CN104625043B - A kind of gold rhodium hollow Nano composite and preparation method thereof - Google Patents
A kind of gold rhodium hollow Nano composite and preparation method thereof Download PDFInfo
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 17
- YDZWPBPSQHXITB-UHFFFAOYSA-N [Rh].[Au] Chemical compound [Rh].[Au] YDZWPBPSQHXITB-UHFFFAOYSA-N 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000010948 rhodium Substances 0.000 claims abstract description 26
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 25
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 24
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000010931 gold Substances 0.000 claims abstract description 23
- 229910052737 gold Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims abstract description 12
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 229910004042 HAuCl4 Inorganic materials 0.000 claims abstract description 10
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 230000010355 oscillation Effects 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
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- 239000007789 gas Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
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- 238000000926 separation method Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
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- 102000039446 nucleic acids Human genes 0.000 abstract description 6
- 108020004707 nucleic acids Proteins 0.000 abstract description 6
- 150000007523 nucleic acids Chemical class 0.000 abstract description 6
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- 239000002131 composite material Substances 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 229910000510 noble metal Inorganic materials 0.000 description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000002086 nanomaterial Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
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- 230000008859 change Effects 0.000 description 5
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- 229920003081 Povidone K 30 Polymers 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- DFCVQVFZSSOGOG-UHFFFAOYSA-N N.[Au] Chemical compound N.[Au] DFCVQVFZSSOGOG-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
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- 150000003283 rhodium Chemical class 0.000 description 1
- -1 rhodium ion Chemical class 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
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Abstract
The invention discloses the golden rhodium hollow Nano composite of a kind of a diameter of 20nm to 70nm, wherein gold is 1:6～10 with the mol ratio of rhodium.The invention also discloses the method preparing this composite, first with CoCl2It is that cobalt colloidal sol prepared by raw material with PVP, then prepares HAuCl4And RhCl3Mixed solution, during then mixed solution is gradually added drop-wise to cobalt colloidal sol, last centrifugation product obtains product.The nano composite material of the present invention is composited by gold and rhodium, size is suitable and in hollow-core construction, there is stronger albumen, nucleic acid binding activity, and there is the strongest mimetic enzyme catalysis activity simultaneously, be expected to obtain extensively application at biomedical, sensor and field of batteries.
Description
Technical field
The invention belongs to field of nanometer material technology, relate to metal nano hollow ball, be specifically related to a kind of there is mimetic enzyme catalysis function
Gold rhodium hollow Nano composite and preparation method thereof.
Background technology
Nano material refers to the most one-dimensional be in nanoscale scope (1-100nm) or by them as substantially
The material that unit is constituted.Nano material has new features and the New function that a lot of macrostate does not has, and its research and application are day by day
Extensively；Wherein noble metal nanometer material is one of research in recent years and application focus.Noble metal nanometer material is by some rare costlinesses
Metal material, such as the nano material of the expensive compositions of noble metal such as gold, ruthenium, rhodium, palladium, platinum, such as nm of gold, Platinum Nanoparticles, nanometer
Palladium etc..
Noble metal nano particles has prominent catalytic performance, can be used as catalyst and promotes the carrying out of multiple chemical reaction.Noble metal
Catalytic performance by such as granular size, specific surface area, crystallinity, granule-morphology, size, surface texture and active position etc.
The impact of many factors.The reactivity of noble metal nano particles and selectivity depend primarily on the crystal face being exposed to particle surface,
The different crystal faces of nanocrystal are different to the absorption of molecule and the ability of desorption in the reaction, can affect activity and the selection of catalyst
Property therefore, the regulation and control pattern of particle and size are a kind of important way changing noble metal nano particles catalytic performance.Researcher
Different methods is used the most successfully to prepare the noble metal nano particles of different morphologies.Typical structure has gold nanorods, gold nano
Cage, Platinum Nanoparticles line, hollow Nano platinum, tetrahedron platinum, cube palladium etc..
