CN106215906A - The preparation and application that a kind of magnetic iron oxide/ammonium phosphomolybdate is composite porous - Google Patents

The preparation and application that a kind of magnetic iron oxide/ammonium phosphomolybdate is composite porous Download PDF

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CN106215906A
CN106215906A CN201610661555.XA CN201610661555A CN106215906A CN 106215906 A CN106215906 A CN 106215906A CN 201610661555 A CN201610661555 A CN 201610661555A CN 106215906 A CN106215906 A CN 106215906A
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iron oxide
ammonium phosphomolybdate
magnetic
composite porous
magnetic iron
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CN106215906B (en
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杨红军
孙景宽
李永
刘学文
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Hebei Jiuyi Nonferrous Metal Technology Co.,Ltd.
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Binzhou University
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract

The present invention relates to the composite porous preparation method of a kind of magnetic iron oxide/ammonium phosphomolybdate and application, belong to nano composite material and environment remediation field.The magnetic ferric oxide nano particles of preparation is added the self assembly process of ammonium phosphomolybdate polygonal crystal by the present invention, and material carries out surface modification, has finally synthesized magnetic iron oxide/ammonium phosphomolybdate composite porous.During in the composite prepared, superparamag-netic iron oxide is embedded in the loose structure of ammonium phosphomolybdate crystal equably, have magnetic recovery and the ammonium phosphomolybdate characteristic to cesium ion selective absorption concurrently, its shape difference rate is little, use during expulsion rate low, in fields such as nuclear pollution process, there is preferable application prospect.

Description

The preparation and application that a kind of magnetic iron oxide/ammonium phosphomolybdate is composite porous
Technical field
The present invention relates to the preparation and application that a kind of magnetic iron oxide/ammonium phosphomolybdate is composite porous, belong to nanometer multiple Condensation material and environment remediation field.
Technical background
The stable development of Nuclear Power Industry provides effective approach for solving world energy sources crisis, but also brings potential core spoke Penetrate pollution secret worry.On the one hand, nuclear power station can produce certain active nucleus waste matter during day-to-day operation；On the other hand, core Once there is careless mistake in terms of management link and trickle operating technology in reactor, the leakage of nuclear material i.e. can occur, pollute and expand Dissipate, bring the most serious disaster to human society and ecological environment.Radiocesium is the main component of nuclear pollution, is decaying Cheng Zhonghui discharges ray and the r ray of intense radiation, even if content is the lowest, also can cause the health of people long-term tight Heavily threaten, even teratogenesis, carcinogenic, mutagenesis.Radiocesium pollution control is also being used general pollution treatment method, example As: 1, shovel soil decontamination method；2, dilution method is ploughed deeply；3, rippability embrane method；4, phytoremediation；5, electro reclamation method；6, solvent Extraction etc..It is long that these methods also exist the cycle, high cost, repairs not thorough, and eurytopicity difference and inefficiency etc. are many Not enough.
Compared with traditional material, nano material has the most excellent physical/chemical properties.Particularly its huge ratio table Area so that it is pollutant are had the absorbability of excellence, and by extensive concern and expectation.In recent years, magnetic Nano composite wood Expect due to its can magnetic recovery, and can work in coordination with and utilize the advantage of each material component to become a kind of and have the new of wide application prospect Type composite.But in existing report there is shape inequality in the composite synthesized by magnetic nanometer composite material preparation technology Even, the technical deficiencies such as functional layer material content is low, easy to fall off, cause magnetic nanometer composite material the most not obtain widely should With.
