CN106215906B - A kind of preparation and application that magnetic iron oxide/ammonium phosphomolybdate is composite porous - Google Patents

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

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CN106215906B
CN106215906B CN201610661555.XA CN201610661555A CN106215906B CN 106215906 B CN106215906 B CN 106215906B CN 201610661555 A CN201610661555 A CN 201610661555A CN 106215906 B CN106215906 B CN 106215906B
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magnetic
iron oxide
ammonium phosphomolybdate
magnetic iron
composite porous
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CN106215906A (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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J20/0259—Compounds of N, P, As, Sb, Bi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/006—Radioactive compounds

Abstract

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

Description

A kind of preparation and application that magnetic iron oxide/ammonium phosphomolybdate is composite porous
Technical field
The present invention relates to a kind of preparation and application that magnetic iron oxide/ammonium phosphomolybdate is composite porous, and it is multiple to belong to nanometer Condensation material and environment remediation field.
Technical background
The stable development of Nuclear Power Industry provides effective approach to solve world energy sources crisis, but also brings potential Nuclear radiation pollution secret worry.On the one hand, nuclear power station will produce certain active nucleus waste matter during day-to-day operation；Another party Once there is careless mistake in terms of management link and subtle operating technology in face, nuclear reactor, i.e., leakage, the pollution of nuclear material can occur And diffusion, bring extremely serious disaster to human society and ecological environment.Radioactive cesium is the main component of nuclear pollution, is being declined The ray and r rays of intense radiation can be released during change, even if content can cause people's health for a long time if very low Seriously threaten in addition teratogenesis, carcinogenic, mutagenesis.General pollution treatment method also is being used to radioactive cesium pollution control, Such as：1, native decontamination method is shoveled；2, dilution method is ploughed deeply；3, rippability embrane method；4, phytoremediation；5, electro reclamation；6, molten Agent extraction etc..These methods are long there is the period, and cost is excessively high, and reparation is not thorough, and eurytopicity difference and inefficiency etc. are all It is mostly insufficient.
Compared with traditional material, nano material has completely new excellent physical/chemical properties.Especially its huge compares table Area makes it have excellent adsorption capacity to pollutant, and by extensive concern and expectation.In recent years, magnetic Nano composite wood Material due to its can magnetic recovery, and can cooperate with using each material component the advantages of and become it is a kind of have wide application prospect it is new Type composite material.But there are shape unevenness for the composite material in existing report synthesized by magnetic nanometer composite material preparation process Even, functional layer material content is low, and the technical deficiencies such as easy to fall off cause magnetic nanometer composite material still not answered widely With.
Ammonium phosphomolybdate has good absorption property to rubidium cesium ion, and the principle of absorption is ion exchange, but phosphomolybdic acid For ammonium sheet as tiny crystalline powder, being directly used in adsorption operations has certain difficulty, in order to overcome this difficult by phosphorus Sour molybdenum fixed ammonium carrier had had been reported that in the research on the carriers such as basic zirconium phosphate, silica gel.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 In, form the ammonium phosphomolybdate suspension of mass percent 2~4%；Add the alginic acid of 0.3~2 times of amount of ammonium phosphomolybdate quality Sodium, stirring make to be sufficiently mixed；Then mixture is instilled in the calcium chloride solution of mass percent 3~10%, reaction 12~48 is small When, obtained spherical products；It detaches, be washed with distilled water, being dried to obtain calcium alginate embedded ammonium phosphomolybdate compound adsorbent. The compound adsorbent can be applied to adsorbing separation, removal rubidium, cesium ion from various solution systems, but make adsorbent after embedding Adsorption efficiency be decreased obviously, the rate of adsorption is substantially reduced, and drastically influences its application.
Chinese invention patent 201410057889.7 discloses a kind of Sodium Polyacrylate growth in situ prussian blue nano grain Sub- composite material and preparation method and application are by 40%~90% polyacrylic acid iron and 10%~60% Prussian blue system At.The preparation method includes the following steps：1）Trivalent iron salt is dissolved in deionized water and glacial acetic acid mixed solution； 2）Addition polymerization sodium acrylate；3）Add K4[Fe(CN)6] or Na4[Fe(CN)6]。
Chinese invention patent 201110380381.7 provides a kind of composite material of extraction caesium -137 easy to operate Preparation method.This approach includes the following steps：(1) it will be stirred with phosphoric acid solution after dissolving zirconium oxychloride；(2) it stands, precipitate, mistake Filter, drying, obtain basic zirconium phosphate；(3) ammonium phosphomolybdate is dissolved with salpeter solution；(4) basic zirconium phosphate is added in ammonium phosphomolybdate solution, is stirred It mixes；(5) it stands, precipitate, be filtered, washed, then drying obtains inorganic particulate material；(6) binder granulation is used, constant weight is dried, Grinding, screening can be obtained composite material.This method is easy to operate, and condition is easy to control；The material is to Cs high selectivities, desorption Also it is easy.
