CN110000370A - A kind of Large ratio surface iridium is black and preparation method thereof - Google Patents
A kind of Large ratio surface iridium is black and preparation method thereof Download PDFInfo
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- CN110000370A CN110000370A CN201910316615.8A CN201910316615A CN110000370A CN 110000370 A CN110000370 A CN 110000370A CN 201910316615 A CN201910316615 A CN 201910316615A CN 110000370 A CN110000370 A CN 110000370A
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- iridium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
Abstract
Black and preparation method thereof the invention discloses a kind of Large ratio surface iridium, preparation methods steps include: (1) ultrasonic dissolution: ammonium chloroiridate being dissolved in a certain amount of ultrapure water and ultrasound-enhanced；(2) spray drying obtains micron order, spherical ammonium chloroiridate powder；(3) microwave calcination decomposes: spherical ammonium chloroiridate powder being placed in micro-wave oven in nitrogen atmosphere and carries out calcining and decomposing, decomposing ammonium chloroiridate sufficiently, to obtain iridium black；(4) after washing, being dry, the black product of Large ratio surface iridium is obtained.Invention enhances dissolution, ammonium chloroiridate solution is spray-dried, and the good micron order of free-running property, spherical ammonium chloroiridate powder is made, and decomposes, washs and to be dried to obtain iridium black using microwave calcination.Present invention process process is simple, easy to implement, and the black purity of iridium is greater than 99.95%, and spherical, free-running property is good, and 2~10 μm of partial size, specific surface area is greater than 30m2/g。
Description
Technical field
The invention belongs to powder metallurgical technologies, and in particular to a kind of preparation method that Large ratio surface iridium is black.
Background technique
Iridium is important materials indispensable in current new energy field, for existing research, in all noble metals,
Ir is unique a kind of high oxygen evolution reaction (OER) and redox reactions (ORR) active member to be provided simultaneously in acid medium
Element.IrO2 is mainly used in OER, and simple substance Ir is then mainly applied to ORR by the effect with precious metals pt and Pd etc..Iridium is in gold
There is preferable electron transport ability when belonging to state, therefore iridium is black is widely used in gas sensitive devices and water electrolytic cell.Iridium (Ir)
And its oxide with the electrocatalysis characteristics such as excellent analysis oxygen and liberation of hydrogen and has good anti-poisoning capability, corrosion resistant candle, conductance
The features such as ability is strong, and iridium is black with high specific surface area, the exposure of reaction active site is more advantageous to, to can be effectively controlled expensive
The usage amount of metal simultaneously obtains good catalytic effect, all shows to the electrochemical catalytic oxidation of chlorine hydrogen reduction, formic acid and ethyl alcohol
Good electro catalytic activity out.Active metal iridium is impregnated on aluminium oxide or other carriers and by being catalyzed made from specially treated
Agent, according to different requirements, the active metal iridium content of catalyst is usually 0.3%~30%, and iridium is black to be used as support type
Catalyst is mainly used in the removing of NOx in vehicle exhaust, the decomposition of rocket engine hydrazine and unsaturated carbon hydrocarbon compound
Hydrogenation reaction.Ir applied to catalytic field needs to have the strong superiority of reactivity height, high catalytic efficiency, adsorption capacity
Matter, this just needs Ir to have very big specific surface area.
Han Yiping et al. has carried out the preparation of the black catalyst of ammoxidation iridium, and technique is to press NH4F, H3BO3 and IrCl3
Certain proportion is soluble in water, ultrasonic mixing 30 minutes, after adjusting pH to 8-9 with ammonium hydroxide, is added dropwise under ultrasound condition a certain amount of
NaBH4 simultaneously continue ultrasound 30 minutes, after being filtered, washed, 55 DEG C drying 12 hours, obtain the black catalyst of iridium, obtained iridium
Powder is nanoscale, but the black specific surface area of iridium prepared by this method is less than 20m2/g and does not refer to purity.
