CN102173400A - Method for preparing metal phosphide based on mechanical mixture of dihydrogen phosphate and metal salt - Google Patents
Method for preparing metal phosphide based on mechanical mixture of dihydrogen phosphate and metal salt Download PDFInfo
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- CN102173400A CN102173400A CN 201110063124 CN201110063124A CN102173400A CN 102173400 A CN102173400 A CN 102173400A CN 201110063124 CN201110063124 CN 201110063124 CN 201110063124 A CN201110063124 A CN 201110063124A CN 102173400 A CN102173400 A CN 102173400A
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Abstract
The invention relates to a method for prearaing metal phosphide by carrying out low-temperature thermal processing on the mechanical mixture of dihydrogen phosphate and metal salt, belonging to the technical field of inorganic nano material preparation. According to the invention, by utilizing the mechanical mixture of the dihydrogen phosphate and the metal salt as a precursor and simultaneously utilizing the reaction between phosphine and metal salt released by thermal decomposition of phosphorous dihydricsalt. If the mechanical mixture of dihydrogen phosphate and supported metal salt is used as the precursor, the supported phosphide can be prepared. The invention has the advantages of controllable sizes of phosphide granules, moderate preparation conditions, excellent process repeatability, stable product quality and good conformity, and is easy to operate and suitable for scale-up production.
Description
Technical field
The invention belongs to the inorganic nano material preparation process technology field, relate to the preparation method of inorganic nano material, specifically the synthetic method of phosphide.Can be applicable to aspects such as battery material, superconducting material and catalytic material.
Background technology
Metal phosphide is a big compound that has metal and characteristic of semiconductor roughly the same the time because its structure with and all have notable attribute and cause that people pay close attention to widely and study at photoelectricity, mechanics, electricity, aspect such as anticorrosive.The physical properties of metal phosphide is similar to nitride, boride, metallic carbide and silicon compound, and they all are the excellence conductors of electricity and heat, and hardness is big and have good thermodynamics and a chemical stability etc.Up to the present, developed the method for many synthetic metal phosphide nano materials, for example: laser catalytic growth method, the evaporation precipitator method, carbon nanotube template, high temperature injection method, thermal decomposition method, solvent-thermal method etc.
The present invention is a precursor with the mechanical mixture of dihydrogen phosphite salt and metal-salt, passes through the novel method of short period of time thermal treatment precursor preparation load simply and unsupported phosphide nano material at low temperatures.
Summary of the invention
Meaning of the present invention is to provide the synthetic method of a kind of load and unsupported phosphide, and this method has synthetic phosphide controllable size, preparation condition gentleness, simple to operate, safety, reaction times is of short duration, good process repeatability, the advantage of constant product quality.
Characteristics of the present invention are can realize preparing different types of phosphide by changing the kind of metal-salt.
Unsupported phosphide synthesis step is as follows:
A certain amount of dihydrogen phosphite salt and metal-salt are mixed with key; then said mixture is packed in the little porcelain boat, put into tube furnace, feed rare gas element or hydrogen as shielding gas; after directly being warmed up to 150-500 ℃ then, thermal treatment 10-180 minute.Under nitrogen protection furnace is reduced to room temperature after reaction finishes, product water is washed till neutrality, obtains corresponding phosphide in 3 hours 60 ℃ of vacuum-dryings.Above-mentioned dihydrogen phosphite salt can be in the periodictable dihydrogen phosphite salt among the IA and IIA or the mixture of dihydrogen phosphite salt.
Loading type phosphide synthesis step is as follows:
A certain amount of carrier was stirred dipping 3 hours in a certain amount of aqueous metal salt, then with carrier suction filtration, washing, the filter cake that obtains obtained corresponding load type metal salt precursor in 3 hours 60 ℃ of vacuum-dryings.Then a certain amount of dihydrogen phosphite salt and load type metal salt precursor are packed in the little porcelain boat, put into tube furnace, feed rare gas element or hydrogen as shielding gas, be warmed up to 150-500 ℃ then after, thermal treatment 10-180 minute.Under nitrogen protection furnace is reduced to room temperature after reaction finishes, product water is washed till neutrality, obtains corresponding phosphide in 3 hours 60 ℃ of vacuum-dryings.Above-mentioned dihydrogen phosphite salt can be in the periodictable dihydrogen phosphite salt among the IA and IIA or the mixture of dihydrogen phosphite salt.Aluminium sesquioxide, silicon-dioxide, molecular sieve, graphite, gac, titanium dioxide, zirconium dioxide etc.