Through retrieval, up to the present ferroso-ferric oxide inlays the preparation method of ammonium phosphomolybdate polygonal crystal and not yet appears in the newspapers Road.
Invention content
The purpose of the present invention is to provide a kind of preparation methods that magnetic iron oxide/ammonium phosphomolybdate is composite porous.This Invention the magnetic ferric oxide nano particles of preparation is added during the self assembly of ammonium phosphomolybdate polygonal crystal, and to material Material carries out surface modification, and it is composite porous to have synthesized magnetic iron oxide/ammonium phosphomolybdate.Magnetic iron oxide is received in the composite material Rice grain is equably embedded in preparation process in the porous structure of ammonium phosphomolybdate crystal, combines magnetic recovery and phosphomolybdic acid Ammonium has preferable application prospect to the characteristic of cesium ion selective absorption in fields such as nuclear pollution processing.
The present invention is achieved through the following technical solutions above-mentioned technical purpose：
A kind of preparation method that magnetic iron oxide/ammonium phosphomolybdate is composite porous, is with magnetic ferric oxide nano particles Magnetic ferric oxide nano particles are uniformly embedded in ammonium phosphomolybdate polygonal crystal using growth in situ self-assembling technique for core It is composite porous that magnetic iron oxide/ammonium phosphomolybdate is prepared in porous structure.
The composite porous preparation method of the magnetic iron oxide/ammonium phosphomolybdate specifically comprises the following steps：
（1）By Superparamagnetic Iron Oxide nano-particle ultrasonic disperse in salpeter solution, 30- is stood after stirring evenly 40min makes magnetic ferric oxide nano particles to be washed with deionized 3-4 times, then by its ultrasonic disperse to deionized water, machine Ammonium molybdate solution is added under tool stirring condition thereto, continues to stir 10-20 min, obtains intermediate solution 1；
（2）Concentrated nitric acid is slowly added into deionized water, potassium pyrophosphate is added in concussion thereto after shaking up, stirring is molten Solution, obtains intermediate solution 2；
（3）Under mechanical agitation, intermediate solution 2 is added dropwise in intermediate solution 1, is continued after stirring 0.8-1.2h Using magnet separation product, makes to be washed with deionized, dries and can be obtained the porous composite wood of magnetic iron oxide/ammonium phosphomolybdate Material.
Applicant has found by preparing experiment, magnetic ferric oxide nano particles grain size and magnetic ferric oxide nano particles with The weight part ratio of potassium pyrophosphate is to influence reaction product magnetic iron oxide/composite porous shape of ammonium phosphomolybdate and fall off The key factor of rate applies having carried out preferably These parameters in experimental basis thus, wherein the magnetic iron oxide is received Rice corpuscles is one kind in ferroso-ferric oxide, r- di-iron trioxides.The grain size of the magnetic ferric oxide nano particles is preferably 8-12 nm.The weight ratio of the magnetic ferric oxide nano particles and potassium pyrophosphate is 1:0.5-5, preferably 1:2.The step Rapid 2）The volume ratio of middle concentrated nitric acid and deionized water is 1:4-9, further preferably 1:7.
Preferably, the composite porous preparation method of the magnetic iron oxide/ammonium phosphomolybdate specifically comprises the following steps：
（1）By the magnetic ferric oxide nano particles ultrasonic disperse of 0.5g superparamagnetism 10nm to 500 mL, 2 M HNO3It is molten In liquid, 35min is stood after stirring evenly, makes magnetic particle to be washed with deionized 3 times, then by its ultrasonic disperse to 200 mL In deionized water, the ammonium molybdate solution of 80 mL, 135.9 mM is added under mechanical agitation thereto, continues stirring 15 Min obtains intermediate solution 1.
