CN109453771A - The preparation of a kind of pyrochlore materials and its application in electro-catalysis production oxygen - Google Patents
The preparation of a kind of pyrochlore materials and its application in electro-catalysis production oxygen Download PDFInfo
- Publication number
- CN109453771A CN109453771A CN201811346102.3A CN201811346102A CN109453771A CN 109453771 A CN109453771 A CN 109453771A CN 201811346102 A CN201811346102 A CN 201811346102A CN 109453771 A CN109453771 A CN 109453771A
- Authority
- CN
- China
- Prior art keywords
- pyrochlore materials
- pyrochlore
- materials
- preparation
- evaporated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 107
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000001301 oxygen Substances 0.000 title claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000004321 preservation Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 11
- -1 nitrate compound Chemical class 0.000 claims abstract description 9
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 238000010792 warming Methods 0.000 claims description 16
- 238000002791 soaking Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 239000011943 nanocatalyst Substances 0.000 abstract 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229910052741 iridium Inorganic materials 0.000 description 7
- 229910000457 iridium oxide Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 5
- 238000009210 therapy by ultrasound 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
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical class [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—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
- B01J23/63—Platinum group metals with rare earths or actinides
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
-
- 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
- C25B11/095—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 of the compounds being organic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a kind of pyrochlore materials, structural formula R2Ir2O7, any in R Ho, Tb, Gd, Nd, Pr.The invention also discloses the preparation methods of above-mentioned pyrochlore materials, comprising: is uniformly mixed iridic chloride, the nitrate compound of R, Citric Acid Mono and deionized water, is then evaporated；S1 is evaporated rear material and is placed in the aqueous precursor gel that heating is expanded in baking oven；Under air conditions, aqueous precursor gel is once heated up, primary to keep the temperature, cooling, then secondary temperature elevation, secondary heat preservation, washing obtain pyrochlore materials.The invention also discloses above-mentioned pyrochlore materials to produce the application in oxygen reaction as catalyst in acid electro-catalysis.The present invention changes the type of presoma, regulates and controls nanocatalyst by R atoms, the activity and stability of oxygen are produced with good electro-catalysis, have very big application prospect.
Description
Technical field
The present invention relates to catalyst technical field, more particularly to a kind of pyrochlore materials preparation and its produce oxygen in electro-catalysis
In application.
Background technique
Electrochemical decomposition water hydrogen manufacturing is a kind of chemical industry means of important alleviating energy crisis, it is reacted by the production oxygen of anode
It is formed with the evolving hydrogen reaction of cathode, is a kind of sustainable, environmentally friendly renewable energy compensation process, has been widely studied.Analysis
Hydrogen reaction is a two-electron shift process, and produces the dynamic process that oxygen reaction is the transfer of four proton coupling electric charges, therefore produce
Oxygen is the dynamics decision process of electrolysis water reaction, is the key factor of current limitation electrolysis water process industryization development.In electricity
In terms of the hydrogen manufacturing of chemical breakdown water, acidic proton exchange membrane (PEM) electrolytic cell has low ohmic losses, height relative to alkaline electrolytic bath
The advantages that voltage efficiency, high gas purity.
At present, it is considered that iridium base and ruthenium-based catalyst are the optimum catalysts that electro-catalysis produces oxygen under acid condition, and
It can be stabilized in acid condition.But the amount of storage of iridium, ruthenium noble metal is rare, and at high cost and intrinsic reactivity is low, therefore, exploitation
It is very attractive and using valence that content containing iridium metals is less, the higher catalyst of latent active produces oxygen for acidic catalyst
Value.
In recent years, in order to reduce iridium content, many effort, which are concentrated mainly on, is distributed to iridium oxide on conductive high surface
It is storaged on body or adulterates on base metal.By adulterating the transition metal such as nickel, cobalt, copper in yttrium oxide, surface-active is improved
High activity is developed in area, active surface hydroxyl coverage rate height and d- track occupy-place, the acidic catalyst of high stability produces oxygen material
Material.In addition it is developed there are also a kind of up-and-coming strategy, not only can be reduced the use of iridium, but also its intrinsic activity can be promoted,
Here it is the complicated iridium oxides of synthesis to be found to have such as iridium acid oxidase object, perovskite and pyrochlore compounds better than standard
IrO2The activity of catalyst.Although compound iridium oxide achieves many progress, for its potential mechanism, especially it is urged
Change the potentially relevant property between activity and electronic structure, still lack basic insight, this sets for the following efficient elctro-catalyst
It counts most important.As the strong correlation electronic system of a kind of typical 5d iridium oxide, pyrochlore iridium oxide R2Ir2O7Electricity
Lotus, spin, track and lattice freedom degree intercouple, and induce a charming schematic phase diagram.In addition, it is big to change R ionic radius
The small 5d electron correlation that can modify Ir in iridium oxide, this may provide a good platform to explore catalytic activity pair
The dependence of electronic structure.
