CN109529824A - A kind of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst and preparation method thereof - Google Patents
A kind of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst and preparation method thereof Download PDFInfo
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- CN109529824A CN109529824A CN201811503037.0A CN201811503037A CN109529824A CN 109529824 A CN109529824 A CN 109529824A CN 201811503037 A CN201811503037 A CN 201811503037A CN 109529824 A CN109529824 A CN 109529824A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 239000011258 core-shell material Substances 0.000 title claims abstract description 96
- 229920001577 copolymer Polymers 0.000 title claims abstract description 95
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 79
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 34
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 33
- 239000008103 glucose Substances 0.000 claims abstract description 33
- 238000005119 centrifugation Methods 0.000 claims abstract description 30
- 238000002156 mixing Methods 0.000 claims abstract description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 239000004332 silver Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000006228 supernatant Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000009413 insulation Methods 0.000 claims abstract description 15
- 238000010792 warming Methods 0.000 claims abstract description 15
- 229910052737 gold Inorganic materials 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 5
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 148
- 239000008367 deionised water Substances 0.000 claims description 54
- 229910021641 deionized water Inorganic materials 0.000 claims description 54
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 45
- 239000010931 gold Substances 0.000 claims description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000006193 liquid solution Substances 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 60
- 239000000047 product Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 56
- 229910001961 silver nitrate Inorganic materials 0.000 description 28
- 238000004090 dissolution Methods 0.000 description 23
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 20
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 15
- 239000003921 oil Substances 0.000 description 15
- 235000019198 oils Nutrition 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- 230000005540 biological transmission Effects 0.000 description 14
- 238000010408 sweeping Methods 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 239000000908 ammonium hydroxide Substances 0.000 description 13
- 239000000725 suspension Substances 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 11
- 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 8
- 229910018949 PtAu Inorganic materials 0.000 description 8
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 7
- 238000005660 chlorination reaction Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- BRSVJNYNWNMJKC-UHFFFAOYSA-N [Cl].[Au] Chemical compound [Cl].[Au] BRSVJNYNWNMJKC-UHFFFAOYSA-N 0.000 description 6
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 4
- 229940120503 dihydroxyacetone Drugs 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 2
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 2
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
Classifications
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- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
- 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
- B01J23/52—Gold
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention belongs to electrocatalysis material field, a kind of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst and preparation method thereof is disclosed.CTAB and glucose are dissolved in silver ammino solution and obtain precursor solution, reacts, is cooled to room temperature at 80~180 DEG C, supernatant is taken after the centrifugation of gained reaction solution, obtains Ag seed solution；PVP and citric acid are dissolved in water, Ag seed solution is then added, 60~120 DEG C are warming up to after stirring and evenly mixing, 2~8h of soluble compound insulation reaction of M is added；Gained reaction solution is washed, is centrifuged to get M@Ag core-shell structure copolymer nanocrystal elctro-catalyst；The M is the mixing of one or more of Au, Pd and Pt.Preparation method simple process of the invention, raw material are easy to get, and gained M@Ag core-shell structure copolymer nanocrystal size and pattern are uniform, can be used for catalyzing glycerol electroxidation preparation high added value product.
Description
Technical field
The invention belongs to electrocatalysis material fields, and in particular to a kind of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst and its system
Preparation Method.
Background technique
Glycerol has very big Development volue as a kind of production by-product.It not only can be from the synthesis of bio-fuel
Middle acquisition obtains during can also generating fatty acid from vegetable oil hydrogenolysis.The glycerol biomass resource important as one kind,
There is very high application value, by many Chemical products that glycerol is process all there is very high Economic Application to be worth, such as
Glyceraldehyde (GLAD), dihydroxyacetone (DHA) (DHA), glyceric acid (GLA), lactic acid (LA), sub- tartaric acid (TA), mesoxalic acid (MA) etc..
