CN102407106B - Preparation method of tubular metal catalyst - Google Patents
Preparation method of tubular metal catalyst Download PDFInfo
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- CN102407106B CN102407106B CN201110314753.6A CN201110314753A CN102407106B CN 102407106 B CN102407106 B CN 102407106B CN 201110314753 A CN201110314753 A CN 201110314753A CN 102407106 B CN102407106 B CN 102407106B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 110
- 239000002184 metal Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000011259 mixed solution Substances 0.000 claims abstract description 43
- 238000004070 electrodeposition Methods 0.000 claims abstract description 38
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 10
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 28
- 239000010931 gold Substances 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 229910052737 gold Inorganic materials 0.000 claims description 19
- 238000009415 formwork Methods 0.000 claims description 16
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 14
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 13
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 13
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 239000002245 particle Substances 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000003880 polar aprotic solvent Substances 0.000 abstract 1
- 101150003085 Pdcl gene Proteins 0.000 description 21
- 230000005540 biological transmission Effects 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 11
- 230000005518 electrochemistry Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 10
- 239000000446 fuel Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000003115 supporting electrolyte Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 239000003863 metallic catalyst Substances 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229940126680 traditional chinese medicines Drugs 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 229910001961 silver nitrate Inorganic materials 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 230000005622 photoelectricity Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention discloses a preparation method of tubular metal catalyst comprising dissolving metal salt and sodium nitrate in dimethyl sulfoxide to obtain mixed solution; taking aluminum oxide porous template with nano path as template, conducting electrochemical deposition of the mixed solution at the nano path, and removing the template to obtain the tubular metal catalyst. The invention takes polar aprotic solvent dimethyl sulfoxide (DMSO) as solvent and electrolyte, since DMSO contains S group with weak absorption effect to metal surface, when metal is reduced to particles, DMSO moleculeswill absorb on the particle surface to inhibit the particle from growing large to make the prepared tubular metal catalyst wall thin and to increase the activated area. Furthermore, DMSO with relatively wide electrochemical window, high dielectric constant and high viscosity can ensure the prepared tubular metal catalyst wall is thin and made of particles, the length diameter ratio is high and the wall is uniform.
Description
Technical field
The present invention relates to catalyst technical field, more particularly, relate to a kind of preparation method of tubular metal catalyst.
Background technology
Along with the growth of world population, the restriction of the human electric power supply ability that usually is subject to supporting that it is movable.Fuel cell can be electric energy with chemical raw material such as hydrogen and oxygen conversion, thereby for guaranteeing that electric power supply provides a kind of solution route, namely, fuel cell is that chemical energy is converted into electric energy, under the effect of metallic catalyst, take hydrogen etc. as fuel, air (oxygen) produces electric energy and a small amount of heat energy as oxidant.And it is water that fuel cell produces the product that discharges behind the electric energy, meets environmental requirement, has solved the intrinsic pollution problem of burning process.Therefore, fuel cell can be widely used in the vehicle power for traction can supply, family and industrial electric energy supply and boats and ships are with fields such as electric power supplies.
At present, the tubular metal catalyst that is used for fuel cell has obtained widely research, and wherein, sacrificing template is the common method of synthetic tubulose metallic catalyst.Germany " applied chemistry " (Angewandte Chemie International Edition, 4060 pages of 46 phases in 2007) reported and passed through the synthetic platinum of galvanic cell substitution reaction and platinum palladium tube shape self-supporting catalyst material take the Ag line as template, this structure can effectively prevent because the platinum that the corrosion of carbon support material causes runs off, stop watt slaking of Pt nanoparticle oersted, the catalyst degradation problem that reduction Pt nanoparticle gathering etc. causes; U.S.'s " JACS " (Journal of the American Chemical Society, 2003 125 phases 13364 pages) has reported that employing Se line is the synthetic platinotron catalyst of template; Germany's " advanced function material " (Advanced Materials, 2009 21 phases 1850 pages) has reported that employing Te line is reducing agent and sacrifices the synthetic platinum nano tube catalyst of template.But all there is following problem in the method for above-mentioned report, namely consume the metal material that comparatively active forerunner's template Ag, Se and Te etc. have certain toxicity, and the method is more complicated wayward.
