CN109092299A - A kind of composite material and preparation method and application having both SERS activity and catalytic activity - Google Patents
A kind of composite material and preparation method and application having both SERS activity and catalytic activity Download PDFInfo
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- CN109092299A CN109092299A CN201810576401.XA CN201810576401A CN109092299A CN 109092299 A CN109092299 A CN 109092299A CN 201810576401 A CN201810576401 A CN 201810576401A CN 109092299 A CN109092299 A CN 109092299A
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- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 230000000694 effects Effects 0.000 title claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 30
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 17
- 101000674278 Homo sapiens Serine-tRNA ligase, cytoplasmic Proteins 0.000 title claims abstract 16
- 101000674040 Homo sapiens Serine-tRNA ligase, mitochondrial Proteins 0.000 title claims abstract 16
- 102100040516 Serine-tRNA ligase, cytoplasmic Human genes 0.000 title claims abstract 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 68
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- AXBVSRMHOPMXBA-UHFFFAOYSA-N 4-nitrothiophenol Chemical compound [O-][N+](=O)C1=CC=C(S)C=C1 AXBVSRMHOPMXBA-UHFFFAOYSA-N 0.000 claims abstract description 13
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 12
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 9
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 229940069328 povidone Drugs 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000007962 solid dispersion Substances 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000012544 monitoring process Methods 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 150000002940 palladium Chemical class 0.000 claims description 8
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 8
- 229940071536 silver acetate Drugs 0.000 claims description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000010531 catalytic reduction reaction Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- 238000004886 process control Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 33
- 238000006555 catalytic reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- WCDSVWRUXWCYFN-UHFFFAOYSA-N 4-aminobenzenethiol Chemical compound NC1=CC=C(S)C=C1 WCDSVWRUXWCYFN-UHFFFAOYSA-N 0.000 description 3
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 3
- 238000004847 absorption spectroscopy Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000011260 aqueous acid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GDSOZVZXVXTJMI-SNAWJCMRSA-N (e)-1-methylbut-1-ene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C(/C)=C(C(O)=O)\CCC(O)=O GDSOZVZXVXTJMI-SNAWJCMRSA-N 0.000 description 1
- BQNPYLXJOMKHIP-UHFFFAOYSA-N 4-nitrobenzenethiol Chemical compound [O-][N+](=O)C1=CC=C(S)C=C1.[O-][N+](=O)C1=CC=C(S)C=C1 BQNPYLXJOMKHIP-UHFFFAOYSA-N 0.000 description 1
- 241000931526 Acer campestre Species 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WYLQRHZSKIDFEP-UHFFFAOYSA-N benzene-1,4-dithiol Chemical compound SC1=CC=C(S)C=C1 WYLQRHZSKIDFEP-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001845 vibrational spectrum Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of composite material and preparation methods and application for having both SERS activity and catalytic activity, and wherein preparation method includes the following steps: that nano silver cube is dispersed in water to obtain nano silver cube dispersion liquid by (1)；(2) aqueous povidone solution and aqueous ascorbic acid are added in nano silver solid dispersion liquid and are sufficiently stirred, then silver-colored presoma is added simultaneously and palladium presoma obtains reaction solution, abundant reaction is stirred at room temperature, finally centrifuge separation simultaneously carries out supersound washing to the solid that centrifugation obtains, obtain Ag/Pd composite material namely the composite material for having both SERS activity and catalytic activity.Compared with prior art, the invention has the benefit that preparation method is simple to operation, reaction condition is mild, process control, obtained silver-colored palladium composite nano materials can be used for the catalytic reduction reaction process that in-situ SERS monitors p-Nitrobenzenethiol.
Description
Technical field
The invention belongs to research and application technical fields, and in particular to a kind of composite wood for having both SERS activity and catalytic activity
Material and its preparation method and application.
Background technique
The detection and analysis that the method for research catalytic reaction process has ultraviolet-visible absorption spectra, chromatography, mass spectrum etc. common
Means, but the resolution ratio of these methods is relatively low and sample pre-treatments are complicated.Surface Enhanced Raman Scattering Spectrum (SERS)
It is a kind of vibrational spectrum with fingerprint property and superelevation detection sensitivity, there is important application value in analysis field.
Catalysis reaction is commonly done in the reaction of catalyst surface and interface, and SERS is a kind of molecular surface spectral technique, therefore, will
The dynamic process that SERS technology is used to monitor catalysis reaction has advantageous advantage, has received widespread attention in recent years.