Summary of the invention
Technical problems based on background technology are urged the invention proposes the preparation of a kind of pyrochlore materials and its in electricity
Change the application produced in oxygen, its electronic structure is regulated and controled by different R atoms, producing it in oxygen reaction in acid electro-catalysis has height
Activity and high stability, and the content of noble metal is greatly reduced by forming iridium oxide, to play it in electro-catalysis
Produce the potential advantages promoted and applied on a large scale in oxygen reaction.
One kind pyrochlore materials proposed by the present invention, structural formula R2Ir2O7, any in R Ho, Tb, Gd, Nd, Pr
Kind.
By controlling the atomic ratio of R atom and Ir atom as 1:1 in the present invention, it is used as and urges in acid electro-catalysis production oxygen reaction
Agent, atomic ratio does not change after catalysis reaction, stable in catalytic performance.
The preparation method of above-mentioned pyrochlore materials proposed by the present invention, includes the following steps:
S1, iridic chloride, the nitrate compound of R, Citric Acid Mono and water are uniformly mixed, are then evaporated；
S2, it S1 is evaporated to rear material is placed in the aqueous precursor gel that heating is expanded in baking oven；
Under S3, air conditions, aqueous precursor gel is once warming up to 380-420 DEG C, is kept the temperature, is cooled down, then secondary temperature elevation
To 850-950 DEG C, heat preservation, washing obtains pyrochlore materials.
Preferably, in S1, evaporated temperature is 75-85 DEG C.
Preferably, in S2, oven temperature is 115-125 DEG C.
Preferably, in S3, the speed once to heat up is 4.5-5.5 DEG C/min, and a soaking time is 3-5h.
Preferably, in S3, cooling method is that nature is down to room temperature.
Preferably, in S3, the speed of secondary temperature elevation is 4.5-5.5 DEG C/min, and secondary soaking time is 22-26h.
Preferably, it in S3, is washed using deionized water.
Above-mentioned pyrochlore materials proposed by the present invention produce the application in oxygen reaction as catalyst in acid electro-catalysis.
The present invention synthesizes pyrochlore materials material R by the simple sol-gal process of a step2Ir2O7, by adjusting presoma
Feed intake to change the type of R, realize under the conditions of 0.1mol/L perchloric acid, with good electro-catalysis produce oxygen activity and
Stability；This oxide structure both reduces noble metal, to reduce the cost of catalyst, and can be adjusted by R atom
Acid electro-catalysis produces oxygen performance, the dependence for providing a good platform to explore catalytic activity to electronic structure.
Detailed description of the invention
Fig. 1 is 6 gained pyrochlore materials Ho of the embodiment of the present invention2Ir2O7, 7 gained pyrochlore materials Tb of embodiment2Ir2O7、
8 gained pyrochlore materials Gd of embodiment2Ir2O7, 9 gained pyrochlore materials Nd of embodiment2Ir2O7, 10 gained pyrochlore of embodiment
Material Pr2Ir2O7Scanning electron microscope as map.
Fig. 2 is 6 gained pyrochlore materials Ho of the embodiment of the present invention2Ir2O7, 7 gained pyrochlore materials Tb of embodiment2Ir2O7、
8 gained pyrochlore materials Gd of embodiment2Ir2O7, 9 gained pyrochlore materials Nd of embodiment2Ir2O7, 10 gained pyrochlore of embodiment
Material Pr2Ir2O7X-ray electronic diffraction map.
Fig. 3 is 6 gained pyrochlore materials Ho of the embodiment of the present invention2Ir2O7, 7 gained pyrochlore materials Tb of embodiment2Ir2O7、
8 gained pyrochlore materials Gd of embodiment2Ir2O7, 9 gained pyrochlore materials Nd of embodiment2Ir2O7, 10 gained pyrochlore of embodiment
Material Pr2Ir2O7With commercial IrO2LSV curve.