Li Yadong of Tsinghua University et al. has prepared the black nanocrystal of iridium, during the preparation process, by chloro-iridic acid and ethyl alcohol,
Linoleic acid is packed into crystallizing kettle after the mixing such as linoleate, in solid-state, oil phase and generation phase transfer and separation process on aqueous phase interface
To prepare iridium nanoparticle.Iridium Nanoparticle Size prepared by the present invention is uniform, and partial size is unified, realizes monodisperse conjunction
At being conducive to improve specific surface area of catalyst and catalytic activity；Due to the black uniform particle diameter of iridium, shown very on chemical property
High catalytic activity and long-time stability.The patent does not refer to the black purity of iridium and specific specific surface area.
Stowell C.A. and the Korgel B.A. in the U.S. disclose a kind of preparation method that iridium is nanocrystalline, specific steps
Are as follows: the iridium presoma that will be present in dioctyl ether under conditions of nitrogen protection is restored with hexadecane diol, reduction temperature
It is 290 DEG C, after reaction, iridium nanocrystalline hexanol precipitating and initial centrifugation remove supernatant, and iridium is nanocrystalline in three chloromethanes
Disperse again in alkane and be precipitated out with hexanol and be centrifuged again again, repeat this washing step ensure to remove iridium it is nanocrystalline in mix
Organic matter and by-product, for obtained iridium nano particles in 1.5-5nm, the product catalytic activity is high, has good stability.The party
Method need to be washed repeatedly, be precipitated, and organic impurities is difficult to cleared, and not refer to specific surface area.
Han Yiping, Luo Peng, Cai is satisfactory, waits the ultra-fine Ir catalyst of to electrocatalysis characteristic [J] physical chemistry of ammoxidation
Report, 2008,24 (9): 1729-1732.
Wang X,Zhuang J,Li YD,et al.A general strategy for nanocrystal
synthesis.[J].Nature,2005,437(7055):121.
Stowell C A,Korgel B A.Iridium Nanocrystal Synthesis and Surface
Coating-Dependent Catalytic Activity[J].Nano Letters,2005,5(7):1203-1207.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods that Large ratio surface iridium is black, while guaranteeing purity, as far as possible
Powder sphericity is improved, its surface area is increased.
The black powder of iridium of the invention be it is spherical, free-running property is good, 1~10 μm of partial size, average grain diameter be 5 μm, purity is greater than
99.95%, specific surface area is greater than 30m2/g.
To achieve the above object, the technical solution of the present invention is as follows:
(1) ultrasonic dissolution: ammonium chloroiridate is dissolved in a certain amount of deionized water and ultrasound-enhanced；
(2) it is spray-dried: step (1) acquired solution being subjected to spray drying treatment, obtains micron order, spherical chloro-iridic acid
Ammonium powder；
(3) microwave calcination: ammonium chloroiridate powder is placed in the logical nitrogen of micro-wave oven and is calcined, divides ammonium chloroiridate sufficiently
Solution；
(4) it washs, is dry: after the dispersion of powder ultrasonic obtained by step (3), washing, is dry, obtaining the black powder of Large ratio surface iridium
Last product.
The present invention has prepared the black powder of Large ratio surface iridium, process flow letter by atomization drying and microwave calcination technique
Single, easy to implement, the purity of gained powder is greater than 99.95%, and spherical, free-running property is good, and 1~10 μm of partial size, large specific surface area
In 30m2/g.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is the XRD analysis map of the black powder of iridium of the present invention；
Fig. 3 a and Fig. 3 b are that the SEM of the black powder of iridium of the present invention schemes.
Specific embodiment
The present invention successively carried out test of many times, now lifts A partial experiment result as reference example and carries out in detail to invention
Describe and verify its effect.
Embodiment 1
The black powder of iridium of the present invention is made by following technique:
(1) ultrasonic dissolution technique: ammonium chloroiridate (purity > 99.95%) is mixed with ionized water 1:20 in mass ratio molten
Solution, adds ultrasound-enhanced, ultrasonic 30min, and the ammonium chloroiridate solution of uniform component is made；
(2) the ammonium chloroiridate solution dissolved drying process with atomizing: is subjected to atomization drying processing, the condition of spray drying
Are as follows: control flow quantity is 5.0ml/min, and atomization air pressure 0.5MPa, drying temperature is 180 DEG C, hot air flowrate 10.0L/
Spherical ammonium chloroiridate powder is made in min；
(3) microwave calcination technique: being placed in the logical nitrogen of micro-wave oven for spherical ammonium chloroiridate powder and calcine, calcination temperature
500 DEG C, calcination time 3h decomposes powder sufficiently；
(4) washing, drying process: adopting and be washed with deionized 5 times, and drying process uses 50 DEG C of dryings of low temperature for 24 hours.
