CN102923669A - Benzoic acid-intercalated laminated transition metal hydroxide one-dimensional nano material with reversible transition structure and preparation method thereof - Google Patents
Benzoic acid-intercalated laminated transition metal hydroxide one-dimensional nano material with reversible transition structure and preparation method thereof Download PDFInfo
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- CN102923669A CN102923669A CN201210459312XA CN201210459312A CN102923669A CN 102923669 A CN102923669 A CN 102923669A CN 201210459312X A CN201210459312X A CN 201210459312XA CN 201210459312 A CN201210459312 A CN 201210459312A CN 102923669 A CN102923669 A CN 102923669A
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Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a benzoic acid-intercalated laminated transition metal hydroxide one-dimensional nano material with a reversible transition structure and a preparation method thereof. The preparation method comprises the following steps: divalent transition metal salt and benzoate are taken as raw materials; the pH value is adjusted by sodium hydroxide; then divalent transition metal salt and benzoate are reacted at the temperature of 25 to 150 DEG C; and the benzoic acid-intercalated laminated transition metal hydroxide one-dimensional nano material with the reversible transition structure can be obtained finally. The method is simple in process, and low in cost, and can achieve large-scale industrial production; and one-dimensional material has anisotropic special characters, thereby being widely applied in fields of magnetics, optics, electrics and the like.
Description
Technical field
The invention belongs to the nano material preparing technical field, be specifically related to a kind of benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material with structure reversible transition character and preparation method thereof.
Background technology
Have laminate structure the anionic super molecular compound since the adjustable sex change of its unique laminate structure and laminate element and interlayer ion get more and more people's extensive concerning.Interlayer is introduced in organic anion, not only can be used as the sorbent material raising to the adsorptive capacity of organic pollutant, also can make material have magnetic, electrochemistry and excellent catalytic performance, make it all have unique advantage in preparation routine and the aspects such as nanometer composite organic-inorganic material, biosensor.
Since carbon nanotube is found, one-dimensional nano structure material receives much concern because of its peculiar optics, electricity, magnetics and mechanical property and the potential application in nano-device structure thereof, and therefore explore preparation low-dimension nano material structurally ordered, excellent property is the focus of research always.Studies show that, the performance of layered hydroxide depends on pattern, structure, the size of material to a great extent.Pattern with the layered hydroxide of the organic intercalation of the methods such as ion-exchange, roasting recovery preparations is generally irregular nanometer sheet (P.Rabu etc., Chem.Mater.2006,18,3005).The preparation of one dimension Nano material of hydrate needs the participation of tensio-active agent, organic solvent or template, (the Adv.Mater. such as Matsui, 2002,14,1216) made Nickel Hydroxide Nanorods Using take aluminum oxide film as template, they are at first take propylene as source of the gas, deposit one deck carbon film by chemical vapour deposition at aluminum oxide film, again it is immersed in the ethanolic soln of nickelous nitrate, put it into afterwards the reactor that sodium hydroxide solution is housed, obtain the nickel hydroxide carbon composite at 150 ℃ of reaction 24h; Cai(Angew.Chem.Int.Ed., 2004,43,4212) etc. made nickel hydroxide nano-tube take aluminum oxide film as template by chemical vapour deposition, they at first soak 30min with aluminum oxide film in nickel nitrate solution, nickel ion is adsorbed on the film, afterwards ammoniacal liquor are slowly dropped on the film of absorbed Ni ion, repeat said process 5 times, again with obtaining the tubulose nickel hydroxide behind the sodium hydroxide solution removal aluminum oxide film.Have the method for preparing the one dimension Nano material of hydrate now all very complicated, yield poorly.
Summary of the invention
The invention provides a kind of preparation method of benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material of simple and easy to control, economical rationality, the monodimension nanometer material that obtains has structure reversible transition character.The method is as raw material take divalent transition metal salt, benzoate, do not need the precipitation agents such as urea, alkaline solution, under 50-150 ℃ condition, react 0.5-48h, finally obtain a kind of benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material with structure reversible transition character.
