CN103194751A - Nickel nanorod-nickel oxide nanosheet hierarchical structure array modified with silver nanoparticles and preparation method and application thereof - Google Patents
Nickel nanorod-nickel oxide nanosheet hierarchical structure array modified with silver nanoparticles and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a nickel nanorod-nickel oxide nanosheet hierarchical structure array modified with silver nanoparticles and a preparation method and application thereof. The array is a nickel nanorod array which consists of conical top-outcropped nickel nanorods and nickel oxide nanosheets attached onto the nickel nanorods, wherein the nickel nanorod array is located on an alumina template, and the surfaces of the nickel nanorods are all modified with the silver nanoparticles. The method comprises the following steps of: firstly carrying out secondary anodic oxidation, reaming and one-side silver film plating on an aluminum sheet; electrodepositing the aluminum sheet in a nickel electrolyte, and then, chemically removing a silver film, so as to obtain the alumina template, in which nickel nanorod arrays are placed; floating the alumina template on the surface of alkaline liquid, and then, soaking the alumina template in concentrated ammonia, so as to obtain the nickel nanorod array which is located on the alumina template, wherein nickel hydroxide nanosheets are attached onto the conical top-outcropped nickel nanorods of the nickel nanorod array; and calcining the nickel nanorod array, and then, sputtering the silver nanoparticles on the surface of the nickel nanorod array, thereby producing a target product. The nickel nanorod-nickel oxide nanosheet hierarchical structure array modified with the silver nanoparticles can serve as a surface-enhanced Raman scattering active substrate, and the content of rhodamine or tetrachlorobiphenyl attached onto the nickel nanorod-nickel oxide nanosheet hierarchical structure array is measured by using a laser Raman spectrometer.
Description
Technical field
The present invention relates to a kind of hierarchy array and preparation method and purposes, especially a kind of nickel nano-pillar of modified by silver nanoparticles-nickel oxide nano sheet hierarchy array and its production and use.
Background technology
Transiting metal nickel has magnetic and good plasticity-, and good erosion resistance.Nanometer nickel has bigger specific surface area because of it, and the excellent properties that shows in many-side and more and more cause people's attention.At present, people have made unremitting effort in order to obtain the nanometer nickel material, as a kind of " metal nickel nano pipe and the preparation method " of Chinese invention patent specification sheets CN100441348C in bulletin on December 10th, 2008.The external diameter of the metal nickel nano pipe of putting down in writing in this specification sheets is 15～150 nanometers; The preparation method will be anode as negative electrode, nickel material through the anodised aluminium foraminous die plate of sensitization and activation earlier, immersion contains in the electrolytic solution of nickel salt, boric acid, under the direct current effect on alumina formwork metal refining nickel, again with the alumina formwork that deposits metallic nickel in the hole through the molten template of going of basic solution, obtain product.But, no matter be product, or its preparation method, all exist weak point, at first, though the nickel nanotube has unknown specific end use, be difficult to identify fast, with sensitivity at the bottom of the active group as surface enhanced Raman scattering (SERS) the fingerprint characteristic information of testing molecule; Secondly, the preparation method can not obtain to have the nickel nanostructure substrate of higher SERS activity.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of rational in infrastructure for overcoming weak point of the prior art, has the nickel nano-pillar-nickel oxide nano sheet hierarchy array of the modified by silver nanoparticles of higher SERS activity.
Another technical problem that the present invention will solve is the preparation method of nickel nano-pillar-nickel oxide nano sheet hierarchy array that a kind of above-mentioned modified by silver nanoparticles is provided.
The present invention will solve also has a technical problem to be the purposes of nickel nano-pillar-nickel oxide nano sheet hierarchy array that a kind of above-mentioned super modified by silver nanoparticles is provided.