Wherein, one of widely used raw material when DHA is cosmetic industry production suncream.Currently, adding in industrial production to glycerol
Work method mainly has direct chemical oxidization method, fermentation method (enzyme process) and electrochemical method, and direct chemical oxidization method is using chemistry meter
Oxidant is measured, such as permanganate, nitric acid and chromic acid strong oxidizer and strong acid, such production process can cause dirt to environment
Dye.Fermentation method (enzyme process) utilizes the principle of fermentation of microorganism, converts three carbon products with high added value for glycerol fermentation, but
It is lower to the selectivity of product.And direct chemical oxidization method and fermentation method can be avoided to bring well using electrochemical method
Many defects, can be very good improve product selectivity and conversion ratio.But the premise of method is to rationally design out
High catalytic activity and highly selective catalyst.Pt, Au, Pd as widely used catalyst in catalyzing glycerol conversion process,
Have in the synthesis of catalyst and refers to utility value well.So far, there are many preparation methods, such as polynary
Alcohol assisted Reduction method, hydrothermal synthesis method, microemulsion method etc., respectively there is superiority and inferiority.The pattern of these preparation methods catalyst multipair greatly is not
It is easy to control, it is difficult to prepare the good catalyst of selectivity.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing a kind of M@Ag
Core-shell structure copolymer nanocrystal elctro-catalyst and preparation method thereof.The method of the present invention uses seed mediating growth method, with silver nitrate and M
Soluble compound is as precursor, using glucose, citric acid as reducing agent, cetyl trimethylammonium bromide (CTAB),
Polyvinylpyrrolidone (PVP) is used as structure directing agent, and water is as reaction dissolvent, by the concentration, the reaction that control reactive material
Temperature, reaction time synthesize the uniform M@Ag core-shell structure copolymer nanocrystal elctro-catalyst of size and shape.
Another object of the present invention is to provide a kind of M@Ag core-shell structure copolymer nanocrystal electricity being prepared by the above method
Catalyst.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst, including following preparation step:
(1) compound concentration is the silver ammino solution of 5~20mmol/L, then sequentially adds CTAB and glucose is uniformly dissolved
To precursor solution；
(2) precursor solution obtained by step (1) is reacted at 80~180 DEG C, is cooled to room temperature after the reaction was completed, by institute
Supernatant is taken after obtaining reaction solution centrifugation, obtains Ag seed solution；
(3) PVP and citric acid are dissolved in water, Ag seed solution obtained by step (2) is then added, is risen after stirring and evenly mixing
2~8h of soluble compound insulation reaction of M is added to 60~120 DEG C in temperature；Gained reaction solution is washed, centrifugation is to get M@
Ag core-shell structure copolymer nanocrystal elctro-catalyst；The M is the mixing of one or more of Au, Pd and Pt.
Preferably, the concentration of CTAB is 20~100mmol/L, the concentration of glucose in precursor solution obtained by step (1)
For 1~10mmol/L.
Preferably, the time of reaction described in step (2) is 3~10h.
Preferably, the concentration that PVP and citric acid described in step (3) are dissolved in water are as follows: 3~6mg/mL of PVP, lemon
4~25mg/mL of acid.
Preferably, the soluble compound of M described in step (3) refers to any in chloroplatinic acid, gold chloride and chlorine palladium acid
One or more kinds of mixing.
Preferably, the soluble compound of M described in step (3) is added with the aqueous solution that concentration is 5~20mmol/L.
Preferably, washing described in step (3) refers to is washed with saturated sodium chloride solution and deionized water.
A kind of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst, is prepared by the above method.
The principle of the invention are as follows: seed mediating growth method is used, using the soluble compound of silver nitrate and M as precursor,
Glucose, citric acid are as reducing agent, and cetyl trimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP) are as knot
Structure directed agents, water synthesize the uniform M@Ag core-shell structure copolymer nanocrystal of size and shape, separately by reaction as reaction dissolvent
Outside, with different noble metal and combinations thereof for shell, using Ag as core, the appearance shape of gained M@Ag core-shell structure copolymer nanocrystal elctro-catalyst
Looks and catalytic performance also have certain difference, can be used as urging for electrochemical method catalysis oxidation glycerol production high added value product
Agent.
Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
(1) present invention prepares M Ag core-shell structure copolymer nanocrystal elctro-catalyst using seed mediating growth method, the method technique letter
Single, raw material is easy to get, has many advantages, such as at low cost, environmentally protective.
(2) M@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the present invention is in uniform core-shell structure copolymer nanocrystalline structure and ruler
It is very little consistent.
Detailed description of the invention
Fig. 1 and Fig. 2 is the transmission electron microscope of Au@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the embodiment of the present invention 3
(TEM) figure.
Fig. 3 is that Au@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the embodiment of the present invention 3 is molten in 0.1M KOH+1M glycerol
Electroxidation CV curve graph in liquid, sweeping speed is 50mV/s, and wherein Au/C is standard catalyst.
Fig. 4 and Fig. 5 is the transmission electron microscope of Pd@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the embodiment of the present invention 8
(TEM) figure.
Fig. 6 is that Pd@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the embodiment of the present invention 8 is molten in 0.1M KOH+1M glycerol
Electroxidation CV curve graph in liquid, sweeping speed is 50mV/s, and wherein Pd/C is standard catalyst.
Fig. 7 and Fig. 8 is the transmission electron microscope of PdAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the embodiment of the present invention 9
(TEM) figure.
