CN102423708B - Nickel-based composite nanomaterial and preparation method thereof as well as porous nickel nanomaterial and preparation method and application thereof - Google Patents
Nickel-based composite nanomaterial and preparation method thereof as well as porous nickel nanomaterial and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a nickel-based composite nanomaterial and a preparation method thereof as well as a porous nickel nanomaterial and a preparation method and application thereof. The method for preparing the nickel-based composite nanomaterial comprises the step of preparing the nickel-based composite nanomaterial by taking soluble nickel salt as a nickel source as well as hexamethylenetetramine and oxalic acid as precipitants through a solution-phase coprecipitation method, wherein the molar ratio of hexamethylenetetramine to oxalic acid is (10:4)-(10:1). The obtained nickel-based composite nanomaterial is of a blossom cluster structure formed by covering nano sheets on the surface of a solid core. The method for preparing the porous nickel nanomaterial comprises the steps of: preparing the nickel-based composite nanomaterial according to the preparation method of the nickel-based composite nanomaterial; and then, carrying out heat treatment to decompose the nickel-based composite nanomaterial in inert atmosphere (such as Ar and N2) at the temperature of 320-360 DEG C to obtain the porous nickel nanomaterial. The obtained porous nickel nanomaterial is of a blossom cluster structure formed by nano sheets. The porous nickel nanomaterial can be used as a liquid-phase hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of nickel-based compound nano material and preparation method, nickel porous nano material and preparation method and application.
Background technology
Porous nanometer material typically refers to the nano material that has many nanoscale apertures in structure.This material has the characteristics of nano material and porous material concurrently, all has potential application prospect (L.S.Zhong et al., Adv.Mater.2006,18,2426-2431 at numerous areas such as catalysis, sensing, absorption, electrode material and biomedicines; S.Z.Chu et al., J.Phys.Chem.B2003,107,6586-6589; Z.H.Jing et al., Adv.Mater.2008,20,4547-4551; F.Jiao et al., Adv.Mater.2007,19,657-660; T.X.T.Sayle et al., Acs Nano 2009,3 3308-3314), is subject to people and pays close attention to widely.The preparation method of porous nanometer material is a lot, comprises layer assembly method, sol-gal process and the moulding method of nanometer etc.In order to introduce pore structure in nano material, generally all need to add template or surfactant in preparation process, first occupy certain space in nano material; After template or removal of surfactant, it takes up space and is released out, obtains porous nanometer material.The subsequent treatment of this process is loaded down with trivial details, and easily causes environmental pollution (J.H.Cho et al., J.Am.Chem.Soc.2006,128,9935-9942; Y.J.Wang et al., Angew.Chem.Int.Ed.2005,44,2888-2892; Z.L.Xiao et al., J.Am.Chem.Soc.2004,126,2316-2317; A.H.Lu et al., Adv.Mater.2006,18,1793-1805), therefore by being more vulnerable to popularization without template (or surfactant-free) method (template-free or surfactant-free) preparation porous nanometer material.Recently, we have developed a kind of simple gas-solid reaction method and have prepared porous nanometer material, the AlN nano material that soon makes in advance is placed in oxygen-containing atmosphere heat treatment, original position produces unsettled intermediate product, and intermediate product decomposes immediately, obtains porous anodic aluminum oxide, this product can keep original pattern (Q.Wu et al. of AlN nano material, J.Phys.Chem.C 2007,111,13315-13320; Wu Qiang levies recklessly, and Wang Xizhang lifts a sail, Chen Yi, Chinese invention patent ZL2007 1 0020568.X).Similarly, first the particular nanostructure of synthetic some unstable compound, then make this unstable compound generation thermal decomposition under certain atmosphere, can obtain the porous nanometer structure of respective material, and the structure of product pattern and unstable compound is consistent.In fact, utilize the method prepare oxide porous nano material have been reported (S.Y.Zeng et al., J.Phys.Chem.C 2008,112,4836-4843; X.F.Zhou et al., J.Phys.Chem.C 2008,112,11722-11728).