Solve technical problem of the present invention, the technical scheme that adopts is: the nickel nano-pillar of modified by silver nanoparticles-nickel oxide nano sheet hierarchy array comprises metallic nickel, particularly
Described metallic nickel is the nickel nano column array of appearing that places on the alumina formwork, described formation is appeared the top of the nickel nano-pillar of appearing of nickel nano column array for conical, described conical top is appeared on the nickel nano-pillar with the nickel oxide nano sheet, and the appear finishing of nickel nano-pillar and nickel oxide nano sheet of described conical top has silver nano-grain;
The appear post height of nickel nano-pillar of described conical top is 100～500nm;
The length of a film of described nickel oxide nano sheet is the thick 1～4nm of being of 20～50nm, sheet;
The particle diameter of described silver nano-grain is 8～12nm, particle gap≤10nm.
As the further improvement of the nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles, the appear column diameter of nickel nano-pillar of the conical top on the described alumina formwork is that 90～110nm, intercolumniation are 20～30nm.
For solving another technical problem of the present invention, another technical scheme that adopts is: the preparation method of the nickel nano-pillar of above-mentioned modified by silver nanoparticles-nickel oxide nano sheet hierarchy array comprises anonizing, and particularly completing steps is as follows:
Step 1 uses two-step anodization method and reaming method to handle to aluminium flake earlier successively, and obtaining bore dia is the through hole alumina formwork of 90～110nm, again in the silver-plated film of the one side of through hole alumina formwork, obtains the alumina formwork that one side is covered with silverskin;
Step 3, the alkaline solution surface that earlier alumina formwork that is equipped with the nickel nano column array in its hole is floated on concentration and be 0.05～0.15mol/L is 5min at least, obtain being equipped with on it alumina formwork of nickel nano column array of appearing, the nickel nano column array of appearing that is equipped with the alumina formwork of the nickel nano column array of appearing on it being placed temperature is that 90～100 ℃, concentration are that the strong aqua of 25～30wt% soaks 30min at least again, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel hydroxide nano sheet;
Step 4, the nickel nano column array on the alumina formwork of being positioned with the nickel hydroxide nano sheet on the nickel nano-pillar of earlier conical top being appeared places and calcines 2h at least under 350～450 ℃, obtaining conical top appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel oxide nano sheet, again on conical top is appeared the nickel nano-pillar with the surface sputtering silver nano-grain that is positioned the nickel nano column array on the alumina formwork of nickel oxide nano sheet, make the nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles.
Further improvement as the preparation method of the nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles, described silver-plated film is for using the magnetic control sputtering device sputter, during sputter, the spacing of alumina formwork and silver-colored target is that the electric current of 2cm, sputter is that time of 40mA, sputter is 10min; Described nickel electrolyte is that concentration is the six hydration nickel sulfate (NiSO of 52.57g/L
46H
2O) be the boric acid (H of 6.18g/L with concentration
3BO
3) mixed solution; Anode during described galvanic deposit is Graphite Electrodes; Described alkaline solution is sodium hydroxide solution, or potassium hydroxide solution, or lithium hydroxide solution; Described sputtering silver nano particle is for using magnetic control sputtering device, during sputter, appear on the nickel nano-pillar the spacing that is positioned nickel nano column array on the alumina formwork and silver-colored target with the nickel oxide nano sheet of conical top is that the electric current of 2cm, sputter is that time of 10mA, sputter is 1～8min.
For solving the technical problem that also has of the present invention, the technical scheme that also has that adopts is: the purposes of the nickel nano-pillar of above-mentioned modified by silver nanoparticles-nickel oxide nano sheet hierarchy array is:
At the bottom of the nickel nano-pillar-active group of nickel oxide nano sheet hierarchy array as surface enhanced Raman scattering with modified by silver nanoparticles, the rhodamine (R6G) that uses laser Raman spectrometer to measure to adhere on it or the content of tetrachloro biphenyl (PCB-77).
As the further improvement of the purposes of the nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles, the excitation wavelength of described laser Raman spectrometer is that 532nm, output rating are that 0.05～0.15mW, integral time are 10～60s.