Fig. 4 is 6 gained pyrochlore materials Ho of the embodiment of the present invention2Ir2O7, 7 gained pyrochlore materials Tb of embodiment2Ir2O7、
8 gained pyrochlore materials Gd of embodiment2Ir2O7, 9 gained pyrochlore materials Nd of embodiment2Ir2O7, 10 gained pyrochlore of embodiment
Material Pr2Ir2O7With commercial IrO2Stability curve.
Fig. 5 is that pyrochlore materials obtained by 1-10 of the embodiment of the present invention produce in oxygen reaction in acid electro-catalysis as catalyst
It is catalyzed schematic diagram.
Specific embodiment
In the following, technical solution of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of pyrochlore materials, structural formula R2Ir2O7, any sort in R Ho, Tb, Gd, Nd, Pr.
Embodiment 2
The preparation method of a kind of pyrochlore materials, includes the following steps:
S1, iridic chloride, the nitrate compound of Ho, Citric Acid Mono and water are uniformly mixed, are then evaporated；
S2, it S1 is evaporated to rear material is placed in the aqueous precursor gel that heating is expanded in baking oven；
Under S3, air conditions, aqueous precursor gel is once warming up to 382 DEG C, is kept the temperature, is cooled down, then secondary temperature elevation to 948
DEG C, heat preservation, washing obtains pyrochlore materials.
Embodiment 3
The preparation method of a kind of pyrochlore materials, includes the following steps:
S1, iridic chloride, the nitrate compound of Tb, Citric Acid Mono and deionized water are uniformly mixed, are then evaporated, steamed
Dry temperature is 76 DEG C；
S2, it S1 is evaporated to rear material is placed in the aqueous precursor gel that heating is expanded in baking oven, oven temperature is 123 DEG C；
Under S3, air conditions, aqueous precursor gel is once warming up to 384 DEG C, the speed once to heat up is 5.2 DEG C/min,
3.5h is kept the temperature, is down to room temperature naturally, then for secondary temperature elevation to 940 DEG C, the speed of secondary temperature elevation is 4.6 DEG C/min, 25h is kept the temperature,
It is washed using deionized water, obtains pyrochlore materials.
Embodiment 4
The preparation method of a kind of pyrochlore materials, includes the following steps:
S1, iridic chloride, the nitrate compound of Nd, Citric Acid Mono and deionized water are uniformly mixed, are then evaporated, steamed
Dry temperature is 84 DEG C；
S2, it S1 is evaporated to rear material is placed in the aqueous precursor gel that heating is expanded in baking oven, oven temperature is 116 DEG C；
Under S3, air conditions, aqueous precursor gel is once warming up to 415 DEG C, the speed once to heat up is 4.6 DEG C/min,
4.5h is kept the temperature, is down to room temperature naturally, then for secondary temperature elevation to 855 DEG C, the speed of secondary temperature elevation is 5.2 DEG C/min, 23h is kept the temperature,
It is washed using deionized water, obtains pyrochlore materials.
Embodiment 5
The preparation method of a kind of pyrochlore materials, includes the following steps:
S1, iridic chloride, the nitrate compound of Pr, Citric Acid Mono and deionized water are uniformly mixed, are then evaporated, steamed
Dry temperature is 78 DEG C；
S2, it S1 is evaporated to rear material is placed in the aqueous precursor gel that heating is expanded in baking oven, oven temperature is 118 DEG C；
Under S3, air conditions, aqueous precursor gel is once warming up to 390 DEG C, the speed once to heat up is 4.9 DEG C/min,
4h is kept the temperature, is down to room temperature naturally, then for secondary temperature elevation to 870 DEG C, the speed of secondary temperature elevation is 4.9 DEG C/min, keeps the temperature 23h, adopts
It is washed with deionized water, obtains pyrochlore materials.
