CN103194751B - 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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- CN103194751B CN103194751B CN201310105993.4A CN201310105993A CN103194751B CN 103194751 B CN103194751 B CN 103194751B CN 201310105993 A CN201310105993 A CN 201310105993A CN 103194751 B CN103194751 B CN 103194751B
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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, nickel nano-pillar-nickel oxide nano sheet hierarchy array of especially a kind of modified by silver nanoparticles and its production and use.
Background technology
Transiting metal nickel has magnetic and good plasticity-, and good erosion resistance.Nano nickel has larger specific surface area because of it, and the excellent properties showing in many-side and more and more cause people's concern.At present, people, in order to obtain nano nickel material, have made unremitting effort, if Chinese invention patent specification sheets CN100441348C is in the one " metal nickel nano pipe and preparation method " of bulletin on December 10th, 2008.The external diameter of the metal nickel nano pipe of recording in this specification sheets is 15～150 nanometers; Preparation method will be first anode as negative electrode, nickel material through the anodised aluminium foraminous die plate of sensitization and activation, immerse in the electrolytic solution containing nickel salt, boric acid, under direct current effect on alumina formwork metal refining nickel, again the alumina formwork that deposits metallic nickel in hole is dissolved to template through basic solution, obtain product.But, no matter be product, or its preparation method, all exist weak point, first,, though Nickel nanotubes has unknown specific end use, be difficult to identify fast, with sensitivity as the active substrate of surface enhanced Raman scattering (SERS) the fingerprint characteristic information of testing molecule; Secondly, preparation method can not obtain the nickel nanostructure substrate with higher SERS activity.
Summary of the invention
The technical problem to be solved in the present invention, for overcoming weak point of the prior art, provides a kind of rational in infrastructure, has 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 for providing a kind of preparation method of nickel nano-pillar-nickel oxide nano sheet hierarchy array of above-mentioned modified by silver nanoparticles.
Technical problem that what the present invention will solve also have is for providing a kind of purposes of nickel nano-pillar-nickel oxide nano sheet hierarchy array of above-mentioned super modified by silver nanoparticles.
Solve technical problem of the present invention, the technical scheme adopting is: nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles comprises metallic nickel, particularly
Described metallic nickel is the nickel nano column array of appearing being placed on 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 in nickel nano-pillar with 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 high 100～500nm of being of post of nickel nano-pillar of described conical top;
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 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 described alumina formwork is that 90～110nm, intercolumniation are 20～30nm.
For solving another technical problem of the present invention, another technical scheme adopting is: the preparation method of nickel nano-pillar-nickel oxide nano sheet hierarchy array of above-mentioned modified by silver nanoparticles comprises anonizing, and particularly completing steps is as follows:
Step 1, is first used two-step anodization method and reaming method to process to aluminium flake successively, and obtaining bore dia is the nanohole alumine template of 90～110nm, then in the silver-plated film of one side of nanohole alumine template, obtains being simultaneously covered with the alumina formwork of silverskin;
Step 2, the alumina formwork that first one side is covered with to silverskin is placed in nickel electrolyte as negative electrode, be at least 1h of galvanic deposit under 1.5～2.5V in volts DS, the one side that obtains being equipped with in its hole 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 nickel nano column array in its hole is covered with to silverskin is placed in concentration, obtains being equipped with in its hole the alumina formwork of nickel nano column array;
Step 3, first the alumina formwork that is equipped with nickel nano column array in its hole is floated on at least 5min of alkaline solution surface that concentration is 0.05～0.15mol/L, obtain being equipped with on it alumina formwork of the nickel nano column array of appearing, the strong aqua that the nickel nano column array of appearing of alumina formwork that is equipped with the nickel nano column array of appearing on it to be placed in to temperature again and to be 90～100 DEG C, concentration be 25～30wt% soaks at least 30min, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is positioned of nickel hydroxide nano sheet;
Step 4, the nickel nano column array on alumina formwork of being positioned with nickel hydroxide nano sheet in the nickel nano-pillar of first conical top being appeared is placed in and at 350～450 DEG C, calcines at least 2h, obtaining conical top appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is positioned of nickel oxide nano sheet, on appearing nickel nano-pillar, conical top has again the surface sputtering silver nano-grain that is positioned the nickel nano column array on alumina formwork of nickel oxide nano sheet, make nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles.
