CN104891448A - A transition metal oxide nanometer material, a preparing method thereof and uses of the material - Google Patents
A transition metal oxide nanometer material, a preparing method thereof and uses of the material Download PDFInfo
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Abstract
A transition metal oxide nanometer material, a preparing method thereof and uses of the material are provided. The preparing method includes adding an ionic liquid and a transition metal salt into a reactor, heating and reacting under a protection atmosphere, performing solid liquid separation, washing obtained solid, drying and calcinating to obtain the nanometer material. The preparing method of the nanometer material is simple, wide in application range, mild in reaction conditions, high in repeatability, high in selectivity and yield, low in cost, free of control of pH value in the reaction process, and free of use of expensive reactors. The morphology of the transition metal oxide can be controlled by adjusting the reaction material ratio, reaction temperature and reaction time.
Description
Technical field
The invention belongs to the preparing technical field of inorganic nano material, relate to a kind of transition metal oxide nano-material, Preparation Method And The Use, particularly relate to a kind of method utilizing ionic liquid and transition metal salt to prepare transition metal oxide nano-material.
Background technology
Transition metal oxide nano-material owing to having cheaper starting materials, productive rate is high, duct is regular and the structure of material, shape and size all can by advantages such as rational design adjustments, have a wide range of applications in separation, absorption, catalysis, photoelectricity, biological medicine etc., become international research frontier very popular in recent years.
The method of current synthesis transition metal oxide nano-material mainly contains: 1, solid phase method.Though this method synthesis technique is simple, composition is not easily even, and particulate is easily reunited, and mean particle dia distribution is wide.2, hydrothermal method.Though the nano-oxide uniform particles that this legal system is standby, but poor reproducibility, particle is general larger, the supplementary means such as (microwave, ultrasonic) cannot be used in reaction, range of reaction temperature is narrower (is generally 15-200 DEG C, minority is high temperature resistant reactor can to 300 DEG C), most of product property is poor.3, chemical gas-phase method.Nano particle diameter size prepared by chemical gas-phase method is little, product purity is high, not easily reunite, component is easy to control, but this method energy consumption is high.4, hydrolysis method.This method preparation technology is simple, and directly can isolate the narrower nano-powder material of particle diameter from solution, output is high, but this method is raw materials used is mostly alkoxide, and cost is higher.5, sol-gel method.The nano-oxide good uniformity that this legal system is standby, purity is high, and particle is thin, but the coking property of gained nano-oxide is poor.
Ionic liquid (Ionic Liquids), also known as ionic liquid at room temperature or room temperature molten salt, is the organic liquid material be composed entirely of ions under room temperature and adjacent temperature.It is liquid state in the scope that near room temperature is very wide, and the zero pour of some ionic liquid even can reach-96 DEG C.Ionic liquid [the emim] [BF to water, atmospheric stability is found from 1992
4] since, obtain fast development about the synthesis of ionic liquid and applied research.But the applied research of ionic liquid in inorganic materials preparation is scarcely out of swaddling-clothes.Because ionic liquid has the physical property of modifying and controlling, in inorganic materials preparation process, it can regulate and control the size of product, shape and dispersiveness, prepares the inorganic materials of different performance, and its application in synthetic materials is causing people more to pay close attention to.
