CN117737786A - Titanium dioxide supported noble metal oxide catalyst and preparation method and application thereof - Google Patents
Titanium dioxide supported noble metal oxide catalyst and preparation method and application thereof Download PDFInfo
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- CN117737786A CN117737786A CN202311618162.7A CN202311618162A CN117737786A CN 117737786 A CN117737786 A CN 117737786A CN 202311618162 A CN202311618162 A CN 202311618162A CN 117737786 A CN117737786 A CN 117737786A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 73
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 43
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- QVCCUCPJAKTFEW-UHFFFAOYSA-N chloric acid gold Chemical compound Cl(=O)(=O)O.[Au] QVCCUCPJAKTFEW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 9
- 229910000457 iridium oxide Inorganic materials 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000009881 electrostatic interaction Effects 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCPPEWQMHAHLGQ-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].C(C)(C)O Chemical compound [O-2].[O-2].[Ti+4].C(C)(C)O HCPPEWQMHAHLGQ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- JKXCZYCVHPKTPK-UHFFFAOYSA-N hydrate;trihydrochloride Chemical compound O.Cl.Cl.Cl JKXCZYCVHPKTPK-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- -1 iridium chloride isopropanol Chemical compound 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 238000013379 physicochemical characterization Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to a titanium dioxide supported noble metal oxide catalyst, and a preparation method and application thereof. With nano titanium dioxide (TiO) 2 ) The method is characterized in that carbon residue coated nano titanium dioxide nano particles with high conductivity are prepared by a carbothermal reduction method as precursors, then, the nano particles are used as carriers, and noble metal oxide nano particles are highly dispersed on the surfaces of the titanium dioxide carriers by an Adam melting method, so that the noble metal oxide catalyst loaded by titanium dioxide is prepared. The catalyst prepared by the invention can be applied to a proton exchange membrane electrolyzed water (PEMWE) anode catalytic layer, can improve the utilization rate of noble metal in the anode catalytic layer and the electrochemical stability thereof, reduces the PEMWE cost and improves the electrochemical stabilityHigh PEMWE lifetime.
Description
Technical Field
The invention belongs to the technical field of water electrolysis, and particularly relates to a titanium dioxide supported noble metal oxide catalyst and a preparation method and application thereof.
Background
The electrolysis of water is a technology for converting electric energy into hydrogen and oxygen, and has wide application prospect in the field of renewable energy hydrogen production. Compared with the traditional Alkaline Water Electrolyzer (AWE), the proton exchange membrane electrolyzed water (PEMWE) system has obvious advantages in the aspects of hydrogen production efficiency, response speed, hydrogen purity and the like. However, PEMWE membrane electrode anodes still depend on noble metals such as iridium, ruthenium and the like and oxides thereof, and the noble metals are used in large amounts (generally 1.5-3mg cm -2 ) Limiting commercial applications of PEMWE. Therefore, there is an urgent need to develop high-utilization noble metal electrocatalytic materials to reduce noble metal usage and cost.
At present, aiming at the development of a noble metal catalyst with high utilization rate, the adoption of a transition metal oxide as a carrier for loading a noble metal active substance is an effective method for reducing the consumption of noble metal. However, most of transition metal oxides are wide bandgap semiconductors, which have poor electron conductivity and are unfavorable for electron transfer during electrocatalytic reaction, resulting in poor electrocatalytic performance. In view of the problem, the present invention proposes to use a highly conductive acid-resistant titanium suboxide-supported catalyst on which noble metal oxide nanoparticles are highly dispersed, which exhibits excellent activity and stability in acid oxygen precipitation reactions.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst carrier titanium dioxide with high conductivity and acid resistance, which is prepared by carbothermic reduction reaction. In the preparation process of the carrier, the carbon residue covers the surface of the high-conductivity carrier in a coating mode, and the existence of the carbon residue can promote the dispersion of the noble metal precursor on the carrier through electrostatic attraction, so that the dispersion of noble metal oxide nano particles on the carrier is facilitated, and the carbon residue can be oxidized and exhausted in the subsequent Adam melting high-temperature treatment process, so that the corrosion of a carbon material under the high potential of a PEMWE anode is avoided; titanium suboxide may additionally provide sufficient electrical conductivity and resistance to electrochemical corrosion.
In addition, the invention provides a catalyst comprising the high-conductivity catalyst carrier, a preparation method and application thereof, and the high-conductivity titanium dioxide carrier loaded noble metal oxide catalyst can remarkably reduce the noble metal dosage in the current polymer water electrolysis tank, improve the noble metal utilization rate in PEMWE and achieve the aim of reducing the cost of the PEMWE membrane electrode.