Noble metal (Ag, Au, Cu) has the SERS activity of excellent surface plasma resonance property (SPR) and superelevation, quilt
It is widely used as SERS base material.The wherein SERS activity highest of silver-colored crystal optimizes the SERS enhancing of the silver nanoparticle crystal of pattern
The factor is up to 107, therefore silver nanoparticle crystal is most widely used SERS material.But the catalytic activity of silver-colored crystal is far below
Au, Pt, Pd crystal.Therefore single Ag or Pd element material cannot be used for SERS monitoring catalytic reaction process, therefore high SERS is living
Property the obtained new material of material and high catalytic performance Material cladding, SERS substrate can not only be used as, while there is high activity
Catalytic performance can be used for SERS monitoring catalytic reaction process.
Summary of the invention
The present invention provides a kind of composite material and preparation method and application for having both SERS activity and catalytic activity, tool
Have the advantages that preparation method is simple, efficient and repetition is good, obtained composite material SERS and catalysis both sides activity is higher.
The technical scheme to solve the above technical problems is that it is a kind of have both SERS activity and catalytic activity it is compound
The preparation method of material comprising following steps:
(1) nano silver cube is dispersed in water to obtain nano silver cube dispersion liquid；
(2) aqueous povidone solution and aqueous ascorbic acid are added in nano silver cube dispersion liquid and are filled
Divide stirring, silver-colored presoma then is added simultaneously and palladium presoma obtains reaction solution, abundant reaction is stirred at room temperature, finally centrifugation point
Supersound washing is carried out from and to the obtained solid of centrifugation, obtain Ag/Pd composite material namely described has both SERS activity and catalysis is lived
The composite material of property.
Based on the above technical solution, the present invention can also have following further specific choice or optimal selection.
Specifically, the concentration of nano silver cube dispersion liquid is 5.0-6.0mg/mL in step (1).
Optimal, the concentration of nano silver cube dispersion liquid is 5.4-5.6mg/mL.
Specifically, the nano silver cube in step (1) is prepared by polyol reduction method, the nano silver cube
Partial size be 40-60nm.
Specifically, the concentration of aqueous povidone solution is 0.5-5mM in step (2), aqueous ascorbic acid
Concentration is 10-150mM, and silver-colored presoma is the silver salt solution of silver content 4-6mM, and palladium presoma is the palladium salt of palladium content 4-6mM
Aqueous solution.
Optimal, the molecular weight of polyvinylpyrrolidone is one of 15000,29000 or 55000.
Specifically, silver salt is silver nitrate or silver acetate, palladium salt is chlorine palladium acid sodium, potassium chloropalladate or chlorine palladium acid.
Specifically, each raw material of above-mentioned concentration: nano silver cube dispersion liquid, aqueous povidone solution, anti-bad
Hematic acid aqueous solution, silver salt solution and palladium salt aqueous solution mix reaction solution when, the volume ratio of dosage is 0.1-1:1-20:
0.1-5:0.5-10:0.5-10.
Specifically, the abundant reaction in step (2) refers to is stirred to react 4-6h at room temperature.
The present invention also provides a kind of composite materials for having both SERS activity and catalytic activity, are prepared by the above method
It obtains.
The present invention also provides the application of the above-mentioned composite material for having both SERS activity and catalytic activity, particularly for
In-situ SERS monitors the reduction reaction process of p-Nitrobenzenethiol (4- nitro thiophenol).
Compared with prior art, beneficial effects of the present invention are as follows:
The present invention under proper condition, using silver nanocubes as template, by room temperature simultaneously introduce silver salt and palladium salt,
Inhibit the displacement of palladium salt and silver nanoparticle crystal reaction from thermodynamics, so that silver salt and palladium salt are reduced agent and are reduced to silver and palladium
Silver nanocubes surface is deposited to simultaneously after simple substance, obtains the Ag/Pd composite material for having both SERS activity and catalytic activity, is made
The advantages that Preparation Method is simple, reaction condition is mild, reaction process is controllable, efficient and repetition is good；Meanwhile it is produced by the present invention compound
Material can be successfully applied to the reaction process of in-situ SERS monitoring palladium chtalyst sodium borohydride reduction 4- nitro thiophenol.