Embodiment 6
A kind of pyrochlore materials Ho2Ir2O7Preparation method, include the following steps:
S1, by six water holmium nitrate of 458.93mg, 334.03mg iridic chloride, 1.26g Citric Acid Mono and 60mL deionization
Water is uniformly mixed, and ultrasonic treatment 5min forms transparent solution, and then 80 DEG C of heating are evaporated；
S2, it S1 is evaporated rear material is placed in baking oven and be warming up to 120 DEG C, the aqueous precursor gel expanded；
Under S3, air conditions, aqueous precursor gel is once warming up to 400 DEG C, the speed once to heat up be 5 DEG C/min, one
Secondary heat preservation 4h, is down to room temperature naturally, and then for secondary temperature elevation to 900 DEG C, the speed of secondary temperature elevation is 5 DEG C/min, secondary heat preservation
For 24 hours, the pyrochlore materials Ho for being washed with deionized to obtain that partial size is 80-150nm is adopted2Ir2O7。
Embodiment 7
A kind of pyrochlore materials Tb2Ir2O7Preparation method, include the following steps:
S1, by six water terbium nitrate of 453.03mg, 334.03mg iridic chloride, 1.26g Citric Acid Mono and 60mL deionization
Water is uniformly mixed, and ultrasonic treatment 5min forms transparent solution, and then 80 DEG C of heating are evaporated；
S2, it S1 is evaporated rear material is placed in baking oven and be warming up to 120 DEG C, the aqueous precursor gel expanded；
Under S3, air conditions, aqueous precursor gel is once warming up to 400 DEG C, the speed once to heat up be 5 DEG C/min, one
Secondary heat preservation 4h, is down to room temperature naturally, and then for secondary temperature elevation to 900 DEG C, the speed of secondary temperature elevation is 5 DEG C/min, secondary heat preservation
For 24 hours, the pyrochlore materials Tb for being washed with deionized to obtain that partial size is 280-300nm is adopted2Ir2O7。
Embodiment 8
A kind of pyrochlore materials Gd2Ir2O7Preparation method, include the following steps:
S1, by six water gadolinium nitrate of 451.36mg, 334.03mg iridic chloride, 1.26g Citric Acid Mono and 60mL deionization
Water is uniformly mixed, and ultrasonic treatment 5min forms transparent solution, and then 80 DEG C of heating are evaporated；
S2, it S1 is evaporated rear material is placed in baking oven and be warming up to 120 DEG C, the aqueous precursor gel expanded；
Under S3, air conditions, aqueous precursor gel is once warming up to 400 DEG C, the speed once to heat up be 5 DEG C/min, one
Secondary heat preservation 4h, is down to room temperature naturally, and then for secondary temperature elevation to 900 DEG C, the speed of secondary temperature elevation is 5 DEG C/min, secondary heat preservation
For 24 hours, the pyrochlore materials Gd for being washed with deionized to obtain that partial size is 300-350nm is adopted2Ir2O7。
Embodiment 9
A kind of pyrochlore materials Nd2Ir2O7Preparation method, include the following steps:
S1, by six water neodymium nitrate of 438.35mg, 334.03mg iridic chloride, 1.26g Citric Acid Mono and 60mL deionization
Water is uniformly mixed, and ultrasonic treatment 5min forms transparent solution, and then 80 DEG C of heating are evaporated；
S2, it S1 is evaporated rear material is placed in baking oven and be warming up to 120 DEG C, the aqueous precursor gel expanded；
Under S3, air conditions, aqueous precursor gel is once warming up to 400 DEG C, the speed once to heat up be 5 DEG C/min, one
Secondary heat preservation 4h, is down to room temperature naturally, and then for secondary temperature elevation to 900 DEG C, the speed of secondary temperature elevation is 5 DEG C/min, secondary heat preservation
For 24 hours, the pyrochlore materials Nd for being washed with deionized to obtain that partial size is 450-500nm is adopted2Ir2O7。
Embodiment 10
A kind of pyrochlore materials Pr2Ir2O7Preparation method, include the following steps:
S1, by six water praseodymium nitrate of 435.01mg, 334.03mg iridic chloride, 1.26g Citric Acid Mono and 60mL deionization
Water is uniformly mixed, and ultrasonic treatment 5min forms transparent solution, and then 80 DEG C of heating are evaporated；
S2, it S1 is evaporated rear material is placed in baking oven and be warming up to 120 DEG C, the aqueous precursor gel expanded；
Under S3, air conditions, aqueous precursor gel is once warming up to 400 DEG C, the speed once to heat up be 5 DEG C/min, one
Secondary heat preservation 4h, is down to room temperature naturally, and then for secondary temperature elevation to 900 DEG C, the speed of secondary temperature elevation is 5 DEG C/min, secondary heat preservation
For 24 hours, the pyrochlore materials Pr for being washed with deionized to obtain that partial size is 400-500nm is adopted2Ir2O7。
By 6 gained pyrochlore materials Ho of embodiment2Ir2O7, 7 gained pyrochlore materials Tb of embodiment2Ir2O7, 8 institute of embodiment
Obtain pyrochlore materials Gd2Ir2O7, 9 gained pyrochlore materials Nd of embodiment2Ir2O7, 10 gained pyrochlore materials of embodiment
Pr2Ir2O7Electron-microscope scanning is carried out, result is as shown in Figure 1.As shown in Figure 1: present invention gained pyrochlore materials R2Ir2O7Grain
Diameter is 80-500nm.