The people such as Cao Jieming have studied the synthesis and characterization of different-shape ZnO nano material in ionic liquid, it has synthesized the nano/micron structures such as the sheet aggregate of ZnO, rod-like aggregates and tower rod aggregate by microwave heating in different imidazolium ionic liquids, investigated the impact of different synthesis condition on appearance of ZnO, the synthetic method of described different-shape ZnO nano material is: 1, prepare Zn (OH)
4 2-precursor solution: 5.5g zinc acetate is dissolved in 50mL deionized water for stirring, adds 16g sodium hydroxide, stirs 15min; 2, with the ZnO nano/micron powder of microwave method synthesis different-shape: by 2mL Zn (OH)
4 2-precursor solution joins in polyfluortetraethylene pipe, add 0.5 ~ 2mL ionic liquid, rock after making it mix, put into microwave oven heating 5 ~ 20min, take out, cool to room temperature, successively add sewage ethanol and deionized water wash, centrifugation, after repeated washing and centrifugation twice, sample is dry under 40 DEG C of vacuum conditions, obtain ZnO.Described ionic liquid is 1-ethanol based-3-Methylimidazole chlorine, 1-ethanol based-3-Methylimidazole tetrafluoride boron, 1-butyl-3-Methylimidazole chlorine and 1-butyl-3-Methylimidazole tetrafluoride boron (Acta PhySico-Chimica Sinica, 2005,21 (6): 668-672).But the metallic compound productive rate that the method prepares is low.CN 1312032C discloses a kind of method preparing metal or metal oxide/carbon nano-tube composite material, and described method for utilize microwave heating to prepare metal or metal oxide/carbon nano-tube composite material in ionic liquid.Specifically, refer to and use trifluoromethane sulfonic acid tetramethyl guanidine, trifluoroacetic acid tetramethyl guanidine, lactic acid tetramethyl guanidine, formic acid tetramethyl guanidine, perchloric acid tetramethyl guanidine, vinylformic acid tetramethyl guanidine, the ionic liquid at room temperature such as methacrylic acid tetramethyl guanidine are as medium, by hydrochloro-auric acid, Platinic chloride, ruthenium chloride, Palladous chloride, rhodium chloride, metal nitrate, the metallic compound that thermal chemical reaction easily occurs metal acetate etc. is dissolved in ionic liquid, and by carbon nanotube ultrasonic disperse in ionic liquid, form stable dispersion system, use microwave heating certain hour, metal or metal oxide/CNT matrix material can be obtained.But specific ionic liquid can only be used in described preparation method, and described ionic liquid can only dissolve section transitions metal-salt.
At present, have in transition metal oxide nano-material preparation method that reaction process is loaded down with trivial details, by product is more, catalyzer is complicated, circulation ratio is low and a problem such as reaction cost is high.
Summary of the invention
For the deficiency that prior art exists, the object of the present invention is to provide a kind of transition metal oxide nano-material, Preparation Method And The Use, described preparation method is simple, and the scope of application is wide, and reaction conditions is gentle, with low cost and selectivity and productive rate higher.
For reaching this object, the present invention by the following technical solutions:
An object of the present invention is the preparation method providing a kind of transition metal oxide nano-material; described preparation method is: add in reactor by ionic liquid and transition metal salt; heat under protective atmosphere and react; carry out solid-liquid separation afterwards; by gained solids wash; drying, roasting, obtains transition metal oxide nano-material.
Ionic liquid of the present invention refers in room temperature or close to presenting salt that is liquid, that be made up of zwitterion completely under room temperature, also referred to as low temperature molten salt.
The present invention uses transition metal salt for raw material, take ionic liquid as template and presoma, under comparatively gentle condition, first prepare transition metal oxide precursor body, then accessed the transition metal oxide nano-material of different-shape by roasting transition metal oxide precursor physical efficiency.
Method technique provided by the invention is simple, the scope of application is wide, repeatability is strong, cost is low, and without the need to control ph or use valuable reactor, obtained transition metal nano-oxide productive rate is higher and the selectivity of its size is higher.
The mass ratio of described ionic liquid and transition metal salt is 5 ~ 88:1, as 6:1,8:1,10:1,15:1,20:1,25:1,28:1,30:1,35:1,38:1,40:1,50:1,60:1,70:1,75:1,80:1 or 85:1.
Preferably, described ionic liquid is glyoxaline ion liquid i.e. ([C2 ~ 10mim] BF containing C2 ~ C10 alkyl
4), as [emim] [BF
4], [PMim] [BF
4], [bmim] [BF
4], be preferably HmimBF
4(1-n-hexyl-3-methyl imidazolium tetrafluoroborate) and/or OmimBF
4(1-octyl group-3-methyl imidazolium tetrafluoroborate).
Preferably, described transition metal salt is the mixture of any one or at least two kinds in the nitrate of transition metal, acetate or oxalate.
Preferably, the transition metal in described transition metal salt is First Transition system metal;
Preferably, the transition metal in described transition metal salt is the combination of any one or at least two kinds in chromium, manganese, zinc, iron, cobalt, nickel or copper.
Preparation method provided by the invention can use the acetate of transition metal, nitrate and oxalate, and the commercialization all of these transition metal salts is therefore, low many compared to methyl ethyl diketone transition metal salt cost.
Described protective atmosphere is nitrogen and/or rare gas.Described protective atmosphere can play the effect blocking ionic liquid and transition metal salt and oxygen reaction, and therefore, other protective atmosphere also can use at this, but considers Cost Problems, described protective atmosphere preferred nitrogen and/or rare gas.