Detailed description of the invention
Fig. 1 is the corresponding TEM figure of Ag/Pd composite material, EDAX figure and distribution diagram of element prepared by the embodiment of the present invention 1,
Wherein (A) is that the TEM of Ag/Pd composite material schemes, and (B) is Ag/Pd composite material EDAX figure, and (C) is Pd in Ag/Pd composite material
The distribution map of element；It (D) is the distribution map of Ag element in Ag/Pd composite material；
Fig. 2 is that Ag/Pd composite material prepared by embodiment 2 is 10 to concentration-6—10-4The dithio-hydroquinone of mol/L
SERS spectrogram；
Fig. 3 prepares Ag/Pd composite material for embodiment 2 and is catalyzed what p-nitrophenol was changed over time by sodium borohydride reduction
Uv atlas；
Fig. 4 is that embodiment 2 prepares Ag/Pd composite material catalysis p-Nitrobenzenethiol by sodium borohydride reduction reaction process
SERS spectrogram.
Specific embodiment
Technical solution provided by the invention is described in further detail below in conjunction with drawings and the specific embodiments, is lifted
Example is served only for explaining the present invention, is not intended to limit the scope of the present invention.
The method used in following embodiment is then conventional method unless otherwise noted, if the drug used is without especially saying
It is bright, it is commercial product.
Embodiment 1
A kind of preparation method for the composite material having both SERS activity and catalytic activity comprising following steps:
(1) preparation of silver nanocubes: 50mL is added in three neck round bottom flask without water glycol (EG), at 150 DEG C
60min is heated under the conditions of oil bath.Then the Na that 500uL concentration is 3mM is rapidly added into flask2S ethylene glycol solution, after 2min
It is continuously added to the silver acetate that 12mL concentration is 180mM PVP (molecular weight 40000) ethylene glycol solution and 4mL concentration is 265mM
Ethylene glycol solution, whole process all carry out under magnetic stirring.The degree carried out with ultraviolet-visible absorption spectroscopy monitoring reaction, when
When maximal ultraviolet absorption peak is appeared near 436nm, flask is taken out and immerses ice-water bath to terminate reaction, is then centrifuged for separating
The silver nanocubes for being about 40nm to partial size after being washed repeatedly with acetone repeatedly, are dispersed in water and are made into mass concentration and are
5.6mg/mL。
(2) preparation of Ag/Pd composite material: at room temperature, by 70 μ L (1) preparation silver nanocubes aqueous solution with
50mL reagent bottle is added in PVP (molecular weight 29000) aqueous solution that 10mL concentration is 2mM, and after magnetic agitation is uniform, 2mL is added
Concentration is the aqueous ascorbic acid of 100mM, is then added at one time silver acetate aqueous solution and 2mL concentration that 2mL concentration is 4mM
For the chlorine palladium aqueous acid of 4mM, magnetic agitation 4h, reaction are completed, are then centrifuged for separating at room temperature, pass through ultrasound repeatedly with water
Washing can finally be dispersed in 0.7mL water and save repeatedly to get Ag/Pd composite material.
Ag/Pd composite material is done into morphology analysis and elemental analysis, referring to attached drawing 1, wherein A figure is the present embodiment technology
Transmission electron microscope (TEM) figure of the Ag/Pd composite material of scheme preparation, by can see in figure, Ag/Pd composite material is complete
Cube pattern；B figure is the EDAX spectrogram of the Ag/Pd composite material of the present embodiment technical solution preparation, and C figure and D figure are this realities
Apply the distribution map of the Pd and Ag element in an Ag/Pd composite material for technical solution preparation, it can be seen that Pd element is wrapped in Ag
The surface of cube.
Embodiment 2
A kind of preparation method for the composite material having both SERS activity and catalytic activity comprising following steps:
(1) preparation of silver nanocubes: 50mL is added in three neck round bottom flask without water glycol (EG), at 150 DEG C
60min is heated under the conditions of oil bath.Then the Na that 500uL concentration is 3mM is rapidly added into flask2S ethylene glycol solution, after 2min
It is continuously added to the silver acetate that 12mL concentration is 180mM PVP (molecular weight 40000) ethylene glycol solution and 8mL concentration is 265mM
Ethylene glycol solution, whole process all carry out under magnetic stirring.The degree carried out with ultraviolet-visible absorption spectroscopy monitoring reaction, when
When maximal ultraviolet absorption peak is appeared near 436nm, flask is taken out and immerses ice-water bath to terminate reaction, is then centrifuged for separating
The silver nanocubes for being about 60nm to partial size after being washed repeatedly with acetone repeatedly, are dispersed in water and are made into mass concentration and are
5.4mg/mL。
(2) preparation of Ag/Pd composite material: at room temperature, by 50 μ L (1) preparation silver nanocubes aqueous solution with
50mL reagent bottle is added in PVP (molecular weight 15000) aqueous solution that 15mL concentration is 4mM, and after magnetic agitation is uniform, 4mL is added
Concentration is the aqueous ascorbic acid of 130mM, is then added at one time silver acetate aqueous solution and 4mL concentration that 4mL concentration is 6mM
For the chlorine palladium aqueous acid of 6mM, magnetic agitation 6h, reaction are completed, are then centrifuged for separating at room temperature, pass through ultrasound repeatedly with water
Washing can finally be dispersed in 0.5mL water and save repeatedly to get Ag/Pd composite material.