Rhodium is a kind of important noble metal.Rhodium (sound is old), English Rhodium, it is derived from rhodon, symbol of element Rh, means " rose
Rare " because the solution of rhodium salt presents the light red color of rose.Monomer rhodium is the noble metal of a kind of rareness.Color is silvery white, gold
Belong to gloss, opaque.Hardness 4～4.5, relative density 12.5.Fusing point is high, is 1955 DEG C.Stable chemical nature.But research is sent out
Existing nanometer rhodium has good catalysis characteristics, such as catalytic hydrogenation reaction, catalyzed alkene formylation reaction, hydrogen peroxide catalytic reaction etc..
The nanometer rhodium of preparation mostly is solid nanometer rhodium, diameter about about 4nm at present.Various catalytic performances because particle diameter is less, to rhodium
Performance limited.Therefore nanometer rhodium is carried out shape control to be particularly important.Chondritic is that specific surface area is maximum
Plant stereochemical structure, although had hollow Platinum Nanoparticles and the report of hollow Nano palladium, but there is no the preparation phase of hollow Nano rhodium at present
Close document.
Nano Au colloid is also referred to as collaurum (colloidalgold), it is possible to use GOLD FROM PLATING SOLUTION ion (Au3+) be reduced and generate (Au),
The dispersion of multiple single gold nano grains will form gold size, jelly solution in aqueous.Gold size solution has dimensional effect,
Along with diameter dimension varies in size, and there is different light scattering effects, so that colloidal gold solution presents claret, red
The various different colors such as look, orange red, aubergine.Nm of gold has preferable biocompatibility, can by gold sulfide linkage,
Gold ammonia key and gold carboxylic key and albumen or nucleic acid directly in conjunction with.Utilizing this characteristic, nm of gold is used for the mark of large biological molecule.
Additionally, nm of gold also has the easily feature such as preparation, relatively large specific surface area, have been widely used for biomolecule (as nucleic acid,
Protein, polysaccharide even cell) detection.Additionally, nm of gold is also extensively used for nano-device, biomedicine, letter
The high-end fields such as breath science and technology.
If combining the respective advantage of nm of gold and nanometer rhodium, a kind of novel complexes of synthesis, then can be provided simultaneously with both can with albumen,
The ability that the large biological molecules such as nucleic acid combine, it may have multiple catalytic capability, can expand its range of application greatly and application is latent
Power.This patent improves for the preparation method of hollow platinum, is prepared for gold rhodium hollow nano-sphere.First with aqueous phase reducing process
Preparing cobalt colloidal sol, the reducing power of recycling cobalt is reduced into single atom rhodium from rhodium ion, forms hollow knot with cobalt for core
Structure, thus prepare gold rhodium nano-hollow ball.
Summary of the invention
In view of this, it is an object of the invention to provide a kind of gold rhodium hollow nano-material and the method preparing this hollow nano-material.
For reaching above-mentioned purpose, the present invention provides following technical scheme:
In the golden rhodium hollow Nano composite of the present invention, gold and the mol ratio of rhodium are 1:6～10, hollow Nano composite straight
Footpath is 20nm to 70nm.
The present invention prepares the method for described gold rhodium hollow Nano composite, it is characterised in that comprise the following steps:
1), prepare cobalt colloidal sol, specifically include:
A), preparation CoCl2Concentration be 0.1-0.2g/L, PVP concentration be the mixing solution of 1.2-3g/L；
B), sonic oscillation processes step a) gained mixing solution；
C), the oxidizing gas in removal step b) solution；
2), preparation HAuCl4And RhCl3Mixed solution, controls wherein HAuCl4And RhCl3Mol ratio be 1:6～10；
3), by step 2) mixed solution be gradually added drop-wise to step 1) prepare cobalt colloidal sol in and open stirring；
4), step with centrifugal separation 3) product i.e. obtain product.
Preferably, when sonic oscillation processes, frequency is 100～120kHZ, and ultrasonic time is 10-20min.