Specific embodiments
Embodiment 1
0.45g sodium dihydrogen phosphite and 0.26g nickelous chloride are put into tube furnace; flow velocity with 20ml/min feeds argon gas; directly be warming up to 200 ℃ then; reaction is 30 minutes under this temperature; the back drops to room temperature in argon shield; product obtained nickel phosphide in 3 hours 80 ℃ of vacuum-dryings behind distilled water wash 2 times.
Embodiment 2
The quality of sodium dihydrogen phosphite in the embodiment 1 is become 0.48g, and the 0.26g nickelous chloride becomes the 0.22g cobalt chloride, and other condition is constant, obtains the phosphatization cobalt.
Embodiment 3
The quality of sodium dihydrogen phosphite in the embodiment 1 is become 0.52g, and the 0.26g nickelous chloride becomes the 0.2g iron protochloride, and other condition is constant, obtains iron phosphide.
Embodiment 4
The quality of sodium dihydrogen phosphite in the embodiment 1 is become 0.48g, and the 0.26g nickelous chloride becomes the 0.17g cupric chloride, and other condition is constant, obtains phosphorized copper.
Embodiment 5
It is constant that temperature in the embodiment 1 is become 250 ℃ of other conditions.
Embodiment 6
It is constant that temperature in the embodiment 1 is become 300 ℃ of other conditions.
Embodiment 7
It is constant that temperature in the embodiment 1 is become 350 ℃ of other conditions.
Embodiment 8
Temperature in the embodiment 1 is become 400 ℃, and other condition is constant.
Embodiment 9
Preparation time in the embodiment 1 is become 60 minutes, and other condition is constant.
Embodiment 10
The 1g nickelous chloride is dissolved in the 100ml distilled water, adds 10g total silicon MCM41 molecular sieve carrier then, stirred dipping 3 hours, filtering and washing is 3 times then, and filter cake is 60 ℃ of vacuum-dryings 3 hours.Filter cake after grinding got put into tube furnace after 1g and 1g hydrogen phosphite disodium mix; flow velocity with 20ml/min feeds nitrogen; directly be warming up to 300 ℃ then; reaction is 1 hour under this temperature; back near room temperature under nitrogen protection; product obtains the nickel phosphide of loading type behind distilled water wash 3 times.
Embodiment 11
Carrier in the embodiment 10 is become gac, and other condition is constant.
Embodiment 12
Carrier in the embodiment 10 is become silicon-dioxide, and other condition is constant.
Claims (3)
1. prepare the method for metal phosphide based on the mechanical mixture of dihydrogen phosphite salt and metal-salt, it is characterized in that comprising the steps:
Unsupported phosphide synthesis step is as follows:
A certain amount of dihydrogen phosphite salt and metal-salt are mixed with key, then said mixture is packed in the little porcelain boat, put into tube furnace, feed rare gas element or hydrogen as shielding gas, after directly being warmed up to 150-500 ℃ then, thermal treatment 10-180 minute, after finishing, reaction under nitrogen protection, furnace is reduced to room temperature, product water is washed till neutrality, obtains corresponding phosphide in 3 hours 60 ℃ of vacuum-dryings;
Loading type phosphide synthesis step is as follows:
A certain amount of carrier was stirred dipping 3 hours in a certain amount of aqueous metal salt, then with the carrier suction filtration, washing, the filter cake that obtains obtained corresponding load type metal salt precursor in 3 hours 60 ℃ of vacuum-dryings, then a certain amount of dihydrogen phosphite salt and load type metal salt precursor are packed in the little porcelain boat, put into tube furnace, feed rare gas element or hydrogen as shielding gas, after being warmed up to 150-500 ℃ then, thermal treatment 10-180 minute, after finishing, reaction under nitrogen protection, furnace is reduced to room temperature, product water is washed till neutrality, obtains corresponding phosphide in 3 hours 60 ℃ of vacuum-dryings;
2. the method for preparing metal phosphide according to the mechanical mixture based on dihydrogen phosphite salt and metal-salt of claim 1 is characterized in that described dihydrogen phosphite salt can be in the periodictable dihydrogen phosphite salt among the IA and IIA or the mixture of dihydrogen phosphite salt;
3. the method for preparing metal phosphide according to the mechanical mixture based on dihydrogen phosphite salt and metal-salt of claim 1 is characterized in that described carrier is aluminium sesquioxide, silicon-dioxide, molecular sieve, graphite, gac, titanium dioxide, zirconium dioxide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201110063124 CN102173400B (en) | 2011-03-16 | 2011-03-16 | Method for preparing metal phosphide based on mechanical mixture of dihydrogen phosphate and metal salt |
