CN107195917A - A kind of AuPdNWs superfine nano forest elctro-catalysts of the vertical-growth on FTO glass and preparation method thereof - Google Patents
A kind of AuPdNWs superfine nano forest elctro-catalysts of the vertical-growth on FTO glass and preparation method thereof Download PDFInfo
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- CN107195917A CN107195917A CN201710407012.XA CN201710407012A CN107195917A CN 107195917 A CN107195917 A CN 107195917A CN 201710407012 A CN201710407012 A CN 201710407012A CN 107195917 A CN107195917 A CN 107195917A
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- 239000011521 glass Substances 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 241000549556 Nanos Species 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052731 fluorine Inorganic materials 0.000 claims abstract 2
- 239000011737 fluorine Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 68
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 230000003647 oxidation Effects 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 16
- 230000004048 modification Effects 0.000 claims description 15
- 238000012986 modification Methods 0.000 claims description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- 239000010931 gold Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 238000007654 immersion Methods 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 229920000557 Nafion® Polymers 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical class OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 5
- 230000010718 Oxidation Activity Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000012360 testing method Methods 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 230000012447 hatching Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- XHSSRBLTUVPKQU-UHFFFAOYSA-N 4-sulfanylbutanimidamide Chemical compound NC(=N)CCCS XHSSRBLTUVPKQU-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 10
- 230000012010 growth Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000005275 alloying Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract description 3
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 239000002070 nanowire Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 235000011083 sodium citrates Nutrition 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 229910003603 H2PdCl4 Inorganic materials 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- DDYSHSNGZNCTKB-UHFFFAOYSA-N gold(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Au+3].[Au+3] DDYSHSNGZNCTKB-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000007773 growth pattern Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
-
- 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
-
- B01J35/33—
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- B01J35/393—
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- B01J35/396—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8846—Impregnation
- H01M4/885—Impregnation followed by reduction of the catalyst salt precursor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/00—Electrodes
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- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
- H01M8/1013—Other direct alcohol fuel cells [DAFC]
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Abstract
The invention discloses a kind of AuPdNWs superfine nano forest elctro-catalysts of vertical-growth on FTO glass, it is characterized in that, the AuPdNWs superfine nanos forest is that based on seed solution method vertical-growth in conductive substrates, wherein conductive substrates are the SnO of fluorine doped2Substrate（FTO glass）, AuPdNWs grows along the direction vertical with substrate, and diameter can reach 10 nm.The invention has the advantages that：The AuPdNWs superfine nanos forest of the vertical and FTO glass growth synthesized using this method is reacted under normal temperature and middle temperature, it is low with cost, favorable reproducibility, preparation technology is simple, the characteristics of experimental period is short, and with unique array sequence nanoforest structure, alloying makes it have excellent catalytic performance.Had a good application prospect in electrochemistry and fuel cell association area.
Description
Technical field
The present invention relates to a kind of preparation side of the vertical-growth AuPdNWs superfine nanos forest elctro-catalyst on FTO glass
Method, belongs to field of fuel cell technology.More particularly to the synthesis and the electro-catalysis application in oxidation of alcohols of nano material.
Compared to traditional fuel or generation technology, fuel cell has higher fuel conversion factor and electrical efficiency.With it
He compares fuel, and liquid fuel such as methanol, ethanol have the advantages such as volume energy density is high, be easily handled, also with mithridatism
With reproducible characteristic, therefore direct alcohol fuel battery (DAFCs) tremendous expansion is brought.DAFCs rely on fuel (methanol or
Ethanol) anode and oxidant negative electrode reaction.No matter negative electrode or anode, be required for efficient catalyst to reduce
Overpotential in electrocatalytic reaction.Nowadays, Pt is generally acknowledged best anode catalyst, but its utilization rate is still limited by it
Cost.Compared with Pt, Pd rich reserves, and there is good catalytic activity for oxidation of ethanol, therefore replace Pt with Pd
Had great application prospect as elctro-catalyst.