Beneficial effect with respect to prior art is, one, use scanning electron microscope, transmission electron microscope and its subsidiary power spectrum tester and X-ray diffractometer to characterize respectively to the target product that makes, by its result as can be known, target product is to be positioned that conical top on the template, that all be modified with nano particle by the surface is appeared nano-pillar and the nanometer sheet had on it is formed; Wherein, template is alumina formwork, nano particle is that particle diameter is the silver nano-grain of 8～12nm, particle gap≤10nm, the conical top nano-pillar of appearing is the conical top of the 100～500nm nickel nano-pillar of appearing for the post height, and nanometer sheet is that length of a film is the nickel oxide nano sheet of 20～50nm, the thick 1～4nm of being of sheet.The nickel nano-pillar of this modified by silver nanoparticles-nickel oxide nano sheet hierarchy array both since its in the big area scope pattern rule, arrange in order, and the diameter of the nickel nano-pillar of forming array and spacing size all can be controlled artificially and make it possess the reliable and stable characteristics of structure, for it is laid a good foundation at the bottom of as stable SERS active group; Top because of the nickel nano-pillar is conical again, has numerous nickel oxide nano sheets on it in addition, makes it to have had the effect of " lightning rod ", and the utmost point is beneficial to and obtains high SERS activity; The surface of numerous nickel oxide nano sheet of also appearing the nickel nano-pillar owing to conical top and having on it all is modified with a large amount of silver nano-grains, and make silver nano-grain very easily produce the very strong local coupling electric field be referred to as " focus " usually each other, the SERS activity when greatly having improved it as substrate; More adhere to semi-conductor and precious metal separately because of nickel oxide and silver, the nickel oxide that invests on the nickel nano-pillar has semi-conductive chemical enhancement, has very strong electromagnetic field enhancement and be modified at its surperficial silver nano-grain, thereby the compound system that both are constituted has not only had the physics enhancement, also because of the direct charge transfer between semi-conductor and the noble metal granule, make this compound system have stronger chemical enhancement, thereby make it have very high surface-enhanced Raman scattering activity; The high-ratio surface and the chemical affinity that have of nickel oxide nano sheet can be detection molecules more adherent point is provided in addition, is highly advantageous to the active adsorption of detection molecules, and then improved the whole SERS activity of substrate widely.Its two, with the target product that makes as the SERS active group at the bottom of, through respectively to rhodamine and 3,3 ', 4,4 '-tetrachloro biphenyl carries out repeatedly many tests in batches, when the concentration of analyte rhodamine is low to moderate 10
-10Mol/L, analyte 3,3 ', 4 when the concentration of 4 '-tetrachloro biphenyl is low to moderate 10-5mol/L, still can detect it effectively, and the consistence of its detection and the multiple spot of repeatability on target product and any point very good all.They are three years old, the preparation method is simple, science, effective: both prepared Stability Analysis of Structures, nickel nano-pillar-nickel oxide nano sheet hierarchy array with modified by silver nanoparticles of higher SERS activity, after making the target product that makes again and laser Raman spectrometer cooperating, possessed environment toxic pollutant rhodamine and 3,3 ', 4,4 '-tetrachloro biphenyl carries out the function of quick trace detection, thereby makes target product very easily in the rapid detection that is widely used for fields such as environment, chemistry, biology.