The template electrochemical method is another important method of synthetic tubulose metallic catalyst, for example, Germany " advanced function material " (Advanced Materials, 1550 pages of 16 phases in 2004) reported that employing multistep template synthesizes the platinum nanotube, but this synthetic method is very complicated, cost is higher, has limited its application." electrochemistry communication " (Electrochemistry Communications, 190 pages of 11 phases in 2009) reported employing Direct Electrochemistry method synthetic platinum nanotube in the aqueous solution, but, because the noble metal standard electrode potential is higher, very easily reduction in the aqueous solution, the tube wall of the platinum nanotube that therefore prepares is thicker, has limited its application in catalyst field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of tubular metal catalyst, and the tubular metal catalyst tube walls of the method preparation is thinner, and active area is larger.
In order to solve above technical problem, the invention provides a kind of preparation method of tubular metal catalyst, comprising:
Step a) is dissolved in the first slaine and sodium nitrate in the dimethyl sulfoxide (DMSO), obtains mixed solution;
Step b) take aluminum oxide porous mould with nanoscale duct as template, described mixed solution is carried out electrochemical deposition at place, described nanoscale duct, obtaining the tubular metal catalyst after removing described template, the operating voltage of described electrochemical deposition is-0.8V～-1.8V.
Preferably, described the first slaine is one or more in the inferior platinum of dichloride, palladium chloride, gold chloride, silver nitrate and the cuprous bromide.
Preferably, the concentration of the first slaine is 10～70mM in the described mixed solution.
Preferably, the concentration of sodium nitrate is 100mM in the described mixed solution.
Preferably, described electrochemical deposition adopts three-electrode system, and auxiliary electrode is platinum electrode, and reference electrode is silver/silver chloride electrode, and working electrode is prepared as follows: described alumina formwork single face is steamed gold.
Preferably, the operating voltage of described electrochemical deposition be-1V～-1.5V.
Preferably, the operating voltage of described electrochemical deposition be-1.2V～-1.5V.
Preferably, the time of electrochemical deposition is 0.1～10h.
Preferably, described step a) is specially:
Step a1) palladium chloride is dissolved in the dimethyl sulfoxide (DMSO), obtains palladium chloride solution;
Step a2) adds gold chloride to described palladium chloride solution, add sodium nitrate after the dissolving, obtain mixed solution.
Preferably, described step a) is specially:
Step a1) successively cuprous bromide and palladium chloride are dissolved in the dimethyl sulfoxide (DMSO), obtain premixed solution;
Step a2) in described the first solution, adds gold chloride, add sodium nitrate after the dissolving, obtain mixed solution.
The invention provides a kind of preparation method of tubular metal catalyst, comprising: the first slaine and sodium nitrate are dissolved in the dimethyl sulfoxide (DMSO), obtain mixed solution; Take aluminum oxide porous mould with nanoscale duct as template, described mixed solution is carried out electrochemical deposition at place, described nanoscale duct, obtain the tubular metal catalyst after removing described template.Compared with prior art, the present invention utilizes polar non-solute dimethyl sulfoxide (DMSO) (DMSO) as solvent and electrolyte, because this DMSO contains the metal surface there is weak adsorbing S group, after metal is reduced the formation granule, the DMSO molecule can be adsorbed in the granule surface, stop it further to grow up, thereby so that the tubular metal catalyst tube walls of preparation is thin and be comprised of less particle, increased active area.