In order to further improve Pd to oxidation of ethanol performance so as to reach Pt level, alloying mode can improve Pd electricity
Catalytically active surface keeps preferable electrode conductivuty and mass transfer performance again while product.Pd base catalyst is loaded on one
On dimension nanometer construction or load to above the carrier of high aspect ratio, such as：On CNT, graphene and activated carbon.But
These methods all can only be trickle improvement Pd to the catalytic performance of oxidation of ethanol.Accordingly, it would be desirable to improved in itself from nano material,
The present invention is prepared for a kind of AuPdNWs superfine nano forest electro-catalysis of vertical-growth on FTO glass using seed solution method
Agent, this method makes it have the synergy in terms of catalytic activity.In addition, the nanoforest of vertical-growth can promote material
Diffusion, increases its electron transfer rate, and the unique growth pattern of this nanoforest can be by expanding FTO transparency areas
To reach the effect of fully lifting electrode surface area, so as to provide new side for the development of electro-catalysis field and portable equipment
To.
The content of the invention
Primary and foremost purpose of the present invention is that providing one kind vertical-growth AuPdNWs superfine nanos forest electricity on FTO glass urges
Agent its preparation method.
Another object of the present invention is to provide above-mentioned the answering in electro-catalysis field in AuPdNWs superfine nanos forest
With.
For achieving the above object, technical scheme is as follows：
A kind of preparation method that vertical-growth AuPdNWs superfine nano forests receive on FTO glass, comprises the following steps：
（1）Aqueous solution of chloraurate, sodium citrate solution, sodium borohydride solution are sequentially added into deionized water, it is stirring while adding,
Synthesize solution of gold nanoparticles（Au NSs）.Gold chloride concentration is the mg/mL of 10 mg/mL ~ 17, sodium citrate in mixed solution
Mass fraction is the wt% of 1 wt% ~ 10, and sodium borohydride concentration is the mg/mL of 2 mg/mL ~ 5.
（2）FTO glass is immersed into APTES（3- aminopropyl triethoxysilanes）Taken after being soaked 10 ~ 30 minutes in solution
Go out, FTO glass is cleaned with deionized water 3 ~ 6 times, then FTO glass is immersed（1）In golden nanometer particle（Au NSs）Solution
In, soak 1 ~ 2 hour, i.e., by golden nanometer particle modification in FTO glass surfaces.
（3）Will（2）In golden nanometer particle modification FTO glass immersion deionized water in clean 2 ~ 3 times, then immerse growth
Soaked 10 ~ 30 minutes in liquid, wherein growth-promoting media is by gold chloride, 4-MBA（4- mercaptobenzoic acids）、AA（Ascorbic acid）According to
Mol ratio is 5:4:12 mixing, ethanol is mixed as solvent.Finally the FTO glass grown is immersed in second alcohol and water,
Room temperature storage is standby.
（4）Will（3）Product is put in MAA（TGA）Solution in heating hatching 2 ~ 3 hours, heating-up temperature is 60
~ 80 DEG C, wherein MAA solution uses deionized water rinse again afterwards by DMF (DMF) as solvent.
（5）Will（4）Middle product is immersed in Pd growth-promoting medias at room temperature, and wherein Pd growth-promoting medias are cooked solvent, chlorine by deionized water
The aqueous solution of palladium acid, PVP（Polyvinylpyrrolidone）, AA（Ascorbic acid）Mix, wherein chlorine palladium acid concentration be 10 mM ~
40 mM, PVP concentration are the mg/mL of 10 mg/mL ~ 40.AA concentration is the mM of 10 mM ~ 40.Most at last obtained AuPdNWs
Superfine nano forest preserves standby in deionized water.
The AuPdNWs superfine nano forests of the above-mentioned vertical-growth on FTO glass are nucleocapsid structures, favorable dispersibility,
Average-size diameter is in 5 ~ 8 nm.
Above-mentioned AuPdNWs superfine nano forest elctro-catalysts are perpendicular to substrate grown.
Au and Pd atomicities are 1 in above-mentioned AuPdNWs superfine nano forest elctro-catalysts:1.