Fig. 9 is the PdAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst of the preparation of the embodiment of the present invention 9 in 0.1M KOH+1M glycerol
Electroxidation CV curve graph in solution, sweeping speed is 50mV/s, and wherein Pd/C, Au/C are standard catalyst.
Figure 10 is the transmission electron microscope (TEM) of Pt@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the embodiment of the present invention 10
Figure.
Figure 11 is the Pt@Ag core-shell structure copolymer nanocrystal elctro-catalyst of the preparation of the embodiment of the present invention 10 in 0.1M KOH+1M glycerol
Electroxidation CV curve graph in solution, sweeping speed is 50mV/s, and wherein Pt/C is standard catalyst.
Figure 12 and Figure 13 is the transmission electricity of PtAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the embodiment of the present invention 11
Mirror (TEM) figure.
Figure 14 is that PtAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the embodiment of the present invention 11 is sweet in 0.1M KOH+1M
Electroxidation CV curve graph in oil solution, sweeping speed is 50mV/s, and wherein Pt/C, Au/C are standard catalyst.
Figure 15 and Figure 16 is the transmission of PtAuPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the embodiment of the present invention 12
Electronic Speculum (TEM) figure.
Figure 17 is the PtAuPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst of the preparation of the embodiment of the present invention 12 in 0.1M KOH+1M
Electroxidation CV curve graph in glycerite, sweeping speed is 50mV/s, and wherein Pt/C, Au/C, Pd/C are standard catalyst.
Figure 18 and Figure 19 is the transmission electricity of PtPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the embodiment of the present invention 13
Mirror (TEM) figure.
Figure 20 is that PtPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst prepared by the embodiment of the present invention 13 is sweet in 0.1M KOH+1M
Electroxidation CV curve graph in oil solution, sweeping speed is 50mV/s, and wherein Pt/C, Pd/C are standard catalyst.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
(1) 85mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 5mmol/L to concentration；110mg CTAB is weighed, 9mg glucose is dissolved in above-mentioned silver ammino solution and obtains
The precursor solution that CTAB concentration is 20mmol/L, concentration of glucose is 1mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 5h at 80 DEG C, is cooled to room temperature；It will
Gained reaction solution takes supernatant as the Ag seed solution of subsequent synthesis Au@Ag core-shell structure copolymer nanocrystal, for use after centrifugation.
(3) 80mg PVP and 100mg citric acid are successively dissolved in 24mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 10mL step (2), is transferred in oil bath after stirring and evenly mixing, after being warming up to 60 DEG C, by the gold chloride of 8mg
It is added to the reaction system after being dissolved into 5mL deionized water and relays continuous insulation reaction 5h.By gained reaction solution and saturated sodium-chloride
After solution mixing stands 6h, the deionized water washing centrifugation 3 times Au Ag core-shell structure copolymer nanocrystal electricity to get even suspension liquid status
Catalyst.
Embodiment 2
(1) 340mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 20mmol/L to concentration；550mg CTAB is weighed, 90mg glucose is dissolved in above-mentioned silver ammino solution and obtains
The precursor solution that CTAB concentration is 100mmol/L, concentration of glucose is 10mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 3h at 180 DEG C, is cooled to room temperature；
By gained reaction solution by centrifugation after, take supernatant as it is subsequent synthesis Au@Ag core-shell structure copolymer nanocrystal Ag seed solution, to
With.
(3) 130mg PVP and 600mg citric acid are successively dissolved in 24mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 20mL step (2), be transferred in oil bath after stirring and evenly mixing, after being warming up to 120 DEG C, by the chlorine gold of 34mg
Acid dissolution into 5mL deionized water after be added to the reaction system and relay continuous insulation reaction 2h.By gained reaction solution and saturation chlorination
After sodium solution mixing is stood for 24 hours, deionized water washing centrifugation 3 times nanocrystalline to get the Au Ag core-shell structure copolymer of even suspension liquid status
Body elctro-catalyst.
Embodiment 3
(1) 170mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 10mmol/L to concentration；270mg CTAB is weighed, 9mg glucose is dissolved in above-mentioned silver ammino solution and obtains
The precursor solution that CTAB concentration is 50mmol/L, concentration of glucose is 1mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 8h at 120 DEG C, is cooled to room temperature；
By gained reaction solution by centrifugation after, take supernatant as it is subsequent synthesis Au@Ag core-shell structure copolymer nanocrystal Ag seed solution, to
With.
(3) 100mg PVP and 500mg citric acid are successively dissolved in 24mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 15mL step (2), be transferred in oil bath after stirring and evenly mixing, after being warming up to 90 DEG C, by the chlorine gold of 17mg
Acid dissolution into 5mL deionized water after be added to the reaction system and relay continuous insulation reaction 3h.By gained reaction solution and saturation chlorination
After sodium solution mixing stands 12h, deionized water washing centrifugation 3 times nanocrystalline to get the Au Ag core-shell structure copolymer of even suspension liquid status
Body elctro-catalyst.