Further, the precondition of the synthetic tubular catalyst of electrochemistry will be higher than the speed that falls in the sense of current (along thickness of pipe direction) far away for the speed of growth that is parallel to the sense of current (along the pipe range direction).Because DMSO has wider electrochemical window, high-k and high viscosity, thereby this wider electrochemical window has guaranteed that electrolyte under lower electrochemistry resultant voltage chemical reaction does not occur, has improved the speed of growth that is parallel to the sense of current; Secondly, high dielectric constant has avoided metal ion to discharge in solution than electronegative potential the time, has guaranteed that metal ion still can be diffused on the electrode to discharge; Again, high viscosity can reduce catalyst in diffusion and the speed of growth perpendicular to the sense of current, is conducive to the formation of tubulose; At last, because that DMSO and complexing of metal ion effect can form is sterically hindered, further reduced the diffusion rate perpendicular to the sense of current.Therefore, the tubular metal catalyst tube walls that the present invention prepares as solvent with DMSO is thinner and be comprised of particle, and draw ratio is high, even tube wall.
Description of drawings
Fig. 1 is the ESEM picture of the tubular metal catalyst of the embodiment of the invention 1 preparation;
Fig. 2 is the transmission electron microscope picture of the tubular metal catalyst of the embodiment of the invention 1 preparation;
Fig. 3 is the transmission electron microscope picture of the tubular metal catalyst of the embodiment of the invention 1 preparation;
Fig. 4 is the transmission electron microscope picture of the tubular metal catalyst of the embodiment of the invention 1 preparation;
Fig. 5 is the transmission electron microscope picture of the tubular metal catalyst of the embodiment of the invention 1 preparation;
Fig. 6 is the ESEM picture of the tubular metal catalyst of the embodiment of the invention 2 preparations;
Fig. 7 is the ESEM picture of the tubular metal catalyst of the embodiment of the invention 3 preparations;
Fig. 8 is the ESEM picture of the tubular metal catalyst of the embodiment of the invention 4 preparations;
Fig. 9 is the ESEM picture of the tubular metal catalyst of the embodiment of the invention 5 preparations;
Figure 10 is the ESEM picture of the tubular metal catalyst of the embodiment of the invention 5 preparations;
Figure 11 is the transmission electron microscope picture of the tubular metal catalyst of the embodiment of the invention 5 preparations;
Figure 12 is the photoelectricity spectrogram of the tubular metal catalyst of the embodiment of the invention 5～8 preparations;
Figure 13 is the ESEM picture of the tubular metal catalyst of the embodiment of the invention 9 preparations;
Figure 14 is the transmission electron microscope picture of the tubular metal catalyst of the embodiment of the invention 9 preparations;
Figure 15 is the ESEM picture of the tubular metal catalyst of the embodiment of the invention 10 preparations;
Figure 16 is the transmission electron microscope picture of the tubular metal catalyst of the embodiment of the invention 10 preparations;
Figure 17 is the ESEM picture of the tubular metal catalyst of the embodiment of the invention 11 preparations;
Figure 18 is the transmission electron microscope picture of the tubular metal catalyst of the embodiment of the invention 11 preparations.
The specific embodiment
The below is clearly and completely described the technical scheme in the embodiment of the invention, and obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that obtains under the creative work prerequisite.
The invention discloses a kind of preparation method of tubular metal catalyst, comprising:
Step is a) with the first slaine and sodium nitrate (NaNO
3) be dissolved in the dimethyl sulfoxide (DMSO) (DMSO), obtain mixed solution;
Step b) take aluminum oxide porous mould with nanoscale duct as template, described mixed solution is carried out electrochemical deposition at place, described nanoscale duct, obtaining the tubular metal catalyst after removing described template, the operating voltage of described electrochemical deposition is-0.8V～-1.8V.