Embodiment 2
Difference from Example 1 is, the ultrasonic dissolution technique: by ammonium chloroiridate (purity > 99.99%) with from
Sub- water 1:40 mixed dissolution in mass ratio, adds ultrasound-enhanced, ultrasonic 40min.It is atomized prilling are as follows: controlling flow quantity is
10.0ml/min, atomization air pressure 0.5MPa, drying temperature are 180 DEG C, hot air flowrate 10.0L/min.The microwave is forged
Firing technique are as follows: 500 DEG C of calcination temperature, calcination time 2h is made the black powder of spherical iridium, but the non-glomeration of amount of powder and reunites tight
Weight；
Embodiment 3
Difference from Example 1 is, the atomization prilling are as follows: control flow quantity is 5.0ml/min, atomization gas
Pressure is 0.5MPa, and drying temperature is 140 DEG C, hot air flowrate 10.0L/min.The microwave calcination technique are as follows: calcination temperature
It 600 DEG C, calcination time 3h, obtains partial size and is 0.1~5 μm of the black powder of iridium, and have a large amount of spherical powders broken；
Embodiment 4
Difference from Example 1 is that the washing, drying process: adopting and be washed with deionized 10 times, drying process
For 24 hours controlled at 100 DEG C of dryings.
Comparative example 1
Embodiment 2 is atomized in granulation process, flow quantity the difference is that ammonium chloroiridate is excessive in mass ratio with ionized water
Excessive, so that granulation process is difficult to carry out completely, part ammonium chloroiridate particle is simultaneously aspherical, and it is serious to reunite, and calcination time is not
Foot, ammonium chloroiridate is undecomposed completely.
Comparative example 2
Embodiment 3 the difference is that atomization drying temperature is too low, make to be atomized granulated pellet fail it is dry in time completely, lead
Precursor powder Particle Breakage and reunion are caused, calcination temperature is excessively high, and spherical particle is further crushed.
Comparative example 3
For embodiment 4 the difference is that washing times are excessive, drying temperature is excessively high, and the black powder second of gained iridium is reunited, than
Surface area reduces.
Purity detecting is carried out to the black powder of iridium prepared by the present invention using glow discharge spectrometry method (GDMS), using specific surface
Tester carries out surface analysis to the black powder of iridium, as a result as shown in Table 1 and Table 2.
The black powder impurity analysis result of 1 iridium of table.
The black powder surface analysis result of 2 iridium of table.
The black powder impurity analysis result of 1 Large ratio surface iridium of table
A kind of micron-size spherical densification tungsten iridium powder and preparation method thereof
Note: GDMS analysis detection is used
The black powder surface analysis result of 2 Large ratio surface iridium of table
Note: specific surface tester analysis detection is used.
Claims (8)
1. a kind of Large ratio surface iridium is black, it is characterised in that: the iridium is black to be spherical, and free-running property is good, 2~10 μm of partial size, average
Partial size is 5 μm.
2. Large ratio surface iridium according to claim 1 is black, it is characterised in that: the purity of powder is greater than 99.95%.
3. Large ratio surface iridium according to claim 1 is black, it is characterised in that: the specific surface area of powder is greater than 30m2/g.
4. a kind of preparation method that Large ratio surface iridium is black, it is characterised in that include following processing step:
(1) ammonium chloroiridate ultrasonic dissolution: is dissolved in the purity of in a certain amount of ultrapure water and ultrasound-enhanced, described ammonium chloroiridate
It is 99.95%, ultrasound is to reinforce dissolving；
(2) it is spray-dried: step (1) acquired solution being subjected to spray drying treatment, obtains micron order, spherical ammonium chloroiridate powder
End；
(3) microwave calcination: spherical ammonium chloroiridate powder is placed in micro-wave oven in nitrogen atmosphere and carries out calcining and decomposing, makes chlorine iridium
It is black that sour ammonium is sufficiently decomposed into iridium；
(4) it washs, is dry: after powder ultrasonic dispensing laundry, drying obtained by step (3), obtaining the black product of Large ratio surface iridium.