Transmission electron microscope (TEM) figure such as Fig. 1 and Fig. 2 institute of Au@Ag core-shell structure copolymer nanocrystal elctro-catalyst manufactured in the present embodiment
Show.By Fig. 1 and Fig. 2 as it can be seen that present invention gained Au@Ag core-shell structure copolymer nanocrystal elctro-catalyst size and shape is uniform, particle ruler
Very little about 100nm.Electroxidation CV of the gained Au@Ag core-shell structure copolymer nanocrystal elctro-catalyst in 0.1M KOH+1M glycerite is bent
Line chart is as shown in figure 3, sweeping speed is 50mV/s, and wherein Au/C is standard catalyst.As seen from Figure 3, present invention gained Au@Ag core-
Shell nanocrystal elctro-catalyst compares Au/C standard catalyst, and the electric current of catalyzing glycerol oxidation significantly improves.
Embodiment 4
(1) 120mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 7.06mmol/L to concentration；220mg CTAB is weighed, 30mg glucose is dissolved in above-mentioned silver ammino solution and obtains
To the precursor solution that CTAB concentration is 40.74mmol/L, concentration of glucose is 3.33mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 10h at 100 DEG C, is cooled to room temperature；
By gained reaction solution by centrifugation after, take supernatant as it is subsequent synthesis Au@Ag core-shell structure copolymer nanocrystal Ag seed solution, to
With.
(3) 130mg PVP and 600mg citric acid are successively dissolved in 24mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 20mL step (2), be transferred in oil bath after stirring and evenly mixing, after being warming up to 120 DEG C, by the chlorine gold of 16mg
Acid dissolution into 5mL deionized water after be added to the reaction system and relay continuous insulation reaction 2h.By gained reaction solution and saturation chlorination
After sodium solution mixing stands 10h, deionized water washing centrifugation 3 times nanocrystalline to get the Au Ag core-shell structure copolymer of even suspension liquid status
Body elctro-catalyst.
Embodiment 5
(1) 200mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 11.76mmol/L to concentration；440mg CTAB is weighed, 18mg glucose is dissolved in above-mentioned silver ammino solution and obtains
To the precursor solution that CTAB concentration is 81.48mmol/L, concentration of glucose is 2mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 8h at 150 DEG C, is cooled to room temperature；
By gained reaction solution by centrifugation after, take supernatant as it is subsequent synthesis Au@Ag core-shell structure copolymer nanocrystal Ag seed solution, to
With.
(3) 100mg PVP and 200mg citric acid are successively dissolved in 30mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 20mL step (2), be transferred in oil bath after stirring and evenly mixing, after being warming up to 100 DEG C, by the chlorine gold of 24mg
Acid dissolution into 5mL deionized water after be added to the reaction system and relay continuous insulation reaction 4h.By gained reaction solution and saturation chlorination
After sodium solution mixing is stood for 24 hours, deionized water washing centrifugation 3 times nanocrystalline to get the Au Ag core-shell structure copolymer of even suspension liquid status
Body elctro-catalyst.
Embodiment 6
(1) 340mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 20mmol/L to concentration；110mg CTAB is weighed, 27mg glucose is dissolved in above-mentioned silver ammino solution and obtains
The precursor solution that CTAB concentration is 20.37mmol/L, concentration of glucose is 3mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 6h at 100 DEG C, is cooled to room temperature；
By gained reaction solution by centrifugation after, take supernatant as it is subsequent synthesis Au@Ag core-shell structure copolymer nanocrystal Ag seed solution, to
With.
(3) 120mg PVP and 500mg citric acid are successively dissolved in 30mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 15mL step (2), be transferred in oil bath after stirring and evenly mixing, after being warming up to 90 DEG C, by the chlorine gold of 32mg
Acid dissolution into 5mL deionized water after be added to the reaction system and relay continuous insulation reaction 3h.By gained reaction solution and saturation chlorination
After sodium solution mixing stands 12h, deionized water washing centrifugation 3 times nanocrystalline to get the Au Ag core-shell structure copolymer of even suspension liquid status
Body elctro-catalyst.
Embodiment 7
(1) 85mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 5mmol/L to concentration；270mg CTAB is weighed, 90mg glucose is dissolved in above-mentioned silver ammino solution and obtains
The precursor solution that CTAB concentration is 50mmol/L, concentration of glucose is 10mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 3h at 120 DEG C, is cooled to room temperature；
By gained reaction solution by centrifugation after, take supernatant as it is subsequent synthesis Au@Ag core-shell structure copolymer nanocrystal Ag seed solution, to
With.