Preferably, in solution, appropriate inert gas first it is slowly introducing, then in solution when removing oxidizing gas in solution
Drip appropriate NaBH4Solution.
Further, described inert gas is nitrogen, and it is 15～20min that nitrogen is passed through the time, and being passed through speed is 1～2cm3/s。
Further, described NaBH4Solution concentration is 0.4-0.6g/L, and its dropping total amount is the 30-40% of cobalt sol volume, every time
Dripping quantity is for taking 200～300 μ L.
Preferably, step 3) dropping HAuCl4And RhCl3Controlling dropping volume every time during mixed solution is 10～40 μ L, always
Amount is 1～2mL.
Preferably, step 4) centrifugal treating time centrifugal speed be 6000-7500rpm, the time is 4-6min.
Preferably, also include step 5), utilize deionized water and the resuspended precipitation purification steps of tri-distilled water 4) separate product step.
The beneficial effects of the present invention is:
The nano composite material of the present invention is composited by gold and rhodium, and size is suitable and in hollow-core construction, have stronger albumen,
Nucleic acid binding activity, and there is the strongest mimetic enzyme catalysis activity simultaneously.It is expected to obtain at biomedical, sensor and field of batteries
Obtain and extensively apply.The present invention prepares the method for gold rhodium hollow nano-material, first with CoCl2It is that Co prepared by raw material with PVP
Colloidal sol, then adds appropriate HAuCl in colloidal sol4And RhCl3Mixed solution, the Co in Co colloidal sol is replaced by gold and rhodium,
It is redissolved in colloidal sol, and gold and rhodium substitute the position of the Co in Co colloidal sol, thus obtain hollow spheres gold rhodium hollow Nano
Composite.The present invention prepares the method for gold rhodium hollow nano-material by 100～120kHZ sonic oscillations, it is possible to obtain size
Uniform Co colloidal sol, the present invention is filled with nitrogen further in Co colloidal sol and drips NaBH4Solution, can remove in colloidal sol
The gases such as dissolved oxygen, are formed in colloidal sol and reduce by force atmosphere, strong the carrying out promoting subsequent reactions.The present invention strictly controls HAuCl4
And RhCl3The dripping quantity of mixed solution, rate of addition and HAuCl4And RhCl3Mass ratio, contribute to the smooth of alternative reaction
Carry out.The present invention adds appropriate PVP material in colloid, it can be ensured that the stability of colloidal dispersion, and is be subsequently generated
Hollow Nano particle provides template, it is to avoid reunite.
Accompanying drawing explanation
In order to make the purpose of the present invention, technical scheme and beneficial effect clearer, the present invention provides drawings described below to illustrate:
Fig. 1 is the TEM figure of embodiment 1 gained sample；
Fig. 2 is the uv scan figure utilizing ultramicrospectrophotometer to record embodiment 1 sample；
Fig. 3 is the curent change curve that difference pulse voltammetry records embodiment 1 gained sample, before wherein a is not for adding hydrogen peroxide
Control curve, b is for adding hydrogen peroxide catalytic curve.
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
Embodiment 1:
The method of the present embodiment preparation gold rhodium hollow nano-material, comprises the following steps:
One, raw material and equipment prepare:
PVP (PVP K30) PVP；RhCl3Purchased from Sigma company (U.S. St. Louis)；NaBH4
Purchased from Chengdu Ke Long chemical reagent factory (China Chengdu)；
SB-80 sonic oscillation instrument, NingBo XinZhi Biology Science Co., Ltd's (ningbo of china)；
Magnetic stirring apparatus, upper Haikang instrument Instrument Ltd. (Chinese Shanghai)；
Electronic balance, Germany Sai Duolisi (Germany's brother's Dettingen)；
JEM-1400 transmission electron microscope, Jeol Ltd. (Japanese)；
50mL beaker, 100mL beaker, EP pipe, spoon, magnetic stir bar and deionized water laboratory are provided for oneself.
