CN103157467B - Ru and / or Ir noble metal oxide and application thereof to oxygen evolution electro-catalysis - Google Patents
Ru and / or Ir noble metal oxide and application thereof to oxygen evolution electro-catalysis Download PDFInfo
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- CN103157467B CN103157467B CN201110419158.9A CN201110419158A CN103157467B CN 103157467 B CN103157467 B CN 103157467B CN 201110419158 A CN201110419158 A CN 201110419158A CN 103157467 B CN103157467 B CN 103157467B
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Abstract
The invention relates to a Ru and / or Ir noble metal oxide with a molecular formula expressed as Ru*Ir1-xO2, wherein x satisfies the relation of: 0<=x<=1. The noble metal oxide is prepared by using an amino modified silicon oxide molecular sieve SBA-15 as a template, and impregnating and reducing the Ru and / or Ir noble metal into surrounding holes of the template housing by Coulomb and capillary effect. The method is a simple preparation method of noble metal oxide with controllable morphology, and applies a hard template method to preparation of binary noble metal oxide to expand its scope of application. The Ru*Ir1-xO2 prepared by the invention shows good oxygen evolution electro-catalysis performance when used as a solid polymer electrolyte (SPE) water electrolyzer anode catalyst. The invention has extensive application value in regenerative fuel cell (RFC), photoelectric catalysis and electrolysis hydrogen generator device.
Description
Technical field
The present invention relates to a kind of oxygen eelctro-catalyst Ru and/or Ir metal oxide containing precious metals of analysing, the amido modified silicon oxide molecular sieve of not removed surfactant of specifically usining is prepared a metal oxide containing precious metals as template, can be applicable to analyse oxygen eelctro-catalyst in SPE water electrolysis, RFC or various electrolysis unit.
Background technology
In recent years, SPE water electrolysis technology because it is efficient, zero-emission, compact conformation, environmental friendliness, product purity advantages of higher, become the study hotspot of hydrogen preparation field, and the highly purified oxygen of its product is also for fields such as space flight, medical treatment, analyses.Yet expensive is the main cause of the further commercial applications of restriction SPE water electrolysis technology, and therefore around how to reduce costs, improving electrolytic efficiency is various countries researcher's focus.
In SPE water electrolytic cell, Oxygen anodic evolution reaction is considered to the main source of electrolytic cell overpotential, and a large amount of experimental works and theoretical research show, has the catalyst of analysing preferably oxygen catalytic activity and mainly concentrate on IrO under strong acidic condition
2, RuO
2on metal oxide containing precious metals.Wherein, RuO
2be considered to the metal oxide that oxygen evolution activity is the highest, but be difficult to steady in a long-term existence; And IrO
2oxygen evolution activity is only second to RuO
2, and good stability, but price is RuO
23～5 times, therefore numerous scholars are by binary composite metal oxide Ru
xir
1-xo
2as its research object.In addition, traditional noble metal method for oxidation of preparing mainly contains Adams roasting method and the large class of sol-gel process two, Adams roasting method is a kind of method that technique is relatively simply prepared metal oxide, by Adams and Shriner etc., in nineteen twenty-three, proposed, but its harsh and larger metal oxide particle to roasting condition has limited it, apply more widely.What at present, the research of the method is mainly concentrated on to other component adds to improve its stability and catalytic activity.United States Patent (USP) [US 4289519] adopts Adams roasting method to prepare RuO
2time, approximately 10% MgO
2add and can significantly improve RuO
2stability, but can affect its oxygen evolution activity.Patent [CN 101733095] is thought and is added the 3rd component Mo, Cr or the W that is less than 10%, is conducive to reduce the size of crystallite, improves its oxygen evolution activity.Meanwhile, more scholar is more prone to adopt sol-gel process to prepare metal oxide containing precious metals, thinks that its gentle roasting condition can suppress the reunion of particle effectively, but these class methods are difficult to form the nano particle of regular functional structure body or homogeneous dispersion.