(3) 90mg PVP and 500mg citric acid are successively dissolved in 30mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 20mL step (2), be transferred in oil bath after stirring and evenly mixing, after being warming up to 80 DEG C, by the chlorine gold of 34mg
Acid dissolution into 5mL deionized water after be added to the reaction system and relay continuous insulation reaction 5h.By gained reaction solution and saturation chlorination
After sodium solution mixing is stood for 24 hours, deionized water washing centrifugation 3 times nanocrystalline to get the Au Ag core-shell structure copolymer of even suspension liquid status
Body elctro-catalyst.
Embodiment 8
(1) 170mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 10mmol/L to concentration；270mg CTAB is weighed, 9mg glucose is dissolved in above-mentioned silver ammino solution and obtains
The precursor solution that CTAB concentration is 50mmol/L, concentration of glucose is 1mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 8h at 120 DEG C, is cooled to room temperature；
By gained reaction solution by centrifugation after, take supernatant as it is subsequent synthesis Pd@Ag core-shell structure copolymer nanocrystal Ag seed solution, to
With.
(3) 100mg PVP and 500mg citric acid are successively dissolved in 24mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 15mL step (2), is transferred in oil bath after stirring and evenly mixing, after being warming up to 90 DEG C, by the chlorine of 12.5mg
Palladium acid dissolution into 5mL deionized water after be added to the reaction system and relay continuous insulation reaction 3h.By gained reaction solution and saturation chlorine
After changing sodium solution mixing standing 12h, the deionized water washing centrifugation 3 times Pd Ag core-shell structure copolymer nanometers to get even suspension liquid status
Crystal elctro-catalyst.
Transmission electron microscope (TEM) figure such as Fig. 4 and Fig. 5 institute of Pd@Ag core-shell structure copolymer nanocrystal elctro-catalyst manufactured in the present embodiment
Show.By Fig. 4 and Fig. 5 as it can be seen that present invention gained Pd@Ag core-shell structure copolymer nanocrystal elctro-catalyst is in uniform core-shell structure copolymer nanocrystal knot
Structure and size is consistent, particle size is about 10~30nm.Gained Pd@Ag core-shell structure copolymer nanocrystal elctro-catalyst is in 0.1M KOH+
Electroxidation CV curve graph in 1M glycerite is as shown in fig. 6, sweeping speed is 50mV/s, and wherein Pd/C is standard catalyst.By Fig. 6
As it can be seen that present invention gained Pd@Ag core-shell structure copolymer nanocrystal elctro-catalyst compares Pd/C standard catalyst, catalyzing glycerol oxidation
Electric current significantly improves.
Embodiment 9
(1) 170mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 10mmol/L to concentration；270mg CTAB is weighed, 9mg glucose is dissolved in above-mentioned silver ammino solution and obtains
The precursor solution that CTAB concentration is 50mmol/L, concentration of glucose is 1mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 8h at 120 DEG C, is cooled to room temperature；
By gained reaction solution by centrifugation after, take supernatant as it is subsequent synthesis PdAu@Ag core-shell structure copolymer nanocrystal Ag seed solution,
For use.
(3) 100mg PVP and 500mg citric acid are successively dissolved in 24mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 15mL step (2), is transferred in oil bath after stirring and evenly mixing, after being warming up to 90 DEG C, by the chlorine palladium of 8.8mg
The gold chloride of acid and 8.6mg are added to the reaction system and relay continuous insulation reaction 3h after being dissolved into 5mL deionized water.Gained is anti-
After answering liquid to mix standing 12h with saturated sodium chloride solution, deionized water washing centrifugation 3 times to get even suspension liquid status
PdAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst.
Transmission electron microscope (TEM) figure such as Fig. 7 and Fig. 8 of PdAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst manufactured in the present embodiment
It is shown.By Fig. 7 and Fig. 8 as it can be seen that present invention gained PdAu@Ag elctro-catalyst is in uniform core-shell structure copolymer nanocrystalline structure and size
Unanimously, particle size is about 50nm.Gained PdAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst is in 0.1M KOH+1M glycerite
In electroxidation CV curve graph as shown in figure 9, sweeping speed is 50mV/s, wherein Pd/C, Au/C are standard catalyst.As seen from Figure 9,
Gained PdAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst of the invention compares Pd/C and Au/C standard catalyst, catalyzing glycerol oxidation
Electric current significantly improve.
Embodiment 10
(1) 170mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 10mmol/L to concentration；270mg CTAB is weighed, 9mg glucose is dissolved in above-mentioned silver ammino solution and obtains
The precursor solution that CTAB concentration is 50mmol/L, concentration of glucose is 1mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 8h at 120 DEG C, is cooled to room temperature；
By gained reaction solution by centrifugation after, take supernatant as it is subsequent synthesis Pt@Ag core-shell structure copolymer nanocrystal Ag seed solution, to
With.