Nickel is a kind of important VIII B group 4 transition metal, is widely used at magnetics, catalysis and alloy manufacture view.Along with the development of nanometer technology, the nickel nano material the application prospect aspect catalytic hydrogenation and magnetic recording material caused the researcher broad interest (J.Masson et al., Appl.Catal.A 1997,161,191-197; K.Nielsch et al., J.Mag.Mag.Mater.2002,249,234-240; J.C.Bao et al., Adv.Mater.2001,13,1631-1633).For example nickel is a kind of catalyst material of aromatic ketone hydrogenation commonly used, acetophenone (ACT) is as the simplest aromatic ketone, important source material (the B.M.Reddy et al. that its C=O selective hydrogenation product benzyl carbinol (PE) is medicine and spices industry, Cataly.Lett.2009,131,328-336).Hydrogenation of acetophenone reaction original adoption homogeneous catalyst is (as hydride LiAlH
4And NaBH
4), although higher to the hydrogenation selectivity of C=O, the catalyst consumption amount is large, can not be recycling, and cause cost high.Develop afterwards heterogeneous catalyst, and adopted the noble metals such as support type Ru, Rh, Pt and Pd to serve as catalyst.Because the noble metal cost is higher, industrial employing Raney Ni makes catalyst, but Raney nickel is very unstable, and (D.Duraczynska et al., Catal.Lett.2011,141,83-94 can burn after ingress of air; A.Drelinkiewicza et al., Catal.Lett.2004,94,143-156; G.F.Santori et al., Appl.Catal.A2004,269,215-223), easy inactivation in use and separation process.If can make a kind of nickel nano material, have larger specific area, more active sites, non-oxidizability preferably, in conjunction with the magnetic property of nickel, the magnetic that just is expected to obtain a kind of function admirable separates hydrogenation catalyst.
Introduce nano grade pore in the nickel nano material, can increase its specific area and avtive spot, thereby be expected to improve its catalytic performance and magnetic behavior (P.Kim et al., Cataly.Lett.2005,104,181-189; P.N.Bartlett et al., J.Mater.Chem.2003,13,2596-2602).Up to now, the report relevant to the research of nickel porous preparations of nanomaterials is less, mostly by template electric-sedimentation method or the preparation of NiO nano material reducing process.Wherein the template electric-sedimentation method is difficult to a large amount of synthesizing, and need add reducing agent such as H in the preparation process of NiO nano material reducing process
2, KBH
4And N
2H
4Loaded down with trivial details and dangerous large (S.M.Zhang et al., Chem.Mater.2009,21,871-883 Deng, preparation process; Y.Z.Mi et al., Mater.Chem.Phys.2005,89,359-361; Y.Li et al., Chem.Engin.J.2008,136,398-408).In sum, how by easy, technology path prepares the nickel porous nano material and has important research and using value cheaply.
Summary of the invention
The invention provides a kind of method for preparing the nickel-based compound nano material, gained nickel-based compound nano material can be in the situation that separately do not add reducing agent and decompose by direct heat and obtain the nickel porous nano material.
The nickel-based compound nano material that the present invention also provides said method to obtain.
The present invention also provides the method for preparing the nickel porous nano material, can be in the situation that separately do not add reducing agent and decompose by direct heat and obtain the nickel porous nano material.
The nickel porous nano material that the present invention also provides said method to obtain.
The present invention also provides the application of above-mentioned nickel porous nano material.
The described method for preparing the nickel-based compound nano material is, take soluble nickel salt as the nickel source, take hexa and oxalic acid as precipitating reagent, prepare the nickel-based compound nano material by the solution phase coprecipitation method, the mol ratio of hexa and oxalic acid is 10: 4～10: 1.
Preferred described solution phase coprecipitation method is, the mixed solution of soluble nickel salt, hexa and oxalic acid is refluxed, separate out solid, cooling rear Separation of Solid and Liquid obtains the nickel-based compound nano material, the molar concentration of the nickel before refluxing in described mixed solution, hexa, oxalic acid is respectively 0.05～0.25mol/L, 0.05～0.25mol/L, 0.005～0.1mol/L.Further preferred, reflux temperature is 90～110 ℃, and return time is 1～10h.Return time should be enough to make precipitation fully, and best return time can be determined by experiment.The length of return time has no significant effect the precipitation pattern;As general knowledge, in order to precipitate fully and to utilize nickel element as far as possible fully, hexa and oxalic acid should be excessive with respect to nickel, and preferred: the molal quantity of nickel is 1: 1.4～1: 1.05 with the ratio of the total mole number of hexa and oxalic acid.
Solution phase coprecipitation method of the present invention is a kind of homogeneous precipitation method.Described Separation of Solid and Liquid adopts this area technological means commonly used, as filtering, wash, drying.Concrete, can be: filter, the washing of water and ethanol be 3～5 times respectively, and oven dry under 50～150 ℃.The described cooling preferred natural type of cooling.
The nickel-based compound nano material of said method gained is the flowers structure that solid core coated with nanometre sheet consists of, and the diameter of single flowers structure is 500 nanometers～6 micron, and the thickness of nanometer sheet is 3～10 nanometers, and width is about 200 nanometers～2 micron.