Meanwhile, along with the development of nanosecond science and technology, numerous scholars have given to pay close attention to significantly to having the research of metal oxide containing precious metals material of the single dispersion of regular pattern.Such material has wide practical use in catalysis, optics, electrochemistry and other functional material field.Yet in the middle of its preparation, particularly to binary metal oxide containing precious metals, how effectively to control catalyst pattern, the nano particle that preparation has regular functional structure or a single dispersion becomes a major challenge of this research field.
At present, utilization has regular adjustable meso-porous molecular sieve material as the template of metal oxide catalyst, can effectively prevent its reunion in preparation process, also can utilize its regulatable porous housing, its structure of nano-copy, forms the functional structure of regular pattern.Wherein, sacrificial core technology is the preparation method who is widely used in having core-shell type structural metal oxide hollow micro capsule of a class, the method is to be mainly template with removable microballoon (as polymer and silicon oxide microsphere), by approach such as surface chemical reaction or coulomb interactions, the surface of desired species template ball is formed to nucleocapsid structure, by the method for roasting or chemical attack, template is removed again, obtained hollow micro capsule.The method of wherein introducing with patent [CN 1683068, CN 1243124] is typical case the most, the method is only for the silicon oxide molecular sieve with microspheric structure, and it carries out partial reduction to the precious metal ion being anchored in silica housing duct, end product yield is low, is unfavorable for large-scale synthetic.The lithographic technique of surface protection (Q.Zhang, I.Lee, J.Ge, F.Zaera, and Y.Yin, Adv.Funct.Mater.2010,20,2201; CN 1281306) be also a quasi-representative utilize molecular sieve as the technology of template.These class methods are mainly that object metal/metal oxide is anchored to behind main body silica housing duct, at its adsorption one deck polyelectrolyte film, to protect top layer master, guest species, mainly occur in the core of main body during etching.These class methods are applicable to the synthetic of most of shell component micro-capsules, but because main body template megohmite insulant silica in housing is difficult to remove completely, the application of such material aspect electro-catalysis is restricted, operating process is simultaneously complicated, in order to form fine and close shell, often need the electroless copper deposition operation through repeatedly, step is comparatively loaded down with trivial details.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of Ru and/or I r metal oxide containing precious metals, the preparation of this metal oxide containing precious metals is to take silicon oxide molecular sieve as template, Ru and/or Ir noble metal dipping are reduced in the housing duct of template, and whole technical process is simple and easy to control, economical rationality.This metal oxide containing precious metals is as SPE water electrolysis anode catalyst, has good oxygen electro catalytic activity and the electrochemical stability of analysing, and is with a wide range of applications at aspects such as RFC, sensor, photoelectrocatalysis, alkaline electrolysis ponds.
For achieving the above object, the technical solution used in the present invention is as follows:
(1) silicon oxide molecular sieve of not removed surfactant is carried out to housing amido modified, amido modified processing method is that silicon oxide molecular sieve is stirred to 0.5～8h in the ethanolic solution of the APS of 0.5～4wt.%, then use absolute ethanol washing, sample after filtration, dry after as the synthetic template of metal oxide containing precious metals, the temperature of above-mentioned processing is 20～80 ℃, the solid-liquid mass ratio of silica and aminopropyl silester is 0.05～0.4;
(2) amido modified silicon oxide molecular sieve in step (1) is dispersed in deionized water, adds one or both of solubility Ru and/or Ir precious metal salt, stir it is fully dissolved, mixing time is 1～12h.Total metal molar concentration that described solubility Ru and/or Ir precious metal salt are dissolved in deionized water is 0.01～0.1M, and the amount of described molecular sieve in deionized water is 0.3～3wt.%;
(3) under nitrogen or the non-oxidizing atmosphere of argon gas, by reducing agent NaBH
4or KBH
4the aqueous solution drop in the precious metal salt solution that step (2) high speed stirs, the reduction reaction time is 1～24h, NaBH
4or KBH
4solution concentration is 0.1～4M, precious metal salt and NaBH
4or KBH
4mol ratio be 0.5～0.02;
(4) solution step (3) being obtained at 20～60 ℃, after still aging 0～12d, separated, solids with deionized water or ethanol wash to pH be 7,40～80 ℃ dry, obtain noble metal/metal oxide containing precious metals and silica complex solid powder;
(5) under air or oxygen atmosphere, by above-mentioned pressed powder high-temperature roasting, 400～800 ℃ of sintering temperatures, 1～5 ℃ of min of temperature programming speed
-1, roasting time 0.5～6h, the complex of acquisition metal oxide containing precious metals and silica;
(6) take the etching agent that HF solution is silica, remove metal oxide containing precious metals and the silica composition of silicon oxide composite unit that step (5) obtains, separating, washing is placed in the vacuum drying oven of 40～80 ℃, acquisition end product Ru
xir
1-xo
2metal oxide containing precious metals.Described HF solution concentration is 5～40wt.%, processing time 1～24h, and temperature is 20～60 ℃, the silica in metal oxide containing precious metals and silicon oxide composite unit and the mol ratio of HF are 0.05～0.25.