(3) 100mg PVP and 500mg citric acid are successively dissolved in 24mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 15mL step (2), is transferred in oil bath after stirring and evenly mixing, after being warming up to 90 DEG C, by the chlorine platinum of 26mg
Acid dissolution into 5mL deionized water after be added to the reaction system and relay continuous insulation reaction 3h.By gained reaction solution and saturation chlorination
After sodium solution mixing stands 12h, deionized water washing centrifugation 3 times nanocrystalline to get the Pt Ag core-shell structure copolymer of even suspension liquid status
Body elctro-catalyst.
Transmission electron microscope (TEM) figure of Pt@Ag core-shell structure copolymer nanocrystal elctro-catalyst manufactured in the present embodiment is as shown in Figure 10.
As seen from Figure 10, present invention gained Pt@Ag core-shell structure copolymer nanocrystal elctro-catalyst is in uniform core-shell structure copolymer nanocrystalline structure and ruler
Very little consistent, particle size is about 10nm.Gained Pt@Ag core-shell structure copolymer nanocrystal elctro-catalyst is in 0.1M KOH+1M glycerite
In electroxidation CV curve graph it is as shown in figure 11, sweeping speed is 50mV/s, wherein Pt/C be standard catalyst.As seen from Figure 11, originally
Invention gained Pt@Ag core-shell structure copolymer nanocrystal elctro-catalyst compares Pt/C standard catalyst, and the electric current of catalyzing glycerol oxidation is significant
It improves.
Embodiment 11
(1) 170mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 10mmol/L to concentration；270mg CTAB is weighed, 9mg glucose is dissolved in above-mentioned silver ammino solution and obtains
The precursor solution that CTAB concentration is 50mmol/L, concentration of glucose is 1mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 8h at 120 DEG C, is cooled to room temperature；
By gained reaction solution by centrifugation after, take supernatant as it is subsequent synthesis PtAu@Ag core-shell structure copolymer nanocrystal Ag seed solution,
For use.
(3) 100mg PVP and 500mg citric acid are successively dissolved in 24mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 15mL step (2), is transferred in oil bath after stirring and evenly mixing, after being warming up to 90 DEG C, by the chlorine platinum of 13mg
The gold chloride of acid and 8.6mg are added to the reaction system and relay continuous insulation reaction 3h after being dissolved into 5mL deionized water.Gained is anti-
After answering liquid to mix standing 12h with saturated sodium chloride solution, deionized water washing centrifugation 3 times to get even suspension liquid status
PtAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst.
Transmission electron microscope (TEM) figure such as Figure 12 and figure of PtAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst manufactured in the present embodiment
Shown in 13.By Figure 12 and Figure 13 as it can be seen that the present invention gained PtAu@Ag elctro-catalyst be in uniform core-shell structure copolymer nanocrystalline structure and
Size is consistent, and particle size is about 30~50nm.Gained PtAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst is in 0.1M KOH+1M
Electroxidation CV curve graph in glycerite is as shown in figure 14, and sweeping speed is 50mV/s, and wherein Pt/C, Au/C are standard catalyst.
As seen from Figure 14, present invention gained PtAu@Ag core-shell structure copolymer nanocrystal elctro-catalyst compares Pt/C and Au/C standard catalyst,
The electric current of catalyzing glycerol oxidation significantly improves.
Embodiment 12
(1) 170mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 10mmol/L to concentration；270mg CTAB is weighed, 9mg glucose is dissolved in above-mentioned silver ammino solution and obtains
The precursor solution that CTAB concentration is 50mmol/L, concentration of glucose is 1mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 8h at 120 DEG C, is cooled to room temperature；
By gained reaction solution after centrifugation, take supernatant molten as the Ag seed of subsequent synthesis PtAuPd@Ag core-shell structure copolymer nanocrystal
Liquid, for use.
(3) 100mg PVP and 500mg citric acid are successively dissolved in 24mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 15mL step (2), is transferred in oil bath after stirring and evenly mixing, after being warming up to 90 DEG C, by the chlorine platinum of 10mg
Acid, the gold chloride of 7mg and the chlorine palladium acid dissolution of 2.5mg into 5mL deionized water after to be added to reaction system relaying continuation of insurance temperature anti-
Answer 3h.After gained reaction solution is mixed standing 12h with saturated sodium chloride solution, deionized water washing centrifugation 3 times to get uniformly outstanding
The PtAuPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst of supernatant liquid state.