The invention also provides a titanium dioxide supported noble metal oxide catalyst, which consists of titanium dioxide carrier nano particles subjected to carbothermal reduction and noble metal oxide nano particles supported on the surface of the titanium dioxide carrier nano particles, wherein the mass of the noble metal oxide is 5-30% of the mass of the titanium dioxide carrier. According to the invention, the high-activity noble metal active nano particles are loaded on the surface of the high-conductivity titanium dioxide carrier, so that the purposes of improving the noble metal utilization rate and improving the catalyst activity are achieved.
The invention adopts the following technical scheme: the titanium dioxide loaded noble metal oxide catalyst has noble metal oxide nanometer particle capable of being dispersed on the surface of carrier, and the average noble metal particle size is 1.2-2.2nm.
In a preferred embodiment of the invention, the support is carbon residue coated titanium suboxide. The presence of carbon residue changes the charged state of the titanium suboxide surface, so that the carrier surface is positively charged, and electrostatic interaction can be utilized to promote the dispersion of the noble metal precursor on the carrier. The titanium dioxide has high conductivity, has strong electron interaction with noble metal oxide, realizes uniform dispersion of the noble metal oxide on the surface of the carrier, has higher conductivity, and realizes low-load and high-dispersion load of the noble metal oxide.
In a preferred embodiment of the present invention, the carbon residue coated titanium suboxide is in the form of nano TiO 2 Is a precursor and is prepared by a carbothermal reduction method; the average grain diameter of the carbon residue coated nano titanium dioxide is about 200-500nm, and the conductivity is 500-1500S cm -1 The titanium dioxide supported noble metal oxide catalyst, nobleThe metal oxide loading is 5 to 30wt%.
In a preferred embodiment of the present invention, the method for preparing carbon residue coated titanium suboxide is specifically as follows:
(1) TiO is mixed with 2 Ultrasonic dispersing in hydrochloric acid-Tris buffer solution and stirring;
(2) According to carbon source and TiO 2 Weighing a carbon source according to the mass ratio of 1:4-2:1, slowly adding the carbon source into the solution prepared in the step (1), stirring for 12-48h, washing with absolute ethyl alcohol, filtering, and drying to obtain TiO 2 A mixture with a carbon source;
(3) TiO obtained in the above (2) 2 And annealing the mixture with a carbon source for a period of time at a certain temperature to obtain carbon residue coated titanium dioxide nano particles.
The invention adopts Adam fusion method to disperse noble metal oxide nano particles on the surface of nano titanium dioxide, and high temperature heat treatment enables residual carbon to be oxidized and decomposed, thus avoiding carbon corrosion of the catalyst under the condition of high potential of PEMWE anode.
In a preferred embodiment of the present invention, in step (1), the pH of the hydrochloric acid-Tris buffer is 8.5, tiO 2 The mass concentration of the dispersion liquid is 3-9mg ml -1 The stirring time is 0.5-2h.
In a preferred embodiment of the present invention, in step (2), the carbon source is selected from at least one of glucose, polyvinyl alcohol, carbon black, dopamine hydrochloride; the drying temperature was 80 ℃.
In a preferred embodiment of the present invention, in step (3), the annealing treatment is performed in a protective atmosphere, the annealing temperature is 700-1050 ℃, and the heat treatment time is 0.25-8 hours; preferably, the protective atmosphere is nitrogen or argon; preferably, the annealing temperature is 850-1000 ℃, maintained for 3-6 hours, and then cooled.
In a preferred embodiment of the present invention, the method for preparing the titanium suboxide-supported noble metal oxide catalyst comprises the steps of:
(4) Dispersing titanium dioxide nano particles coated by carbon residue in isopropanol, and uniformly stirring and mixing;
(5) Weighing noble metal precursors, dispersing the noble metal precursors in isopropanol, and uniformly stirring and mixing the noble metal precursors;
(6) Slowly adding the mixed solution obtained in the step (5) into the solution obtained in the step (4), and then stirring and mixing uniformly;
(7) Adding the ground sodium nitrate into the solution obtained in the step (6), and uniformly stirring and mixing;
(8) Evaporating the solution obtained in the step (7) to dryness to obtain isopropanol, grinding, performing heat treatment in air at 200-550 ℃ for 0.5-5h, and then cooling.
In a preferred embodiment of the present invention, in step (5), the noble metal precursor is selected from one or a combination of several of noble metal elements iridium, ruthenium, platinum, palladium, rhodium, silver, gold chloric acid, acetic acid or acetylacetonate complex; the noble metal oxide loading is 5 to 30wt%.
In a preferred embodiment of the present invention, the method of stirring and mixing in steps (4) - (7) specifically comprises one or more of stirring, ultrasound and shaking, or recycling of the multiple modes, each mode having a duration in the range of 0.5-3 hours;
in a preferred embodiment of the invention, in step (7), the mass ratio of sodium nitrate to noble metal precursor is from 30:1 to 60:1.