Ammonium phosphomolybdate has good absorption property to rubidium cesium ion, and the principle of absorption is ion exchange, but phosphomolybdic acid Ammonium is originally as tiny crystalline powder, and being directly used in adsorption operations has certain difficulty, in order to overcome this difficulty by phosphorus Acid molybdenum fixed ammonium carrier research on the carrier such as zirconium phosphate, silica gel had had been reported that.Chinese patent application 200910021878.2 have supplied a kind of calcium alginate embedded ammonium phosphomolybdate compound adsorbent, and ammonium phosphomolybdate is first dissolved in water by it In, form mass percent 2～the ammonium phosphomolybdate suspension of 4%；Add the alginic acid of ammonium phosphomolybdate quality 0.3～2 times amount Sodium, stirring makes to be sufficiently mixed；Then mixture is instilled mass percent 3～10% calcium chloride solution in, reaction 12～48 is little Time, the spherical products obtained；Separate, with distilled water wash, be dried to obtain calcium alginate embedded ammonium phosphomolybdate compound adsorbent. This compound adsorbent can be applicable to adsorbing separation, removal rubidium, cesium ion from various solution systems, but makes adsorbent after embedding Adsorption efficiency be decreased obviously, the rate of adsorption is substantially reduced, drastically influence its application.
Chinese invention patent 201410057889.7 discloses a kind of sodium polyacrylate growth in situ prussian blue nano grain Sub-composite and its preparation method and application, it is the Prussian blue system of the polyacrylic acid iron by 40%～90% and 10%～60% Become.Described preparation method comprises the steps: 1) trivalent iron salt is dissolved in deionized water and glacial acetic acid mixed solution； 2) sodium polyacrylate is added；3) K is added4[Fe(CN)6] or Na4[Fe(CN)6]。
Chinese invention patent 201110380381.7 provides a kind of simple to operate composite extracting caesium-137 Preparation method.The method comprises the following steps: (1) will stir with phosphoric acid solution after dissolved oxygen zirconium chloride；(2) stand, precipitate, mistake Filter, drying, obtain zirconium phosphate；(3) with salpeter solution dissolved phosphorus ammonium molybdate；(4) zirconium phosphate is added in ammonium phosphomolybdate solution, stirs Mix；(5) stand, precipitate, filter, wash, then dry and obtain inorganic particulate material；(6) use binding agent pelletize, dry constant weight, Grind, screening i.e. can get composite.The method is simple to operate, and condition is easily controlled；This material is high to Cs selectivity, desorbing The easiest.
Through retrieval, up to the present ferroso-ferric oxide is inlayed the preparation method of ammonium phosphomolybdate polygonal crystal and is not yet appeared in the newspapers Road.
Summary of the invention
It is an object of the invention to provide the preparation method that a kind of magnetic iron oxide/ammonium phosphomolybdate is composite porous.This During the magnetic ferric oxide nano particles of preparation is added the self assembly of ammonium phosphomolybdate polygonal crystal by invention, and to material Material carries out surface modification, has synthesized magnetic iron oxide/ammonium phosphomolybdate composite porous.In this composite, magnetic iron oxide is received Rice grain is embedded in the loose structure of ammonium phosphomolybdate crystal in preparation process equably, combines magnetic recovery and phosphomolybdic acid The ammonium characteristic to cesium ion selective absorption, has preferable application prospect in fields such as nuclear pollution process.
The present invention is achieved through the following technical solutions above-mentioned technical purpose:
The preparation method that a kind of magnetic iron oxide/ammonium phosphomolybdate is composite porous, is with magnetic ferric oxide nano particles as core, Utilize growth in situ self-assembling technique, magnetic ferric oxide nano particles is uniformly embedded in ammonium phosphomolybdate polygonal crystal porous knot Structure prepares magnetic iron oxide/ammonium phosphomolybdate composite porous.