As the further embodiment of beneficial effect, the one, the appear column diameter of nickel nano-pillar of the conical top on the preferred alumina formwork is that 90～110nm, intercolumniation are 20～30nm, haves laid a good foundation at the bottom of obtaining to have higher SERS active group.The 2nd, silver-plated film is preferably and uses the magnetic control sputtering device sputter, and during sputter, the spacing of alumina formwork and silver-colored target is that the electric current of 2cm, sputter is that time of 40mA, sputter is 10min, is beneficial to the silverskin that obtains suitable thickness.The 3rd, it is the mixed solution of the boric acid of 6.18g/L that nickel electrolyte is preferably six hydration nickel sulfate and the concentration that concentration is 52.57g/L, is convenient to carry out effectively the galvanic deposit of nickel nano-pillar.The 4th, the anode during galvanic deposit is preferably Graphite Electrodes, is convenient to effectively carrying out of galvanic deposit.The 5th, alkaline solution is preferably sodium hydroxide solution, or potassium hydroxide solution, or lithium hydroxide solution, not only makes the source of raw material than horn of plenty, also makes the easier enforcement of preparation technology and flexibly.The 6th, the sputtering silver nano particle is preferably the use magnetic control sputtering device, during sputter, appear on the nickel nano-pillar the spacing that is positioned nickel nano column array on the alumina formwork and silver-colored target with the nickel oxide nano sheet of conical top is that the electric current of 2cm, sputter is that time of 10mA, sputter is 1～8min, is beneficial to the suitable target product of density of the silver nano-grain that obtains modifying.The 7th, the excitation wavelength of laser Raman spectrometer is preferably 532nm, output rating and is preferably 0.05～0.15mW, integral time and is preferably 10～60s, not only guaranteed the accuracy that detects, also be easy to target product and detect rhodamine and 3,3 ', 4, the giving full play to of 4 '-tetrachloro biphenyl performance.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 is the intermediate product to making---appear on the nickel nano-pillar the target product that is positioned the nickel nano column array on the alumina formwork and makes with the nickel oxide nano sheet of conical top uses one of result that scanning electron microscope (SEM), transmission electron microscope (TEM) and its power spectrum (EDS) tester that attaches and X-ray diffraction (XRD) instrument characterize respectively.Wherein, Fig. 1 a is the side-looking SEM image of intermediate product, the left illustration in the image be intermediate product overlook enlarged image, right illustration is the TEM image of single intermediate product; Fig. 1 b is XRD spectra, from bottom to top curve is respectively the XRD spectral line of the Ni nano-pillar of appearing, the XRD spectral line of Ni nano-pillar-Ni (OH) 2 nanometer sheet hierarchy arrays of obtaining in this XRD spectra after strong aqua is handled, and the XRD spectral line of the Ni nano-pillar-NiO nanometer sheet hierarchy array that obtains after the calcining; Fig. 1 c is the SEM image of target product; Fig. 1 d is the EDS spectrogram of the target product of intermediate product and sputter different time silver.
Fig. 2 uses one of result that laser Raman spectrometer characterizes to the target product that contains the different concns rhodamine.Its confirmed with target product as the SERS active group at the bottom of, can detect the trace rhodamine that adheres on it.
Fig. 3 is to getting 5 points at random on the target product shown in Fig. 1 c, the Raman spectrogram that uses laser radiation to obtain, and this spectrogram shows that target product has extraordinary consistence.
Fig. 4 is to containing different concns 3,3 ', 4, and the target product of 4 '-tetrachloro biphenyl uses one of result that laser Raman spectrometer characterizes.Its confirmed with target product as the SERS active group at the bottom of, can detect the trace 3,3 ', 4 that adheres on it, 4 '-tetrachloro biphenyl.
Embodiment
At first buy from market or make with ordinary method:
Aluminium flake; Be the nickel electrolyte that the six hydration nickel sulfate of 52.57g/L and mixed solution that concentration is the boric acid of 6.18g/L are formed by concentration; Concentration is the concentrated nitric acid of 60～80wt%; Sodium hydroxide solution, potassium hydroxide solution and lithium hydroxide solution as alkaline solution; Concentration is the strong aqua of 25～30wt%.
Then,
Embodiment 1
The concrete steps of preparation are:
Step 1 uses two-step anodization method and reaming method to handle to aluminium flake earlier successively, and obtaining bore dia is that 90nm, pitch of holes are the through hole alumina formwork of 20nm.Use magnetic control sputtering device sputter silverskin in the one side of through hole alumina formwork again; During sputter, the spacing of alumina formwork and silver-colored target is that the electric current of 2cm, sputter is that time of 40mA, sputter is 10min, obtains the alumina formwork that one side is covered with silverskin.