Transmission electron microscope (TEM) figure such as Figure 15 of PtAuPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst manufactured in the present embodiment and
Shown in Figure 16.By Figure 15 and Figure 16 as it can be seen that present invention gained PtAuPd@Ag elctro-catalyst is in uniform core-shell structure copolymer nanocrystal knot
Structure and size is consistent, particle size is about 30~50nm.Gained PtAuPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst is in 0.1M
Electroxidation CV curve graph in KOH+1M glycerite is as shown in figure 17, and sweeping speed is 50mV/s, and wherein Pt/C, Au/C, Pd/C are
Standard catalyst.As seen from Figure 17, present invention gained PtAuPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst compared to Pt/C, Au/C and
The electric current of Pd/C standard catalyst, catalyzing glycerol oxidation significantly improves.
Embodiment 13
(1) 170mg silver nitrate is weighed, dissolution in deionized water, obtains silver nitrate solution, and ammonium hydroxide is then added dropwise and is prepared into
The silver ammino solution for being 10mmol/L to concentration；270mg CTAB is weighed, 9mg glucose is dissolved in above-mentioned silver ammino solution and obtains
The precursor solution that CTAB concentration is 50mmol/L, concentration of glucose is 1mmol/L.
(2) precursor solution obtained by step (1) is transferred in reaction kettle, reacts 8h at 120 DEG C, is cooled to room temperature；
By gained reaction solution by centrifugation after, take supernatant as it is subsequent synthesis PtPd@Ag core-shell structure copolymer nanocrystal Ag seed solution,
For use.
(3) 100mg PVP and 500mg citric acid are successively dissolved in 24mL deionized water；After it is completely dissolved, add
Enter Ag seed solution obtained by 15mL step (2), is transferred in oil bath after stirring and evenly mixing, after being warming up to 90 DEG C, by the chlorine platinum of 13mg
The chlorine palladium acid dissolution of acid and 8.8mg into 5mL deionized water after be added to the reaction system and relay continuous insulation reaction 3h.Gained is anti-
After answering liquid to mix standing 12h with saturated sodium chloride solution, deionized water washing centrifugation 3 times to get even suspension liquid status
PtPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst.
Transmission electron microscope (TEM) figure such as Figure 18 and figure of PtPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst manufactured in the present embodiment
Shown in 19.By Figure 18 and Figure 19 as it can be seen that the present invention gained PtPd@Ag elctro-catalyst be in uniform core-shell structure copolymer nanocrystalline structure and
Size is consistent, and particle size is about 10nm.Gained PtPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst is in 0.1M KOH+1M glycerol
Electroxidation CV curve graph in solution is as shown in figure 20, and sweeping speed is 50mV/s, and wherein Pt/C, Pd/C are standard catalyst.By scheming
20 as it can be seen that present invention gained PtPd@Ag core-shell structure copolymer nanocrystal elctro-catalyst compares Pt/C and Pd/C standard catalyst, catalysis
The electric current of glycerol oxidation significantly improves.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst, it is characterised in that including following preparation step:
(1) compound concentration is the silver ammino solution of 5~20mmol/L, then sequentially adds CTAB and glucose is uniformly dissolved before obtaining
Drive liquid solution；
(2) precursor solution obtained by step (1) is reacted at 80~180 DEG C, is cooled to room temperature after the reaction was completed, gained is anti-
Supernatant is taken after answering liquid to be centrifuged, obtains Ag seed solution；
(3) PVP and citric acid are dissolved in water, Ag seed solution obtained by step (2) is then added, is warming up to after stirring and evenly mixing
60~120 DEG C, 2~8h of soluble compound insulation reaction of M is added；Gained reaction solution is washed, centrifugation is to get M@Ag
Core-shell structure copolymer nanocrystal elctro-catalyst；The M is the mixing of one or more of Au, Pd and Pt.
2. a kind of preparation method of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst according to claim 1, it is characterised in that:
The concentration of CTAB is 20~100mmol/L in precursor solution obtained by step (1), and the concentration of glucose is 1~10mmol/L.
3. a kind of preparation method of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst according to claim 1, it is characterised in that:
The time of reaction described in step (2) is 3~10h.
4. a kind of preparation method of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst according to claim 1, it is characterised in that step
Suddenly the concentration that PVP described in (3) and citric acid are dissolved in water are as follows: 3~6mg/mL of PVP, 4~25mg/mL of citric acid.
5. a kind of preparation method of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst according to claim 1, it is characterised in that:
The soluble compound of M described in step (3) refer in chloroplatinic acid, gold chloride and chlorine palladium acid any one or it is two or more
Mixing.
6. a kind of preparation method of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst according to claim 1, it is characterised in that:
The soluble compound of M described in step (3) is added with the aqueous solution that concentration is 5~20mmol/L.