By 6 gained pyrochlore materials Ho of embodiment2Ir2O7, 7 gained pyrochlore materials Tb of embodiment2Ir2O7, 8 institute of embodiment
Obtain pyrochlore materials Gd2Ir2O7, 9 gained pyrochlore materials Nd of embodiment2Ir2O7, 10 gained pyrochlore materials of embodiment
Pr2Ir2O7X-ray electronic diffraction is carried out, result is as shown in Figure 2.As shown in Figure 2: present invention gained pyrochlore materials R2Ir2O7
It is corresponding with standard card intact at Xiang Junyi.
By 6 gained pyrochlore materials Ho of embodiment2Ir2O7, 7 gained pyrochlore materials Tb of embodiment2Ir2O7, 8 institute of embodiment
Obtain pyrochlore materials Gd2Ir2O7, 9 gained pyrochlore materials Nd of embodiment2Ir2O7, 10 gained pyrochlore materials of embodiment
Pr2Ir2O7Catalysis schematic diagram as catalyst is as shown in figure 5, by Ho2Ir2O7、Tb2Ir2O7、Gd2Ir2O7、Nd2Ir2O7、
Pr2Ir2O7The catalytic performance test that acid electro-catalysis produces oxygen is carried out, specific as follows:
By 1mg present invention gained pyrochlore materials R2Ir2O7It is mixed with 4mg XC-72 active carbon, is added to the second of 0.5mL
In the perfluorinated sulfonic acid mixed solution of alcohol, the water of 0.4mL and 0.03mL, ultrasonic 1h, then take the sample drop of 4 μ L in diameter be 3mm
Glass-carbon electrode on, working electrode is used as after dry, in the HClO of 0.1mol/L4It is measured in solution as electrochemical decomposition
The activity of water catalyst for producing oxygen；Wherein the scanning speed of linear sweep voltammetry be 5mV/s, gained LSV curve as shown in figure 3,
Gained stability curve is as shown in Figure 4.
As shown in Figure 3: in 10mA/cm2When, 6 gained pyrochlore materials Ho of embodiment2Ir2O7Overpotential be 297mV, it is real
Apply 7 gained pyrochlore materials Tb of example2Ir2O7Overpotential be 325mV, 8 gained pyrochlore materials Gd of embodiment2Ir2O7It is excessively electric
Position is 353mV, 9 gained pyrochlore materials Nd of embodiment2Ir2O7Overpotential be 396mV, 10 gained pyrochlore materials of embodiment
Pr2Ir2O7Overpotential be 408mV, show pyrochlore materials R obtained by the present invention2Ir2O7Catalytic performance be an advantage over commercial IrO2
's.
As shown in Figure 4: 9 gained pyrochlore materials Nd of embodiment2Ir2O7With 10 gained pyrochlore materials Pr of embodiment2Ir2O7
After the test of 10000s constant current, the 9 gained pyrochlore materials Nd of embodiment in 10mA/cm22Ir2O7It is burnt with obtained by embodiment 10
Green stone material Pr2Ir2O7Overpotential improve only 29% and 18% respectively, show pyrochlore materials R obtained by the present invention2Ir2O7
Catalytic stability it is good.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of pyrochlore materials, which is characterized in that its structural formula is R2Ir2O7, any in R Ho, Tb, Gd, Nd, Pr.
2. the preparation method of a kind of pyrochlore materials as described in claim 1, which comprises the steps of:
S1, iridic chloride, the nitrate compound of R, Citric Acid Mono and water are uniformly mixed, are then evaporated；
S2, it S1 is evaporated to rear material is placed in the aqueous precursor gel that heating is expanded in baking oven；
Under S3, air conditions, aqueous precursor gel is once warming up to 380-420 DEG C, is kept the temperature, cooling, then secondary temperature elevation is extremely
850-950 DEG C, heat preservation, washing obtains pyrochlore materials.