（2）It is accurate to measure 2.5 ml concentrated nitric acids, it is slowly added into 17.5 ml deionized waters, after concussion shakes up 1.0 g potassium pyrophosphates are added thereto, stir to dissolve, obtain intermediate solution 2.
（3）Controlling reaction temperature is 30-40 DEG C under mechanical agitation, and intermediate solution 2 is added dropwise to intermediate solution 1 In, continue to use magnet separation product after stirring 1 h, makes to be washed with deionized 3 times, 40 DEG C of drying can be obtained magnetic oxygen It is composite porous to change iron/ammonium phosphomolybdate.
In preparation method described above, the step 3）In the speed that is added dropwise be no faster than 50 drops/minute.
The embodiment of the present invention 6 shows magnetic ferric oxide nano particles grain size, magnetic iron oxide and potassium pyrophosphate mass ratio, The concentration of oxidant nitric acid, rate of addition and be stirred to react the time be influence magnetic iron oxide/ammonium phosphomolybdate it is composite porous An important factor for quality.Magnetic iron oxide/ammonium phosphomolybdate prepared by comparing embodiment 1- embodiments 5 is composite porous can be with Find out when magnetic iron oxide and potassium pyrophosphate mass ratio are 1:2, physical property performance is more excellent.1-5 of the embodiment of the present invention The composite porous shape difference rate expulsion rate of prepared magnetic iron oxide/ammonium phosphomolybdate is low, and the rate of recovery is high, real with comparison It applies a 1- comparative examples 5 and compares the difference with conspicuousness, wherein the most with the quality of the composite material prepared by embodiment 1 It is excellent, it is highly preferred embodiment of the present invention.I.e. when magnetic ferric oxide nano particles grain size is 10nm, magnetic iron oxide and pyrophosphoric acid Potassium mass ratio is 1:2, the volume ratio of concentrated nitric acid and deionized water is 1:7, and rate of addition is no faster than 50 drops/minute, when stirring Between when being not less than 1h, the shape difference rate of preparation-obtained composite material is minimum, rate of recovery highest, and expulsion rate is minimum.
It is porous compound that the magnetic iron oxide/ammonium phosphomolybdate being prepared according to above-mentioned preparation method is also claimed in the present invention Material.
The present invention be also claimed the magnetic iron oxide/ammonium phosphomolybdate it is composite porous adsorbing separation rubidium, caesium from Application in son.Prepared magnetic iron oxide/ammonium phosphomolybdate is composite porous in the present invention, can be used for water body, soil, big The cesium ions such as gas pollute the reparation of environment, and the removal rate of caesium can reach 95% or more in middle low pollution environment.
Magnetic iron oxide/ammonium phosphomolybdate proposed by the invention is composite porous, is to be with magnetic inorganic nano corpuscle It is more to be uniformly embedded in ammonium phosphomolybdate polygonal crystal using growth in situ self-assembling technique by core for magnetic ferric oxide nano particles The composite material constituted in pore structure.The composite porous structure of prepared obtained magnetic iron oxide/ammonium phosphomolybdate As depicted in figs. 1 and 2, by attached drawing it can be seen that the size of magnetic ferric oxide nano particles core is in 10 nm or so, polygonal crystal Composite shapes rule, for diameter between 1~12 μm, composite inner is porous, and bore dia is 50 nm or so.
The present invention has following technical advantage compared with prior art：
1）Magnetic iron oxide/ammonium phosphomolybdate provided by the present invention is composite porous be different from before the absorption reported The composite material of caesium particle, its internal porous have big specific surface, have good dispersibility, magnetic response high in water, brilliant Change degree is high, when being accordingly used in the separation or removal of radioactive element caesium, has separation simple and the absorptivity of unit materials High advantage.
2）The method of the present invention takes full advantage of the characteristic of magnetic material, is detached using magnet, there is raw material to be easy to get, preparation side Method is simple rapidly, is suitable for mass producing.Due to its inner porosity and possessed Large ratio surface, good dispersibility And Magneto separate characteristic, high cesium ion selectivity are with important application prospects in fields such as nuclear pollution processing.
Description of the drawings
Fig. 1, which is that magnetic iron oxide/ammonium phosphomolybdate is composite porous, is amplifying 200,000 times of scanning electron microscope (SEM) photograph.
Fig. 2, which is that magnetic iron oxide/ammonium phosphomolybdate is composite porous, is amplifying 500,000 times of scanning electron microscope (SEM) photograph.