The method for preparing the nickel porous nano material is first to prepare according to the method described above the nickel-based compound nano material; Then at inert atmosphere (as Ar gas, N
2Gas) at 320～360 ℃ of temperature heat treatment decompose the nickel-based compound nano material, obtain the nickel porous nano material, preferred heat treatment time is 10min～3h (till obtaining pure Ni with whole decomposition, too short the decomposition not exclusively of time, the oversize sintering that easily causes Ni of time).This method is decomposed described nickel-based compound nano material by direct heat and is obtained the nickel porous nano material, does not need separately to add other reducing agent.Heat treatment temperature has material impact to composition and the pattern of nickel porous nano material.When heat treatment temperature was low, nickel-based compound can not decompose fully; And heat treatment temperature too Gao Zehui cause the nickel porous nano material generation sintering that generates, shape nickel particle obtains reuniting.Best pyrolysis temperature is 335～340 ℃.
The nickel porous nano material that said method obtains is the flowers structure that nanometer sheet consists of, and the diameter of single flowers structure is 500 nanometers～6 micron, and the thickness of nanometer sheet is 3～10 nanometers, and width is about 200 nanometers～2 micron.Nanometer sheet edge roughness, surface produce the aperture of many random distributions.
The Ni-based compound N iC that comprises in precipitation gained nickel-based compound
2O
42H
2O and α-Ni (OH)
2Unstable, easily decompose after heat treatment.With the thermal decomposition process of the above-mentioned nickel-based compound nano material of TG-DSC-MS technical monitoring, find that the heat treatment in air and Ar gas of this predecessor obtains different product (accompanying drawing 3, accompanying drawing 4).The XRD result shows that thermal decomposition obtains nickel oxide in air, and thermal decomposition obtains metallic nickel (accompanying drawing 5) in Ar gas.
The predecessor nickel-based compound nano material nickel oxide nano material that pyrolysis obtains in air keeps the pattern of predecessor substantially, is the nanometer sheet edge roughening of flowers, and has produced from the teeth outwards the aperture (accompanying drawing 6) of some disorder distribution.The predecessor nickel nano material that pyrolysis obtains in Ar gas forms the (pattern that has substantially kept predecessor by porous chips, after just core decomposes, volume significantly dwindles and porose existence, therefore can not be referred to as solid core), and the roughening of nanometer sheet edge, and produced from the teeth outwards the aperture (accompanying drawing 7) of some disorder distribution.Pyrolysis temperature has material impact to composition and the pattern of nickel porous nano material, when pyrolysis temperature lower (as＜333 ℃), also has impurity (accompanying drawing 5) in the nickel product that obtains; When pyrolysis temperature is higher (as 400 ℃), nickel product is the nickel particle of sintering shape.Pyrolysis temperature also has appreciable impact to the specific area of nickel product, and the specific area of the nickel porous nano material that 335 ℃ of pyrolysis obtain is about 24.5m
2/ g, and the specific area of the nano nickel particles that 400 ℃ of pyrolysis obtain only is 2.9m
2/ g (accompanying drawing 8).The magnetic test shows that the nickel porous nano material has stronger ferromagnetism, can utilize external magnetic field (as magnet) to be separated (accompanying drawing 9).
Described nickel porous nano material can be used as liquid phase hydrogenating catalyst.Catalyst with the nickel porous nano material that makes is reacted as hydrogenation of acetophenone shows very high acetophenone conversion and benzyl carbinol selective, and this catalyst can be by the use of magnetic separating cycle, and cyclical stability is high, and the oxidation resistance of catalyst is also stronger.
The experimentation of described catalytic reaction is as follows: hydrogenation reaction is carried out in autoclave, take the aqueous isopropanol of potassium hydroxide as solvent, adds a certain amount of acetophenone and nickel porous nano material, and is filled with～H of 2MPa
2Reaction temperature is 100 ℃, and reaction is chilled to room temperature after 1 hour naturally under stirring condition.Product separates detection through gas chromatography-mass spectrometry chromatogram (shimadzu GCMS-QP2010 plus), and is undertaken quantitatively by the peak area of chromatographic peak.After primary first-order equation was completed, Raney nickel was separated from solution with magnet, and was used as the catalyst of hydrogenation reaction next time.
For verifying the oxidation resistance of this catalyst, the nickel porous nano material is placed in Muffle furnace, in air in 100 ℃ of (being the temperature of hydrogenation reaction) heat treatment 1～4h, and then for above-mentioned catalytic reaction, by the effect of Raney nickel to the hydrogenation of acetophenone reaction before and after the contrast oxidation processes, discovery difference wherein can be ignored substantially.