The invention also protects the application of the titanium dioxide supported noble metal oxide catalyst in PEMWE membrane electrodes.
Compared with the prior art, the invention uses nano titanium dioxide (TiO 2 ) The method is characterized in that carbon residue coated nano titanium dioxide nano particles with high conductivity are prepared by a carbothermal reduction method as precursors, then, the nano particles are used as carriers, and noble metal oxide nano particles are highly dispersed on the surfaces of the titanium dioxide carriers by an Adam melting method, so that the noble metal oxide catalyst loaded by titanium dioxide is prepared. The catalyst prepared by the invention can be applied to a proton exchange membrane electrolyzed water (PEMWE) anode catalytic layer, can improve the utilization rate of noble metal in the anode catalytic layer and the electrochemical stability thereof, reduce the PEMWE cost and prolong the service life of the PEMWE.
In addition, carbon residue existing after carbothermal reduction reaction can change the charge on the surface of titanium dioxide, promote electrostatic interaction with noble metal precursor, thereby realizing uniform dispersion of precursor and being beneficial to uniform dispersion of noble metal oxide on the carrier.
The preparation method of the titanium dioxide supported noble metal oxide catalyst provided by the invention has the advantages of strong controllability, simple preparation process and low raw material cost, and is beneficial to large-scale commercial use.
The noble metal content in the existing polymer electrolyzed water anode catalytic layer is generally higher, the total noble metal content in the membrane electrode can be reduced by more than 70% by adopting the high-conductivity catalyst carrier provided by the invention, the performance is not reduced, and the cost of the membrane electrode can be obviously reduced.
The titanium dioxide carrier prepared by the invention has strong electrochemical corrosion resistance and strong metal anchoring sites, and is beneficial to improving the electrocatalytic stability of the noble metal oxide catalyst.
Drawings
Further description is provided below with reference to the accompanying drawings.
FIG. 1 is an X-ray diffraction pattern of titanium dioxide in example 1.
FIGS. 2-4 are electrochemical performance of the titanium suboxide-supported noble metal oxide catalysts of examples 1-3.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
Example 1:
300mg of nano titanium dioxide is ultrasonically dissolved in 50ml of hydrochloric acid-Tris buffer (pH=8.5) and stirred for 0.5h; 150mg of dopamine hydrochloride was slowly added to the above solution and stirred for 24h. Washing with absolute ethanol, suction filtering, and oven drying at 80deg.C to obtain polydopamine coated TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Polydopamine coated TiO 2 In a tube furnace N 2 Heat treatment is carried out for 5 hours at the temperature of 950 ℃ to obtain titanium dioxide nano-particles; subsequently, 67.2mg of titanium suboxide was dispersed in 10ml of isopropanol and stirred for 1h; at the same time 35.2mgIridium trichloride hydrate is dispersed in 5ml of isopropanol and stirred for 1h; slowly adding the iridium chloride isopropanol solution into the titanium dioxide isopropanol dispersion solution to obtain a solution, and then stirring for 1h; then adding 1.5g of ground sodium nitrate, stirring for 1h, evaporating isopropanol at 80 ℃, grinding, and performing heat treatment for 3h in air at 300 ℃ to obtain a titanium dioxide supported iridium oxide catalyst;
the catalyst of example 1 was subjected to a three-electrode test in which the working electrode was a gold disk electrode and the total amount of catalyst supported on the electrode was 0.8mg cm (electrolyte was 0.5M sulfuric acid) -2 The OER activity of the catalyst exceeded the performance of unsupported iridium oxide (@ 1.53V) as shown in FIG. 2 at 10mAcm -2 The overpotential at the current density of 244mV and 250mV, respectively, effectively reduced the 70wt% Ir usage.
The titanium dioxide loaded iridium oxide catalyst is subjected to physicochemical characterization. FIG. 1 shows characteristic diffraction peaks of titanium suboxide. FIG. 2 is a graph of linear voltammetric scans for the supported oxygen evolution catalyst and the unsupported iridium oxide catalyst prepared in example 1. As can be seen from FIG. 2, the potentials required for the electrode catalytic reaction are different at different current densities, when the current density is 10mA cm -2 When the overpotential of the titanium oxide-supported iridium oxide catalyst prepared in example 1 is lower than that of unsupported IrO 2 . While relative to unsupported IrO 2 The mass activity of the titanium dioxide supported iridium oxide catalyst at 1.53V is improved by about 8.5 times.
Example 2
The operating conditions were the same as in example 1, except that the heat treatment temperature in air was 350 ℃. The titanium dioxide-supported iridium oxide catalyst prepared in example 2 has an overpotential lower than that of unsupported IrO 2 . While relative to unsupported IrO 2 The mass activity of the titanium dioxide supported iridium oxide catalyst at 1.53V was improved by about 7.5 times (fig. 3).