As the preparation method's of nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles further improvement, described silver-plated film is for using magnetic control sputtering device sputter, when 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) with the concentration boric acid (H that is 6.18g/L
3bO
3) mixed solution; Anode when 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, when sputter, the electric current that it is 2cm, sputter that conical top is appeared in nickel nano-pillar with the spacing that is positioned nickel nano column array on alumina formwork and silver-colored target of nickel oxide nano sheet is that the 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 adopting is: the purposes of nickel nano-pillar-nickel oxide nano sheet hierarchy array of above-mentioned modified by silver nanoparticles is:
Active substrate using nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles as surface enhanced Raman scattering, uses laser Raman spectrometer to measure the rhodamine (R6G) that adheres on it or the content of tetrachloro biphenyl (PCB-77).
As the further improvement of the purposes of 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 respectively scanning electron microscope, transmission electron microscope and its subsidiary power spectrum tester and X-ray diffractometer to characterize to the target product making, from its result, target product is to be positioned that conical top in template, that be all modified with nano particle by surface is appeared nano-pillar and the nanometer sheet had on it forms; 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 high 100～500nm of being of the post nickel nano-pillar of appearing, 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.Nickel nano-pillar-nickel oxide nano sheet hierarchy array of this modified by silver nanoparticles both due to its within the scope of big area 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 feature of structure, lay a good foundation for setting it as stable SERS active substrate; Because the top of nickel nano-pillar is conical, have numerous nickel oxide nano sheets on it again in addition, make it to have had the effect of " lightning rod ", the utmost point is beneficial to and obtains high SERS activity; Also because the surface of numerous nickel oxide nano sheet that conical top is appeared nickel nano-pillar and have on it is all modified with a large amount of silver nano-grains, and make silver nano-grain very easily produce each other the very strong local coupling electric field that is conventionally referred to as " focus ", greatly improve the SERS activity while setting it as substrate; More because nickel oxide and silver adhere to semi-conductor and precious metal separately, the nickel oxide investing in nickel nano-pillar has semi-conductive chemical enhancement, there is very strong Electromagnetic enhancement effect and be modified at its surperficial silver nano-grain, thereby make the compound system that both form not only there is physics enhancement, also because the direct electric charge between semi-conductor and noble metal granule shifts, make this compound system there is stronger chemical enhancement, thereby make it have very high surface-enhanced Raman scattering activity; In addition nickel oxide nano sheet has high-ratio surface and chemical affinity, can be detection molecules more adherent point be provided, the active adsorption being highly advantageous to detection molecules, and then improved widely the overall SERS activity of substrate.Its two, using the target product making as SERS active substrate, 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 all very good of the consistence of its detection and the multiple spot of repeatability on target product and any point.They are three years old, preparation method is simple, science, effective: both prepared Stability Analysis of Structures, there is nickel nano-pillar-nickel oxide nano sheet hierarchy array of the modified by silver nanoparticles of higher SERS activity, after the target product that makes again to make coordinates with laser Raman spectrometer, possess 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 the 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 preferential oxidation aluminum alloy pattern plate is that 90～110nm, intercolumniation are 20～30nm, has higher SERS active substrate and haves laid a good foundation for obtaining.The 2nd, silver-plated film is preferably and uses magnetic control sputtering device sputter, and when 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, nickel electrolyte is preferably the mixed solution of the boric acid that six hydration nickel sulfate that concentration is 52.57g/L and concentration are 6.18g/L, is convenient to effectively carry out the galvanic deposit of nickel nano-pillar.The 4th, anode when 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 compared with horn of plenty, also makes preparation technology more easily implement and flexibly.The 6th, sputtering silver nano particle is preferably use magnetic control sputtering device, when sputter, it is that time of 10mA, sputter is 1～8min that conical top is appeared in nickel nano-pillar with the electric current that nickel nano column array on alumina formwork and the spacing of silver-colored target are 2cm, sputter of being positioned of nickel oxide nano sheet, is beneficial to the suitable target product of density of the silver nano-grain that obtains modification.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 guarantee the accuracy detecting, be also easy to target product and detect rhodamine and 3,3 ', 4, the giving full play to of 4 '-tetrachloro biphenyl performance.