Preferably; the gauge pressure of described protective atmosphere heats when being 1 ~ 3kPa again; raw material now in reactor also reacts, and the gauge pressure as protective atmosphere is 1kPa, 1.2kPa, 1.5kPa, 1.8kPa, 2kPa, 2.2kPa, 2.5kPa, 2.8kPa or 3kPa etc.
The temperature of described reaction is 150 ~ 300 DEG C, as 160 DEG C, 170 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, 250 DEG C, 270 DEG C, 280 DEG C or 290 DEG C etc.
By heating, the present invention promotes that the decomposition of ionic liquid produces negatively charged ion, make itself and transition metal salt decompose the transition-metal cation produced interact thus generate transition metal oxide precursor body, the further thermolysis then through transition metal oxide precursor body can obtain transition metal oxide nano-material.
Preferably, the time of described reaction is 0 ~ 10h, do not comprise 0, as 2min, 5min, 10min, 0.5h, 1h, 1.5h, 2h, 3h, 4h, 4.5h, 5h, 6h, 7h, 8h, 9h or 9.5h etc., carry out in the process that described reaction can heat up at reactor, when reactor reaches default temperature, can lower the temperature immediately.
Preferably, stir in the process of described reaction.
Preferably, the speed of described stirring is 200 ~ 2000r/min, as 250r/min, 300r/min, 400r/min, 500r/min, 700r/min, 900r/min, 1000r/min, 1300r/min, 1500r/min, 1700r/min, 1800r/min or 1900r/min etc.
Preferably, after described reaction completes, reactor carries out solid-liquid separation after being cooled to 20 ~ 70 DEG C again, as being cooled to 25 DEG C, 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C or 65 DEG C etc.
Described solid-liquid separation plays the effect of liquid in separating reaction still and solid, and the mode of described solid-liquid separation can be filtration or centrifugation.
The method preparing transition metal oxide nano-material provided by the invention, by modulation ionic liquid and the material ratio of transition metal salt and the temperature and time of reaction, can control the pattern of final product-transition metal oxide nano-material.When ionic liquid and transition metal salt mass ratio are 5:1 ~ 20:1, when temperature of reaction is 80 ~ 170 DEG C, when the reaction times is 0 ~ 1h, do not comprise 0, gained transition metal oxide nano-particles is column; When ionic liquid and transition metal salt mass ratio are greater than 20:1, temperature of reaction, between 180 ~ 250 DEG C, when the reaction times is 0 ~ 10h, does not comprise 0, and gained nanoparticle is spherical.
The solvent that described washing uses is polar solvent, is preferably dehydrated alcohol and/or methyl alcohol.
Preferably, the mass ratio of described solvent and gained solid is 40 ~ 100:1, as 45:1,50:1,55:1,60:1,70:1,80:1,90:1 or 95:1 etc.
Preferably, the temperature of described drying is 40 ~ 180 DEG C, as 50 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 130 DEG C, 150 DEG C, 160 DEG C or 175 DEG C etc.
The temperature of described roasting is 300 ~ 800 DEG C, as 310 DEG C, 315 DEG C, 325 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C or 750 DEG C etc.
Preferably, the time of described roasting is 3 ~ 8h, as 3.5h, 4h, 4.5h, 5h, 6h, 6.5h, 7h or 7.5h etc.
Preferably, described roasting is carried out in static atmosphere of air.
Preferably, described roasting is carried out in crucible.
As long as described reactor containing inflation mechanism, whipping appts and intensification control device, is convenient to emptying for the air in reactor and control reaction process, and solvent thermal reaction can be carried out.
As preferred technical scheme, the preparation method of described transition metal oxide nano-material comprises the following steps:
(1) ionic liquid and transition metal salt are added in reactor mix, obtain compound;
(2) in reactor, protective atmosphere is filled with, by emptying for the air in reactor, and make the gauge pressure of protective atmosphere in reactor be 1 ~ 3kPa, reacting by heating still afterwards, makes compound react 0 ~ 10h under 150 ~ 300 DEG C of conditions, does not comprise 0, carry out solid-liquid separation again, gained solid is through washing, dry, obtains transition metal oxide precursor body;
(3) transition metal oxide precursor body roasting 3 ~ 8h in the static atmosphere of air of 300 ~ 800 DEG C is obtained transition metal oxide nano-material.
Two of object of the present invention is to provide a kind of basis transition metal oxide nano-material that preparation method described above prepares, and the pattern of described transition metal oxide nano-material is: column or spherical.
Three of object of the present invention is the purposes providing a kind of described transition metal oxide nano-material, and it is for separating of, absorption, catalysis, photoelectricity or biomedicine field.