Step 3, earlier the alumina formwork that is equipped with the nickel nano column array in its hole being floated on concentration is the alkaline solution surface 7min of 0.05mol/L; Wherein, alkaline solution is sodium hydroxide solution, obtains being equipped with on it alumina formwork of nickel nano column array of appearing.The nickel nano column array of appearing that is equipped with the alumina formwork of the nickel nano column array of appearing on it being placed temperature is that 90 ℃, concentration are that the strong aqua of 25wt% soaks 34min again, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel hydroxide nano sheet.
Step 4, the nickel nano column array that is positioned on the alumina formwork with the nickel hydroxide nano sheet on the nickel nano-pillar of earlier conical top being appeared places 350 ℃ of calcining 3h down, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel oxide nano sheet.Re-use magnetic control sputtering device surface sputtering silver nano-grain that is positioned the nickel nano column array on the alumina formwork with the nickel oxide nano sheet on conical top is appeared the nickel nano-pillar, during sputter, appear on the nickel nano-pillar the spacing that is positioned nickel nano column array on the alumina formwork and silver-colored target with the nickel oxide nano sheet of conical top is that the electric current of 2cm, sputter is that time of 10mA, sputter is 1min.Make and be similar to shown in Fig. 1 c, and the nickel of the modified by silver nanoparticles shown in the curve among Fig. 1 d nano-pillar-nickel oxide nano sheet hierarchy array.
The concrete steps of preparation are:
Step 1 uses two-step anodization method and reaming method to handle to aluminium flake earlier successively, and obtaining bore dia is that 93nm, pitch of holes are the through hole alumina formwork of 23nm.Use magnetic control sputtering device sputter silverskin in the one side of through hole alumina formwork again; During sputter, the spacing of alumina formwork and silver-colored target is that the electric current of 2cm, sputter is that time of 40mA, sputter is 10min, obtains the alumina formwork that one side is covered with silverskin.
Step 3, earlier the alumina formwork that is equipped with the nickel nano column array in its hole being floated on concentration is the alkaline solution surface 6.5min of 0.08mol/L; Wherein, alkaline solution is sodium hydroxide solution, obtains being equipped with on it alumina formwork of nickel nano column array of appearing.The nickel nano column array of appearing that is equipped with the alumina formwork of the nickel nano column array of appearing on it being placed temperature is that 93 ℃, concentration are that the strong aqua of 26wt% soaks 33min again, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel hydroxide nano sheet.
Step 4, the nickel nano column array that is positioned on the alumina formwork with the nickel hydroxide nano sheet on the nickel nano-pillar of earlier conical top being appeared places 380 ℃ of calcining 2.8h down, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel oxide nano sheet.Re-use magnetic control sputtering device surface sputtering silver nano-grain that is positioned the nickel nano column array on the alumina formwork with the nickel oxide nano sheet on conical top is appeared the nickel nano-pillar, during sputter, appear on the nickel nano-pillar the spacing that is positioned nickel nano column array on the alumina formwork and silver-colored target with the nickel oxide nano sheet of conical top is that the electric current of 2cm, sputter is that time of 10mA, sputter is 2.5min.Make and be similar to shown in Fig. 1 c, and the nickel of the modified by silver nanoparticles shown in the curve among Fig. 1 d nano-pillar-nickel oxide nano sheet hierarchy array.
Embodiment 3
The concrete steps of preparation are:
Step 1 uses two-step anodization method and reaming method to handle to aluminium flake earlier successively, and obtaining bore dia is that 95nm, pitch of holes are the through hole alumina formwork of 25nm.Use magnetic control sputtering device sputter silverskin in the one side of through hole alumina formwork again; During sputter, the spacing of alumina formwork and silver-colored target is that the electric current of 2cm, sputter is that time of 40mA, sputter is 10min, obtains the alumina formwork that one side is covered with silverskin.
Step 3, earlier the alumina formwork that is equipped with the nickel nano column array in its hole being floated on concentration is the alkaline solution surface 6min of 0.1mol/L; Wherein, alkaline solution is sodium hydroxide solution, obtains being equipped with on it alumina formwork of nickel nano column array of appearing.The nickel nano column array of appearing that is equipped with the alumina formwork of the nickel nano column array of appearing on it being placed temperature is that 95 ℃, concentration are that the strong aqua of 28wt% soaks 32min again, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel hydroxide nano sheet.