Brief description of the 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---conical top is appeared in nickel nano-pillar and to be used respectively one of result that scanning electron microscope (SEM), transmission electron microscope (TEM) and its subsidiary power spectrum (EDS) tester and X-ray diffraction (XRD) instrument characterize with the target product that is positioned the nickel nano column array on alumina formwork and makes of nickel oxide nano sheet.Wherein, the side-looking SEM image that Fig. 1 a is intermediate product, the TEM image that what the left illustration in image was intermediate product overlook enlarged image, right illustration are single intermediate product; Fig. 1 b is XRD spectra, in this XRD spectra curve be from bottom to top 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 after strong aqua is processed, and the XRD spectral line of the Ni nano-pillar-NiO nanometer sheet hierarchy array obtaining after 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 is that target product to containing different concns rhodamine uses one of result that laser Raman spectrometer characterizes.It has confirmed using target product as SERS active substrate, can detect the trace rhodamine adhering on it.
Fig. 3 is to get at random 5 points 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 one of result that the target product use laser Raman spectrometer of 4 '-tetrachloro biphenyl characterizes.It has confirmed using target product as SERS active substrate, can detect the trace 3,3 ', 4 adhering on it, 4 '-tetrachloro biphenyl.
Embodiment
First buy from market or make by ordinary method:
Aluminium flake; The six hydration nickel sulfate that is 52.57g/L by concentration and concentration are the nickel electrolyte that the mixed solution of the boric acid of 6.18g/L forms; Concentration is the concentrated nitric acid of 60～80wt%; As sodium hydroxide solution, potassium hydroxide solution and the lithium hydroxide solution of alkaline solution; Concentration is the strong aqua of 25～30wt%.
Then,
Embodiment 1
The concrete steps of preparation are:
Step 1, is first used two-step anodization method and reaming method to process to aluminium flake successively, and obtaining bore dia is the nanohole alumine template that 90nm, pitch of holes are 20nm.Use magnetic control sputtering device sputter silverskin in the one side of nanohole alumine template again; When 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 one side and be covered with the alumina formwork of silverskin.
Step 2, the alumina formwork that first one side is covered with to silverskin is anode as negative electrode, graphite, is placed in nickel electrolyte, is galvanic deposit 2h under 1.5V in volts DS, the one side that obtains being equipped with in its hole nickel nano column array is covered with the alumina formwork of silverskin.It is that the concentrated nitric acid of 60wt% is got rid of silverskin that the alumina formwork that again one side that is equipped with nickel nano column array in its hole is covered with to silverskin is placed in concentration, obtains being equipped with in its hole the alumina formwork of nickel nano column array.
Step 3, first the alumina formwork that is equipped with nickel nano column array in its hole being floated on to 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 the nickel nano column array of appearing.The strong aqua that the nickel nano column array of appearing of alumina formwork that is equipped with the nickel nano column array of appearing on it to be placed in to temperature again and to be 90 DEG C, concentration be 25wt% soaks 34min, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is positioned of nickel hydroxide nano sheet.
Step 4, the nickel nano column array on alumina formwork of being positioned with nickel hydroxide nano sheet in the nickel nano-pillar of first conical top being appeared is placed at 350 DEG C and calcines 3h, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is 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 alumina formwork with nickel oxide nano sheet on conical top is appeared nickel nano-pillar, when sputter, the electric current that it is 2cm, sputter that conical top is appeared in nickel nano-pillar with the spacing that is positioned nickel nano column array on alumina formwork and silver-colored target of nickel oxide nano sheet is that the time of 10mA, sputter is 1min.Make and be similar to shown in Fig. 1 c, and nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles as shown in the curve in Fig. 1 d.