Compared with prior art, beneficial effect of the present invention is:
The preparation method of transition metal oxide nano-material provided by the invention is simple, reaction conditions is gentle, without the need to controlling the pH value of reaction process or using valuable reactor, the scope of application is wide, repeatable strong, cost is low, and controls the pattern of transition metal oxide by the temperature and time that the material that modulation reacts when reacts, the transition metal oxide nano-material selectivity of preparation can up to 100%, and productive rate can reach 50 ~ 95%.
Accompanying drawing explanation
Fig. 1 is X-ray powder diffraction (XRD), and wherein, a is the XRD spectral line of the nano-ZnO that embodiment 12 obtains; B is the nanometer MnO that embodiment 4 obtains
2xRD spectral line; C is the XRD spectral line of the nano NiO obtained after the obtained roasting of embodiment 7; D is the nano Co that embodiment 10 obtains
3o
4xRD spectral line.
Fig. 2 is scanning electron microscope diagram (SEM), and wherein, Fig. 2 a is the nanometer MnO that embodiment 4 obtains
2sEM; Fig. 2 b is the nano Co that embodiment 10 obtains
3o
4sEM; Fig. 2 c is the SEM of the nano-ZnO that embodiment 12 obtains; Fig. 2 d is the SEM of the nano NiO that embodiment 7 obtains.
Fig. 3 is transmission electron microscope figure (TEM), and wherein, Fig. 3 a is the nanometer MnO that example 4 obtains
2tEM; Fig. 3 b is the TEM figure of the nano NiO that example 7 obtains; Fig. 3 c is the nano Co that example 10 obtains
3o
4tEM; Fig. 3 d is the TEM figure of the nano-ZnO that example 12 obtains.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
Each raw material used in following examples and reaction kit those skilled in the art obtain easily by being purchased.
Embodiment 1
(1) by 1g manganese acetate and 5g OmimBF
4join in reactor, stir 3min, obtain compound.
(2) in reactor, N is filled with
2, the air in emptying reactor, and make N in reactor
2gauge pressure be 1kPa; Reacting by heating still, make compound at 150 DEG C of reaction 10h, heat up and all stir in reaction process, stirring velocity is 200r/min; After reaction terminates, question response still temperature is cooled to 70 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, in an oven 180 DEG C of dry 2h dry MnF
2.
(3) by MnF
2be placed in crucible, 300 DEG C of roasting 8h under static atmosphere of air, columnar nanometer Manganse Dioxide, productive rate is 56%.
Embodiment 2
(1) by 1g manganous oxalate and 88g HmimBF
4add in reactor, stir 3min, obtain compound.
(2) in reactor, N is filled with
2, the air in emptying reactor, and make N in reactor
2gauge pressure be 3kPa; Reacting by heating still, make compound at 300 DEG C of reaction 1min, heat up and all stir in reaction process, stirring velocity is 2000r/min; After reaction terminates, question response still temperature reduces to 20 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 100mL methanol wash three times, be placed on 40 DEG C of dry 12h in baking oven dry MnF
2.
(3) by MnF
2be placed in crucible, 800 DEG C of roasting 3h in static atmosphere of air, spherical nano-manganese dioxide, productive rate is 80%.
Embodiment 3
(1) by 1g manganous nitrate and 50g OmimBF
4add in reactor, stir 3min, obtain compound;
(2) in reactor, N is filled with
2, the air in emptying reactor, and make N in reactor
2gauge pressure be 2kPa; Reacting by heating still, temperature rise rate is 10 DEG C/min, and stop heating when temperature reaches 200 DEG C, the speed of carrying out stirring in temperature-rise period is 1000r/min; Naturally cooling, question response still temperature reduces to 50 DEG C, opens reactor, pours out supernatant liquid, and the mixture of bottom settlings 80mL methyl alcohol and dehydrated alcohol washs three times, be placed on 80 DEG C of dry 2h in baking oven dry MnF
2.
(3) by MnF
2be placed in crucible, 500 DEG C of roasting 5h in static atmosphere of air, spherical nano-manganese dioxide, productive rate 84%.
Embodiment 4
(1) by 1g manganese acetate and 28g OmimBF
4join in reactor, stir 3min, obtain compound.
(2) in reactor, N is filled with
2, make the air in reactor emptying, keep N in reactor
2gauge pressure be 1kPa; Reacting by heating still, make compound at 220 DEG C of reaction 2h, heat up and all stir in reaction process, stirring velocity is 800r/min; After reaction terminates, question response still temperature is cooled to 20 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, in an oven 80 DEG C of dry 2h dry MnF
2.