HMS, SBA-15 or MCM-41 that silicon oxide molecular sieve described in above-mentioned steps (1) is not removed surfactant.
Surfactant described in above-mentioned steps (1) is that described surfactant is long chain alkyl primary amine, triblock copolymer P123 or the chain alkyl quaternary amine of preparing template C12～18 of silicon oxide molecular sieve.
The described solubility ruthenium salt of above-mentioned steps (2) can be the RuCl containing the crystallization water
3, Ru (Ac)
3, K
2ruCl
5or Na
2ruCl
5, solubility Ir salt is the IrCl containing the crystallization water
3, IrCl
4, Ir (Ac)
4, H
2irCl
6, K
2irCl
6or Na
2irCl
6.
Using the metal oxide containing precious metals of above-mentioned preparation as SPE water electrolysis anode catalyst, the technical scheme of film-catalyst assembly is: by spraying, turn the technology such as pressure by homodisperse Precious Metal and ionomer material (as
) be deposited on the anode-side of cationic polymer dielectric film, loading 0.5～3mg cm
-2, cathode side use Pt catalyst (Pt/C) or Pt are black, Pt loading 0.1～1mg cm
-2.
The good implementation condition of the present invention is:
Silicon oxide molecular sieve used can be the various silica with mesopore molecular sieve structure, has high heat endurance and the feature of regulatable porous even housing.
Silicon oxide molecular sieve is by processing in the ethanolic solution at aminopropyl silester, at its housing by the amino groups of a large amount of alkalescence of grappling, by the effect of coulomb interaction, capillary force, metal ion can be anchored in the housing duct of silicon oxide molecular sieve, and the existence of inner layer sheet surface-active agent, to effectively stop metal ion to spread to internal layer, final reduction reaction will mainly betide in the shell layer duct of silicon oxide molecular sieve.
Therefore due in Ru, Ir coreduction process, Ir is difficult to be reduced compared with Ru, is conducive to form the core-shell type structure that Ru is wrapped up by Ir, has good oxygen electro catalytic activity and the stability analysed during used as oxygen-separating catalyst.
In still aging process, will there is short grained dissolving, the growing up of large crystal grain, nearly a step makes metal uniform deposition in the shell layer of silicon oxide molecular sieve.
Advantage of the present invention is mainly reflected in:
The Ru that the present invention obtains, Ir metal oxide containing precious metals nano-copy the shell layer structure of template silica, there is little particle diameter, large BET specific area (100～300m
2g
-1) with the feature of high porosity (0.3～0.6), therefore Ru of the present invention
xir
1-xo
2in the application of analysing oxygen eelctro-catalyst, there is bright prospect.Meanwhile, the present invention is the preparation for binary Ru, Ir metal oxide containing precious metals by die method, has expanded its range of application.
The inventive method is simple and easy to control, economical rationality, and product preparation efficiency is high.