With the nickel porous nano material that the makes catalyst as the hydrogenation of acetophenone reaction, under above-mentioned reaction condition, the conversion ratio of acetophenone is 97%, benzyl carbinol be selectively 98.3%.Catalyst separates by magnetic and can be recycled, cyclical stability fine (after 10 circulations, catalytic performances are without obvious decline).After oxidation processes, compare without significant change with freshly prepd catalyst by its catalytic performance in air for this catalyst, and antioxygenic property also fine (accompanying drawing 10) is described.
Main feature of the present invention and advantage are as follows:
1. by the unsettled nickel-based compound nano material of pyrolysis, directly obtain the nickel porous nanostructured in the situation that do not need separately to add reducing agent, preparation process is easy, environmental protection, cost are low, and can prepare in a large number.
2. the nickel porous nano material that makes has classification nanostructure, and specific area is larger, and rough surface, and active sites is many.
3. the nickel nano material has stronger magnetic and Catalytic Hydrogenation Properties, can be used as the magnetic separating catalyst, the hydrogenation reactions such as catalysis hydrogenation of acetophenone, and realize the easy separation of catalyst and recycling.
4. reaction has good catalytic effect to hydrogenation of acetophenone with the nickel porous nano material that makes in the present invention, and under the reaction condition of gentleness, the conversion ratio of acetophenone is 97%, benzyl carbinol be selectively 98.3%.
5. the antioxygenic property of the prepared nickel porous catalyst of the present invention is fine.
6. nickel porous nano material provided by the invention also can be used as the magnetic separating catalyst of other aromatic ketone hydrogenation reaction.
Description of drawings
Fig. 1. transmission electron microscope photo (a, b), stereoscan photograph (c) and the X-ray diffraction spectrum (d) of flowers shape nickel-based compound nano material (embodiment 1 product).(d) in ◆ marker peak can belong to α-Ni (OH)
2 
Marker peak can belong to NiC
2O
42H
2O。
Fig. 2. infrared (FTIR) spectrum of flowers shape nickel-based compound nano material (embodiment 1 product).In conjunction with X-ray diffraction spectrum and TG-MS as can be known, predecessor is by α-Ni (OH)
2And NiC
2O
42H
2O forms, and at α-Ni (OH)
2The interlayer intercalation nitrate ion and formaldehyde molecule (due to Ni (OH) the 2nd, lamellar compound, its interlamellar spacing is about 7 nanometers, easily intercalation ion and little molecule.Nickel oxalate is not lamellar compound, and we have prepared pure nickel oxalate, and result shows and wherein do not contain nitrate anion and formaldehyde.Product is through repeatedly still having nitrate ion and formaldehyde to exist after washing, if be not intercalated in the interlayer of nickel hydroxide be easy to wash away).
Fig. 3. predecessor (embodiment 1 product) is heat treated TG-DSC curve in air and Ar gas respectively.
Fig. 4. predecessor (embodiment 1 product) is heat treated DTG curve and MS spectrum (a, Ar gas in air and Ar gas respectively; B, air).
Fig. 5. predecessor heat treatment under different temperatures in Ar gas (embodiment 1 product) reaches the XRD spectra of 340 ℃ of heat treatments (embodiment 4 products) products therefrom in air.In air, heat-treated products is NiO, and in Ar gas, heat-treated products is Ni, contains impurity (using the * mark) lower than 333 ℃ the time in product.
Fig. 6. stereoscan photograph (a), transmission electron microscope photo (b, c) and the high resolution electron microscopy photo (d) of predecessor 340 ℃ of heat treatment gained NiO products (embodiment 4 products) in air.
Fig. 7. transmission electron microscope and the high resolution electron microscopy photo of predecessor 335 ℃ (a-c) and 400 ℃ of (d) heat treatment products therefroms (product of embodiment 1 and embodiment 7 respectively) in Ar gas.
Fig. 8. the N of predecessor 335 ℃ (a) and 400 ℃ of (b) heat treatment products therefroms (product of embodiment 1 and embodiment 7 respectively) in Ar gas
2The adsorption-desorption thermoisopleth.
Fig. 9. predecessor M-H magnetic hysteresis of 335 ℃ and 400 ℃ of heat treatment products therefroms (product of embodiment 1 and embodiment 7 respectively) in Ar gas is returned curve.