Step 4, the nickel nano column array that is positioned on the alumina formwork with the nickel hydroxide nano sheet on the nickel nano-pillar of earlier conical top being appeared places 400 ℃ of calcining 2.5h down, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel oxide nano sheet.Re-use magnetic control sputtering device surface sputtering silver nano-grain that is positioned the nickel nano column array on the alumina formwork with the nickel oxide nano sheet on conical top is appeared the nickel nano-pillar, during sputter, appear on the nickel nano-pillar the spacing that is positioned nickel nano column array on the alumina formwork and silver-colored target with the nickel oxide nano sheet of conical top is that the electric current of 2cm, sputter is that time of 10mA, sputter is 5min.Make shown in Fig. 1 c, and the nickel of the modified by silver nanoparticles shown in the curve among Fig. 1 d nano-pillar-nickel oxide nano sheet hierarchy array.
Embodiment 4
The concrete steps of preparation are:
Step 1 uses two-step anodization method and reaming method to handle to aluminium flake earlier successively, and obtaining bore dia is that 98nm, pitch of holes are the through hole alumina formwork of 28nm.Use magnetic control sputtering device sputter silverskin in the one side of through hole alumina formwork again; During sputter, the spacing of alumina formwork and silver-colored target is that the electric current of 2cm, sputter is that time of 40mA, sputter is 10min, obtains the alumina formwork that one side is covered with silverskin.
Step 3, earlier the alumina formwork that is equipped with the nickel nano column array in its hole being floated on concentration is the alkaline solution surface 5.5min of 0.13mol/L; Wherein, alkaline solution is sodium hydroxide solution, obtains being equipped with on it alumina formwork of nickel nano column array of appearing.The nickel nano column array of appearing that is equipped with the alumina formwork of the nickel nano column array of appearing on it being placed temperature is that 98 ℃, concentration are that the strong aqua of 29wt% soaks 31min again, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel hydroxide nano sheet.
Step 4, the nickel nano column array that is positioned on the alumina formwork with the nickel hydroxide nano sheet on the nickel nano-pillar of earlier conical top being appeared places 430 ℃ of calcining 2.3h down, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel oxide nano sheet.Re-use magnetic control sputtering device surface sputtering silver nano-grain that is positioned the nickel nano column array on the alumina formwork with the nickel oxide nano sheet on conical top is appeared the nickel nano-pillar, during sputter, appear on the nickel nano-pillar the spacing that is positioned nickel nano column array on the alumina formwork and silver-colored target with the nickel oxide nano sheet of conical top is that the electric current of 2cm, sputter is that time of 10mA, sputter is 6.5min.Make and be similar to shown in Fig. 1 c, and the nickel of the modified by silver nanoparticles shown in the curve among Fig. 1 d nano-pillar-nickel oxide nano sheet hierarchy array.
The concrete steps of preparation are:
Step 1 uses two-step anodization method and reaming method to handle to aluminium flake earlier successively, and obtaining bore dia is that 100nm, pitch of holes are the through hole alumina formwork of 30nm.Use magnetic control sputtering device sputter silverskin in the one side of through hole alumina formwork again; During sputter, the spacing of alumina formwork and silver-colored target is that the electric current of 2cm, sputter is that time of 40mA, sputter is 10min, obtains the alumina formwork that one side is covered with silverskin.
Step 3, earlier the alumina formwork that is equipped with the nickel nano column array in its hole being floated on concentration is the alkaline solution surface 5min of 0.15mol/L; Wherein, alkaline solution is sodium hydroxide solution, obtains being equipped with on it alumina formwork of nickel nano column array of appearing.The nickel nano column array of appearing that is equipped with the alumina formwork of the nickel nano column array of appearing on it being placed temperature is that 100 ℃, concentration are that the strong aqua of 30wt% soaks 30min again, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel hydroxide nano sheet.