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| CN 201110063124 CN102173400B (en) | 2011-03-16 | 2011-03-16 | Method for preparing metal phosphide based on mechanical mixture of dihydrogen phosphate and metal salt |
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| CN102173400A true CN102173400A (en) | 2011-09-07 |
| CN102173400B CN102173400B (en) | 2013-01-30 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941674A (en) * | 2015-06-18 | 2015-09-30 | 西南大学 | Catalyst for loading cobalt phosphide on activated carbon as well as preparation and application of catalyst |
| CN105819418A (en) * | 2016-03-07 | 2016-08-03 | 常州大学 | Method for loading nanometer metal phosphide on porous carbon |
| CN106450305A (en) * | 2016-11-15 | 2017-02-22 | 哈尔滨工程大学 | Preparation method of lithium ion battery cathode material CoP/C |
| CN107313064A (en) * | 2017-06-12 | 2017-11-03 | 太原理工大学 | Metal boron or the α Fe of phosphide modification2O3The preparation method and application of light anode material |
| CN109759099A (en) * | 2019-03-04 | 2019-05-17 | 河南城建学院 | A kind of photochemical catalyst and preparation method thereof, application |
| CN110127655A (en) * | 2019-05-31 | 2019-08-16 | 江苏大学 | The method that one-step calcination method prepares the phosphatization cobalt electrode material of biomass carbon load |
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| US3798058A (en) * | 1967-06-19 | 1974-03-19 | V Chiola | Refractory metal phosphate and phosphide coatings for refractory metal leads and process for producing metal phosphides |
| CN1463792A (en) * | 2002-06-03 | 2003-12-31 | 北京石油化工学院材料与化工学院 | Novel molybdenum phosphorized hydrogenation desulfurization denitrification de-olefin catalyst and method for making same |
| CN1492025A (en) * | 2003-08-27 | 2004-04-28 | 大连理工大学 | Process for preparing load type transition metal phoshpide deep hydrogenation desulfurizing catalyst |
| CN1660695A (en) * | 2004-02-26 | 2005-08-31 | 中国科学院大连化学物理研究所 | Method for preparing phosphide of transition metal |
| CN101857207A (en) * | 2010-06-08 | 2010-10-13 | 南开大学 | Preparation method and application of transition metal phosphide Co2P |
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2011
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Patent Citations (5)
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| US3798058A (en) * | 1967-06-19 | 1974-03-19 | V Chiola | Refractory metal phosphate and phosphide coatings for refractory metal leads and process for producing metal phosphides |
| CN1463792A (en) * | 2002-06-03 | 2003-12-31 | 北京石油化工学院材料与化工学院 | Novel molybdenum phosphorized hydrogenation desulfurization denitrification de-olefin catalyst and method for making same |
| CN1492025A (en) * | 2003-08-27 | 2004-04-28 | 大连理工大学 | Process for preparing load type transition metal phoshpide deep hydrogenation desulfurizing catalyst |
| CN1660695A (en) * | 2004-02-26 | 2005-08-31 | 中国科学院大连化学物理研究所 | Method for preparing phosphide of transition metal |
| CN101857207A (en) * | 2010-06-08 | 2010-10-13 | 南开大学 | Preparation method and application of transition metal phosphide Co2P |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941674A (en) * | 2015-06-18 | 2015-09-30 | 西南大学 | Catalyst for loading cobalt phosphide on activated carbon as well as preparation and application of catalyst |
| CN104941674B (en) * | 2015-06-18 | 2017-10-10 | 西南大学 | Catalyst of phosphatization cobalt and its preparation method and application is loaded on a kind of activated carbon |
| CN105819418A (en) * | 2016-03-07 | 2016-08-03 | 常州大学 | Method for loading nanometer metal phosphide on porous carbon |
| CN106450305A (en) * | 2016-11-15 | 2017-02-22 | 哈尔滨工程大学 | Preparation method of lithium ion battery cathode material CoP/C |
| CN106450305B (en) * | 2016-11-15 | 2019-04-12 | 哈尔滨工程大学 | A kind of preparation method of lithium ion battery negative material CoP/C |
| CN107313064A (en) * | 2017-06-12 | 2017-11-03 | 太原理工大学 | Metal boron or the α Fe of phosphide modification2O3The preparation method and application of light anode material |
| CN109759099A (en) * | 2019-03-04 | 2019-05-17 | 河南城建学院 | A kind of photochemical catalyst and preparation method thereof, application |
| CN110127655A (en) * | 2019-05-31 | 2019-08-16 | 江苏大学 | The method that one-step calcination method prepares the phosphatization cobalt electrode material of biomass carbon load |
| CN110127655B (en) * | 2019-05-31 | 2023-01-17 | 江苏大学 | Method for preparing biomass carbon-loaded cobalt phosphide electrode material by one-step calcination method |
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| CN102173400B (en) | 2013-01-30 |
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