the doped bismuth oxide particles according to any one of claims 1-7.
9. A method for preparing a doped bismuth oxide composite material according to claim 8, comprising the steps of:
doped bismuth oxide particles produced by the process according to any one of claims 1 to 7;
dispersing soluble platinum salt, a carbon material and the doped bismuth oxide particles in alcohol to obtain a mixed liquid, wherein the mass ratio of Pt to the carbon material to the doped bismuth oxide particles is 10: 60-80: 10-30; and
and mixing a reducing agent with the mixed liquid, and fully reacting to obtain the doped bismuth oxide composite material.
10. The method of claim 9, wherein the soluble platinum salt is H2PtCl6；
The carbon material is selected from at least one of carbon black, carbon fiber, mesocarbon microbeads, natural graphite, glassy carbon, activated carbon, highly-oriented graphite, carbon black, diamond, carbon nanotubes, fullerene and graphene;
the alcohol is methanol, ethanol, propanol or butanol.
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