Step 4, the nickel nano column array that is positioned on the alumina formwork with the nickel hydroxide nano sheet on the nickel nano-pillar of earlier conical top being appeared places 450 ℃ of calcining 2h down, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel oxide nano sheet.Re-use magnetic control sputtering device surface sputtering silver nano-grain that is positioned the nickel nano column array on the alumina formwork with the nickel oxide nano sheet on conical top is appeared the nickel nano-pillar, during sputter, appear on the nickel nano-pillar the spacing that is positioned nickel nano column array on the alumina formwork and silver-colored target with the nickel oxide nano sheet of conical top is that the electric current of 2cm, sputter is that time of 10mA, sputter is 8min.Make and be similar to shown in Fig. 1 c, and the nickel of the modified by silver nanoparticles shown in the curve among Fig. 1 d nano-pillar-nickel oxide nano sheet hierarchy array.
Select the sodium hydroxide solution as alkaline solution more respectively for use, or potassium hydroxide solution, or lithium hydroxide solution, repeat above-described embodiment 1～5, made equally as or be similar to shown in Fig. 1 c, and the nickel of the modified by silver nanoparticles shown in the curve among Fig. 1 d nano-pillar-nickel oxide nano sheet hierarchy array.
The purposes of the nickel nano-pillar of modified by silver nanoparticles-nickel oxide nano sheet hierarchy array is:
At the bottom of the nickel nano-pillar-active group of nickel oxide nano sheet hierarchy array as surface enhanced Raman scattering with modified by silver nanoparticles, the rhodamine that uses laser Raman spectrometer to measure to adhere on it or the content of tetrachloro biphenyl obtain as or are similar to Fig. 2 or result shown in Figure 4; Wherein, the excitation wavelength of laser Raman spectrometer is that 532nm, output rating are that 0.05～0.15mW, integral time are 10～60s.
Obviously, those skilled in the art can carry out various changes and modification to nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles of the present invention and its production and use and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1. the nickel of modified by silver nanoparticles nano-pillar-nickel oxide nano sheet hierarchy array comprises metallic nickel, it is characterized in that:
Described metallic nickel is the nickel nano column array of appearing that places on the alumina formwork, described formation is appeared the top of the nickel nano-pillar of appearing of nickel nano column array for conical, described conical top is appeared on the nickel nano-pillar with the nickel oxide nano sheet, and the appear finishing of nickel nano-pillar and nickel oxide nano sheet of described conical top has silver nano-grain;
The appear post height of nickel nano-pillar of described conical top is 100～500nm;
The length of a film of described nickel oxide nano sheet is the thick 1～4nm of being of 20～50nm, sheet;
The particle diameter of described silver nano-grain is 8～12nm, particle gap≤10nm.
2. the nickel of modified by silver nanoparticles according to claim 1 nano-pillar-nickel oxide nano sheet hierarchy array is characterized in that the appear column diameter of nickel nano-pillar of conical top on the alumina formwork is that 90～110nm, intercolumniation are 20～30nm.