Specific implementation mode
The present invention is further described below by way of specific embodiment, but those skilled in the art should be able to know, the implementation Example does not limit scope of patent protection of the present invention in any way.
A kind of composite porous preparation method of 1 magnetic iron oxide/ammonium phosphomolybdate of embodiment
The preparation method specifically comprises the following steps：
（1）By the magnetic ferric oxide nano particles ultrasonic disperse of 10 nm of 0.5g superparamagnetism to 500 mL, 2 M HNO3 In solution, 35min is stood after stirring evenly, makes magnetic particle to be washed with deionized 3 times, then by its ultrasonic disperse to 200 In mL deionized waters, the ammonium molybdate solution of 80 mL, 135.9 mM is added under mechanical agitation thereto, continues stirring 15 Min obtains intermediate solution 1.
（2）It is accurate to measure 2.5 ml concentrated nitric acids, it is slowly added into 17.5 ml deionized waters, after concussion shakes up 1.0 g potassium pyrophosphates are added thereto, stir to dissolve, obtain intermediate solution 2.
（3）Controlling reaction temperature is 35 DEG C under mechanical agitation, and intermediate solution 2 is added dropwise in intermediate solution 1, Continue to use magnet separation product after stirring 1 h, makes to be washed with deionized 3 times, 40 DEG C of drying can be obtained magnetic oxygenated Iron/ammonium phosphomolybdate is composite porous.
A kind of composite porous preparation method of 2 magnetic iron oxide/ammonium phosphomolybdate of embodiment
The preparation method specifically comprises the following steps：
（1）By the magnetic ferric oxide nano particles ultrasonic disperse of 0.2g superparamagnetism 8nm to 500 mL, 2 M HNO3It is molten In liquid, 30min is stood after stirring evenly, makes magnetic particle to be washed with deionized 4 times, then by its ultrasonic disperse to 200 mL In deionized water, the ammonium molybdate solution of 80 mL, 135.9 mM is added under mechanical agitation thereto, continues stirring 10 Min obtains intermediate solution 1.
（2）It is accurate to measure 4 ml concentrated nitric acids, it is slowly added into 16ml deionized waters, is shaken after shaking up thereto 1.0 g potassium pyrophosphates are added, stir to dissolve, obtain intermediate solution 2.
（3）Controlling reaction temperature is 30 DEG C under mechanical agitation, and intermediate solution 2 is added dropwise in intermediate solution 1, Continue to use magnet separation product after stirring 0.8h, makes to be washed with deionized 4 times, 40 DEG C of drying can be obtained magnetic oxygenated Iron/ammonium phosphomolybdate is composite porous.
A kind of composite porous preparation method of 3 magnetic iron oxide/ammonium phosphomolybdate of embodiment
The preparation method specifically comprises the following steps：
（1）By the magnetic ferric oxide nano particles ultrasonic disperse of 12 nm of 0.2g superparamagnetism to 500 mL, 2 M HNO3 In solution, 40min is stood after stirring evenly, makes magnetic particle to be washed with deionized 3 times, then by its ultrasonic disperse to 200 In mL deionized waters, the ammonium molybdate solution of 80 mL, 135.9 mM is added under mechanical agitation thereto, continues stirring 20 Min obtains intermediate solution 1.
（2）It is accurate to measure 2 ml concentrated nitric acids, it is slowly added into 18 ml deionized waters, is shaken after shaking up to it 1.0 g potassium pyrophosphates of middle addition, stir to dissolve, obtain intermediate solution 2.
（3）Controlling reaction temperature is 40 DEG C under mechanical agitation, and intermediate solution 2 is added dropwise in intermediate solution 1, Continue to use magnet separation product after stirring 1.2 h, makes to be washed with deionized 3 times, 40 DEG C of drying can be obtained magnetic oxygenated Iron/ammonium phosphomolybdate is composite porous.
A kind of composite porous preparation method of 4 magnetic iron oxide/ammonium phosphomolybdate of embodiment
The preparation method specifically comprises the following steps：
（1）By the magnetic ferric oxide nano particles ultrasonic disperse of 10 nm of 1.0g superparamagnetism to 500 mL, 2 M HNO3 In solution, 30min is stood after stirring evenly, makes magnetic particle to be washed with deionized 3 times, then by its ultrasonic disperse to 200 In mL deionized waters, the ammonium molybdate solution of 80 mL, 135.9 mM is added under mechanical agitation thereto, continues stirring 15 Min obtains intermediate solution 1.