Embodiment 2
The concrete steps of preparation are:
Step 1, is first used two-step anodization method and reaming method to process to aluminium flake successively, and obtaining bore dia is the nanohole alumine template that 93nm, pitch of holes are 23nm.Use magnetic control sputtering device sputter silverskin in the one side of nanohole alumine template again; When 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 one side and be covered with the alumina formwork of silverskin.
Step 2, the alumina formwork that first one side is covered with to silverskin is anode as negative electrode, graphite, is placed in nickel electrolyte, is galvanic deposit 1.8h under 1.75V in volts DS, the one side that obtains being equipped with in its hole nickel nano column array is covered with the alumina formwork of silverskin.It is that the concentrated nitric acid of 65wt% is got rid of silverskin that the alumina formwork that again one side that is equipped with nickel nano column array in its hole is covered with to silverskin is placed in concentration, obtains being equipped with in its hole the alumina formwork of nickel nano column array.
Step 3, first the alumina formwork that is equipped with nickel nano column array in its hole being floated on to 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 the nickel nano column array of appearing.The strong aqua that the nickel nano column array of appearing of alumina formwork that is equipped with the nickel nano column array of appearing on it to be placed in to temperature again and to be 93 DEG C, concentration be 26wt% soaks 33min, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is positioned of nickel hydroxide nano sheet.
Step 4, the nickel nano column array on alumina formwork of being positioned with nickel hydroxide nano sheet in the nickel nano-pillar of first conical top being appeared is placed at 380 DEG C and calcines 2.8h, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is 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 alumina formwork with nickel oxide nano sheet on conical top is appeared nickel nano-pillar, when sputter, the electric current that it is 2cm, sputter that conical top is appeared in nickel nano-pillar with the spacing that is positioned nickel nano column array on alumina formwork and silver-colored target of nickel oxide nano sheet is that the time of 10mA, sputter is 2.5min.Make and be similar to shown in Fig. 1 c, and nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles as shown in the curve in Fig. 1 d.
Embodiment 3
The concrete steps of preparation are:
Step 1, is first used two-step anodization method and reaming method to process to aluminium flake successively, and obtaining bore dia is the nanohole alumine template that 95nm, pitch of holes are 25nm.Use magnetic control sputtering device sputter silverskin in the one side of nanohole alumine template again; When 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 one side and be covered with the alumina formwork of silverskin.
Step 2, the alumina formwork that first one side is covered with to silverskin is anode as negative electrode, graphite, is placed in nickel electrolyte, is galvanic deposit 1.5h under 2V in volts DS, the one side that obtains being equipped with in its hole nickel nano column array is covered with the alumina formwork of silverskin.It is that the concentrated nitric acid of 70wt% is got rid of silverskin that the alumina formwork that again one side that is equipped with nickel nano column array in its hole is covered with to silverskin is placed in concentration, obtains being equipped with in its hole the alumina formwork of nickel nano column array.
Step 3, first the alumina formwork that is equipped with nickel nano column array in its hole being floated on to 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 the nickel nano column array of appearing.The strong aqua that the nickel nano column array of appearing of alumina formwork that is equipped with the nickel nano column array of appearing on it to be placed in to temperature again and to be 95 DEG C, concentration be 28wt% soaks 32min, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is positioned of nickel hydroxide nano sheet.
Step 4, the nickel nano column array on alumina formwork of being positioned with nickel hydroxide nano sheet in the nickel nano-pillar of first conical top being appeared is placed at 400 DEG C and calcines 2.5h, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is 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 alumina formwork with nickel oxide nano sheet on conical top is appeared nickel nano-pillar, when sputter, the electric current that it is 2cm, sputter that conical top is appeared in nickel nano-pillar with the spacing that is positioned nickel nano column array on alumina formwork and silver-colored target of nickel oxide nano sheet is that the time of 10mA, sputter is 5min.Make as shown in Fig. 1 c, and nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles as shown in the curve in Fig. 1 d.
Embodiment 4
The concrete steps of preparation are:
Step 1, is first used two-step anodization method and reaming method to process to aluminium flake successively, and obtaining bore dia is the nanohole alumine template that 98nm, pitch of holes are 28nm.Use magnetic control sputtering device sputter silverskin in the one side of nanohole alumine template again; When 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 one side and be covered with the alumina formwork of silverskin.