The composite porous preparation method of described magnetic iron oxide/ammonium phosphomolybdate specifically includes following steps:
(1) by Superparamagnetic Iron Oxide nanoparticle ultrasonic disperse in salpeter solution, stand 30-40min after stirring, make It is washed with deionized magnetic ferric oxide nano particles 3-4 time, then by its ultrasonic disperse to deionized water, mechanical agitation bar It is added thereto to ammonium molybdate solution under part, continues stirring 10-20 min, obtain intermediate solution 1；
(2) being slowly added in deionized water by concentrated nitric acid, concussion is added thereto to potassium pyrophosphate, stirring and dissolving after shaking up, obtain Intermediate solution 2；
(3) under mechanical agitation, intermediate solution 2 is added dropwise in intermediate solution 1, uses after continuing stirring 0.8-1.2h Magnet separation product, makes to be washed with deionized, dries that i.e. to can get magnetic iron oxide/ammonium phosphomolybdate composite porous.
Applicant is found by preparation experiment, magnetic ferric oxide nano particles particle diameter and magnetic ferric oxide nano particles with The ratio of weight and number of potassium pyrophosphate is to affect product magnetic iron oxide/composite porous shape of ammonium phosphomolybdate and come off The key factor of rate, applies for for this having carried out These parameters preferably in experimental basis, and wherein said magnetic iron oxide is received Rice corpuscles is the one in ferroso-ferric oxide, r-iron sesquioxide.The particle diameter of described magnetic ferric oxide nano particles is preferably 8-12 nm.Described magnetic ferric oxide nano particles is 1:0.5-5, preferably 1:2 with the weight ratio of potassium pyrophosphate.Described step Rapid 2) in, concentrated nitric acid is 1:4-9, more preferably 1:7 with the volume ratio of deionized water.
Preferably, the preparation method that described magnetic iron oxide/ammonium phosphomolybdate is composite porous specifically includes following steps:
(1) by the magnetic ferric oxide nano particles ultrasonic disperse of 0.5g superparamagnetism 10nm to 500 mL 2 M HNO3Solution In, stand 35min after stirring, make to be washed with deionized magnetic particle 3 times, then by its ultrasonic disperse to 200 mL In deionized water, under mechanical agitation, it is added thereto to the ammonium molybdate solution of 80 mL 135.9 mM, continues stirring 15 Min, obtains intermediate solution 1.
(2) accurately measure 2.5 ml concentrated nitric acids, be slowly added in 17.5 ml deionized waters, after concussion shakes up Being added thereto to 1.0 g potassium pyrophosphates, stirring makes it dissolve, obtains intermediate solution 2.
(3) control reaction temperature under mechanical agitation and be 30-40 DEG C, intermediate solution 2 is added dropwise to intermediate solution 1 In, using Magnet separation product after continuing stirring 1 h, make to be washed with deionized 3 times, 40 DEG C of drying i.e. can get magnetic oxygen Change ferrum/ammonium phosphomolybdate composite porous.
In preparation method described above, the speed being added dropwise in described step 3) is no faster than 50 droplets/minute.
The embodiment of the present invention 6 shows, magnetic ferric oxide nano particles particle diameter, magnetic iron oxide and potassium pyrophosphate mass ratio, The concentration of oxidant nitric acid, rate of addition and stirring response time are that to affect magnetic iron oxide/ammonium phosphomolybdate composite porous The key factor of quality.Magnetic iron oxide/ammonium phosphomolybdate prepared by comparing embodiment 1-embodiment 5 is composite porous permissible Find out when magnetic iron oxide and potassium pyrophosphate mass ratio are 1:2, and the performance of its physical property is the most excellent.Embodiment of the present invention 1-5 Prepared magnetic iron oxide/ammonium phosphomolybdate composite porous shape difference rate expulsion rate is low, and the response rate is high, and it is real with contrast Execute example 1-comparative example 5 and compare the difference with significance, wherein with the quality of the composite prepared by embodiment 1 the most Excellence, for highly preferred embodiment of the present invention.It is i.e. 10nm, magnetic iron oxide and pyrophosphoric acid when magnetic ferric oxide nano particles particle diameter Potassium mass ratio is 1:2, and concentrated nitric acid is 1:7 with the volume ratio of deionized water, and rate of addition is no faster than 50 droplets/minute, during stirring Between when being not less than 1h, the shape difference rate of preparation-obtained composite is minimum, and the response rate is the highest, and expulsion rate is minimum.