Accompanying drawing explanation
Fig. 1. the IrO that the molecular sieve SBA-15 of take is prepared as template
2transmission electron microscope figure;
Fig. 2. the Ru that the molecular sieve SBA-15 of take is prepared as template
xir
1-xo
2xRD collection of illustrative plates;
Fig. 3. the Ru that the molecular sieve SBA-15 of take is prepared as template
xir
1-xo
2linear scan curve, 0.5M H
2sO
4, scan frequency 2mVs
-1;
The polarization curve of Fig. 4 .SPE water electrolytic cell, anode catalyst loading 2mgcm
-2, negative electrode 40wt.%Pt/C, Pt loading 0.4mgcm
-2,
115 films, electrode area 5cm
2, 80 ℃ of probe temperatures;
The about 140h life test of Fig. 5 .SPE water electrolytic cell, 80 ℃ of probe temperatures, current density 500mAcm
-2;
Fig. 6. the Ru that the molecular sieve HMS of take is prepared as template
xir
1-xo
2linear scan curve, 0.5 M H
2sO
4, scan frequency 2mVs
-1.
The specific embodiment
Embodiment 1
Taking 4g surfactant P123 is dissolved in 93g deionized water, adding 25g concentration is 37wt.% hydrochloric acid, in 40 ℃, stirs 2h, dropping 8.8g ethyl orthosilicate (TEOS), stir 24h, move in pyroreaction still, in 120 ℃ of standing 24h, naturally cooling after, filter, pressed powder washs to non-foam by deionized water, and 60 ℃ of dry 24h, prepare silicon oxide molecular sieve SBA-15.
Get 2.5g SBA-15 and be scattered in the ethanolic solution of APS that 150mL concentration is 1wt.%, under room temperature, stir 4h, filter, absolute ethanol washing, repeat 5 times, in 60 ℃ of vacuum drying, obtain amido modified silicon oxide molecular sieve SBA-15.Get the amido modified SBA-15 of 0.45g and be scattered in the deionized water of 40mL, add the H containing 3～5 crystallizations water
2irCl
6, making total precious metal ion concentration is 0.08M, stir after dipping 4h, and at 50 ℃, N
2the lower 1 M NaBH that drips of protection
4solution, makes NaBH
4with the mol ratio of precious metal ion be 5: 1, after reaction 6h, still aging 12h under room temperature, separation, water washing is to pH=7,80 ℃ of vacuum drying move in tube furnace, 550 ℃ of roasting 4h, heating rate is 2 ℃ of min
-1.After cooling, with 15wt.%HF solution, remove silica template, separated, washing, repeats 5 times, in 80 ℃ of vacuum drying, and preparation IrO
2, be designated as S-IrO
2.
Embodiment 2
Adopt the identical method of embodiment 1 to test, difference from Example 1 is, but adds the RuCl containing 3～5 crystallizations water
3with H
2irCl
6substitute H
2irCl
6, wherein the precursor mol ratio of Ru and I r is 1: 4, preparation Ru
0.2ir
0.8o
2, be designated as S-Ru
0.2ir
0.8o
2.
Embodiment 3
Adopt the identical method of embodiment 1 to test, difference from Example 1 is, but adds the RuCl containing 3～5 crystallizations water
3with H
2irCl
6substitute H
2irCl
6, wherein the precursor mol ratio of Ru and Ir is 4: 1, preparation Ru
0.8ir
0.2o
2, be designated as S-Ru
0.8ir
0.2o
2.
The S-IrO that as can be seen from Figure 1 prepared by embodiment 1
2the structure with nano bar-shape, illustrates that it has copied the shell layer mechanism of SBA-15.The catalyst of embodiment 1～3 preparation has the structure of typical Rutile Type as can be seen from Figure 2, calculates S-Ru by Sherrer formula
xir
1-xo
2average crystal grain size is 5～7nm.
From the linear scan curve of Fig. 3, can find out S-Ru
xir
1-xo
2analyse oxygen electro catalytic activity and strengthen along with the increase of Ru content, more obvious near initial oxygen evolution potential especially.