（2）It is accurate to measure 2.2ml concentrated nitric acids, it is slowly added into 17.8 ml deionized waters, concussion shakes up backward 1.0 g potassium pyrophosphates are wherein added, stir to dissolve, obtain intermediate solution 2.
（3）Controlling reaction temperature is 30 DEG C under mechanical agitation, and intermediate solution 2 is added dropwise in intermediate solution 1, Continue to use magnet separation product after stirring 1.2 h, makes to be washed with deionized 3 times, 40 DEG C of drying can be obtained magnetic oxygenated Iron/ammonium phosphomolybdate is composite porous.
A kind of composite porous preparation method of 5 magnetic iron oxide/ammonium phosphomolybdate of embodiment
The preparation method specifically comprises the following steps：
（1）By the magnetic ferric oxide nano particles ultrasonic disperse of 12 nm of 1.5g superparamagnetism to 500 mL, 2 M HNO3 In solution, 30min is stood after stirring evenly, makes magnetic particle to be washed with deionized 3 times, then by its ultrasonic disperse to 200 In mL deionized waters, the ammonium molybdate solution of 80 mL, 135.9 mM is added under mechanical agitation thereto, continues stirring 15 Min obtains intermediate solution 1.
（2）It is accurate to measure 2.4 ml concentrated nitric acids, it is slowly added into 17.6 ml deionized waters, after concussion shakes up 1.0 g potassium pyrophosphates are added thereto, stir to dissolve, obtain intermediate solution 2.
（3）Controlling reaction temperature is 40 DEG C under mechanical agitation, and intermediate solution 2 is added dropwise in intermediate solution 1, Continue to use magnet separation product after stirring 1.1 h, makes to be washed with deionized 3 times, 40 DEG C of drying can be obtained magnetic oxygenated Iron/ammonium phosphomolybdate is composite porous.
Comparative example 1
In addition to the grain size of magnetic ferric oxide nano particles is 16nm, remaining preparation process is the same as embodiment 1.
Comparative example 2
In addition to the grain size of magnetic ferric oxide nano particles is 6nm, remaining preparation process is the same as embodiment 1.
Comparative example 3
Except step 2）Middle concentrated nitric acid volume is 1.5ml, deionized water 18.5ml, remaining is prepared with process example 1.
Comparative example 4
Except step 2）Middle concentrated nitric acid volume is 5ml, deionized water 15ml, remaining is prepared with process example 1.
Comparative example 5
Except step 3）In the speed that is added dropwise be 30 drops/point, mixing time is outside 0.5h, remaining technique is the same as embodiment 1.
The measuring physical properties of 6 composite material of the present invention of embodiment
1- of embodiment of the present invention embodiments 5 are measured respectively, composite material prepared by comparative example 1- comparative examples 5 Shape difference rate, the rate of recovery, expulsion rate.Wherein shape difference rate is to form the shape difference of composite material, using scanning electron Microscope is measured.The rate of recovery is step 3）The reasonable opinion of weight of the middle composite material actually obtained obtains the hundred of composite material Divide rate；Expulsion rate is expulsion rate after composite material impregnates for 24 hours in 0.1 M hydrochloric acid solutions.The measurement result of each parameter such as 1 institute of table Show.
The measuring physical properties result of 1 composite material of the present invention of table
As can be seen from Table 1, magnetic ferric oxide nano particles grain size, magnetic iron oxide and potassium pyrophosphate mass ratio, oxidation The concentration of agent nitric acid, rate of addition and be stirred to react the time be influence the composite porous quality of magnetic iron oxide/ammonium phosphomolybdate An important factor for.
Magnetic iron oxide/ammonium phosphomolybdate prepared by comparing embodiment 1- embodiments 5 is composite porous it can be seen that working as Magnetic iron oxide is 1 with potassium pyrophosphate mass ratio:2, physical property performance is more excellent.