The AuPdNWs superfine nano forests elctro-catalyst of the above-mentioned vertical-growth on FTO glass is applied to oxidation of alcohols etc.
Electro-catalysis association area.
A kind of test side of AuPdNWs superfine nano forest electro-catalysis of the vertical-growth on FTO glass to oxidation of ethanol
Method, its feature comprises the following steps：
（1）The AuPdNWs superfine nanos forest grown in FTO is directly added dropwise 5 μ L's as working electrode toward electrode surface
Nafion（5 wt %）, dry naturally at room temperature, saturated calomel electrode is as reference electrode, and Pt electrodes are as to electrode, group
Into three-electrode system.
（2）It is gloomy using cyclic voltammetry test AuPdNWs superfine nanos of vertical-growth on FTO glass under alkalescence condition
The alcohol oxidation activity of woods, electrolyte solution is 1M NaOH+1M C2H5OH, in N2CV curves, sweep speed are tested under atmosphere
For 50 mV/s, scanning range is in the V of 0 V ~ 1.4（vs RHE）.
（3）It is gloomy using cyclic voltammetry test AuPdNWs superfine nanos of vertical-growth on FTO glass under acid condition
The alcohol oxidation activity of woods, electrolyte solution is 0.5 M H2SO4 + 1M C2H5OH, in N2CV curves, scanning are tested under atmosphere
Speed is 50 mV/s.Scanning range is in the V of 0 V ~ 1.2（vs RHE）.
Compared with prior art, the invention has the advantages that：
The AuPdNWs superfine nanos forest of the vertical and FTO glass growth synthesized using this method is anti-under normal temperature and middle temperature
Should, favorable reproducibility low with cost, preparation technology is simple, the characteristics of experimental period is short, and is received with unique array sequence
Rice forest structure, alloying makes it have excellent catalytic performance.Have well in electrochemistry and fuel cell association area
Application prospect.
Brief description of the drawings：
It is from left to right FTO glass respectively that Fig. 1, which is, grow the FTO glass for having AuNWs superfine nano forests, growth AuPdNWs
The FTO glass of superfine nano forest.
Fig. 2 is the scanning electron microscope diagram of AuNWs superfine nano forests.
Fig. 3 is the scanning electron microscope diagram of AuPdNWs superfine nano forests.
Fig. 4 is the transmission electron microscope figure for the AuNWs superfine nanowires peeled off from substrate FTO glass.
Fig. 5 is the transmission electron microscope figure for the AuPdNWs superfine nanowires peeled off from substrate FTO glass.
Fig. 6 is AuPdNWs superfine nanos forest, Pd/C, the AuPdNWs superfine nanowires peeled off from substrate FTO glass
CV curves（Alkalescence condition）.
Fig. 7 is AuPdNWs superfine nanos forest, the chronoa mperometric plot of Pd/C electrodes.
Fig. 8 is AuPdNWs superfine nanos forest, Pd/C, the AuPdNWs superfine nanowires peeled off from substrate FTO glass
CV curves（Acid condition）.
Embodiment
The present invention is expanded on further below by embodiment, but the implementation of the present invention is not limited to this.
Embodiment 1
（1）100 μ L aqueous solution of chloraurate are sequentially added into 20 mL deionized waters（17 mg/mL）, 160 μ L sodium citrates it is molten
Liquid（1 wt%）, 620 μ L sodium borohydride solutions（5 mg/mL）, it is stirring while adding, form solution of gold nanoparticles（AuNSs）.
（2）By FTO glass（2 cm2）Immerse APTES（3- aminopropyl triethoxysilanes, 1 μ L/mL, ethanol：Water=1:
1）Taken out after being soaked 15 minutes in solution, FTO glass is cleaned with deionized water 5 times, then FTO glass is immersed（1）In Jenner
Rice corpuscles solution（AuNSs）In solution, soak 1 hour, i.e., by golden nanometer particle modification in FTO glass surfaces.