Among the present invention, described the first slaine is preferably platinous chloride (PtCl
2), palladium chloride (PdCl
2), gold chloride (AuCl
3HCl4H
2O), silver nitrate (AgNO
3) and cuprous bromide (CuBr) in one or more.Because method provided by the invention can prepare one pack system tubular metal catalyst and multicomponent tubular metal catalyst, therefore, when preparation one pack system tubular metal catalyst, described the first slaine is preferably precious metal salt, more preferably PtCl
2, PdCl
2, AuCl
3HCl4H
2O or AgNO
3During preparation multicomponent tubular metal catalyst, described the first slaine is preferably PtCl
2, PdCl
2, AuCl
3HCl4H
2O, AgNO
3With several among the CuBr.Wherein, PdCl
2Dissolving method in DMSO is preferably: add PdCl in DMSO
2, leave standstill 0.8～2h after the stirring, preferably leave standstill 1h, do not continue to stir after part becomes white wait dissolving, so repeatedly until fully dissolving.
During preparation multicomponent tubular metal catalyst, the interpolation order of each component has certain impact to the solubility property of component, for example, described step a) can for: step a1) with PdCl
2Be dissolved among the DMSO, obtain PdCl
2Solution; Step a2) to described PdCl
2Solution adds AuCl
3HCl4H
2O adds NaNO after the dissolving
3, obtain mixed solution, this mixed solution is through step b) after can obtain PdAu tubular metal catalyst.Perhaps, described step a) can for: step a1) CuBr is dissolved among the DMSO, obtains CuBr solution; Step a2) adds PdCl to described CuBr solution
2, add NaNO after the dissolving
3, obtain mixed solution, this mixed solution is through step b) after can obtain PdCu tubular metal catalyst.In addition, described step a) can also for: step a1) successively with CuBr and PdCl
2Be dissolved among the DMSO, obtain premixed solution; Step a2) in described the first solution, adds AuCl
3HCl4H
2O adds NaNO after the dissolving
3, obtain mixed solution, this mixed solution is through step b) after can obtain PdAuCu tubular metal catalyst.Simultaneously, NaNO
3Be the supporting electrolyte in this preparation process, be beneficial to the generation of electrochemical reaction.Described step concrete steps a) are not limited only to above-mentioned reactions steps, and at the first slaine that adopts not simultaneously, the interpolation of each component order can suitably be adjusted.
The DMSO that the present invention adopts contains has weak adsorbing S group to the metal surface, after metal is reduced the formation granule, the DMSO molecule can be adsorbed in the granule surface, stop it further to grow up, make the tubular metal catalyst tube walls of preparation thinner and formed by particle, thereby improved active surface area greatly.And after synthetic finishing, the DMSO molecule is very easily removed by water or ethanol again, has guaranteed the catalyst surface cleaning.
Further, the precondition of the synthetic tubular catalyst of electrochemistry will be higher than the speed that falls in the sense of current (along thickness of pipe direction) far away for the speed of growth that is parallel to the sense of current (along the pipe range direction).The present invention utilizes polar non-solute DMSO as solvent and electrolyte, because DMSO has wider electrochemical window, high-k and high viscosity, this wider electrochemical window has guaranteed that electrolyte under lower electrochemistry resultant voltage chemical reaction does not occur, has improved the speed of growth that is parallel to the sense of current; Secondly, high dielectric constant has avoided metal ion to discharge in solution than electronegative potential the time, has guaranteed that metal ion still is diffused into electrode and discharges; Again, high viscosity can reduce catalyst in diffusion and the speed of growth perpendicular to the sense of current, is conducive to the formation of tubular structure; At last, because that DMSO and complexing of metal ion effect can form is sterically hindered, further reduced the diffusion rate perpendicular to the sense of current.Therefore, the present invention is thinner as the tubular metal catalyst tube walls that solvent prepares with DMSO, and active area is larger, even tube wall, and draw ratio is high.
In addition, the component of tubular metal catalyst provided by the invention is adjustable, namely in DMSO solution, it is no longer practical that electrode potential under the aqueous environment will become, reduction potential no longer is subjected to the constraint of electrode potential, the ratio of each composition of the tubular metal catalyst that can prepare by the operating voltage control of regulating electrolyte ratio and electrochemical deposition.