The composite porous shape difference rate of magnetic iron oxide/ammonium phosphomolybdate prepared by 1-5 of the embodiment of the present invention falls off Rate is low, and the rate of recovery is high, the difference with conspicuousness compared with comparative example 1- comparative examples 5, wherein with 1 institute of embodiment The quality of the composite material of preparation is the most excellent, is highly preferred embodiment of the present invention.I.e. when magnetic ferric oxide nano particles grain size For 10nm, magnetic iron oxide is 1 with potassium pyrophosphate mass ratio:2, the volume ratio of concentrated nitric acid and deionized water is 1:7, and speed is added dropwise Degree is no faster than 50 drops/minute, and when mixing time is not less than 1h, the shape difference rate of preparation-obtained composite material is minimum, returns Yield highest, expulsion rate are minimum.

Claims (7)

1. a kind of preparation method that magnetic iron oxide/ammonium phosphomolybdate is composite porous, is with magnetic ferric oxide nano particles Magnetic ferric oxide nano particles are uniformly embedded in ammonium phosphomolybdate polygonal crystal using growth in situ self-assembling technique for core It is composite porous that magnetic iron oxide/ammonium phosphomolybdate is prepared in porous structure,
It specifically comprises the following steps：
(1) Superparamagnetic Iron Oxide nano-particle ultrasonic disperse is stood 30-40min after stirring evenly, made in salpeter solution Magnetic ferric oxide nano particles are washed with deionized 3-4 times, then by its ultrasonic disperse to deionized water, mechanical agitation item Ammonium molybdate solution is added under part thereto, continues to stir 10-20min, obtains intermediate solution 1；
(2) concentrated nitric acid is slowly added into deionized water, potassium pyrophosphate is added after shaking up in concussion thereto, and stirring and dissolving obtains Intermediate solution 2；
(3) under mechanical agitation, intermediate solution 2 is added dropwise in intermediate solution 1, continues to use after stirring 0.8-1.2h Magnet separation product makes to be washed with deionized, dries that can be obtained magnetic iron oxide/ammonium phosphomolybdate composite porous；
The magnetic ferric oxide nano particles are one kind in ferroso-ferric oxide, γ-di-iron trioxide；The magnetic oxygen The grain size for changing Fe nanometer particles is 8-12nm；The weight ratio of the magnetic ferric oxide nano particles and potassium pyrophosphate is 1:0.5- 5；The volume ratio of concentrated nitric acid and deionized water is 1 in the step 2):4-9.
2. the composite porous preparation method of magnetic iron oxide/ammonium phosphomolybdate according to claim 1, feature exist In the weight ratio of the magnetic ferric oxide nano particles and potassium pyrophosphate is 1:2；Concentrated nitric acid and deionization in the step 2) The volume ratio of water is 1:7.
3. the composite porous preparation method of magnetic iron oxide/ammonium phosphomolybdate according to claim 1, feature exist In specifically comprising the following steps：
(1) by the magnetic ferric oxide nano particles ultrasonic disperse of 0.5g superparamagnetism 10nm to 500mL 2MHNO3In solution, stirring 35min is stood after uniformly, makes magnetic particle to be washed with deionized 3 times, then by its ultrasonic disperse to 200mL deionized waters In, the ammonium molybdate solution of 80mL 135.9mM is added under mechanical agitation thereto, continues to stir 15min, obtains intermediate molten Liquid 1；
(2) 2.5ml concentrated nitric acids are accurately measured, are slowly added into 17.5ml deionized waters, concussion adds thereto after shaking up Enter 1.0g potassium pyrophosphates, stir to dissolve, obtains intermediate solution 2；
(3) controlling reaction temperature is 30-40 DEG C under mechanical agitation, and intermediate solution 2 is added dropwise in intermediate solution 1, Continue to use magnet separation product after stirring 1h, make to be washed with deionized 3 times, 40 DEG C of drying can be obtained magnetic iron oxide/ Ammonium phosphomolybdate is composite porous.
4. special according to the composite porous preparation method of any magnetic iron oxide/ammonium phosphomolybdates of claim 1-3 Sign is that the speed being added dropwise in the step 3) is not more than 50 drops/minute.
5. a kind of magnetic iron oxide/ammonium phosphomolybdate being prepared according to any claims of claim 1-4 is porous multiple Condensation material.
6. magnetic iron oxide/ammonium phosphomolybdate described in claim 5 is composite porous in adsorbing separation rubidium ion or cesium ion In application.
7. application according to claim 6, which is characterized in that the porous composite wood of magnetic iron oxide/ammonium phosphomolybdate Reparation of the material for rubidium ion or cesium ion pollution environment.
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