Step 2, the alumina formwork that first one side is covered with to silverskin is anode as negative electrode, graphite, is placed in nickel electrolyte, is galvanic deposit 1.3h under 2.25V in volts DS, the one side that obtains being equipped with in its hole nickel nano column array is covered with the alumina formwork of silverskin.It is that the concentrated nitric acid of 75wt% is got rid of silverskin that the alumina formwork that again one side that is equipped with nickel nano column array in its hole is covered with to silverskin is placed in concentration, obtains being equipped with in its hole the alumina formwork of nickel nano column array.
Step 3, first the alumina formwork that is equipped with nickel nano column array in its hole being floated on to 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 the nickel nano column array of appearing.The strong aqua that the nickel nano column array of appearing of alumina formwork that is equipped with the nickel nano column array of appearing on it to be placed in to temperature again and to be 98 DEG C, concentration be 29wt% soaks 31min, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is positioned of nickel hydroxide nano sheet.
Step 4, the nickel nano column array on alumina formwork of being positioned with nickel hydroxide nano sheet in the nickel nano-pillar of first conical top being appeared is placed at 430 DEG C and calcines 2.3h, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is 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 alumina formwork with nickel oxide nano sheet on conical top is appeared nickel nano-pillar, when sputter, the electric current that it is 2cm, sputter that conical top is appeared in nickel nano-pillar with the spacing that is positioned nickel nano column array on alumina formwork and silver-colored target of nickel oxide nano sheet is that the time of 10mA, sputter is 6.5min.Make and be similar to shown in Fig. 1 c, and nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles as shown in the curve in Fig. 1 d.
Embodiment 5
The concrete steps of preparation are:
Step 1, is first used two-step anodization method and reaming method to process to aluminium flake successively, and obtaining bore dia is the nanohole alumine template that 100nm, pitch of holes are 30nm.Use magnetic control sputtering device sputter silverskin in the one side of nanohole alumine template again; When 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 one side and be covered with the alumina formwork of silverskin.
Step 2, the alumina formwork that first one side is covered with to silverskin is anode as negative electrode, graphite, is placed in nickel electrolyte, is galvanic deposit 1h under 2.5V in volts DS, the one side that obtains being equipped with in its hole nickel nano column array is covered with the alumina formwork of silverskin.It is that the concentrated nitric acid of 80wt% is got rid of silverskin that the alumina formwork that again one side that is equipped with nickel nano column array in its hole is covered with to silverskin is placed in concentration, obtains being equipped with in its hole the alumina formwork of nickel nano column array.
Step 3, first the alumina formwork that is equipped with nickel nano column array in its hole being floated on to 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 the nickel nano column array of appearing.The strong aqua that the nickel nano column array of appearing of alumina formwork that is equipped with the nickel nano column array of appearing on it to be placed in to temperature again and to be 100 DEG C, concentration be 30wt% soaks 30min, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is positioned of nickel hydroxide nano sheet.
Step 4, the nickel nano column array on alumina formwork of being positioned with nickel hydroxide nano sheet in the nickel nano-pillar of first conical top being appeared is placed at 450 DEG C and calcines 2h, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is 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 alumina formwork with nickel oxide nano sheet on conical top is appeared nickel nano-pillar, when sputter, the electric current that it is 2cm, sputter that conical top is appeared in nickel nano-pillar with the spacing that is positioned nickel nano column array on alumina formwork and silver-colored target of nickel oxide nano sheet is that the time of 10mA, sputter is 8min.Make and be similar to shown in Fig. 1 c, and nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles as shown in the curve in Fig. 1 d.
Select respectively again the sodium hydroxide solution as alkaline solution, or potassium hydroxide solution, or lithium hydroxide solution, repeat above-described embodiment 1～5, make equally as or be similar to as shown in Fig. 1 c, and nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles as shown in the curve in Fig. 1 d.