Step a) in, the concentration of the first slaine is preferably 10～70mM in the described mixed solution, more preferably 20～60mM, more preferably 30～50mM; NaNO in the described mixed solution
3Concentration be preferably 80～120mM, more preferably 90～110mM, more preferably 100mM.The concentration of the first slaine in the mixed solution and supporting electrolyte NaNO
3Concentration be two performance indications that impact forms the tubular metal catalyst, concentration is too low can not to synthesize tubular structure, concentration is too high can to increase pipe thickness.In addition, obtain preferably it being left standstill behind the mixed solution and deposit, leave standstill in the process at it, sufficient coordination has occured in the first slaine and DMSO, and time of repose is preferably 6～20h, more preferably 8～15h, more preferably 10～12h.
At step b) in, described electrochemical deposition adopts three-electrode system, auxiliary electrode is platinum electrode, reference electrode is silver/silver chloride electrode, working electrode is the gold-plated alumina formwork of single face, preferably is prepared as follows: described alumina formwork single face is steamed gold, and preferred, this single face steams golden thickness and is preferably 30～50nm, more preferably 40nm; The operating voltage of described electrochemical deposition is-0.8V～-1.8V, be preferably-1V～-1.5V, more preferably-1.2V～-1.5V, the tubular metal catalyst tube walls of being synthesized during greater than-1.0V when operating voltage is thicker, and the tubular metal catalyst tube walls of being synthesized during less than-1.8V when operating voltage is too thin.The time of electrochemical deposition of the present invention is preferably 0.1～10h, more preferably 0.5～5h, more preferably 0.8～2h.In the present invention, the operating voltage of this electrochemical deposition can fluctuate in above-mentioned scope, and adjusts the concentration of electrolyte thereupon; After perhaps reconciling concentration of electrolyte, by adjusting within the specific limits its operating voltage, can guarantee that equally the tubular metal catalyst for preparing has thinner, the uniform characteristics of tube wall.
Adopt the tubular metal catalyst of said method preparation to be comprised of the particle less than 8nm, active high, active surface area is large, and still can keep good tubulose pattern through ultrasonic processing.By bi-component tubular metal catalyst and ternary component tubular metal catalyst have been carried out the electro-catalysis test, after Pd and Au composition Pd/Au system, electrochemical oxidation ability to ethanol improves a lot, active in commercially available Pt/C catalyst, and very high electro-catalysis stability is arranged, can be applicable to direct oxidation of ethanol fuel cell (DAFC) anode catalyst; Work as Pd, Au and Cu can improve electrochemistry oxygen/hydrogen peroxide reducing power and very high stability is arranged after forming ternary system, and be active in commercially available Pt/C catalyst, can be applicable to fuel battery cathod catalyst.
In order to further specify technical scheme of the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, but should be appreciated that these describe just as further specifying the features and advantages of the present invention, rather than to the restriction of claim of the present invention.
The chemical reagent that adopts in the embodiment of the invention is commercial.
The electrochemistry of embodiment 1 one pack system palladium tube shape metallic catalyst is synthetic
Be to add 0.177g PdCl in the beaker of 100mL at volume
2With 50mL DMSO (Shanghai traditional Chinese medicines group), with mechanical agitation dissolving part PdCl
2Later on sealing was placed one hour, treated undissolved PdCl
2Change the later again stirring and dissolving of white into, so repeatedly, until whole PdCl
2Dissolve complete adds later on the NaNO of 100mM/L
3Supporting electrolyte obtains the first mixed solution after sealing and standing is spent the night;
The gold layer that one side of the alumina formwork that commercial Britain Whatman company is produced is steamed upper 40nm thickness is to form the annular substrates electrode, and it is the duct that (is obtained by sem test) about 300nm that described alumina formwork has diameter;
With the 100mL beaker as electrolytic cell, take above-mentioned alumina formwork as template, described the first mixed solution is carried out the constant potential electrochemical deposition at the place, duct of described alumina formwork, electrochemical deposition adopts three-electrode system, as working electrode, platinum electrode is auxiliary electrode with described gold layer, and silver/silver chloride electrode is reference electrode, the operating voltage of electrochemical deposition is-1.0V that the electrochemical deposition set of time is 1h;
Template after described electrochemical deposition finished is removed the DMSO solution of remained on surface with a small amount of alcohol flushing, drying at room temperature, then clean the gold layer that steams on the template fully with the alumina particle of diameter 50nm～1 μ m, put into about the sodium hydroxide solution 1h of 1M/L and dissolve described template and ultrasonic dispersion, obtain the second mixed solution, described the second mixed solution centrifugation, distilled water are cleaned 3 times, clean 3 times with ethanol again, obtain one pack system Pd tubular metal catalyst.