（3）Will（2）In golden nanometer particle modification FTO glass immersion deionized water in clean 2 times, then immerse growth-promoting media
Middle immersion 10 minutes, wherein growth-promoting media is by 150 μ L chlorauric acid solutions（17 mg/mL）, 600 μ L concentration be 10 mM 4-
MBA（4- mercaptobenzoic acids）, 900 μ L concentration be 20 mM AA（Ascorbic acid）It is 5 according to mol ratio:4:12 mixing, 2.1
ML ethanol is mixed as solvent.Finally the FTO glass grown is immersed in second alcohol and water, room temperature storage is standby, finally
The FTO glass electro catalytic electrodes of AuNWs superfine nanos forest modification are made.
Fig. 2 is the scanning electron microscopy of the AuNWs superfine nano forests of vertical-growth on FTO glass prepared by this example
Figure, it is seen that nanoforest grows along the direction vertical with substrate FTO glass, dense and evenly distributed, length can reach μm
Rank.
Fig. 4 is the transmission electron microscope of the AuNWs superfine nanowires peeled off from substrate FTO glass prepared by embodiment 1
Figure.Diameter is in 3 ~ 5 nm.
Embodiment 2
（1）100 μ L aqueous solution of chloraurate are sequentially added into 20 mL deionized waters（10 mg/mL）, 160 μ L sodium citrates it is molten
Liquid（1wt%）, 620 μ L sodium borohydride solutions（3.8 mg/mL）, it is stirring while adding, form solution of gold nanoparticles（AuNSs）.
（2）By FTO glass（2 cm2）Immerse APTES（3- aminopropyl triethoxysilanes, 1 μ L/mL, ethanol：Water=1:
1）Taken out after being soaked 15 minutes in solution, FTO glass is cleaned with deionized water 5 times, then FTO glass is immersed（1）In Jenner
Rice corpuscles solution（AuNSs）In solution, soak 1 hour, i.e., by golden nanometer particle modification in FTO glass surfaces.
（3）Will（2）In golden nanometer particle modification FTO glass immersion deionized water in clean 2 times, then immerse growth-promoting media
Middle immersion 30 minutes, wherein growth-promoting media is by 150 μ L chlorauric acid solutions（17 mg/mL）, 600 μ L concentration be 10 mM 4-
MBA（4- mercaptobenzoic acids）, 900 μ L concentration be 20 mM AA（Ascorbic acid）It is 5 according to mol ratio:4:12 mixing, 2.1
ML ethanol is mixed as solvent.Finally the FTO glass grown is immersed in second alcohol and water, room temperature storage is standby.
（4）Will（3）Product is put in 1 μ L/mL MAA（TGA）Hatch 2 hours in 70 DEG C of heating in solution, its
Middle MAA solution as solvent, uses deionized water rinse again afterwards by DMF (DMF).
（5）Will（4）In middle product immersion Pd growth-promoting medias, Pd growth-promoting medias by 200 μ L H2PdCl4（20 mM, H2O）、40 µ
L PVP（20 mg/mL, H2O）, 400 μ L AA（10 mM, H2O）And 2 mL deionized waters as solvent, finally obtain
The FTO glass of AuPdNWs superfine nanos forest modification is immersed in standby in deionized water.
（6）Directly using the AuPdNWs superfine nano forests grown in FTO as working electrode, 5 μ are added dropwise toward electrode surface
L Nafion（5 wt%）, natural air drying electrode at room temperature, saturated calomel electrode is as reference electrode, and Pt electrodes are as to electricity
Pole, constitutes three-electrode system.The AuPdNWs superfine nanos line electrode and Pt/C electrodes for departing from FTO glass are prepared, with ethanol and going
Ionized water 1:1 is well mixed, and 5 μ L Nafion is added dropwise（5 wt%）, then glassy carbon electrode surface is coated in, it is stand-by after drying up naturally.
Wherein Pd is 17.6 μ g/cm in the load capacity of AuPdNWs superfine nanowires and Pd/C electrodes2, the surface area of working electrode
It is 0.28 cm2, by 1M NaOH+ 1M C2H5OH solution is used as electrolyte solution.