The preparation process of a kind of benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material with structure reversible transition character of the present invention is as follows:
(1) prepare respectively divalent transition metal salts solution and benzoate solution, the concentration of divalent transition metal salts solution is 0.05-1M, and the concentration of benzoate is 0.1-2M;
(2) benzoate solution and divalent transition metal salts solution are poured in the four-hole boiling flask, the mol ratio of divalent transition metal salt and benzoate is 2:1-1:2, reacts 0.5-48h under the 50-150 ℃ of condition;
(3) spend CO after reaction is finished
2Deionized water centrifuge washing, product are at room temperature dry, namely obtain a kind of benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material with structure reversible transition character.
Divalent transition metal salt described in the step (1) is Co (NO
3)
26H
2O, CoCl
26H
2O, Ni (NO
3)
26H
2O, NiCl
26H
2O, NiSO
46H
2O, Cu (NO
3)
23H
2O, CuCl
22H
2Among the O one or more.
Benzoate described in the step (1) is Sodium Benzoate or potassium benzoate.
The benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material with structure reversible transition character of above-mentioned preparation is placed under 60-230 ℃ or the vacuum condition, the laminate of this nano material loses coordinated water, color changes, cool to them below 60 ℃ or remove vacuum condition, water coordination in the laminate absorbed air, color is recovered very soon, and this structural changes to cause colour-change be reversible variation.
A kind of benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material with structure reversible transition character of above-mentioned preparation is applied to temperature switch or humidity sensor.
It is raw material that the present invention adopts divalent transition metal salt, benzoate first, do not need the precipitation agents such as urea, alkaline solution, prepared a kind of have the benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material of structure reversible transition character and the polynary transition metal hydroxide monodimension nanometer material of benzoate anion intercalation stratiform of structure reversible transition character.The method technique is simple, and is with low cost, can realize large-scale industrial production; Under differing temps, different humidity condition, the gain and loss of laminate coordinated water makes the material can the reversible transformation of implementation structure, and is accompanied by the variation of color sample, and good reproducibility.This special property of material makes it have widespread use as temperature switch or at aspects such as air humidity sensors.
Description of drawings
Fig. 1 is the XRD spectra of the benzoate anion intercalation stratiform cobaltous hydroxide monodimension nanometer material with structure reversible transition character that obtains of embodiment 1.
Fig. 2 is the stereoscan photograph (SEM) of the benzoate anion intercalation stratiform cobaltous hydroxide monodimension nanometer material with structure reversible transition character that obtains of embodiment 1.
Fig. 3 is the EDX spectrogram of the benzoate anion intercalation stratiform cobaltous hydroxide monodimension nanometer material with structure reversible transition character that obtains of embodiment 1.
Fig. 4 is the infrared spectrum of the benzoate anion intercalation stratiform cobaltous hydroxide monodimension nanometer material with structure reversible transition character that obtains of embodiment 1.
Fig. 5 is the TEM spectrogram of the benzoate anion intercalation stratiform cobaltous hydroxide monodimension nanometer material with structure reversible transition character that obtains of embodiment 1.
Fig. 6 is the stereoscan photograph (SEM) of the benzoate anion intercalation stratiform cobaltous hydroxide monodimension nanometer material with structure reversible transition character that obtains of embodiment 2.
Fig. 7 is the stereoscan photograph (SEM) of the benzoate anion intercalation stratiform nickel hydroxide monodimension nanometer material with structure reversible transition character that obtains of embodiment 3.
Embodiment
1. take by weighing the Co (NO of 5.8206g
3)
26H
2CO is removed in the O adding
2Deionized water is configured to 100ml divalent transition metal salts solution, takes by weighing the adding of 5.7640g Sodium Benzoate and removes CO
2Deionized water is configured to the 100ml salts solution;
2. PhCOONa solution and divalent transition metal salts solution are poured in the four-hole boiling flask, reacted 48h under 95 ℃ of conditions, stirring velocity is 200r/min;
3. after reaction finished, the slurries cold filtration spent CO
2Deionized water wash 3 times, centrifugation obtains product under room temperature dry 12 hours, the benzoate anion intercalation stratiform cobaltous hydroxide monodimension nanometer material that obtains having structure reversible transition character.