3. the preparation method of pyrochlore materials according to claim 2, which is characterized in that in S1, evaporated temperature 75-85
℃。
4. the preparation method of the pyrochlore materials according to Claims 2 or 3, which is characterized in that in S2, oven temperature 115-
125℃。
5. according to the preparation method of any one of the claim 2-4 pyrochlore materials, which is characterized in that primary to heat up in S3
Speed be 4.5-5.5 DEG C/min, soaking time is 3-5h.
6. according to the preparation method of any one of the claim 2-5 pyrochlore materials, which is characterized in that in S3, cooling method
To be down to room temperature naturally.
7. according to the preparation method of any one of the claim 2-6 pyrochlore materials, which is characterized in that in S3, secondary temperature elevation
Speed be 4.5-5.5 DEG C/min, secondary soaking time be 22-26h.
8. according to the preparation method of any one of the claim 2-7 pyrochlore materials, which is characterized in that in S3, using go from
Sub- water is washed.
9. a kind of pyrochlore materials as described in claim 1 produce the application in oxygen reaction as catalyst in acid electro-catalysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811346102.3A CN109453771A (en) | 2018-11-13 | 2018-11-13 | The preparation of a kind of pyrochlore materials and its application in electro-catalysis production oxygen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811346102.3A CN109453771A (en) | 2018-11-13 | 2018-11-13 | The preparation of a kind of pyrochlore materials and its application in electro-catalysis production oxygen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109453771A true CN109453771A (en) | 2019-03-12 |
Family
ID=65610169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811346102.3A Pending CN109453771A (en) | 2018-11-13 | 2018-11-13 | The preparation of a kind of pyrochlore materials and its application in electro-catalysis production oxygen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109453771A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111689531A (en) * | 2020-06-03 | 2020-09-22 | 中国科学院物理研究所 | Low heat conductivity metallic material and preparation method thereof |
| CN115970688A (en) * | 2023-01-19 | 2023-04-18 | 江苏擎动新能源科技有限公司 | Catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101022887A (en) * | 2004-09-18 | 2007-08-22 | 约翰森·马瑟公开有限公司 | Compound having a pyrochlore-structure and its use as a catalyst carrier in water gas shift reaction |
| CN104591267A (en) * | 2015-02-04 | 2015-05-06 | 济南大学 | Multifunctional neodymium stannate nanosphere composite oxide material with single-phase pyrochlore structure |
| CN105026316A (en) * | 2013-07-11 | 2015-11-04 | 沙特基础工业全球技术公司 | Method of making pyrochlores |
| CN108144607A (en) * | 2017-12-26 | 2018-06-12 | 吉林大学 | Iridium acid strontium class catalyst, preparation method and its application in terms of electro-catalysis cracks acid aquatic products oxygen |
-
2018
- 2018-11-13 CN CN201811346102.3A patent/CN109453771A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101022887A (en) * | 2004-09-18 | 2007-08-22 | 约翰森·马瑟公开有限公司 | Compound having a pyrochlore-structure and its use as a catalyst carrier in water gas shift reaction |
| CN105026316A (en) * | 2013-07-11 | 2015-11-04 | 沙特基础工业全球技术公司 | Method of making pyrochlores |
| CN104591267A (en) * | 2015-02-04 | 2015-05-06 | 济南大学 | Multifunctional neodymium stannate nanosphere composite oxide material with single-phase pyrochlore structure |
| CN108144607A (en) * | 2017-12-26 | 2018-06-12 | 吉林大学 | Iridium acid strontium class catalyst, preparation method and its application in terms of electro-catalysis cracks acid aquatic products oxygen |
Non-Patent Citations (6)
| Title |
|---|
| DAIKI YANAGISHIMA: "Metal-Nonmetal Changeover in Pyrochlore Iridates", 《JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN》 * |
| HIROSHI TAKATSU ET AL: "Comparative study of low-temperature x-ray diffraction experiments on R2Ir2O7 (R = Nd, Eu, and Pr)", 《PHYSICAL REVIEW B》 * |
| JAEMIN KIM,: "High-Performance Pyrochlore-Type Yttrium Ruthenate Electrocatalyst for Oxygen Evolution Reaction in Acidic Media", 《J. AM. CHEM. SOC.》 * |