Fig. 1 is from left to right FTO glass, the FTO glass of AuNWs superfine nanos forest modification successively, and AuPdNWs is ultra-fine to be received
The FTO glass pictorial diagrams of meter Sen Lin modifications.
Fig. 3 is the scanning of vertical-growth AuPdNWs superfine nanos forest elctro-catalyst on FTO glass prepared by this example
Electron micrograph, it is seen that nanoforest grows along the direction vertical with FTO glass, dense and evenly distributed,
Fig. 5 is the transmission electron microscope figure of the AuPdNWs superfine nanowires peeled off from substrate FTO glass prepared by this example.
Diameter is in 5 ~ 8 nm.
This example evaluates the vertical nanowires forest elctro-catalyst with cyclic voltammetry in the basic conditions to oxidation of ethanol
Electro catalytic activity, sweep speed is 50 mV/s.As Fig. 6 be the AuPdNWs superfine nanos forest that is grown on FTO glass and
Depart from the AuPdNWs superfine nanowires of FTO substrates and the CV curves of Pd/C electrodes.It can be seen that oxidation of ethanol peak exists
1.0V（vs. RHE）, wherein the AuPdNWs superfine nano forest oxidations of ethanol peak mass ratio of vertical-growth is electric on FTO glass
Current density is 2237.7 A/g, and the oxidation of ethanol peak quality of Pd/C electrodes is 172.6 A/g than current density, and the former is the latter
12.9 times, and the AuPdNWs superfine nanowires on FTO surfaces are peeled off as working electrode, the oxidation peak mass ratio of its oxidation of ethanol
Current density is 7.8 times of Pd/C, illustrates the AuPdNWs superfine nanos forest of particular vertical growth because its unique morphology has
More preferable oxidation of ethanol electro catalytic activity, Fig. 7 is AuPdNWs superfine nanos forest and Pd/C electrodes in 0.87 V（vs. RHE）
Chronoamperometry curve.
Embodiment 3
（1）100 μ L aqueous solution of chloraurate are sequentially added into 20 mL deionized waters（14 mg/mL）, 160 μ L sodium citrates it is molten
Liquid（10wt%）, 620 μ L sodium borohydride solutions（2 mg/mL）, it is stirring while adding, form solution of gold nanoparticles（AuNSs）.
（2）By FTO glass（2 cm2）Immerse APTES（3- aminopropyl triethoxysilanes, 1 μ L/mL, ethanol：Water=1:
1）Taken out after being soaked 15 minutes in solution, FTO glass is cleaned with deionized water 5 times, then FTO glass is immersed（1）In Jenner
Rice corpuscles solution（AuNSs）In solution, soak 1 hour, i.e., by golden nanometer particle modification in FTO glass surfaces.
（3）Will（2）In golden nanometer particle modification FTO glass immersion deionized water in clean 2 times, then immerse growth-promoting media
Middle immersion 15 minutes, wherein growth-promoting media is by 150 μ L chlorauric acid solutions（17 mg/mL）, 600 μ L concentration be 10 mM 4-
MBA（4- mercaptobenzoic acids）, 900 μ L concentration be 20 mM AA（Ascorbic acid）It is 5 according to mol ratio:4:12 mixing, 2.1
ML ethanol is mixed as solvent.Finally the FTO glass grown is immersed in second alcohol and water, room temperature storage is standby.