Embodiment 3
A kind of preparation method for the composite material having both SERS activity and catalytic activity comprising following steps:
(1) preparation of silver nanocubes: 50mL is added in three neck round bottom flask without water glycol (EG), at 150 DEG C
60min is heated under the conditions of oil bath.Then the Na that 500uL concentration is 3mM is rapidly added into flask2S ethylene glycol solution, after 2min
It is continuously added to the silver acetate that 12mL concentration is 180mM PVP (molecular weight 40000) ethylene glycol solution and 6mL concentration is 265mM
Ethylene glycol solution, whole process all carry out under magnetic stirring.The degree carried out with ultraviolet-visible absorption spectroscopy monitoring reaction, when
When maximal ultraviolet absorption peak is appeared near 436nm, flask is taken out and immerses ice-water bath to terminate reaction, is then centrifuged for separating
The silver nanocubes for being about 40nm to partial size after being washed repeatedly with acetone repeatedly, are dispersed in water and are made into mass concentration and are
5.0mg/mL。
(2) preparation of Ag/Pd composite material: at room temperature, by 100 μ L (1) preparation silver nanocubes aqueous solution with
50mL reagent bottle is added in PVP (molecular weight 55000) aqueous solution that 20mL concentration is 0.5mM, after magnetic agitation is uniform, is added
5mL concentration be 30mM aqueous ascorbic acid, be then added at one time 0.5mL concentration be 6mM silver acetate aqueous solution and
0.5mL concentration is the chlorine palladium aqueous acid of 6mM, at room temperature magnetic agitation 5h, and reaction is completed, is then centrifuged for separating, logical with water
It crosses ultrasound to be washed repeatedly repeatedly to get Ag/Pd composite material, can finally be dispersed in 0.6mL water and save.
SERS activity and catalytic activity detection
SERS Activity determination: it is 10 that concentration, which is added, in Ag/Pd composite material prepared by appropriate embodiment 2-4—10-6mol/L
Isosorbide-5-Nitrae-diphenyl disulfide phenol in, carry out the test of SERS spectrogram, test results are shown in figure 2, from spectrogram it can be seen that, the increasing of Raman
It is potent should be very strong, sensitivity is higher, can achieve 10 to Isosorbide-5-Nitrae-diphenyl disulfide phenol detectable concentration-6mol/L。
Catalytic activity detection: being 2 × 10 in 2mL concentration-4In the 4- nitrophenol solution of mol/L be added 5mL deionized water,
1mL concentration is the Ag/Pd composite nanoparticle aqueous dispersions 0.1mL of 50mg/mL sodium borohydride aqueous solution and the preparation of embodiment 2,
Abundant magnetic agitation and separated in time, detect rapidly the uv absorption spectra of solution.The ultra-violet absorption spectrum measured is such as
Shown in Fig. 3, from spectrogram it can be seen that, in 13min, the 4- nitrophenol characteristic absorption peak at 400nm under alkaline condition
Intensity gradually decreases, and when the reaction time is 13min, it is good to show that the Ag/Pd composite material of preparation has up to 90% for conversion ratio
Catalytic activity.