The present invention is also claimed the magnetic iron oxide/ammonium phosphomolybdate porous prepared according to above-mentioned preparation method and is combined Material.
The present invention be also claimed described magnetic iron oxide/ammonium phosphomolybdate composite porous adsorbing separation rubidium, caesium from Application in son.Magnetic iron oxide/ammonium phosphomolybdate prepared in the present invention is composite porous, can be used for water body, soil, big The cesium ions such as gas pollute the reparation of environment, and in middle low pollution environment, the clearance of caesium can reach more than 95%.
Magnetic iron oxide/ammonium phosphomolybdate proposed by the invention is composite porous, is to be with magnetic inorganic nano corpuscle Core, utilizes growth in situ self-assembling technique, magnetic ferric oxide nano particles is uniformly embedded in ammonium phosphomolybdate polygonal crystal many The composite constituted in pore structure.The structure that prepared obtained magnetic iron oxide/ammonium phosphomolybdate is composite porous As depicted in figs. 1 and 2, accompanying drawing can be seen that the size of magnetic ferric oxide nano particles core is at about 10 nm, polygonal crystal Composite shapes rule, diameter is between 1～12 μm, and composite inner porous, bore dia is about 50 nm.
The present invention compared with prior art has a following technical advantage:
1) magnetic iron oxide/ammonium phosphomolybdate provided by the present invention is composite porous be different from before the absorption caesium grain reported The composite of son, its internal porous, there is big specific surface, water has good dispersibility, magnetic response high, crystallization journey Degree height, when thus be accordingly used in the separation of radioelement caesium or remove, has simple and unit materials the absorbance of separation high Advantage.
2) the inventive method takes full advantage of the characteristic of magnetic material, uses Magnet to separate, have raw material be easy to get, the side of preparation Method is simply rapid, be suitable for large-scale production.Due to its inner porosity and the Large ratio surface being had, good dispersibility And Magneto separate characteristic, high cesium ion selectivity, in fields such as nuclear pollution process, there is important application prospect.
Accompanying drawing explanation
Fig. 1 is that magnetic iron oxide/ammonium phosphomolybdate is composite porous at the scanning electron microscope (SEM) photograph amplifying 200,000 times.
Fig. 2 is that magnetic iron oxide/ammonium phosphomolybdate is composite porous at the scanning electron microscope (SEM) photograph amplifying 500,000 times.
Detailed description of the invention
Further describe the present invention below by way of specific embodiment, but those skilled in the art should be able to know, described enforcement Example also limits scope of patent protection of the present invention never in any form.
The preparation method that 1 one kinds of magnetic iron oxide/ammonium phosphomolybdates of embodiment are composite porous
Described preparation method specifically includes following steps:
(1) by the magnetic ferric oxide nano particles ultrasonic disperse of 0.5g superparamagnetism 10 nm to 500 mL 2 M HNO3Solution In, stand 35min after stirring, make to be washed with deionized magnetic particle 3 times, then by its ultrasonic disperse to 200 mL In deionized water, under mechanical agitation, it is added thereto to the ammonium molybdate solution of 80 mL 135.9 mM, continues stirring 15 Min, obtains intermediate solution 1.
(2) accurately measure 2.5 ml concentrated nitric acids, be slowly added in 17.5 ml deionized waters, after concussion shakes up Being added thereto to 1.0 g potassium pyrophosphates, stirring makes it dissolve, obtains intermediate solution 2.
(3) controlling reaction temperature under mechanical agitation is 35 DEG C, intermediate solution 2 is added dropwise in intermediate solution 1, Using Magnet separation product after continuing stirring 1 h, make to be washed with deionized 3 times, 40 DEG C of drying i.e. can get magnetic oxygenated Ferrum/ammonium phosphomolybdate is composite porous.