Figure 10. the nickel porous nano material is cycle-index-conversion ratio and selective relation curve during as the catalyst of hydrogenation of acetophenone reaction, and the filled symbols representative is selective (wherein ◆ represent the selective of 1-phenylethanol; ▲ represent the selective of 1-cyclohexyl methyl ketone; ● represent the selective of cyclohexyl ethyl alcohol), open symbols represents conversion ratio, wherein symbol ☆ represents the conversion ratio of 400 ℃ of heat treatment gained Ni beaded catalysts.Cycle-index 1～9 finger catalyst is used for the number of times of catalytic reaction after magnetic separates, result shows the good cycling stability of catalyst; The data of the 10th time show that corresponding to Raney nickel being placed in the experimental result that is used for catalytic reaction after 100 ℃ of oxidation 4h of Muffle furnace the antioxygenic property of catalyst is good.
Figure 11. transmission electron microscope photo and the X-ray diffraction spectrum of the predecessor for preparing when only adding hexa (a, c) and only adding oxalic acid (b, d) for precipitating reagent.Obtain the translucent flowers structural material in center when only being precipitating reagent with hexa, consist of α-Ni (OH)
2(◆) and a small amount of
Multiphase; Obtain the nickel oxalate blocky-shaped particle when only being precipitating reagent with oxalic acid.
Figure 12. the X-ray diffraction spectrum of gained predecessor 335 ℃ of heat treatment products therefroms in Ar gas when only adding hexa shows that product is the mixture of nickel and nickel oxide.
The specific embodiment
With 1.2g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, under constantly stirring, 10mL is dissolved with 0.56g hexa and 0.1g oxalic acid hydrate (H
2C
2O
42H
2O) solution dropwise adds in nickel nitrate solution.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.14mol/L, 0.14mol/L, 0.027mol/L, the mol ratio of hexa and oxalic acid is 10: 1.9, and the molal quantity of nickel is 1: 1.17 with the ratio of the total mole number of hexa and oxalic acid.Be warming up to 100 ℃, refluxed 5～6 hours.The nature cooled and filtered, after repeatedly washing and dry, water and ethanol gets green predecessor (as shown in Figure 1, flowers structure for solid core coated with nanometre sheet formation, the diameter of single flowers structure is about 2～4 microns, nanometer sheet ground thickness is about 3～10 nanometers, and width is about 200 nanometers～2 micron).Green predecessor is placed in the tube furnace center, is warming up to 335 ℃ after bleeding in Ar gas, and keep 1h, obtain nickel porous nano material (accompanying drawing 7a-c).The nickel porous nano material is the flowers structure that nanometer sheet consists of, for predecessor, the flowers structure has caving in to a certain degree, the diameter of single flowers structure is 2～4 microns, the thickness of nanometer sheet is 3～10 nanometers, width is about 200 nanometers～2 micron, and nanometer sheet edge roughness, surface produce the aperture of many random distributions.When preparing green predecessor, the raw material consumption can amplify by multiple.
Gained nickel porous nano material is placed in the aqueous solution (or isopropyl alcohol) and after ultrasonic processing 1min, can be dispersed in solution; When place a magnet outside bottle, can see the nickel porous nano material rapidly (＜10s) gather near magnet one side.Moving magnet can make the nickel porous nano material separate from solution, and solution becomes clarification, and is residual without nickel material.
With 0.45g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, under constantly stirring, 10mL is dissolved with 0.21g hexa and 0.02g oxalic acid hydrate (H
2C
2O
42H
2O) solution dropwise adds in nickel nitrate solution.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.05mol/L, 0.05mol/L, 0.005mol/L, the mol ratio of hexa and oxalic acid is 10: 1, and the molal quantity of nickel is 1: 1.07 with the ratio of the total mole number of hexa and oxalic acid.Be warming up to 90 ℃, refluxed 10 hours.The nature cooled and filtered, after water and ethanol repeatedly wash and dry green predecessor, its pattern and accompanying drawing 1 are similar, diameter is about 500 nanometers～2 micron.Green predecessor is placed in the tube furnace center, is warming up to 335～340 ℃ after bleeding in Ar gas, and keep 1h, obtain the nickel porous nano material.The nickel porous nano material is the flowers structure that nanometer sheet consists of, for predecessor, the flowers structure has caving in to a certain degree, the diameter of single flowers structure is 500 nanometers～2 micron, the thickness of nanometer sheet is 3～10 nanometers, width is about 200 nanometers～2 micron, and nanometer sheet edge roughness, surface produce the aperture of many random distributions.When preparing green predecessor, the raw material consumption can amplify by multiple.