Two, Preparatory work of experiment:
1, under running water, 2 50mL beakers, 1 100mL beaker and 2 spoons are scrubbed clean with test tube；
2, in sonic oscillation instrument, add the running water of the most about 4～5cm height.Glass dropper, magnetic stir bar and spoon
Put in 100mL beaker, pour 80mL deionized water submergence into；
3,2 beakers are put in sonic oscillation instrument, open instrument oscillation cleaning, frequency about 100～120kHZ, the most ultrasonic
10 minutes, change the running water in sonic oscillation instrument respectively and the deionized water in beaker continue ultrasonic, continual ultrasonic clean 30～
40min。
4, close sonic oscillation instrument, take out beaker, outwell the water in beaker.Beaker, spoon and magnetic stir bar are put into baking box
42 DEG C of dry for standby.
Three, preparation gold rhodium nano-hollow ball compound, is carried out in the following order:
A) on electronic balance, weigh 5～10mg CoCl2·6H2O and 60～150mgPVP, pours in 100mL beaker；Add
Enter 50mL tri-distilled water.
B) beaker is put on magnetic stirring apparatus, opens instrument, stirring at low speed solution, make CoCl2·6H2O and PVP is the most molten
Solve.
C) beaker is put in sonic oscillation instrument, open Ultrasound Instrument, frequency about 100～120kHZ, ultrasonic 15 minutes.
D) close beaker mouth with preservative film, fall to insert 20 μ L lancet head ventilations.
E) glass dropper it is installed on the steam hose of nitrogen cylinder, turns on nitrogen cylinder switch, regulate air velocity.
F) glass dropper is inserted in the middle of beaker preservative film, is immersed in CoCl2In solution, rush nitrogen and continue 15～20min clocks.
G) 10 μ g NaBH are weighed4, fall in another 100mL beaker, add 20mL tri-distilled water.It is placed on magnetic stirring apparatus
Gentle agitation is dissolved.
H) filling CoCl2The beaker of solution is placed on magnetic stirring apparatus, opens agitator, is adjusted to moderate-speed mixer.
I) draw 200～300 μ LNaBH every time4Solution instills CoCl2In solution, until adding 20mLNaBH4Solution,
It is stirred for 10～25min.
J) dropping HAuCl4With RhCl3 mixed solution (150 μ L:1100 μ L), dropping volume is 10～40 μ L every time, always
Amount is 1～2mL.
K) sol solution being sub-packed in 10mL centrifuge tube to be centrifuged, 7000rpm is centrifuged 5min.
L) supernatant is abandoned, by the resuspended precipitation of 8mL deionized water.
M) centrifugal, 7000rpm is centrifuged 5min.
N) (13), (14) step 2 time are repeated.
O) abandon supernatant, collect precipitation.
P) by the 3～4mL resuspended precipitations of tri-distilled water, 4 DEG C save backup.
Performance test:
1, clean copper puts 3～5 μ L sample on the net, after 37 DEG C dry, with Jeol Ltd.'s JEM-1400 transmission electricity
Mirror TEM characterizes, and result is as shown in Figure 1.
As seen from Figure 1, products therefrom is obvious hollow-core construction, the diameter of hollow ball from 20nm to 70nm, and
And due to cobalt sol templates protectant PVP K30 molecule, hollow-core construction is many in linear array, the phenomenons such as reunion does not occur；
This explanation present invention has successfully prepared the nano-hollow composite that diameter is moderate.
2, uv scan sign is carried out with U.S.'s Thermo Scientific NanoDrop 2000 ultramicrospectrophotometer,
Sweep limits is 190nm to 840nm, and result is as shown in Figure 2.
As seen from Figure 2, synthetic sample have 2 maximum absorption bands, one of them is positioned at 198nm, and value is 0.669；Separately
One is positioned near 393nm, and testing result is 0.668, and this shows that gold rhodium nano-hollow ball absworption peak position then there occurs displacement,
It is near 400nm from 525nm displacement, shows that, along with the formation of gold rhodium nano-complex particle, particle size changes, and ultraviolet is inhaled
Receive peak along with there occurs change.