Product characterizes gained through SEM and is long 7 μ m, the monodimension nano stick of diameter 70-90nm.Product is placed under 60-230 ℃ the high temperature or vacuum condition, laminate loses coordinated water, color becomes blueness by pink colour, it is cooled to below 60 ℃, perhaps shift out vacuum chamber, water coordination in the laminate absorbed air, color is very fast to be pink colour by blue restoration, and this structural changes to cause colour-change be reversible variation.
1. take by weighing the Co (NO of 1.4551g
3)
26H
2CO is removed in the O adding
2Deionized water is configured to 100ml divalent transition metal salts solution, takes by weighing the adding of 1.4410g Sodium Benzoate and removes CO
2Deionized water is configured to 100ml solution;
2. PhCOONa solution and divalent transition metal salts solution are poured in the four-hole boiling flask, reacted 48h under 60 ℃ of conditions, stirring velocity is 200r/min;
3. after reaction finished, the slurries cold filtration spent CO
2Deionized water wash 3 times, centrifugation obtains product under room temperature dry 12 hours, the benzoate anion intercalation stratiform cobaltous hydroxide monodimension nanometer material that obtains having structure reversible transition character.
Product characterizes gained through SEM and is long 170 μ m, the 1-dimention nano fiber of diameter 125nm.Product is placed under 60-230 ℃ the high temperature or vacuum condition, laminate loses coordinated water, color becomes blueness by pink colour, it is cooled to below 60 ℃, perhaps shift out vacuum chamber, water coordination in the laminate absorbed air, color is very fast to be pink colour by blue restoration, and this structural changes to cause colour-change be reversible variation.
Embodiment 3
1. take by weighing the Ni (NO of 29.08g
3)
26H
2CO is removed in the O adding
2Deionized water is configured to 100ml divalent transition metal salts solution, takes by weighing the adding of 28.82g Sodium Benzoate and removes CO
2Deionized water is configured to 150ml solution;
2. PhCOONa solution and divalent transition metal salts solution are poured in the four-hole boiling flask, reacted 48h under 95 ℃ of conditions, stirring velocity is 200r/min;
3. after reaction finished, the slurries cold filtration spent CO
2Deionized water wash 3 times, centrifugation obtains product under room temperature dry 12 hours, the benzoate anion intercalation stratiform nickel hydroxide monodimension nanometer material that obtains having structure reversible transition character.
Product characterizes gained through SEM and is long 2 μ m, the monodimension nano stick of diameter 70nm.Product is placed under 60-230 ℃ the high temperature or vacuum condition, laminate loses coordinated water, color becomes yellow-green colour by green, it is cooled to below 60 ℃, perhaps shift out vacuum chamber, water coordination in the laminate absorbed air, color is very fast by reverting to green by yellow-green colour, and this structural changes to cause colour-change be reversible variation.
1. take by weighing the Co (NO of 2.9103g
3)
26H
2Ni (the NO of O and 2.9080g
3)
26H
2CO is removed in the O adding
2Deionized water is configured to 100ml divalent transition metal salts solution, takes by weighing the adding of 5.7640g Sodium Benzoate and removes CO
2Deionized water is configured to the 100ml salts solution;
2. PhCOONa solution and divalent transition metal salts solution are poured in the four-hole boiling flask, utilized the hydrolysis reaction of benzoate anion ion to produce hydroxyl, react 48h under 95 ℃ of conditions, stirring velocity is 200r/min;
3. after reaction finished, the slurries cold filtration spent CO
2Deionized water wash 3 times, centrifugation obtains product under room temperature dry 12 hours, the benzoate anion intercalation bimetal cobalt nickel dam shape oxyhydroxide monodimension nanometer material that obtains having structure reversible transition character.
Product characterizes gained through SEM and is long 7 μ m, the monodimension nano stick of diameter 70-90nm.Product is placed under 60-230 ℃ the high temperature or vacuum condition, laminate loses coordinated water, color becomes blueness by pink colour, it is cooled to below 60 ℃, perhaps shift out vacuum chamber, water coordination in the laminate absorbed air, color is very fast to be pink colour by blue restoration, and this structural changes to cause colour-change be reversible variation.