Utilize SEM that the tubular metal catalyst of present embodiment preparation is observed, as shown in Figure 1, this tubular metal catalyst is tubular structure.Fig. 2, Figure 3 shows that the transmission electron microscope picture of the tubular metal catalyst of present embodiment preparation, by transmission electron microscope the tube wall of tubular metal catalyst is observed and shown that the tube wall of this tubular metal catalyst is comprised of the bead of 20～50nm.Such as Fig. 4, shown in Figure 5, the observed result that obtains by further amplification shows that the nanometer bead is comprised of the particle of 3～6nm.
Embodiment 2～4
Utilize the preparation method identical with embodiment 1, respectively with PtCl
2, AuCl
3HCl4H
2O and AgNO
3Being slaine, the operating voltage of electrochemical deposition is respectively-1.3V ,-1.5V ,-1.0V; The electrochemical deposition time is respectively 6h, 5h, 1h; The molal quantity of the sodium hydroxide solution that adopts is 1M/L; Prepare respectively one pack system Pt tubular metal catalyst, Au tubular metal catalyst and Ag tubular metal catalyst.The ESEM picture of Pt tubular metal catalyst, Au tubular metal catalyst and the Ag tubular metal catalyst of embodiment 2～4 preparations is respectively such as Fig. 6, Fig. 7 and shown in Figure 8.
The electrochemistry of embodiment 5 bi-component PdAu tubular metal catalyst is synthetic
Be to add 0.0885g PdCl in the beaker of 100mL at volume
2With 40mL DMSO (Shanghai traditional Chinese medicines group), with mechanical agitation dissolving part PdCl
2Later on sealing was placed 1 hour, treated undissolved PdCl
2Change the later again stirring and dissolving of white into, so repeatedly, until whole PdCl
2Dissolve complete adds later on the NaNO of 100mM/L
3Supporting electrolyte obtains the first mixed solution after sealing and standing is spent the night;
The gold layer that one side of the alumina formwork that commercial Britain Whatman company is produced is steamed upper 40nm thickness is to form the annular substrates electrode, and described alumina formwork has the duct that diameter is (sem test acquisition) about 300nm;
The AuCl that adds 1mL in described the first mixed solution
3HCl4H
2O solution and constant volume obtain the second mixed solution to 50ml; With the 100mL beaker as electrolytic cell, take above-mentioned alumina formwork as template, described the second mixed solution is carried out the constant potential electrochemical deposition at the place, duct of described alumina formwork, electrochemical deposition adopts three-electrode system, as working electrode, platinum electrode is auxiliary electrode with described gold layer, and silver/silver chloride electrode is reference electrode, the operating voltage of electrochemical deposition is-1.3V that the electrochemical deposition set of time is 0.1～2h;
Template after described electrochemical deposition finished is removed the DMSO solution of remained on surface with a small amount of alcohol flushing, drying at room temperature, then clean the gold layer that steams on the template fully with the alumina particle of diameter 50nm～1 μ m, put into about the sodium hydroxide solution 1h of 1M/L and dissolve described template and ultrasonic dispersion, obtain the 3rd mixed solution, described the second mixed solution centrifugation, distilled water are cleaned 3 times, clean 3 times with ethanol again, obtain bi-component PdAu tubular metal catalyst.