3. the preparation method of the nickel of the described modified by silver nanoparticles of claim 1 nano-pillar-nickel oxide nano sheet hierarchy array comprises anonizing, it is characterized in that completing steps is as follows:
Step 1 uses two-step anodization method and reaming method to handle to aluminium flake earlier successively, and obtaining bore dia is the through hole alumina formwork of 90～110nm, again in the silver-plated film of the one side of through hole alumina formwork, obtains the alumina formwork that one side is covered with silverskin;
Step 2, the alumina formwork that earlier one side is covered with silverskin places nickel electrolyte as negative electrode, be galvanic deposit 1h at least under 1.5～2.5V in volts DS, the one side that obtains being equipped with in its hole the nickel nano column array is covered with the alumina formwork of silverskin, it is that the concentrated nitric acid of 60～80wt% is got rid of silverskin that the alumina formwork that again one side that is equipped with the nickel nano column array in its hole is covered with silverskin places concentration, obtains being equipped with in its hole the alumina formwork of nickel nano column array;
Step 3, the alkaline solution surface that earlier alumina formwork that is equipped with the nickel nano column array in its hole is floated on concentration and be 0.05～0.15mol/L is 5min at least, obtain being equipped with on it alumina formwork of nickel nano column array of appearing, the nickel nano column array of appearing that is equipped with the alumina formwork of the nickel nano column array of appearing on it being placed temperature is that 90～100 ℃, concentration are that the strong aqua of 25～30wt% soaks 30min at least again, obtains conical top and appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel hydroxide nano sheet;
Step 4, the nickel nano column array on the alumina formwork of being positioned with the nickel hydroxide nano sheet on the nickel nano-pillar of earlier conical top being appeared places and calcines 2h at least under 350～450 ℃, obtaining conical top appears on the nickel nano-pillar with the nickel nano column array on the alumina formwork of being positioned of nickel oxide nano sheet, again on conical top is appeared the nickel nano-pillar with the surface sputtering silver nano-grain that is positioned the nickel nano column array on the alumina formwork of nickel oxide nano sheet, make the nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles.
4. the preparation method of the nickel of modified by silver nanoparticles according to claim 3 nano-pillar-nickel oxide nano sheet hierarchy array, it is characterized in that silver-plated film is for using the magnetic control sputtering device sputter, during sputter, the spacing of alumina formwork and silver-colored target is that the electric current of 2cm, sputter is that time of 40mA, sputter is 10min.
5. the preparation method of the nickel of modified by silver nanoparticles according to claim 3 nano-pillar-nickel oxide nano sheet hierarchy array is characterized in that nickel electrolyte is that concentration is that six hydration nickel sulfate and the concentration of 52.57g/L is the mixed solution of the boric acid of 6.18g/L.
6. the preparation method of the nickel of modified by silver nanoparticles according to claim 3 nano-pillar-nickel oxide nano sheet hierarchy array, the anode when it is characterized in that galvanic deposit is Graphite Electrodes.
7. the preparation method of the nickel of modified by silver nanoparticles according to claim 3 nano-pillar-nickel oxide nano sheet hierarchy array is characterized in that alkaline solution is sodium hydroxide solution, or potassium hydroxide solution, or lithium hydroxide solution.
8. the preparation method of the nickel of modified by silver nanoparticles according to claim 3 nano-pillar-nickel oxide nano sheet hierarchy array, it is characterized in that the sputtering silver nano particle is for using magnetic control sputtering device, during sputter, appear on the nickel nano-pillar the spacing that is positioned nickel nano column array on the alumina formwork and silver-colored target with the nickel oxide nano sheet of conical top is that the electric current of 2cm, sputter is that time of 10mA, sputter is 1～8min.
9. the purposes of the nickel of the described modified by silver nanoparticles of claim 1 nano-pillar-nickel oxide nano sheet hierarchy array is characterized in that:
At the bottom of the nickel nano-pillar-active group of nickel oxide nano sheet hierarchy array as surface enhanced Raman scattering with modified by silver nanoparticles, the rhodamine that uses laser Raman spectrometer to measure to adhere on it or the content of tetrachloro biphenyl.
10. the purposes of the nickel of modified by silver nanoparticles according to claim 9 nano-pillar-nickel oxide nano sheet hierarchy array, the excitation wavelength that it is characterized in that laser Raman spectrometer is that 532nm, output rating are that 0.05～0.15mW, integral time are 10～60s.
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| CN108375565A (en) * | 2018-01-23 | 2018-08-07 | 中央民族大学 | A kind of nano-cone array composite S RES substrates and preparation method |
| CN109112598A (en) * | 2018-08-28 | 2019-01-01 | 宁波大学 | A kind of method of iron nano-dot matrix auxiliary preparation self assembly strawberry-like gold SRES substrate |
| CN113278923A (en) * | 2021-04-29 | 2021-08-20 | 安徽大学 | Silver nano-column-silver nano-tube composite structure array and preparation method and application thereof |
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