The preparation method that 2 one kinds of magnetic iron oxide/ammonium phosphomolybdates of embodiment are composite porous
Described preparation method specifically includes following steps:
(1) by the magnetic ferric oxide nano particles ultrasonic disperse of 0.2g superparamagnetism 8nm to 500 mL 2 M HNO3In solution, After stirring stand 30min, make to be washed with deionized magnetic particle 4 times, then its ultrasonic disperse to 200 mL is gone from In sub-water, under mechanical agitation, it is added thereto to the ammonium molybdate solution of 80 mL 135.9 mM, continues stirring 10 min, To intermediate solution 1.
(2) accurately measure 4 ml concentrated nitric acids, be slowly added in 16ml deionized water, concussion shake up after wherein Adding 1.0 g potassium pyrophosphates, stirring makes it dissolve, obtains intermediate solution 2.
(3) controlling reaction temperature under mechanical agitation is 30 DEG C, intermediate solution 2 is added dropwise in intermediate solution 1, Using Magnet separation product after continuing stirring 0.8h, make to be washed with deionized 4 times, 40 DEG C of drying i.e. can get magnetic oxygenated Ferrum/ammonium phosphomolybdate is composite porous.
The preparation method that 3 one kinds of magnetic iron oxide/ammonium phosphomolybdates of embodiment are composite porous
Described preparation method specifically includes following steps:
(1) by the magnetic ferric oxide nano particles ultrasonic disperse of 0.2g superparamagnetism 12 nm to 500 mL 2 M HNO3Solution In, stand 40min after stirring, make to be washed with deionized magnetic particle 3 times, then by its ultrasonic disperse to 200 mL In deionized water, under mechanical agitation, it is added thereto to the ammonium molybdate solution of 80 mL 135.9 mM, continues stirring 20 Min, obtains intermediate solution 1.
(2) accurately measure 2 ml concentrated nitric acids, be slowly added in 18 ml deionized waters, concussion shake up backward its Middle addition 1.0 g potassium pyrophosphate, stirring makes it dissolve, obtains intermediate solution 2.
(3) controlling reaction temperature under mechanical agitation is 40 DEG C, intermediate solution 2 is added dropwise in intermediate solution 1, Using Magnet separation product after continuing stirring 1.2 h, make to be washed with deionized 3 times, 40 DEG C of drying i.e. can get magnetic oxygenated Ferrum/ammonium phosphomolybdate is composite porous.
The preparation method that 4 one kinds of magnetic iron oxide/ammonium phosphomolybdates of embodiment are composite porous
Described preparation method specifically includes following steps:
(1) by the magnetic ferric oxide nano particles ultrasonic disperse of 1.0g superparamagnetism 10 nm to 500 mL 2 M HNO3Solution In, stand 30min after stirring, make to be washed with deionized magnetic particle 3 times, then by its ultrasonic disperse to 200 mL In deionized water, under mechanical agitation, it is added thereto to the ammonium molybdate solution of 80 mL 135.9 mM, continues stirring 15 Min, obtains intermediate solution 1.
(2) accurately measuring 2.2ml concentrated nitric acid, be slowly added in 17.8 ml deionized waters, concussion shakes up backward Wherein adding 1.0 g potassium pyrophosphates, stirring makes it dissolve, obtains intermediate solution 2.
(3) controlling reaction temperature under mechanical agitation is 30 DEG C, intermediate solution 2 is added dropwise in intermediate solution 1, Using Magnet separation product after continuing stirring 1.2 h, make to be washed with deionized 3 times, 40 DEG C of drying i.e. can get magnetic oxygenated Ferrum/ammonium phosphomolybdate is composite porous.
The preparation method that 5 one kinds of magnetic iron oxide/ammonium phosphomolybdates of embodiment are composite porous
Described preparation method specifically includes following steps:
(1) by the magnetic ferric oxide nano particles ultrasonic disperse of 1.5g superparamagnetism 12 nm to 500 mL 2 M HNO3Solution In, stand 30min after stirring, make to be washed with deionized magnetic particle 3 times, then by its ultrasonic disperse to 200 mL In deionized water, under mechanical agitation, it is added thereto to the ammonium molybdate solution of 80 mL 135.9 mM, continues stirring 15 Min, obtains intermediate solution 1.