（4）Will（3）Product is put in 1 μ L/mL MAA（TGA）Solution in 80 DEG C heating hatching 2 hours, its
Middle MAA solution as solvent, uses deionized water rinse again afterwards by DMF (DMF).At room temperature will afterwards
Modification AuNWs superfine nano forests FTO glass be put in Pd growth-promoting medias, Pd growth-promoting medias by 200 μ L H2PdCl4（20 mM,
H2O）, 40 μ L PVP（20 mg/mL, H2O）, 400 μ L AA（10 mM, H2O）And 2 mL deionized waters as solvent, most
The FTO glass that AuPdNWs superfine nanos forest is modified afterwards is immersed in standby in deionized water.（5）It will directly grow in FTO
5 μ L Nafion is added dropwise toward electrode surface as working electrode for AuPdNWs superfine nanos forest（5 wt%）, it is natural at room temperature
Electrode is air-dried, saturated calomel electrode constitutes three-electrode system as reference electrode, Pt electrodes as to electrode.Prepare from FTO
AuPdNWs superfine nanowires working electrode and Pd/C electrodes that glass is peeled off, with ethanol and deionized water 1:1 is well mixed, drop
Plus 5 μ L Nafion（5 wt%）, then glassy carbon electrode surface is coated in, it is stand-by after drying up naturally.Wherein Pd receives AuPdNWs is ultra-fine
The load capacity of rice noodles and Pd/C electrodes is all 17.6 μ g/cm2, the surface area of working electrode is 0.28cm2, by 0.5 M
H2SO4 + 1M C2H5OH solution is used as electrolyte solution.
This example evaluates the vertical nanowires forest elctro-catalyst with cyclic voltammetry in acid condition to oxidation of ethanol
Electro catalytic activity, sweep speed is 50 mV/s.As Fig. 8 be the AuPdNWs superfine nanos forest that is grown on FTO glass and
The AuPdNWs superfine nanowires and the CV curves of commercialization Pd/C electrodes peeled off from FTO glass.According to ECSA=QH/0.45*
[Au], ECSA=QPdO/ 0.405* [Pd], wherein Au2O3Reduction peak is in 1.15V（vs.RHE）Left and right, PdO reduction peaks are 0.70
（vs.RHE）Left and right.[Au] and [Pd] is the load capacity of Au and Pd in electrode surface, can calculate and obtain：Vertical-growth
AuPdNWs superfine nanos forest, the AuPdNWs superfine nanowires peeled off from FTO glass, Pd/C electrochemical surface area difference
For 110.1 m2/g、81.8 m2/g、43.3 m2/g.Illustrate the AuPdNWs superfine nano forests of particular vertical growth in acidity
Under the conditions of also have preferable oxidation of ethanol electro catalytic activity.
Above-described embodiment is ratio preferably embodiment, but embodiments of the present invention are not restricted to above-mentioned implementation of the invention
Example, others on the basis of the principle of the invention change, modify, substitute and combination etc. mode within the scope of the present invention.
Claims (8)
1. the AuPdNWs superfine nano forest elctro-catalysts of a kind of vertical-growth on FTO glass, it is characterised in that described
AuPdNWs superfine nano forests are that wherein conductive substrates are fluorine dopeds based on seed solution method vertical-growth in conductive substrates
SnO2Substrate（FTO glass）, AuPdNWs grows along the direction vertical with substrate, and diameter can reach 10 nm.
2. a kind of AuPdNWs elctro-catalysts of vertical-growth according to claim 1, it is characterised in that its synthetic method
It is seed solution method, its specific synthesis step is as follows：
（1）The aqueous solution, sodium citrate solution, sodium borohydride solution of gold chloride are sequentially added into deionized water, side edged is stirred
Mix, synthesize solution of gold nanoparticles（Au NSs）, gold chloride concentration is the mg/mL of 10 mg/mL ~ 17, lemon in mixed solution
Sour sodium mass fraction is the wt% of 1 wt% ~ 10, and sodium borohydride concentration is the mg/Ml of 2 mg/mL ~ 5；
（2）FTO glass is immersed into APTES（3- aminopropyl triethoxysilanes）Take out, use after being soaked 10 ~ 30 minutes in solution
Deionized water cleaning FTO glass 3 ~ 6 times, then FTO glass is immersed（1）In golden nanometer particle（Au NSs）In solution, leaching
Bubble 1 ~ 2 hour, i.e., by golden nanometer particle modification in FTO glass surfaces；
（3）Will（2）In golden nanometer particle modification FTO glass immersion deionized water in clean 2 ~ 3 times, then immerse in growth-promoting media
Immersion 10 ~ 30 minutes, wherein growth-promoting media is by gold chloride, 4-MBA（4- mercaptobenzoic acids）、AA（Ascorbic acid）According to mole
Than for 5:4:12 mixing, ethanol is mixed as solvent.