7. a kind of preparation method of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst according to claim 1, it is characterised in that:
Washing refers to described in step (3) is washed with saturated sodium chloride solution and deionized water.
8. a kind of M@Ag core-shell structure copolymer nanocrystal elctro-catalyst, it is characterised in that: pass through the described in any item sides of claim 1~7
Method is prepared.
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| CN201810628507X | 2018-06-19 | ||
| CN2018106284768 | 2018-06-19 | ||
| CN2018106290241 | 2018-06-19 | ||
| CN201810629621.4A CN108940275A (en) | 2018-06-19 | 2018-06-19 | A kind of Pt@Ag core-shell structure copolymer nanocrystal elctro-catalyst and preparation method thereof |
| CN2018106296248 | 2018-06-19 | ||
| CN201810629024.1A CN108786796A (en) | 2018-06-19 | 2018-06-19 | A kind of PtAuPd@Ag core-shell structure copolymer nanocrystal elctro-catalysts and preparation method thereof |
| CN201810629624.8A CN108786797A (en) | 2018-06-19 | 2018-06-19 | A kind of PtAu@Ag core-shell structure copolymer nanocrystal elctro-catalysts and preparation method thereof |
| CN201810629062.7A CN108842166A (en) | 2018-06-19 | 2018-06-19 | A kind of Pd@Ag core-shell structure copolymer nanocrystal elctro-catalyst and preparation method thereof |
| CN201810628500.8A CN108723387A (en) | 2018-06-19 | 2018-06-19 | A kind of PdAu@Ag core-shell structure copolymer nanocrystal elctro-catalysts and preparation method thereof |
| CN201810628507.XA CN108907223A (en) | 2018-06-19 | 2018-06-19 | A kind of Au@Ag core-shell structure copolymer nanocrystal elctro-catalyst and preparation method thereof |
| CN2018106285008 | 2018-06-19 | ||
| CN2018106296214 | 2018-06-19 | ||
| CN2018106290627 | 2018-06-19 | ||
| CN201810628476.8A CN108745353A (en) | 2018-06-19 | 2018-06-19 | A kind of PtPd@Ag core-shell structure copolymer nanocrystal elctro-catalysts and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113036168A (en) * | 2021-03-04 | 2021-06-25 | 合肥工业大学 | Cubic PtPd @ Pt core-shell nano cage electrocatalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101263A (en) * | 2007-07-20 | 2008-01-09 | 苏州大学 | Core-shell nano granule with high activity surface intensified raman spectrum and preparation method thereof |
| CN105771979A (en) * | 2016-03-22 | 2016-07-20 | 安徽师范大学 | Platinum/silver alloy nano-particle catalyst, method for preparing same and application of platinum/silver alloy nano-particle catalyst |
| CN107983951A (en) * | 2018-01-08 | 2018-05-04 | 合肥学院 | A kind of preparation method of raspberry shape gold nanoparticle |
-
2018
- 2018-12-10 CN CN201811503037.0A patent/CN109529824B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101101263A (en) * | 2007-07-20 | 2008-01-09 | 苏州大学 | Core-shell nano granule with high activity surface intensified raman spectrum and preparation method thereof |
| CN105771979A (en) * | 2016-03-22 | 2016-07-20 | 安徽师范大学 | Platinum/silver alloy nano-particle catalyst, method for preparing same and application of platinum/silver alloy nano-particle catalyst |
| CN107983951A (en) * | 2018-01-08 | 2018-05-04 | 合肥学院 | A kind of preparation method of raspberry shape gold nanoparticle |
Non-Patent Citations (4)
| Title |
|---|
| MAJIONG JIANG, ET AL: "Epitaxial overgrowth of platinum on palladium nanocrystals", 《NANOSCALE》 * |
| SIVA KUMAR-KRISHNAN，E T AL: "A general seed-mediated approach to the synthesis of AgM (M =Au, Pt, and Pd) core–shell nanoplates and their SERS properties", 《RSC ADVANCES》 * |
| YONGFANG ZHOU,ET AL: "Selective electro-oxidation of glycerol over Pd and Pt@Pd nanocubes", 《ELECTROCHEMISTRY COMMUNICATIONS》 * |
| YUN-MIN CHANG, ET AL: "High-yield water-based synthesis of truncated silver nanocubes", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113036168A (en) * | 2021-03-04 | 2021-06-25 | 合肥工业大学 | Cubic PtPd @ Pt core-shell nano cage electrocatalyst and preparation method and application thereof |
| CN113036168B (en) * | 2021-03-04 | 2022-07-05 | 合肥工业大学 | Cubic PtPd @ Pt core-shell nano cage electrocatalyst and preparation method and application thereof |
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