With 2.2g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, under constantly stirring, 10mL is dissolved with 1.05g hexa and 0.35g oxalic acid hydrate (H
2C
2O
42H
2O) solution dropwise adds in nickel nitrate solution.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.25mol/L, 0.25mol/L, 0.09mol/L, the mol ratio of hexa and oxalic acid is 10: 3.6, and the molal quantity of nickel is 1: 1.36 with the ratio of the total mole number of hexa and oxalic acid.Be warming up to 110 ℃, refluxed 1 hour.The nature cooled and filtered gets green predecessor after water and ethanol repeatedly wash and dries, its pattern and accompanying drawing 1 are similar, and diameter is about 3～6 microns, and the diameter of solid core becomes large.Green predecessor is placed in the tube furnace center, is warming up to 335～340 ℃ after bleeding in Ar gas, and keep 1h, obtain the nickel porous nano material.The nickel porous nano material is the flowers structure that nanometer sheet consists of, for predecessor, the flowers structure has caving in to a certain degree, the diameter of single flowers structure is 3～6 microns, the thickness of nanometer sheet is 3～10 nanometers, width is about 200 nanometers～2 micron, and nanometer sheet edge roughness, surface produce the aperture of many random distributions.When preparing green predecessor, the raw material consumption can amplify by multiple.
With 1.2g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, under constantly stirring, 10mL is dissolved with 0.56g hexa and 0.1g oxalic acid hydrate (H
2C
2O
42H
2O) solution dropwise adds in nickel nitrate solution.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.14mol/L, 0.14mol/L, 0.027mol/L, the mol ratio of hexa and oxalic acid is 10: 1.9, and the molal quantity of nickel is 1: 1.17 with the ratio of the total mole number of hexa and oxalic acid.Be warming up to 100 ℃, refluxed 5～6 hours.The nature cooled and filtered gets green predecessor (accompanying drawing 1) after water and ethanol repeatedly wash and dries.Green predecessor is placed in the tube furnace center, is warming up to 340 ℃ in air, and keep 2h, obtain porous nickel oxide nano material (accompanying drawing 6).When preparing green predecessor, the raw material consumption can amplify by multiple.
Embodiment 5 flowers shape nickel-based compound nano material and porous nickel oxide preparations of nanomaterials.
With 0.45g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, under constantly stirring, 10mL is dissolved with 0.21g hexa and 0.02g oxalic acid hydrate (H
2C
2O
42H
2O) solution dropwise adds in nickel nitrate solution.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.05mol/L, 0.05mol/L, 0.005mol/L, the mol ratio of hexa and oxalic acid is 10: 1, and the molal quantity of nickel is 1: 1.07 with the ratio of the total mole number of hexa and oxalic acid.Be warming up to 90 ℃, refluxed 10 hours.The nature cooled and filtered, after water and ethanol repeatedly wash and dry green predecessor, its pattern and accompanying drawing 1 are similar, diameter is about 500 nanometers～2 micron.Green predecessor is placed in the tube furnace center, is warming up to 340 ℃ in air, and keep 1h, obtain the porous nickel oxide nano material.When preparing green predecessor, the raw material consumption can amplify by multiple.
With 2.2g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, under constantly stirring, 10mL is dissolved with 1.05g hexa and 0.35g oxalic acid hydrate (H
2C
2O
42H
2O) solution dropwise adds in nickel nitrate solution.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.25mol/L, 0.25mol/L, 0.09mol/L, the mol ratio of hexa and oxalic acid is 10: 3.6, and the molal quantity of nickel is 1: 1.36 with the ratio of the total mole number of hexa and oxalic acid.Be warming up to 110 ℃, refluxed 1 hour.The nature cooled and filtered gets green predecessor (accompanying drawing 1) after water and ethanol repeatedly wash and dries, its pattern and accompanying drawing 1 are similar, and diameter is about 3～6 microns, and the diameter of solid core becomes large.Green predecessor is placed in the tube furnace center, is warming up to 340 ℃ in air, and keep 1h, obtain the porous nickel oxide nano material.When preparing green predecessor, the raw material consumption can amplify by multiple.
The preparation of embodiment 7 flowers shape nickel-based compound nano materials and nano nickel particles.
With 1.2g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, under constantly stirring, 10mL is dissolved with 0.56g hexa and 0.1g oxalic acid hydrate (H
2C
2O
42H
2O) solution dropwise adds in nickel nitrate solution.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.14mol/L, 0.14mol/L, 0.027mol/L, the mol ratio of hexa and oxalic acid is 10: 1.9, and the molal quantity of nickel is 1: 1.17 with the ratio of the total mole number of hexa and oxalic acid.Be warming up to 100 ℃, refluxed 5～6 hours.The nature cooled and filtered gets green predecessor (accompanying drawing 1) after water and ethanol repeatedly wash and dries.Green predecessor is placed in the tube furnace center, be warming up to 400 ℃ after bleeding in Ar gas, and keep 1h, and obtain size and be 30～150 nanometers and the nano nickel particles (accompanying drawing 7d) of bonding mutually, be that the nickel porous nano material is under higher temperature due to sintering.