The application example of SERS in-situ monitoring 4- nitro thiophenol catalysis reduction
Example 2 prepares Ag/Pd aqueous nancomposite dispersion liquid 0.2mL and 1mL concentration is 10-4The 4- nitrobenzene of mol/L
Thiophenol ethanol solution mixes in centrifuge tube, after standing 1h at room temperature, by the nanoparticle ethyl alcohol of functionalization and washing
Remove extra 4- nitro thiophenol.Then the nanoparticle of 4- nitro thiophenol function is dispersed in 0.2ml water, with 0.2mL
After 5mg/mL sodium borohydride aqueous solution is transferred to homemade PDMS groove after mixing, the optics of Raman spectrometer is placed it in
On micro-platform, in the Raman signal of point acquisition at regular intervals.Optical maser wavelength used is 532nm, and the signal acquisition time is
5s.It can be seen that over time by Fig. 4 A, 4- nitro thiophenol is located at 1109,1137 and 1570cm-1Feature
Raman shift peak intensity weakens rapidly, in 13min, completely disappears.The reduzate 4- aminothiophenol of 4- nitro thiophenol
Characteristic peak be located at 1593cm-1, in 4min, there is the characteristic peak of 4- aminothiophenol, SERS spectrogram is complete in 13min
It is shown as the characteristic peak of 4- aminothiophenol.The result shows that 4- nitro thiophenol can be reduced to 4- aminobenzene by quick and complete
Thiophenol, it was demonstrated that Ag/Pd composite material prepared by the present invention can be applied to SERS in-situ monitoring catalytic reaction process.
In addition, taking nanoparticle subnumber 20 μ L identical with population in above-mentioned 0.2mL Ag/Pd aqueous nancomposite dispersion liquid
Silver nanocubes aqueous dispersions carry out catalysis reduction and SERS in-situ monitoring to 4- nitro thiophenol.The SERS of reaction process is composed
Figure is shown in Fig. 4 B, it can be seen that when being 30min between when reacted, 4- nitro thiophenol is located at 1108,1132 and 1570cm-1's
Characteristic Raman is displaced that peak intensity is essentially unchanged, shows silver nanocubes substantially and cannot be catalyzed that the reduction of 4- nitro thiophenol is anti-
It answers.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method for the composite material for having both SERS activity and catalytic activity, which comprises the steps of:
(1) nano silver cube is dispersed in water to obtain nano silver cube dispersion liquid；
(2) aqueous povidone solution and aqueous ascorbic acid are added in nano silver solid dispersion liquid and are sufficiently stirred
It mixes, silver-colored presoma then is added simultaneously and palladium presoma obtains reaction solution, abundant reaction is stirred at room temperature, is finally centrifugated simultaneously
Supersound washing is carried out to the obtained solid of centrifugation, obtains Ag/Pd composite material namely SERS activity and the catalytic activity of having both
Composite material.
2. a kind of preparation method of composite material for having both SERS activity and catalytic activity according to claim 1, special
Sign is that the concentration of nano silver cube dispersion liquid is 5.0-6.0mg/mL in step (1).
3. a kind of preparation method of composite material for having both SERS activity and catalytic activity according to claim 2, special
Sign is that the concentration of nano silver cube dispersion liquid is 5.4-5.6mg/mL.
4. a kind of preparation of composite material for having both SERS activity and catalytic activity according to any one of claims 1 to 3
Method, which is characterized in that the nano silver cube in step (1) is prepared by polyol reduction method, the nano silver cube
The partial size of body is 40-60nm.
5. a kind of preparation method of composite material for having both SERS activity and catalytic activity according to claim 4, special
Sign is that the concentration of aqueous povidone solution is 0.5-5mM in step (2), and the concentration of aqueous ascorbic acid is 10-
150mM, silver-colored presoma are the silver salt solution of silver content 4-6mM, and palladium presoma is the palladium salt aqueous solution of palladium content 4-6mM.
6. a kind of preparation method of composite material for having both SERS activity and catalytic activity according to claim 5, special
Sign is that the molecular weight of polyvinylpyrrolidone is one of 15000,29000 or 55000.
7. a kind of preparation method of composite material for having both SERS activity and catalytic activity according to claim 5, special
Sign is that silver salt is silver nitrate or silver acetate, and palladium salt is chlorine palladium acid sodium, potassium chloropalladate or chlorine palladium acid.
8. a kind of preparation method of composite material for having both SERS activity and catalytic activity according to claim 5, special
Sign is, nano silver cube dispersion liquid, aqueous povidone solution, aqueous ascorbic acid, silver salt solution and palladium
The volume ratio of saline solution dosage is 0.1-1:1-20:0.1-5:0.5-10:0.5-10.
9. a kind of composite material for having both SERS activity and catalytic activity, which is characterized in that pass through any one of claim 1 to 8
The method is prepared.
10. a kind of application for the composite material for having both SERS activity and catalytic activity as claimed in claim 9, feature exist
In, for in-situ SERS monitoring p-Nitrobenzenethiol reduction reaction process.
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