Claims (5)
1. the preparation method with benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material of structure reversible transition character is characterized in that, its concrete preparation process is as follows:
1) prepare respectively divalent transition metal salts solution and benzoate solution, the concentration of divalent transition metal salts solution is 0.05-1M, and the concentration of benzoate is 0.1-2M;
2) benzoate solution and divalent transition metal salts solution are poured in the four-hole boiling flask, the mol ratio of divalent transition metal salt and benzoate is (2:1)-(1:2), reacts 0.5-48h under the 50-150 ℃ of condition;
3) spend CO after reaction is finished
2Deionized water centrifuge washing, product are at room temperature dry, namely obtain a kind of benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material with structure reversible transition character.
2. preparation method according to claim 1 is characterized in that, the divalent transition metal salt described in the step 1) is Co (NO
3)
26H
2O, CoCl
26H
2O, Ni (NO
3)
26H
2O, NiCl
26H
2O, NiSO
46H
2O, Cu (NO
3)
23H
2O, CuCl
22H
2Among the O one or more.
3. preparation method according to claim 1 is characterized in that, the benzoate described in the step 1) is Sodium Benzoate or potassium benzoate.
4. a kind of benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material with structure reversible transition character of method according to claim 1 preparation, it is characterized in that, be placed under 60-230 ℃ or the vacuum condition, the laminate of this nano material loses coordinated water, color changes, and cools to them below 60 ℃ or removes vacuum condition, the water coordination in the laminate absorbed air, color is recovered very soon, and this structural changes to cause colour-change be reversible variation.
5. a kind of benzoate anion intercalation stratiform transition metal hydroxide monodimension nanometer material with structure reversible transition character according to claim 4 is applied to temperature switch or humidity sensor.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006718A (en) * | 2016-05-11 | 2016-10-12 | 北京化工大学 | Zinc-sulfide, cuprous-sulfide and carbon nanocomposite and preparing method thereof |
| CN108057461A (en) * | 2016-11-07 | 2018-05-22 | 中国科学院大连化学物理研究所 | A kind of cobalt hydroxide catalyst of organic group intercalation modification and its preparation and application |
| CN109502656A (en) * | 2018-11-29 | 2019-03-22 | 兰州金通储能动力新材料有限公司 | A kind of spherical Co (II) Co (III) hydrotalcite-like materials and preparation method thereof |
| CN110412101A (en) * | 2018-04-27 | 2019-11-05 | 天津大学 | The layered double hydroxide gas sensor and its preparation method and application of surface Argent grain modification |
| CN114130221A (en) * | 2021-12-01 | 2022-03-04 | 山东融星膜材料科技有限公司 | High-pressure-resistant polypropylene hollow fiber deoxygenation membrane and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211790A (en) * | 2011-03-04 | 2011-10-12 | 北京化工大学 | Salicylate intercalation layered metal hydroxide nano rod and preparation method thereof |
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2012
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211790A (en) * | 2011-03-04 | 2011-10-12 | 北京化工大学 | Salicylate intercalation layered metal hydroxide nano rod and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006718A (en) * | 2016-05-11 | 2016-10-12 | 北京化工大学 | Zinc-sulfide, cuprous-sulfide and carbon nanocomposite and preparing method thereof |
| CN106006718B (en) * | 2016-05-11 | 2018-07-24 | 北京化工大学 | A kind of zinc sulphide, cuprous sulfide and carbon nano-composite material and preparation method thereof |
| CN108057461A (en) * | 2016-11-07 | 2018-05-22 | 中国科学院大连化学物理研究所 | A kind of cobalt hydroxide catalyst of organic group intercalation modification and its preparation and application |
| CN110412101A (en) * | 2018-04-27 | 2019-11-05 | 天津大学 | The layered double hydroxide gas sensor and its preparation method and application of surface Argent grain modification |
| CN110412101B (en) * | 2018-04-27 | 2022-02-22 | 天津大学 | Application of layered double hydroxide gas sensor in detection of ethanol |
| CN109502656A (en) * | 2018-11-29 | 2019-03-22 | 兰州金通储能动力新材料有限公司 | A kind of spherical Co (II) Co (III) hydrotalcite-like materials and preparation method thereof |
| CN114130221A (en) * | 2021-12-01 | 2022-03-04 | 山东融星膜材料科技有限公司 | High-pressure-resistant polypropylene hollow fiber deoxygenation membrane and preparation method and application thereof |
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