The preparation of embodiment 8 flowers shape nickel-based compound nano materials and nano nickel particles.
With 0.45g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, under constantly stirring, 10mL is dissolved with 0.21g hexa and 0.02g oxalic acid hydrate (H
2C
2O
42H
2O) solution dropwise adds in nickel nitrate solution.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.05mol/L, 0.05mol/L, 0.005mol/L, the mol ratio of hexa and oxalic acid is 10: 1, and the molal quantity of nickel is 1: 1.07 with the ratio of the total mole number of hexa and oxalic acid.Be warming up to 90 ℃, refluxed 10 hours.The nature cooled and filtered, after water and ethanol repeatedly wash and dry green predecessor, its pattern and accompanying drawing 1 are similar, diameter is about 500 nanometers～2 micron.Green predecessor is placed in the tube furnace center, is warming up to 400 ℃ after bleeding in Ar gas, and keeps 1～2h, obtain the nano nickel particles of the sintering shape of pattern such as accompanying drawing 7d.
The preparation of embodiment 9 flowers shape nickel-based compound nano materials and nano nickel particles.
With 2.2g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, under constantly stirring, 10mL is dissolved with 1.05g hexa and 0.35g oxalic acid hydrate (H
2C
2O
42H
2O) solution dropwise adds in nickel nitrate solution.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.25mol/L, 0.25mol/L, 0.09mol/L, the mol ratio of hexa and oxalic acid is 10: 3.6, and the molal quantity of nickel is 1: 1.36 with the ratio of the total mole number of hexa and oxalic acid.Be warming up to 110 ℃, refluxed 1 hour.The nature cooled and filtered gets green predecessor after water and ethanol repeatedly wash and dries, its pattern and accompanying drawing 1 are similar, and diameter is about 3～6 microns, and the diameter of solid core becomes large.Green predecessor is placed in the tube furnace center, is warming up to 400 ℃ after bleeding in Ar gas, and keeps 1～2h, obtain the nano nickel particles of pattern such as accompanying drawing 7d sintering shape.
10 of embodiment are take hexa as the translucent Ni in precipitating reagent preparing centre (OH)
2Flowers shape nano material and nickel and nickel oxide porous nanometer material.
With 1.2g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, during the solution that 10mL is dissolved with the 0.56g hexa under constantly stirring dropwise adds nickel nitrate solution.Be warming up to 100 ℃, refluxed 5～6 hours.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.14mol/L, 0.14mol/L, 0.027mol/L, the mol ratio of hexa and oxalic acid is 10: 1.9, and the molal quantity of nickel is 1: 1.17 with the ratio of the total mole number of hexa and oxalic acid.The nature cooled and filtered gets green predecessor (accompanying drawing 11a, c) after water and ethanol repeatedly wash and dries.Green predecessor is placed in the tube furnace center, is warming up to 335 ℃ after bleeding in Ar gas, and keeps 1～2h, obtain the porous nanometer material (accompanying drawing 12) of nickel and nickel oxide mixture.When preparing green predecessor, the raw material consumption can amplify by multiple.
11 of embodiment are take hexa as the translucent Ni in precipitating reagent preparing centre (OH)
2Flowers shape nano material and nickel and nickel oxide porous nanometer material.
With 0.45g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, during the solution that 10mL is dissolved with the 0.21g hexa under constantly stirring dropwise adds nickel nitrate solution.Be warming up to 90 ℃, refluxed 10 hours.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.05mol/L, 0.05mol/L, 0.005mol/L, the mol ratio of hexa and oxalic acid is 10: 1, and the molal quantity of nickel is 1: 1.07 with the ratio of the total mole number of hexa and oxalic acid.The nature cooled and filtered, after water and ethanol repeatedly wash and dry green predecessor, its pattern and accompanying drawing 11a are similar, diameter is about 500 nanometers～2 micron.Green predecessor is placed in the tube furnace center, is warming up to 335～340 ℃ after bleeding in Ar gas, and keeps 1～2h, obtain the porous nanometer material of nickel and nickel oxide mixture.When preparing green predecessor, the raw material consumption can amplify by multiple.
12 of embodiment are take hexa as the translucent Ni in precipitating reagent preparing centre (OH)
2Flowers shape nano material and nickel and nickel oxide porous nanometer material.