5. a kind of preparation method that Large ratio surface iridium is black according to claim 4, it is characterised in that: described in step (1)
The mass ratio of ammonium chloroiridate and ultrapure water is 1:20~100；20~60min of ultrasonic time.
6. a kind of preparation method that Large ratio surface iridium is black according to claim 4, it is characterised in that: step (2) described spray
The dry condition of mist are as follows: control flow quantity is 1.0~10.0ml/min, and atomization air pressure is 0.1~1MPa, drying temperature 120
~250 DEG C, hot air flowrate is 1.0~10.0L/min.
7. a kind of preparation method that Large ratio surface iridium is black according to claim 4, it is characterised in that: described in step (3)
Microwave calcination condition are as follows: 500~800 DEG C of calcination temperature, 1~5h of calcination time.
8. a kind of preparation method that Large ratio surface iridium is black according to claim 4, it is characterised in that: described in step (4)
Washing process uses milli-Q water 5~20 times, 50~100 DEG C of dry 12~36h.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116243A (en) * | 1995-04-17 | 1996-02-07 | 中国有色金属工业总公司昆明贵金属研究所 | Method for making pure iridium |
| CN101985696A (en) * | 2010-12-01 | 2011-03-16 | 金川集团有限公司 | Method for extracting iridium from iridium containing materials |
| CN102296183A (en) * | 2011-08-19 | 2011-12-28 | 天津市化学试剂研究所 | Method for preparing high-purity platinum |
| CN105458278A (en) * | 2015-12-08 | 2016-04-06 | 贵研铂业股份有限公司 | Preparation method of high-purity spherical ruthenium powder |
| CN106166613A (en) * | 2016-08-18 | 2016-11-30 | 贵研铂业股份有限公司 | A kind of micron-size spherical W Mo alloy powder and preparation method thereof |
| CN108217754A (en) * | 2017-12-25 | 2018-06-29 | 贵研铂业股份有限公司 | A kind of Large ratio surface IrO2Preparation method |
| CN108296491A (en) * | 2018-01-24 | 2018-07-20 | 贵研铂业股份有限公司 | A kind of spherical iridium raw powder's production technology of micron order |
| CN108311714A (en) * | 2017-12-18 | 2018-07-24 | 贵研铂业股份有限公司 | A kind of micron-size spherical Pt-Ru alloy powder, preparation method thereofs |
| CN108620600A (en) * | 2017-12-18 | 2018-10-09 | 贵研铂业股份有限公司 | A kind of high-purity Large ratio surface platinum black and preparation method thereof |
-
2019
- 2019-04-19 CN CN201910316615.8A patent/CN110000370A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116243A (en) * | 1995-04-17 | 1996-02-07 | 中国有色金属工业总公司昆明贵金属研究所 | Method for making pure iridium |
| CN101985696A (en) * | 2010-12-01 | 2011-03-16 | 金川集团有限公司 | Method for extracting iridium from iridium containing materials |
| CN102296183A (en) * | 2011-08-19 | 2011-12-28 | 天津市化学试剂研究所 | Method for preparing high-purity platinum |
| CN105458278A (en) * | 2015-12-08 | 2016-04-06 | 贵研铂业股份有限公司 | Preparation method of high-purity spherical ruthenium powder |
| CN106166613A (en) * | 2016-08-18 | 2016-11-30 | 贵研铂业股份有限公司 | A kind of micron-size spherical W Mo alloy powder and preparation method thereof |
| CN108311714A (en) * | 2017-12-18 | 2018-07-24 | 贵研铂业股份有限公司 | A kind of micron-size spherical Pt-Ru alloy powder, preparation method thereofs |
| CN108620600A (en) * | 2017-12-18 | 2018-10-09 | 贵研铂业股份有限公司 | A kind of high-purity Large ratio surface platinum black and preparation method thereof |
| CN108217754A (en) * | 2017-12-25 | 2018-06-29 | 贵研铂业股份有限公司 | A kind of Large ratio surface IrO2Preparation method |
| CN108296491A (en) * | 2018-01-24 | 2018-07-20 | 贵研铂业股份有限公司 | A kind of spherical iridium raw powder's production technology of micron order |
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