(3) by MnF
2be placed in crucible, 500 DEG C of roasting 6h under static atmosphere of air, spherical nano-manganese dioxide, productive rate 77%.
Embodiment 5
(1) by 1g manganous oxalate and 28g OmimBF
4join in reactor, stir 3min, obtain compound.
(2) in reactor, N is filled with
2, make the air in reactor emptying, keep N in reactor
2gauge pressure be 1kPa; Reacting by heating still, make compound at 250 DEG C of reaction 2h, heat up and all stir in reaction process, stirring velocity is 800r/min; After reaction terminates, question response still temperature is cooled to 20 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, in an oven 80 DEG C of dry 2h dry MnF
2.
(3) by MnF
2be placed in crucible, 500 DEG C of roasting 6h under static atmosphere of air, spherical nano-manganese dioxide, productive rate 93%.
Embodiment 6
(1) by 1g manganous nitrate and 28g OmimBF
4join in reactor, stir 3min, obtain compound.
(2) in reactor, N is filled with
2, make the air in reactor emptying, keep N in reactor
2gauge pressure be 1kPa; Reacting by heating still, make compound at 250 DEG C of reaction 2h, heat up and all stir in reaction process, stirring velocity is 800r/min; After reaction terminates, question response still temperature is cooled to 20 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, in an oven 80 DEG C of dry 2h dry MnF
2.
(3) by MnF
2be placed in crucible, 500 DEG C of roasting 6h under static atmosphere of air, spherical nano-manganese dioxide, productive rate 69%.
Embodiment 7
(1) by 1g nickel acetate and 28g OmimBF
4add in reactor, stir 3min, obtain compound;
(2) in reactor, N is filled with
2, make the air in reactor emptying, make N in reactor
2gauge pressure be 2kPa; Reacting by heating still, make compound at 250 DEG C of reaction 1h, heat up and all stir in reaction process, stirring velocity is 900r/min; After reaction terminates, question response still temperature reduces to 20 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, be placed on 80 DEG C of dry 2h in baking oven dry NiF
2.
(3) by NiF
2be placed in crucible, 550 DEG C of roasting 7h in static atmosphere of air, spherical nano-nickel oxide, productive rate 55%.
Embodiment 8
(1) by 1g nickel acetate and 28g HmimBF
4add in reactor, stir 3min, obtain compound;
(2) in reactor, N is filled with
2, make the air in reactor emptying, make N in reactor
2gauge pressure be 3kPa; Reacting by heating still, make compound at 250 DEG C of reaction 1h, heat up and all stir in reaction process, stirring velocity is 900r/min; After reaction terminates, question response still temperature reduces to 20 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, be placed on 80 DEG C of dry 2h in baking oven dry NiF
2.
(3) by NiF
2be placed in crucible, 550 DEG C of roasting 7h in static atmosphere of air, spherical nano-nickel oxide, productive rate 87%.
Embodiment 9
(1) by 1g nickelous oxalate and 28g OmimBF
4add in reactor, stir 3min, obtain compound;
(2) in reactor, N is filled with
2, make the air in reactor emptying, make N in reactor
2gauge pressure be 2kPa; Reacting by heating still, make compound at 250 DEG C of reaction 1h, heat up and all stir in reaction process, stirring velocity is 900r/min; After reaction terminates, question response still temperature reduces to 20 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, be placed on 80 DEG C of dry 2h in baking oven dry NiF
2.
(3) by NiF
2be placed in crucible, 550 DEG C of roasting 7h in static atmosphere of air, spherical nano-nickel oxide, productive rate 65%.
Embodiment 10
(1) by 1g Cobaltous diacetate and 28g OmimBF
4add in reactor, stir 3min, obtain compound;
(2) in reactor, N is filled with
2, the air in emptying reactor, and make N in reactor
2gauge pressure be 1kPa; Reacting by heating still, make compound at 250 DEG C of reaction 1h, heat up and all stir in reaction process, stirring velocity is 900r/min; After reaction terminates, question response still temperature reduces to 25 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, be placed on 80 DEG C of dry 2h in baking oven dry CoF
2.
(3) by CoF
2be placed in crucible, 550 DEG C of roasting 7h in static atmosphere of air, spherical nanometer cobalt oxide, productive rate 68%.