3. last immerse the FTO glass grown in second alcohol and water, room temperature storage is standby；
（4）Will（3）Product is put in MAA（TGA）Solution in heating hatching 2 ~ 3 hours, heating-up temperature be 60 ~ 80 DEG C,
Wherein MAA solution is cleaned with deionized water again afterwards by DMF (DMF) as solvent；
（5）Will（4）Middle product is in room immersion Pd growth-promoting medias, and wherein Pd growth-promoting medias are cooked solvent, the water of chlorine palladium acid by deionized water
Solution, PVP（Polyvinylpyrrolidone）、AA（Ascorbic acid）Mix, be most made what is grown on FTO glass at last
AuPdNWs preserves standby in deionized water.
4. a kind of AuPdNWs superfine nano forest elctro-catalysts of vertical-growth on FTO glass according to claim 2
Apply in oxidation of ethanol catalytic field.
5. a kind of AuPdNWs superfine nano forest electro-catalysis of the vertical-growth on FTO glass is to the method for testing of oxidation of ethanol,
Its feature comprises the following steps：
（1）The AuPdNWs superfine nanos forest grown in FTO is directly added dropwise 5 μ L's as working electrode toward electrode surface
Nafion（5 wt %）, dry naturally at room temperature, saturated calomel electrode is as reference electrode, and Pt electrodes are as to electrode, group
Into three-electrode system.
6.（2）The AuPdNWs superfine nano forests of the vertical-growth on FTO glass are tested under alkalescence condition using cyclic voltammetry
Alcohol oxidation activity, electrolyte solution be 1M NaOH+1M C2H5OH, in N2CV curves are tested under atmosphere, sweep speed is
50 mV/s, scanning range is in the V of 0 V ~ 1.4（vs RHE）.
7.（3）The AuPdNWs superfine nano forests of the vertical-growth on FTO glass are tested under acid condition using cyclic voltammetry
Alcohol oxidation activity, electrolyte solution be 0.5 M H2SO4 + 1M C2H5OH, in N2CV curves, scanning speed are tested under atmosphere
Rate is 50 mV/s.
8. scanning range is in the V of 0 V ~ 1.2（vs RHE）.
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| CN107863538A (en) * | 2017-11-03 | 2018-03-30 | 大连大学 | A kind of electrode and its application for alcohol catalysis |
| CN111370716A (en) * | 2019-08-14 | 2020-07-03 | 南京工业大学 | Superfine three-dimensional platinum nanowire array growing on substrate under control of strong ligand and method thereof |
| CN112705724A (en) * | 2020-12-07 | 2021-04-27 | 南京工业大学 | Adjustable gold nanostructure and preparation method and application thereof |
| US11591701B2 (en) | 2019-05-21 | 2023-02-28 | King Fahd University Of Petroleum And Minerals | Pd-comprising electrocatalysts suitable for water splitting |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107863538A (en) * | 2017-11-03 | 2018-03-30 | 大连大学 | A kind of electrode and its application for alcohol catalysis |
| CN107863538B (en) * | 2017-11-03 | 2020-09-04 | 大连大学 | Electrode for ethanol catalysis and application thereof |
| US11591701B2 (en) | 2019-05-21 | 2023-02-28 | King Fahd University Of Petroleum And Minerals | Pd-comprising electrocatalysts suitable for water splitting |
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| CN111370716A (en) * | 2019-08-14 | 2020-07-03 | 南京工业大学 | Superfine three-dimensional platinum nanowire array growing on substrate under control of strong ligand and method thereof |
| CN111370716B (en) * | 2019-08-14 | 2022-07-05 | 南京工业大学 | Superfine three-dimensional platinum nanowire array growing on substrate under control of strong ligand and method thereof |
| CN112705724A (en) * | 2020-12-07 | 2021-04-27 | 南京工业大学 | Adjustable gold nanostructure and preparation method and application thereof |
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