| KAZUYUKI MATSUHIRA ET AL，: "Metal–Insulator Transitions in Pyrochlore Oxides Ln2Ir2O7", 《JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN》 * |
| KAZUYUKI MATSUHIRA ET AL: ""Metal–Insulator Transitions in Pyrochlore Oxides Ln2Ir2O7"", 《JOURNAL OF THE PHYSICAL SOCIETY OF JAPAN》 * |
| PEI-CHIEH SHIH ET AL: "Single-Phase Pyrochlore Y2Ir2O7 Electrocatalyst on the Activity of Oxygen Evolution Reaction", 《ACS APPL. ENERGY MATER.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111689531A (en) * | 2020-06-03 | 2020-09-22 | 中国科学院物理研究所 | Low heat conductivity metallic material and preparation method thereof |
| CN111689531B (en) * | 2020-06-03 | 2021-05-25 | 中国科学院物理研究所 | Low heat conductivity metallic material and preparation method thereof |
| CN115970688A (en) * | 2023-01-19 | 2023-04-18 | 江苏擎动新能源科技有限公司 | Catalyst and preparation method thereof |
| CN115970688B (en) * | 2023-01-19 | 2023-10-13 | 江苏擎动新能源科技有限公司 | Catalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110227496B (en) | Microspherical Fe-doped trinickel disulfide nano-structure material composed of nanosheets, and preparation method and application thereof | |
| CN109225270B (en) | Ni3S2@ NiV-LDH heterostructure bifunctional electrocatalyst, preparation method and application | |
| CN106025302A (en) | Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material | |
| CN111672514A (en) | Bifunctional electrocatalytic material and preparation method and application thereof | |
| CN108531938A (en) | A kind of three-dimensional multistage structure cobalt nickel aluminium ternary metal elctro-catalyst and its preparation and application for oxygen evolution reaction | |
| Xue et al. | CoSe x nanocrystalline-dotted CoCo layered double hydroxide nanosheets: a synergetic engineering process for enhanced electrocatalytic water oxidation | |
| CN110639534B (en) | Oxygen evolution electrocatalytic material and preparation method and application thereof | |
| CN106694005A (en) | Preparation method of electric catalyst for acidic fully-decomposed water | |
| Singh et al. | Tuning the properties of CoFe-layered double hydroxide by vanadium substitution for improved water splitting activity | |
| KR101901223B1 (en) | Multifunctional non-platinum supported catalyst for automotive fuel cells and method for manufacturing the same | |
| CN110611105B (en) | Preparation method of ORR catalyst | |
| CN111450851B (en) | Preparation method of sulfur-doped cobalt-based nano oxygen evolution electrocatalyst | |
| CN110846680A (en) | Preparation method of multi-defect and active site electrocatalyst | |
| Ambriz-Peláez et al. | Defected NiFe layered double hydroxides on N-doped carbon nanotubes as efficient bifunctional electrocatalyst for rechargeable zinc–air batteries | |
| CN111468120B (en) | CoFeNiO X Layered hollow nanocage electrocatalyst and preparation method and application thereof | |
| CN109453771A (en) | The preparation of a kind of pyrochlore materials and its application in electro-catalysis production oxygen | |
| Song et al. | Progress and perspective of single‐atom catalysts for membrane electrode assembly of fuel cells | |
| CN113948725B (en) | Preparation method of dual-functional microporous layer type gas diffusion layer, gas diffusion layer and catalytic electrode | |
| CN114959791A (en) | Preparation method of Mg-doped NiFe-based (oxy) hydroxide and oxygen evolution electrocatalysis application thereof | |
| EP3670702A1 (en) | Electrode material | |
| CN111111718A (en) | Preparation method of multi-metal phosphorus-doped electrocatalyst derived based on binary LDH | |
| CN113774425B (en) | Preparation method and application of Ru-modified FeCo @ NF electrocatalyst | |
| CN111151281A (en) | C3N4Modified Co3O4Self-supported ultrathin porous nanosheet and preparation method and application thereof | |
| CN112779559B (en) | Preparation method of efficient grain boundary catalyst and application of efficient grain boundary catalyst in proton exchange membrane electrolytic cell | |
| CN116770323A (en) | Iridium single-site modified cobalt spinel electrocatalytic material and electrocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190312 |
|
| RJ01 | Rejection of invention patent application after publication |