(2) accurately measure 2.4 ml concentrated nitric acids, be slowly added in 17.6 ml deionized waters, after concussion shakes up Being added thereto to 1.0 g potassium pyrophosphates, stirring makes it dissolve, obtains intermediate solution 2.
(3) controlling reaction temperature under mechanical agitation is 40 DEG C, intermediate solution 2 is added dropwise in intermediate solution 1, Using Magnet separation product after continuing stirring 1.1 h, make to be washed with deionized 3 times, 40 DEG C of drying i.e. can get magnetic oxygenated Ferrum/ammonium phosphomolybdate is composite porous.
Comparative example 1
Except the particle diameter of magnetic ferric oxide nano particles is in addition to 16nm, and remaining preparation technology is with embodiment 1.
Comparative example 2
Except the particle diameter of magnetic ferric oxide nano particles is in addition to 6nm, and remaining preparation technology is with embodiment 1.
Comparative example 3
Except step 2) in concentrated nitric acid volume be 1.5ml, deionized water is 18.5ml, remaining preparation with process example 1.
Comparative example 4
Except step 2) in concentrated nitric acid volume be 5ml, deionized water is 15ml, remaining preparation with process example 1.
Comparative example 5
Except the speed being added dropwise in step 3) is 30 droplets/point, mixing time is outside 0.5h, and remaining technique is with embodiment 1.
The measuring physical properties of embodiment 6 composite of the present invention
Measure embodiment of the present invention 1-embodiment 5, the shape of the composite of comparative example 1-comparative example 5 preparation respectively Variance rate, the response rate, expulsion rate.Wherein shape difference rate is to form the shape difference of composite, uses scanning electron microscopy Mirror is measured.The response rate is the percentage that in step 3), the reasonable opinion of the weight of the actual composite obtained obtains composite Rate；Expulsion rate is that composite soaks expulsion rate after 24h in 0.1 M hydrochloric acid solution.The measurement result of each parameter such as table 1 institute Show.
The measuring physical properties result of table 1 composite of the present invention
As can be seen from Table 1, magnetic ferric oxide nano particles particle diameter, magnetic iron oxide and potassium pyrophosphate mass ratio, oxidant nitre The concentration of acid, rate of addition and stirring response time are the weights affecting the composite porous quality of magnetic iron oxide/ammonium phosphomolybdate Want factor.
Composite porous can be seen that of magnetic iron oxide/ammonium phosphomolybdate prepared by comparing embodiment 1-embodiment 5 is worked as Magnetic iron oxide and potassium pyrophosphate mass ratio are 1:2, and the performance of its physical property is the most excellent.
Magnetic iron oxide/ammonium phosphomolybdate composite porous shape difference rate prepared by embodiment of the present invention 1-5 comes off Rate is low, and the response rate is high, and it has the difference of significance compared with comparative example 1-comparative example 5, wherein with embodiment 1 institute The quality of the composite of preparation is the most excellent, for highly preferred embodiment of the present invention.I.e. when magnetic ferric oxide nano particles particle diameter For 10nm, magnetic iron oxide and potassium pyrophosphate mass ratio are 1:2, and concentrated nitric acid is 1:7 with the volume ratio of deionized water, and dropping speed Degree is no faster than 50 droplets/minute, and when mixing time is not less than 1h, the shape difference rate of preparation-obtained composite is minimum, returns Yield is the highest, and expulsion rate is minimum.

Claims (10)

1. the preparation method that magnetic iron oxide/ammonium phosphomolybdate is composite porous, it is with magnetic ferric oxide nano particles For core, utilize growth in situ self-assembling technique, magnetic ferric oxide nano particles is uniformly embedded in ammonium phosphomolybdate polygonal crystal Loose structure prepares magnetic iron oxide/ammonium phosphomolybdate composite porous.