The catalyst of embodiment 1～3 preparation is assembled into electrolytic cell as SPE water electrolysis anode anode catalyst.Fig. 4 be its at 80 ℃, polarization curve during atmospheric operation, has reflected that each electrolytic cell has good electrolysis performance, and along with the increase of Ru content, Ru
xir
1-xo
2analyse oxygen electro catalytic activity and strengthen, more obvious under low current density especially; And under high current density, due to RuO
2unstability, limit it and active further promote.As can be seen from Figure 5 in the stable operation of 140h, each electrolytic cell decomposition voltage is significantly decay not, but along with the increase of Ru content, the stability of electrolytic cell also decreases.
Embodiment 4
The HMS of take prepares Ru as template
xir
1-xo
2, the specific embodiment is: 10g lauryl amine is dissolved in 80g ethanol/100g water, drips 41.5g ethyl orthosilicate under high-speed stirred, stir 1h, standing 20h, suction filtration, deionized water, absolute ethanol washing to non-foam produce, place 110 ℃ of curing oven 8h, obtain silicon oxide molecular sieve HMS.Amido modifiedly according to the method for embodiment 1, carry out.
Take respectively in the deionized water that the above-mentioned amido modified HMS of 0.25g is well-dispersed in 20mL (totally 6 groups), add respectively the RuCl containing 3～5 crystallizations water
3, H
2irCl
6(mol ratio is respectively Ru: (Ru+Ir)=1,0.8,0.6,0.4,0.2 or 0), total precious metal ion concentration is 0.08M, stirs after 4h, at N
2under condition, drip excessive 1M NaBH
4solution, after reaction 6h, standing 12h, separation, deionized water is washed to pH=7, and 80 ℃ of vacuum drying move in tube furnace, 550 ℃ of roasting 4h in air, heating rate is 2 ℃ of min
-1.After cooling, with 15wt.%HF, remove silica template, separated, washing, repeats 5 times, in 80 ℃ of vacuum drying, and preparation Ru
xir
1-xo
2, be designated as H-Ru
xir
1-xo
2.
From the linear scan curve of Fig. 6, can find out the H-Ru that adopts molecular sieve HMS to prepare
xir
1-xo
2analyse oxygen electro catalytic activity and also reflected the trend as Fig. 3,, near initial oxygen evolution potential, analyse oxygen electro catalytic activity and strengthen along with the increase of Ru content, but under high decomposition voltage, RuO
2unstability, limited the further enhancing of its activity.
Claims (7)
1. Ru and/or an Ir metal oxide containing precious metals, is characterized in that: described metal oxide containing precious metals useful molecules formula Ru
xir
1-xo
2represent, 0≤x≤1 wherein, described metal oxide containing precious metals is to take the silicon oxide molecular sieve of not removed surfactant to be prepared from as template; Prepare according to the following procedure,
(1) take the silicon oxide molecular sieve of not removed surfactant is template, aminopropyl silester is the dressing agent of silicon oxide molecular sieve, ethanol is solvent, by controlling the reaction condition of aminopropyl silester and template, amino in a large amount of alkalescence of its surface graft, the concentration of aminopropyl silester in absolute ethyl alcohol is 0.5～4wt.%, the solid-liquid mass ratio of silica and aminopropyl silester is 0.05～0.4, reaction temperature is 20～80 ℃, reaction time is 0.5～8h, then be separated by filtration, after ethanol washing, move in 40～80 ℃ of vacuum drying ovens, dry 4～24h,
(2) the amido modified silicon oxide molecular sieve of above-mentioned preparation is dispersed in deionized water, add solubility Ru and/or Ir precious metal salt, stirring is fully dissolved it, total metal molar concentration that described solubility Ru and/or Ir precious metal salt are dissolved in deionized water is 0.01～0.1M, and the amount of described molecular sieve in deionized water is 0.3～3wt.%;
(3) under nitrogen or the non-oxidizing atmosphere of argon gas, by reducing agent NaBH
4or KBH
4the aqueous solution drop in the precious metal salt solution of above-mentioned high-speed stirred, the reduction reaction time is 1～24h, described NaBH
4or KBH
4the molar concentration of solution is 0.1～4M, total precious metal ion and NaBH
4or KBH
4mol ratio be 0.5～0.02;
(4) by the solution of step (3) gained at 20～60 ℃ after still aging 0～12d, it is neutral that separated, solids washs to solution with deionized water or ethanol, 40～80 ℃ dry, obtains noble metal/metal oxide containing precious metals and silica complex solid powder
(5) in air or oxygen atmosphere, above-mentioned pressed powder is moved to tubular type kiln roasting, from room temperature temperature programming to 400～800 ℃, 1～5 ℃ of min of temperature programming speed
-1, then in 400～800 ℃ of sintering temperatures, roasting time 2～6h, the complex of acquisition metal oxide containing precious metals and silica;
(6) take the etching agent that HF solution is silica, remove the silica composition of above-mentioned complex, separating, washing is placed in the vacuum drying chamber of 40～80 ℃, obtains end product Ru
xir
1-xo
2.