Embodiment 11
(1) by 1g cobalt oxalate and 28g HmimBF
4add in reactor, stir 3min, obtain compound;
(2) in reactor, N is filled with
2, the air in emptying reactor, and make N in reactor
2gauge pressure be 1kPa; Reacting by heating still, make compound at 250 DEG C of reaction 1h, heat up and all stir in reaction process, stirring velocity is 900r/min; After reaction terminates, question response still temperature reduces to 25 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, be placed on 80 DEG C of dry 2h in baking oven dry CoF
2.
(3) by CoF
2be placed in crucible, 550 DEG C of roasting 7h in static atmosphere of air, spherical nanometer cobalt oxide, productive rate 57%.
Embodiment 12
(1) by 1g Cobaltous diacetate and 28g OmimBF
4add in reactor, stir 3min, obtain compound;
(2) in reactor, N is filled with
2, the air in emptying reactor, and make N in reactor
2gauge pressure be 1kPa; Reacting by heating still, make compound at 250 DEG C of reaction 1h, heat up and all stir in reaction process, stirring velocity is 900r/min; After reaction terminates, question response still temperature reduces to 25 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, be placed on 80 DEG C of dry 2h in baking oven dry CoF
2.
(3) by CoF
2be placed in crucible, 550 DEG C of roasting 7h in static atmosphere of air, spherical nanometer cobalt oxide, productive rate 79%.
Embodiment 13
(1) by 1g zinc acetate and 28g OmimBF
4add in reactor, stir 3min, obtain compound;
(2) in reactor, N is filled with
2, the air in emptying reactor, and make N in reactor
2gauge pressure be 1kPa; Reacting by heating still, make compound at 230 DEG C of reaction 1h, heat up and all stir in reaction process, stirring velocity is 1000r/min; After reaction terminates, question response still temperature reduces to 25 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, be placed on 80 DEG C of dry 2h in baking oven dry ZnF
2.
(3) by ZnF
2be placed in crucible, 550 DEG C of roasting 7h in static atmosphere of air, spherical nano zine oxide, productive rate 84%.
Embodiment 14
(1) by 1g zinc oxalate and 28g HmimBF
4add in reactor, stir 3min, obtain compound;
(2) in reactor, N is filled with
2, the air in emptying reactor, and make N in reactor
2gauge pressure be 1kPa; Reacting by heating still, make compound at 230 DEG C of reaction 1h, heat up and all stir in reaction process, stirring velocity is 1000r/min; After reaction terminates, question response still temperature reduces to 25 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, be placed on 80 DEG C of dry 2h in baking oven dry ZnF
2.
(3) by ZnF
2be placed in crucible, 550 DEG C of roasting 7h in static atmosphere of air, spherical nano zine oxide, productive rate 62%.
Embodiment 15
(1) by 1g zinc nitrate and 28g OmimBF
4add in reactor, stir 3min, obtain compound;
(2) in reactor, N is filled with
2, the air in emptying reactor, and make N in reactor
2gauge pressure be 1kPa; Reacting by heating still, make compound at 230 DEG C of reaction 1h, heat up and all stir in reaction process, stirring velocity is 1000r/min; After reaction terminates, question response still temperature reduces to 25 DEG C, opens reactor, pours out supernatant liquid, bottom settlings 40mL absolute ethanol washing three times, be placed on 80 DEG C of dry 2h in baking oven dry ZnF
2.
(3) by ZnF
2be placed in crucible, 550 DEG C of roasting 7h in static atmosphere of air, spherical nano zine oxide, productive rate 59%.
The transition metal oxide utilizing Rigaku company D/Max-2500 type X-ray diffractometer, Amada Co., Ltd. JEM-2010 type transmission electron microscope and power & light company of U.S. Noran system six type scanning electronic microscope obtained to embodiment 4, embodiment 7, embodiment 10 and embodiment 12 characterizes, result as shown in Figure 1, Figure 2 and Figure 3.Four kinds of obtained as can be seen from Figure 1 transition metal nano-oxide main spectral line all can and its body phase oxide spectral line overlap, prove that the standby oxide compound of this legal system is transition metal oxide; Outside transition metal oxide obtained is as can be seen from Figure 2 reunited apart from small portion, most of size distribution is comparatively even, and particle dia is near 200nm; Nanometer MnO obtained as can be seen from Figure 3
2for columnar structure, post height about 100nm, base diameter is about 10nm, and obtained nano NiO, nano Co
3o
4all have duct with nano-ZnO, duct radius, between 5 ~ 20nm, is typical mesoporous material.