The preparation method that magnetic iron oxide/ammonium phosphomolybdate the most according to claim 1 is composite porous, its feature exists In, it specifically includes following steps:
(1) by Superparamagnetic Iron Oxide nanoparticle ultrasonic disperse in salpeter solution, stand 30-40min after stirring, make It is washed with deionized magnetic ferric oxide nano particles 3-4 time, then by its ultrasonic disperse to deionized water, mechanical agitation bar It is added thereto to ammonium molybdate solution under part, continues stirring 10-20 min, obtain intermediate solution 1；
(2) being slowly added in deionized water by concentrated nitric acid, concussion is added thereto to potassium pyrophosphate, stirring and dissolving after shaking up, obtain Intermediate solution 2；
(3) under mechanical agitation, intermediate solution 2 is added dropwise in intermediate solution 1, uses after continuing stirring 0.8-1.2h Magnet separation product, makes to be washed with deionized, dries that i.e. to can get magnetic iron oxide/ammonium phosphomolybdate composite porous.
The preparation method that magnetic iron oxide/ammonium phosphomolybdate the most according to claim 2 is composite porous, its feature exists In, described magnetic ferric oxide nano particles is the one in ferroso-ferric oxide, r-iron sesquioxide.
The preparation method that magnetic iron oxide/ammonium phosphomolybdate the most according to claim 2 is composite porous, its feature exists In, the particle diameter of described magnetic ferric oxide nano particles is 8-12 nm.
The preparation method that magnetic iron oxide/ammonium phosphomolybdate the most according to claim 2 is composite porous, its feature exists In, described magnetic ferric oxide nano particles is 1:0.5-5, preferably 1:2 with the weight ratio of potassium pyrophosphate；Described step 2) in Concentrated nitric acid is 1:4-9, preferably 1:7 with the volume ratio of deionized water.
The preparation method that magnetic iron oxide/ammonium phosphomolybdate the most according to claim 2 is composite porous, its feature exists In, specifically include following steps:
(1) by the magnetic ferric oxide nano particles ultrasonic disperse of 0.5g superparamagnetism 10nm to 500 mL 2 M HNO3In solution, After stirring stand 35min, make to be washed with deionized magnetic particle 3 times, then its ultrasonic disperse to 200 mL is gone from In sub-water, under mechanical agitation, it is added thereto to the ammonium molybdate solution of 80 mL 135.9 mM, continues stirring 15 min, To intermediate solution 1；
(2) accurately measure 2.5 ml concentrated nitric acids, be slowly added in 17.5 ml deionized waters, concussion shake up backward its Middle addition 1.0 g potassium pyrophosphate, stirring makes it dissolve, obtains intermediate solution 2；
(3) control reaction temperature under mechanical agitation and be 30-40 DEG C, intermediate solution 2 is added dropwise in intermediate solution 1, Using Magnet separation product after continuing stirring 1 h, make to be washed with deionized 3 times, 40 DEG C of drying i.e. can get magnetic oxygenated Ferrum/ammonium phosphomolybdate is composite porous.
7., according to the preparation method that the arbitrary described magnetic iron oxide/ammonium phosphomolybdate of claim 1-6 is composite porous, it is special Levying and be, the speed being added dropwise in described step 3) is not more than 50 droplets/minute.
8. magnetic iron oxide/ammonium phosphomolybdate the porous prepared according to the arbitrary described claim of claim 1-7 is again Condensation material.
9. magnetic iron oxide/the ammonium phosphomolybdate described in claim 8 is composite porous at adsorbing separation rubidium ion or cesium ion In application.
Application the most according to claim 9, it is characterised in that described magnetic iron oxide/ammonium phosphomolybdate porous composite wood Material pollutes the reparation of environment for rubidium ion or cesium ion.
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