The purposes of nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles is:
Active substrate using nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles as surface enhanced Raman scattering, use laser Raman spectrometer to measure the rhodamine that adheres on it or the content of tetrachloro biphenyl, obtain as or be similar to the result as shown in Fig. 2 or Fig. 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 and not depart from the spirit and scope of the present invention nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles of the present invention and its production and use.Like this, if to these amendments of the present invention with within modification belongs to the scope of the claims in the present invention and equivalent technologies thereof, the present invention is also 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 being placed on 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 in nickel nano-pillar with 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 high 100～500nm of being of post of nickel nano-pillar of described conical top;
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 alumina formwork is that 90～110nm, intercolumniation are 20～30nm.
3. a preparation method for the nickel of modified by silver nanoparticles nano-pillar-nickel oxide nano sheet hierarchy array described in claim 1, comprises anonizing, it is characterized in that completing steps is as follows:
Step 1, is first used two-step anodization method and reaming method to process to aluminium flake successively, and obtaining bore dia is the nanohole alumine template of 90～110nm, then in the silver-plated film of one side of nanohole alumine template, obtains being simultaneously covered with the alumina formwork of silverskin;
Step 2, the alumina formwork that first one side is covered with to silverskin is placed in nickel electrolyte as negative electrode, be at least 1h of galvanic deposit under 1.5～2.5V in volts DS, the one side that obtains being equipped with in its hole 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 nickel nano column array in its hole is covered with to silverskin is placed in concentration, obtains being equipped with in its hole the alumina formwork of nickel nano column array;
Step 3, first the alumina formwork that is equipped with nickel nano column array in its hole is floated on at least 5min of alkaline solution surface that concentration is 0.05～0.15mol/L, obtain being equipped with on it alumina formwork of the nickel nano column array of appearing, the strong aqua that the nickel nano column array of appearing of alumina formwork that is equipped with the nickel nano column array of appearing on it to be placed in to temperature again and to be 90～100 DEG C, concentration be 25～30wt% soaks at least 30min, obtains conical top and appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is positioned of nickel hydroxide nano sheet;
Step 4, the nickel nano column array on alumina formwork of being positioned with nickel hydroxide nano sheet in the nickel nano-pillar of first conical top being appeared is placed in and at 350～450 DEG C, calcines at least 2h, obtaining conical top appears in nickel nano-pillar with the nickel nano column array on alumina formwork that is positioned of nickel oxide nano sheet, on appearing nickel nano-pillar, conical top has again the surface sputtering silver nano-grain that is positioned the nickel nano column array on alumina formwork of nickel oxide nano sheet, make 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 magnetic control sputtering device sputter, when 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 the six hydration nickel sulfate of 52.57g/L and the mixed solution of the boric acid that concentration is 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 while 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 sputtering silver nano particle is for using magnetic control sputtering device, when sputter, the electric current that it is 2cm, sputter that conical top is appeared in nickel nano-pillar with the spacing that is positioned nickel nano column array on alumina formwork and silver-colored target of nickel oxide nano sheet is that the time of 10mA, sputter is 1～8min.
9. a purposes for the nickel of modified by silver nanoparticles nano-pillar-nickel oxide nano sheet hierarchy array described in claim 1, is characterized in that:
Active substrate using nickel nano-pillar-nickel oxide nano sheet hierarchy array of modified by silver nanoparticles as surface enhanced Raman scattering, uses laser Raman spectrometer to measure the rhodamine or 3 adhering on it, 3 ', 4, the content of 4 '-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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| CN104099567B (en) * | 2014-07-24 | 2016-05-18 | 中国科学院合肥物质科学研究院 | Silver nanoparticle post cluster array and its production and use |
| CN105442015B (en) * | 2015-11-11 | 2017-10-13 | 北京工业大学 | Unpolarized dependence SERS substrate, preparation and the application of a kind of high stability |
| 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 |
| CN109112598B (en) * | 2018-08-28 | 2020-06-26 | 宁波大学 | Method for preparing self-assembled myrica gold SERS substrate with assistance of iron nano dot matrix |
| CN113278923B (en) * | 2021-04-29 | 2023-05-23 | 安徽大学 | Silver nano column-silver nano tube composite structure array and preparation method and application thereof |
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