3, the test gained sample catalytic action to hydrogen peroxide:
The most immobilized 1～3 μM of golden rhodium complex, puts into the 0.1M acetic acid-vinegar containing 0.01% electron mediator thionine
In acid sodium cushioning liquid (pH5.5).Utilize electrochemistry difference pulse voltammetry (DPV) to detect, collect addition one respectively
Determining the current peak before and after the hydrogen peroxide of concentration to change, thus analyze the catalysis activity of gold rhodium nano-hollow ball, result is as shown in Figure 3.
As seen from Figure 3, before not adding hydrogen peroxide, thionine current peak position is at-0.21V, and size is 14 μ A, is adding
Enter hydrogen peroxide make its final concentration of 0.025% time, thionine current peak position excursion is to-0.34V, size of current 37 μ A, at gold rhodium
Under nano-hollow ball catalysis, current absolute value adds 23 μ A, and current value adds 164.29%.Show gold rhodium nano-hollow ball
Decomposing hydrogen dioxide solution is had the strongest catalytic action.
In sum, the golden rhodium nano-hollow ball that the present embodiment prepares has stronger albumen, nucleic acid binding activity, and has simultaneously
There is the strongest mimetic enzyme catalysis activity.It is expected to obtain extensively application at biomedical, sensor and field of batteries.
Finally illustrating, preferred embodiment above is only in order to illustrate technical scheme and unrestricted, although by above-mentioned
The present invention is described in detail by preferred embodiment, it is to be understood by those skilled in the art that can in form and
In details, it is made various change, without departing from claims of the present invention limited range.
Claims (6)
1. the method for preparation gold rhodium hollow Nano composite, it is characterised in that in described gold rhodium hollow Nano composite, gold is 1:6～10 with the mol ratio of rhodium, its a diameter of 20 nm to 70 nm；Method comprises the following steps:
1), prepare cobalt colloidal sol, specifically include:
A), preparation CoCl2Concentration is 0.1-0.2 g/L, and PVP concentration is the mixing solution of 1.2-3 g/L；
B), sonic oscillation processes step a) gained mixing solution；When sonic oscillation processes, frequency is 100～120 kHZ, and ultrasonic time is 10-20 min；
C), the oxidizing gas in removal step b) solution；
2), preparation HAuCl4And RhCl3Mixed solution, controls wherein HAuCl4And RhCl3Mol ratio be 1:6～10；
3), by step 2) mixed solution be gradually added drop-wise to step 1) prepare cobalt colloidal sol in and open stirring；Dropping HAuCl4And RhCl3Controlling dropping volume every time during mixed solution is 10～40 μ L, and total amount is 1～2 mL；
4), step with centrifugal separation 3) product i.e. obtain product.
The method preparing gold rhodium hollow Nano composite the most according to claim 1, it is characterised in that: in solution, first it is slowly introducing appropriate inert gas when removing oxidizing gas in solution, then solution drips appropriate NaBH4Solution.
The method preparing gold rhodium hollow Nano composite the most according to claim 2, it is characterised in that: described inert gas is nitrogen, and it is 15～20 min that nitrogen is passed through the time, and being passed through speed is 1 ~ 2cm3/s。
The method preparing gold rhodium hollow Nano composite the most according to claim 2, it is characterised in that: described NaBH4Solution concentration is 0.4-0.6 g/L, and its dropping total amount is the 30-40 % of cobalt sol volume, and each dripping quantity is for taking 200～300 μ L.
The method preparing gold rhodium hollow Nano composite the most according to claim 1, it is characterised in that: during step 4) centrifugal treating, centrifugal speed is 6000-7500 rpm, and the time is 4-6 min.
Prepare the most according to claim 1 gold rhodium hollow Nano composite method, it is characterised in that: also include step 5), utilize deionized water and the resuspended precipitation purification steps of tri-distilled water 4) separate product step.
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