Example 3
The operating conditions were the same as in example 1, except that the noble metal oxide was IrRuO supported 2 And the heat treatment temperature in the air was 350 ℃. The supported catalyst prepared in example 3 had an overpotential lower than that of unsupported IrO 2 . While relative to unsupported IrO 2 The mass activity of the titanium dioxide supported iridium oxide catalyst at 1.53V was improved by about 6 times (fig. 4).
While the invention has been described above with reference to exemplary embodiments, it will be apparent that the invention is not limited by the foregoing aspects, but rather is intended to cover various modifications and adaptations of the invention without departing from its spirit and scope.
Claims (9)
1. The titanium dioxide supported noble metal oxide catalyst is characterized in that the noble metal oxide nano particles can be highly dispersed on the surface of a carrier, and the average particle size of the noble metal oxide nano particles is 1.2-2.2nm.
2. The supported noble metal oxide catalyst of claim 1, wherein the support is carbon residue coated titanium oxide.
3. The supported noble metal oxide catalyst of claim 2, wherein said carbon residue coated titanium oxide is a nano-TiO 2 Is a precursor and is prepared by a carbothermal reduction method; the average grain diameter of the carbon residue coated nano titanium dioxide is about 200-500nm, and the conductivity is 500-1500S cm -1 The titanium dioxide carries a noble metal oxide catalyst, and the noble metal oxide loading is 5-30wt%.
4. The titanium suboxide-supported noble metal oxide catalyst of claim 3, wherein said carbon residue coated titanium suboxide preparation method is specifically as follows:
(1) TiO is mixed with 2 Ultrasonic dispersing in hydrochloric acid-Tris buffer solution and stirring;
(2) According to carbon source and TiO 2 Weighing a carbon source according to the mass ratio of 1:4-2:1, and slowly adding the carbon source into the mixture prepared in the step (1)Stirring the solution for 12 to 48 hours, washing with absolute ethyl alcohol, filtering and drying to obtain TiO 2 A mixture with a carbon source;
(3) TiO obtained in the above (2) 2 And annealing the mixture with a carbon source for a period of time at a certain temperature to obtain carbon residue coated titanium dioxide nano particles.
5. The supported noble metal oxide catalyst of claim 4, wherein in step (1), the pH of the hydrochloric acid-Tris buffer is 8.5, tiO 2 The mass concentration of the dispersion liquid is 3-9mg ml -1 Stirring for 0.5-2h; in the step (2), the carbon source is at least one selected from glucose, polyvinyl alcohol, carbon black and dopamine hydrochloride; the drying temperature was 80 ℃.
6. The titanium suboxide-supported noble metal oxide catalyst of claim 4, wherein in step (3), the annealing treatment is performed in a protective atmosphere, the annealing temperature is 700-1050 ℃, and the heat treatment time is 0.25-8 hours; preferably, the protective atmosphere is nitrogen or argon; preferably, the annealing temperature is 850-1000 ℃, kept for 3-6 hours, and then cooled.
7. The method for producing a titanium suboxide-supported noble metal oxide catalyst according to any one of claims 1 to 6, comprising the steps of:
(4) Dispersing titanium dioxide nano particles coated by carbon residue in isopropanol, and uniformly stirring and mixing;
(5) Weighing noble metal precursors, dispersing the noble metal precursors in isopropanol, and uniformly stirring and mixing the noble metal precursors;
(6) Slowly adding the mixed solution obtained in the step (5) into the solution obtained in the step (4), and then stirring and mixing uniformly;
(7) Adding the ground sodium nitrate into the solution obtained in the step (6), and uniformly stirring and mixing;
(8) Evaporating the solution obtained in the step (7) to dryness to obtain isopropanol, grinding, performing heat treatment in air at 200-550 ℃ for 0.5-5h, and then cooling.
8. The method according to claim 7, wherein in the step (5), the noble metal precursor is selected from one or a combination of several of noble metal elements iridium, ruthenium, platinum, palladium, rhodium, silver, gold chloric acid, chlorate, acetate or acetylacetone complex; the noble metal oxide loading is 5-30wt%;
preferably, the stirring and mixing method in the steps (4) - (7) specifically comprises one or more modes of stirring, ultrasonic and vibration, or recycling of the modes, wherein the duration of each mode is in the range of 0.5-3h;
preferably, in the step (7), the mass ratio of the sodium nitrate to the noble metal precursor is 30:1-60:1.
9. Use of the titanium suboxide-supported noble metal oxide catalyst according to claims 1-6 or prepared by the preparation method according to any one of claims 7-8 in PEMWE membrane electrodes.
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