Utilize SEM that the PdAu tubular metal catalyst of present embodiment preparation is observed, such as Fig. 9, shown in Figure 10, this PdAu tubular metal catalyst is tubular structure and disperses better.Figure 11 is the transmission electron microscope picture of the PdAu tubular metal catalyst of present embodiment preparation, by transmission electron microscope the tube wall of tubular metal catalyst is observed to show this tubular metal catalyst tube walls even thickness.In addition, the elemental map result of this tubular metal catalyst shows Pd and Au element Uniform Dispersion in the tubular structure.
Embodiment 6～8
Utilize the preparation method identical with embodiment 5, the AuCl of adding 2mL, 4mL, 6mL
3HCl4H
2O solution, operating voltage is respectively-1.4V ,-1.5V and-1.6V, prepare respectively bi-component PdAu tubular metal catalyst.
Bi-component PdAu tubular metal catalyst to embodiment 5～8 preparation carries out the photoelectric table analysis, the result as shown in figure 12, the content of gold is along with AuCl in the PdAu tubular metal catalyst
3HCl4H
2The increase of O solution addition and increasing, the Pd atomic ratio is respectively 95%, 80%, 65% and 50%.
The electrochemistry of embodiment 9 three component PdAuCu tubular metal catalyst is synthetic
Be to add 0.0715g CuBr (Shanghai traditional Chinese medicines group) and 40mLDMSO (Shanghai traditional Chinese medicines group) in the beaker of 100mL at volume, add until completely dissolved 0.0885g PdCl
2, with mechanical agitation dissolving part PdCl
21h is placed in later on sealing, treats undissolved PdCl
2Change the later again stirring and dissolving of white into, so repeatedly, until whole PdCl
2Dissolve complete adds later on the NaNO of 100mM/L
3Supporting electrolyte obtains the first mixed solution after sealing and standing is spent the night;
The gold layer that one side of the alumina formwork that commercial Britain Whatman company is produced is steamed upper 40nm thickness is to form the annular substrates electrode, and described alumina formwork has the duct that diameter is (sem test acquisition) about 300nm;
The AuCl that adds 2mL in described the first mixed solution
3HCl4H
2O solution and constant volume obtain the second mixed solution to 50ml; With the 100mL beaker as electrolytic cell, take above-mentioned alumina formwork as template, described the second mixed solution is carried out the constant potential electrochemical deposition at the place, duct of described alumina formwork, electrochemical deposition adopts three-electrode system, as working electrode, platinum electrode is auxiliary electrode with described gold layer, and silver/silver chloride electrode is reference electrode, the operating voltage of electrochemical deposition is-1.5V that the electrochemical deposition set of time is 0.1～2h;
Template after described electrochemical deposition finished is removed the DMSO solution of remained on surface with a small amount of alcohol flushing, drying at room temperature, then clean the gold layer that steams on the template fully with the alumina particle of diameter 50nm～1 μ m, put into about the sodium hydroxide solution 1h of 1M/L and dissolve described template and ultrasonic dispersion, obtain the 3rd mixed solution, described the second mixed solution centrifugation, distilled water are cleaned 3 times, clean 3 times with ethanol again, obtain three component PdAuCu tubular metal catalyst, the PdAuCu atomic ratio is 42/3/55.
Utilize SEM that the PdAuCu tubular metal catalyst of present embodiment preparation is observed, as shown in figure 13, this tubular metal catalyst is tubular structure.As shown in figure 14, be the transmission electron microscope picture of the tubular metal catalyst of present embodiment preparation, by transmission electron microscope the tube wall of tubular metal catalyst observed and shown that this tubular metal catalyst tube walls even thickness is comprised of the particle about 5nm; In addition, the elemental map result of this tubular metal catalyst shows Pd in the tubular structure, Au and Cu element Uniform Dispersion.