Embodiment 16
Take the nano Co that 0.1g embodiment 12 is obtained
3o
4added in the beaker containing methyl orange dye that (concentration of methyl orange dye is 20mg/L, volume is 200mL), by Beijing Puxi General Instrument Co., Ltd after 30min: TU-1900 type twin-beam ultraviolet-visible spectrophotometer tests its absorbancy, calculate according to the decreasing value of its absorbancy and know: 0.1g nano Co
3o
4can adsorb the tropeolin-D falling 70% when 30min, and merchandise active carbon also can only adsorb to fall the tropeolin-D of 10% under the same conditions, and the nano Co that the present invention prepares is described
3o
4there is excellent absorption property.
Embodiment 17
Take the nano Co that 0.1g embodiment 12 is obtained
3o
4added (20mg/L in the beaker containing rhodamine B dyestuff, 200mL), by Beijing Puxi General Instrument Co., Ltd after 30min: TU-1900 type twin-beam ultraviolet-visible spectrophotometer tests its absorbancy, calculate according to the decreasing value of its absorbancy and know: 0.1g nano Co
3o
4can adsorb the rhodamine B falling 90% when 30min, and merchandise active carbon also can only adsorb to fall the rhodamine B of 7% under the same conditions, and the nano Co that the present invention prepares is described
3o
4there is excellent absorption property.
Embodiment 18
Take the nano NiO that 0.5g embodiment 9 prepares, loaded silica tube and be placed on fixed bed device, before starting reaction, in reaction system, pass into O with the speed of 20mL/min in advance
22 hours, then pass into oxygen at 200 DEG C and carry out activation 2h, the method that temperature of reaction adopts staged to heat up, first react from 20 DEG C, then raise 10 DEG C at every turn and carry out testing until the appearance of CO, be the activation temperature of methane.Experiment proves that this nano NiO gets final product catalytic activation methane 230 DEG C time, makes it be converted into CO.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a transition metal oxide nano-material; it is characterized in that; described preparation method is: add in reactor by ionic liquid and transition metal salt; heat under protective atmosphere and react; carry out solid-liquid separation afterwards, by gained solids wash, dry; roasting, obtains transition metal oxide nano-material.
2. preparation method according to claim 1, is characterized in that, the mass ratio of described ionic liquid and transition metal salt is 5 ~ 88:1;
Preferably, described ionic liquid is the glyoxaline ion liquid containing C2 ~ C10 alkyl, is preferably HmimBF
4and/or OmimBF
4;
Preferably, described transition metal salt is the mixture of any one or at least two kinds in the nitrate of transition metal, acetate or oxalate;
Preferably, the transition metal in described transition metal salt is First Transition system metal;
Preferably, the transition metal in described transition metal salt is the combination of any one or at least two kinds in chromium, manganese, zinc, iron, cobalt, nickel or copper.
3. preparation method according to claim 1 and 2, is characterized in that, described protective atmosphere is nitrogen and/or rare gas;
Preferably, heat again when the gauge pressure of described protective atmosphere is 1 ~ 3kPa.
4. according to the preparation method one of claim 1-3 Suo Shu, it is characterized in that, the temperature of described reaction is 150 ~ 300 DEG C;
Preferably, the time of described reaction is 0 ~ 10h, and does not comprise 0;
Preferably, stir in the process of described reaction;
Preferably, the speed of described stirring is 200 ~ 2000r/min.
Preferably, after described reaction completes, reactor carries out solid-liquid separation after being cooled to 20 ~ 70 DEG C again.
5. according to the preparation method one of claim 1-4 Suo Shu, it is characterized in that, the solvent that described washing uses is dehydrated alcohol and/or methyl alcohol;
Preferably, the mass ratio of described solvent and gained solid is 40 ~ 100:1;
Preferably, the temperature of described drying is 40 ~ 180 DEG C.
6. according to the preparation method one of claim 1-5 Suo Shu, it is characterized in that, the temperature of described roasting is 300 ~ 800 DEG C;
Preferably, the time of described roasting is 3 ~ 8h;
Preferably, described roasting is carried out in static atmosphere of air;
Preferably, described roasting is carried out in crucible.
7. according to the preparation method one of claim 1-6 Suo Shu, it is characterized in that, described reactor contains inflation mechanism, whipping appts and intensification control device.