With 2.2g Ni (NO
3)
26H
2O is dissolved in 20mL distilled water, during the solution that 10mL is dissolved with the 1.05g hexa under constantly stirring dropwise adds nickel nitrate solution.In the gained mixed solution, the molar concentration of nickel, hexa, oxalic acid is respectively 0.25mol/L, 0.25mol/L, 0.09mol/L, the mol ratio of hexa and oxalic acid is 10: 3.6, and the molal quantity of nickel is 1: 1.36 with the ratio of the total mole number of hexa and oxalic acid.Be warming up to 110 ℃, refluxed 1 hour.The nature cooled and filtered gets green predecessor after water and ethanol repeatedly wash and dries, its pattern and accompanying drawing 11a are similar, and diameter is about 3～6 microns.Green predecessor is placed in the tube furnace center, is warming up to 335～340 ℃ after bleeding in Ar gas, and keeps 1～2h, obtain the porous nanometer material of nickel and nickel oxide mixture.When preparing green predecessor, the raw material consumption can amplify by multiple.
Can be seen by above-described embodiment and comparative examples, alone hexa is precipitating reagent, can only obtain Ni (OH)
2Hollow flowers; Alone oxalic acid is precipitating reagent, can only obtain NiC
2O
4Nano particle, and precipitation produces fast; When therefore hexa and oxalic acid are used in our judgement at the same time as precipitating reagent, first generate NiC
2O
4Nano particle, then as nuclearing centre, Ni (OH)
2Nanometer sheet obtains solid flowers at its surface deposition.
Embodiment 13 use nickel porous nano materials are as the magnetic separating catalyst of hydrogenation of acetophenone reaction.
Hydrogenation reaction is carried out in autoclave.Add the potassium hydroxide of 15mg, the acetophenone of 0.3mL and the nickel porous nano material (embodiment 1 product) of 30mg in the isopropyl alcohol of 15mL, and be filled with～H of 2MPa
2Be warmed up to 100 ℃, reaction is chilled to room temperature after 1 hour naturally under stirring condition.Under above-mentioned reaction condition, the conversion ratio of acetophenone be 97%, 1-phenylethanol be selectively 98.3%, 1-cyclohexyl methyl ketone selective be～1.2%, 1-cyclohexyl ethyl alcohol be selectively～0.5%.Catalyst separates by magnetic and can be recycled, cyclical stability fine (after 10 circulations, catalytic performances are without obvious decline) (accompanying drawing 10).As to adopt embodiment 7 products obtained therefroms be catalyst, and under the same conditions, acetophenone conversion is only 83% in (in accompanying drawing 10 shown in ☆).
Claims (8)
1. method for preparing the nickel-based compound nano material, it is characterized in that, take soluble nickel salt as the nickel source, take hexa and oxalic acid as precipitating reagent, prepare the nickel-based compound nano material by the solution phase coprecipitation method, the mol ratio of hexa and oxalic acid is 10:4～10:1; The mixed solution of soluble nickel salt, hexa and oxalic acid is refluxed, separate out solid, cooling rear Separation of Solid and Liquid obtains the nickel-based compound nano material, the molar concentration of the nickel before refluxing in described mixed solution, hexa, oxalic acid is respectively 0.05～0.25mol/L, 0.05～0.25mol/L, 0.005～0.10mol/L; Reflux temperature is 90～110 ℃, and return time is 1～10h.
2. the nickel-based compound nano material of the described method gained of claim 1, it is characterized in that described nickel-based compound nano material is the flowers structure that solid core coated with nanometre sheet consists of, the diameter of single flowers structure is 500 nanometers～6 micron, the thickness of nanometer sheet is 3～10 nanometers, and width is 200 nanometers～2 micron.
3. a method for preparing the nickel porous nano material, is characterized in that, first prepares the nickel-based compound nano material according to the described method of claim 1; Then in inert atmosphere at 320～360 ℃ of temperature heat treatment decompose the nickel-based compound nano material, obtain the nickel porous nano material.
4. the method for preparing the nickel porous nano material as claimed in claim 3, is characterized in that, heat treatment temperature is 335～340 ℃.
5. the method for preparing the nickel porous nano material as claimed in claim 3, is characterized in that, heat treatment time is 10min～3h.
6. the nickel porous nano material that in claim 3-5, the described method of any one obtains, it is characterized in that, described nickel porous nano material is the flowers structure that nanometer sheet consists of, the diameter of single flowers structure is 500 nanometers～6 micron, the thickness of nanometer sheet is 3～10 nanometers, width is 200 nanometers～2 micron, and nanometer sheet edge roughness, surface produce the aperture of many random distributions.
7. nickel porous nano material claimed in claim 6 is as the application of liquid phase hydrogenating catalyst.
8. application as claimed in claim 7, is characterized in that, described liquid phase hydrogenating catalyst is the catalyst of hydrogenation of acetophenone reaction.
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