2. according to metal oxide containing precious metals described in claim 1, it is characterized in that: the concentration of described HF solution is 5～40wt.%, the processing time is 1～24h, and temperature is 20～60 ℃.
3. according to metal oxide containing precious metals described in claim 2, it is characterized in that: the mol ratio of described silica and HF is 0.05～0.25.
4. according to metal oxide containing precious metals described in claim 1, it is characterized in that: described molecular sieve is that the chain alkyl quaternary amine of long chain alkyl primary amine, triblock copolymer P123 or C12～18 of employing C12～18 is the molecular sieve that surfactant prepares, and described molecular sieve is HMS, SBA-15 or MCM-41.
5. according to metal oxide containing precious metals described in claim 1, it is characterized in that: described solubility Ru salt is the RuCl containing the crystallization water
3, Ru (Ac)
3, K
2ruCl
5or Na
2ruCl
5, solubility Ir salt is the IrCl containing the crystallization water
3, IrCl
4, Ir (Ac)
4, H
2irCl
6, K
2irCl
6or Na
2irCl
6.
6. described in claim 1～5 any one, Ru, Ir metal oxide containing precious metals are being analysed the application of oxygen eelctro-catalyst.
7. according to the application of metal oxide containing precious metals described in claim 6, it is characterized in that: described metal oxide containing precious metals is applied in RFC, photoelectrocatalysis, SPE water electrolytic cell or alkaline water electrolytic generator as oxygen-separating catalyst.
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| CN107557820A (en) * | 2017-09-21 | 2018-01-09 | 王成彦 | A kind of preparation method of ternary compound oxides inert anode |
| CN108043437B (en) * | 2017-11-09 | 2023-09-22 | 国家电网公司 | Preparation method of hollow SiC carrier type Ir-Ru catalyst |
| CN108579763B (en) * | 2018-05-10 | 2021-09-17 | 吉林晟航科技发展有限公司 | Nano metal catalyst with good stability and application thereof |
| CN110813274B (en) * | 2018-08-10 | 2020-12-01 | 中国科学院大连化学物理研究所 | Superfine bimetal IrRu nano linear catalyst and preparation and application thereof |
| CN111151244A (en) * | 2020-01-05 | 2020-05-15 | 复旦大学 | Ruthenium-based composite oxide material prepared by sol-gel method, and preparation method and application thereof |
| CN111420658B (en) * | 2020-04-22 | 2023-07-04 | 上海大学 | Ir/Ru alloy oxygen precipitation catalyst and preparation method and application thereof |
| CN113463118B (en) * | 2021-05-12 | 2022-03-11 | 肯特催化材料股份有限公司 | Energy-saving production process of tetrapropylammonium hydroxide and tetrapropylammonium hydroxide aqueous solution prepared by same |
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| CN101181679A (en) * | 2007-11-02 | 2008-05-21 | 中国科学院上海硅酸盐研究所 | Meso-porous C/WO3 electro-catalyst and preparation method thereof |
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| CN1874841A (en) * | 2003-10-29 | 2006-12-06 | 尤米科尔股份公司及两合公司 | Precious metal oxide catalyst for water electrolysis |
| CN1683068A (en) * | 2005-02-13 | 2005-10-19 | 复旦大学 | Method for preparing metal oxide hollow microcapsule |
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