8. according to the preparation method one of claim 1-7 Suo Shu, it is characterized in that, described preparation method comprises the following steps:
(1) ionic liquid and transition metal salt are added in reactor mix, obtain compound;
(2) in reactor, protective atmosphere is filled with, air in emptying reactor, and make the gauge pressure of protective atmosphere in reactor be 1 ~ 3kPa, reacting by heating still afterwards, makes compound react 0 ~ 10h under 150 ~ 300 DEG C of conditions, does not comprise 0, carry out solid-liquid separation again, gained solid is through washing, dry, obtains transition metal oxide precursor body;
(3) transition metal oxide precursor body roasting 3 ~ 8h in the static atmosphere of air of 300 ~ 800 DEG C is obtained transition metal oxide nano-material.
9. according to the transition metal oxide nano-material that the preparation method one of claim 1-8 Suo Shu prepares, it is characterized in that, the pattern of described transition metal oxide nano-material is: column or spherical.
10. the purposes of transition metal oxide nano-material according to claim 9, it is for separating of, absorption, catalysis, photoelectricity or biomedicine field.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540550A (en) * | 2015-12-23 | 2016-05-04 | 中国电子科技集团公司第四十九研究所 | Preparation method for metal oxide materials |
| CN106048221A (en) * | 2016-08-22 | 2016-10-26 | 东北大学 | Method for extracting light rare earth elements in acidic solution by using ionic liquid [OMIM] BF4 |
| CN106423166A (en) * | 2016-10-20 | 2017-02-22 | 绍兴文理学院 | Compounding method for cuprous oxide visible photocatalyst |
| CN108091760A (en) * | 2016-11-23 | 2018-05-29 | 清华大学 | Regulate and control the method for hydrogeneous transition metal oxide phase transformation |
| CN108529691A (en) * | 2018-04-24 | 2018-09-14 | 电子科技大学 | Sheet metal oxide and its controllable synthesis method and purposes |
| CN114074951A (en) * | 2020-08-17 | 2022-02-22 | 厦门稀土材料研究所 | Method for preparing rare earth fluoride by using fluorinated ionic liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011007731A1 (en) * | 2009-07-14 | 2011-01-20 | 日本アエロジル株式会社 | Surface-modified metal oxide powder and process for producing same |
| CN102502871A (en) * | 2011-11-04 | 2012-06-20 | 华东师范大学 | Method for synthesizing three-dimensional porous ferric oxide nano rod cluster |
-
2015
- 2015-05-19 CN CN201510255687.8A patent/CN104891448B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011007731A1 (en) * | 2009-07-14 | 2011-01-20 | 日本アエロジル株式会社 | Surface-modified metal oxide powder and process for producing same |
| CN102502871A (en) * | 2011-11-04 | 2012-06-20 | 华东师范大学 | Method for synthesizing three-dimensional porous ferric oxide nano rod cluster |
Non-Patent Citations (1)
| Title |
|---|
| 朱海燕: ""离子液体及其溶液中纳米氧化物复合杂化材料的合成与性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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| CN105540550A (en) * | 2015-12-23 | 2016-05-04 | 中国电子科技集团公司第四十九研究所 | Preparation method for metal oxide materials |
| CN106048221A (en) * | 2016-08-22 | 2016-10-26 | 东北大学 | Method for extracting light rare earth elements in acidic solution by using ionic liquid [OMIM] BF4 |
| CN106048221B (en) * | 2016-08-22 | 2018-01-19 | 东北大学 | One kind uses ionic liquid [OMIM] BF4The method for extracting LREE in acid solution |
| CN106423166A (en) * | 2016-10-20 | 2017-02-22 | 绍兴文理学院 | Compounding method for cuprous oxide visible photocatalyst |
| CN106423166B (en) * | 2016-10-20 | 2019-04-26 | 绍兴文理学院 | A kind of synthetic method of cuprous oxide visible light catalyst |
| CN108091760A (en) * | 2016-11-23 | 2018-05-29 | 清华大学 | Regulate and control the method for hydrogeneous transition metal oxide phase transformation |
| CN108529691A (en) * | 2018-04-24 | 2018-09-14 | 电子科技大学 | Sheet metal oxide and its controllable synthesis method and purposes |
| CN114074951A (en) * | 2020-08-17 | 2022-02-22 | 厦门稀土材料研究所 | Method for preparing rare earth fluoride by using fluorinated ionic liquid |
| CN114074951B (en) * | 2020-08-17 | 2023-08-29 | 厦门稀土材料研究所 | Method for preparing rare earth fluoride by using fluorinated ionic liquid |
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