Embodiment 10～11
Utilize the preparation method identical with embodiment 9, add respectively the AuCl of 4mL and 6mL
3HCl4H
2O solution, operating voltage is respectively-1.6V and-1.7V, prepare respectively the PdAuCu atomic ratio and be 35/13/52 tubular metal catalyst and PdAuCu atomic ratio and be 21/21/58 tubular metal catalyst.
Utilize SEM that the tubular metal catalyst of embodiment 10 and embodiment 11 preparations is observed, Figure 15 is the surface sweeping Electronic Speculum picture of the tubular metal catalyst of embodiment 10 preparations, and this tubular metal catalyst is tubular structure.As shown in figure 16, be the transmission electron microscope picture of the tubular metal catalyst of embodiment 10 preparation, by transmission electron microscope the tube wall of tubular metal catalyst observed and shown that this tubular metal catalyst tube walls even thickness is comprised of the particle about 5nm; In addition, the elemental map result of this tubular metal catalyst shows Pd in the tubular structure, Au and Cu element Uniform Dispersion.
Figure 17 be embodiment 11 preparation the tubular metal catalyst sweep the Electronic Speculum picture, this tubular metal catalyst is tubular structure.As shown in figure 18, be the transmission electron microscope picture of the tubular metal catalyst of embodiment 11 preparation, by transmission electron microscope the tube wall of tubular metal catalyst observed and shown that this tubular metal catalyst tube walls even thickness is comprised of the particle about 5nm; In addition, the elemental map result of this tubular metal catalyst shows Pd in the tubular structure, Au and Cu element Uniform Dispersion.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be apparent concerning those skilled in the art, and General Principle as defined herein can in the situation that does not break away from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (7)
1. the preparation method of a tubular metal catalyst comprises:
Step a) is dissolved in the first slaine and sodium nitrate in the dimethyl sulfoxide (DMSO), obtains mixed solution;
Described step a) is specially:
A1) cuprous bromide is dissolved in the dimethyl sulfoxide (DMSO), obtains cuprous bromide solution;
A2) palladium chloride is dissolved in the cuprous bromide solution, obtains aqueous premix;
A3) in described aqueous premix, add sodium nitrate, add again gold chloride after sealing and standing is spent the night, obtain mixed solution;
Step b) is take aluminum oxide porous mould with nanoscale duct as template, described mixed solution is carried out electrochemical deposition at place, described nanoscale duct, obtaining the tubular metal catalyst after removing described template, the operating voltage of described electrochemical deposition is-0.8V～-1.8V.
2. preparation method according to claim 1 is characterized in that, the concentration of the first slaine is 10～70mM in the described mixed solution.
3. preparation method according to claim 1 is characterized in that, the concentration of sodium nitrate is 100mM in the described mixed solution.
4. preparation method according to claim 1, it is characterized in that described electrochemical deposition adopts three-electrode system, auxiliary electrode is platinum electrode, reference electrode is silver/silver chloride electrode, and working electrode is prepared as follows: described alumina formwork single face is steamed gold.
5. preparation method according to claim 1 is characterized in that, the operating voltage of described electrochemical deposition is-and 1V～-1.5V.
6. preparation method according to claim 5 is characterized in that, the operating voltage of described electrochemical deposition is-and 1.2V～-1.5V.
7. preparation method according to claim 1 is characterized in that, the time of electrochemical deposition is 0.1～10h.
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| Chun-Hua Cui et al..Remarkable Enhancement of Electrocatalytic Activity by Tuning the Interface of Pd-Au Bimetallic Nanoparticle Tubes.《ACS NANO》.2011,第5卷(第5期),第4211页ABSTRACT部分以及第4216-42217页METHODS部分. |
| Remarkable Enhancement of Electrocatalytic Activity by Tuning the Interface of Pd-Au Bimetallic Nanoparticle Tubes;Chun-Hua Cui et al.;《ACS NANO》;20110420;第5卷(第5期);第4211页ABSTRACT部分以及第4216-42217页METHODS部分 * |
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