CN102407106A - Preparation method of tubular metal catalyst - Google Patents
Preparation method of tubular metal catalyst Download PDFInfo
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- CN102407106A CN102407106A CN2011103147536A CN201110314753A CN102407106A CN 102407106 A CN102407106 A CN 102407106A CN 2011103147536 A CN2011103147536 A CN 2011103147536A CN 201110314753 A CN201110314753 A CN 201110314753A CN 102407106 A CN102407106 A CN 102407106A
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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 60
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000011259 mixed solution Substances 0.000 claims abstract description 44
- 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 22
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 11
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 11
- 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 compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 30
- 239000010931 gold Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 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
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 18
- 238000009415 formwork Methods 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 12
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 12
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 11
- 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
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 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
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 10
- 239000000446 fuel Substances 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 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
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000009826 distribution Methods 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
- 235000012149 noodles Nutrition 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
- 230000015572 biosynthetic process Effects 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
- 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
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 239000010970 precious metal Substances 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 molecules will 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 tubular metal Preparation of catalysts method.
Background technology
Along with the growth of world population, the human restriction that usually receives the electric energy deliverability that can support that it is movable.Fuel cell can be an electric energy with chemical raw material such as hydrogen and oxygen conversion; Thereby for guaranteeing that the electric energy supply provides a kind of solution route; That is, fuel cell is that chemical energy is converted into electric energy, under the effect of metallic catalyst; With hydrogen etc. is fuel, and air (oxygen) produces electric energy and small amount of thermal energy as oxidant.And it is water that fuel cell produces the product that discharges behind the electric energy, and compliance with environmental protection requirements has solved the intrinsic pollution problem of burning process.Therefore, fuel cell can be widely used in vehicle towed with electric energy supply, family and industrial electric energy supply and boats and ships with fields such as electric energy supplies.
At present, the tubular metal catalyst that is used for fuel cell has obtained extensive studies, and wherein, sacrificing template is the common method of synthetic tubulose metallic catalyst.Germany " applied chemistry " (Angewandte Chemie International Edition; 4060 pages of 2007 46 phases) reported with the Ag line to be that template is passed through synthetic platinum of galvanic cell substitution reaction and platinum palladium tube shape self-supporting catalyst material; 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 phase 13364 pages) has reported that employing Se line is the synthetic platinotron catalyst of template; Germany's " advanced function material " (Advanced Materials, 2009 21 phase 1850 pages) has reported that employing Te line is a reducing agent and sacrifice the synthetic platinum nano tube catalyst of template.But all there is following problem in above-mentioned reported method, promptly consumes the metal material that comparatively active forerunner's template Ag, Se and Te etc. have certain toxicity, and this method is complicated wayward.
The template electrochemical method is other a kind of important method of synthetic tubulose metallic catalyst; For example; Germany's " advanced function material " (Advanced Materials, 2004 16 phase 1550 pages) has reported that employing multistep template synthesize the platinum nanotube, but this synthetic method complicacy very; Cost is higher, has limited its application." electrochemistry communication " (Electrochemistry Communications; 190 pages of 2009 11 phases) 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 that the present invention will solve is to provide a kind of tubular metal Preparation of catalysts method, and the tubular metal catalyst tube walls of this method preparation is thinner, and active area is bigger.
In order to solve above technical problem, the present invention provides a kind of tubular metal Preparation of catalysts method, comprising:
Step a) is dissolved in first slaine and sodium nitrate in the dimethyl sulfoxide (DMSO), obtains mixed solution;
Step b) is a template with the aluminum oxide porous mould with nanoscale duct; Said mixed solution is carried out electrochemical deposition at place, said nanoscale duct; Obtaining the tubular metal catalyst after removing said template, the operating voltage of said electrochemical deposition is-0.8V～-1.8V.
Preferably, said 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 first slaine is 10～70mM in the said mixed solution.
Preferably, the concentration of sodium nitrate is 100mM in the said mixed solution.
Preferably, said electrochemical deposition adopts three-electrode system, and auxiliary electrode is a platinum electrode, and reference electrode is silver/silver chloride electrode, and working electrode prepares according to following method: said alumina formwork single face is steamed gold.
Preferably, the operating voltage of said electrochemical deposition be-1V～-1.5V.
Preferably, the operating voltage of said electrochemical deposition be-1.2V～-1.5V.
Preferably, the time of electrochemical deposition is 0.1～10h.
Preferably, said step a) is specially:
Step a1) palladium chloride is dissolved in the dimethyl sulfoxide (DMSO), obtains palladium chloride solution;
Step a2) add gold chloride to said palladium chloride solution, the dissolving back adds sodium nitrate, obtains mixed solution.
Preferably, said 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 said first solution, add gold chloride, the dissolving back adds sodium nitrate, obtains mixed solution.
The present invention provides a kind of tubular metal Preparation of catalysts method, comprising: first slaine and sodium nitrate are dissolved in the dimethyl sulfoxide (DMSO), obtain mixed solution; With the aluminum oxide porous mould with nanoscale duct is template, and said mixed solution is carried out electrochemical deposition at said nanoscale duct place, obtains the tubular metal catalyst after removing said template.Compared with prior art; The present invention utilizes polar non-solute dimethyl sulfoxide (DMSO) (DMSO) as solvent and electrolyte and since this DMSO contain the metal surface had a little less than adsorbing S group, when metal be reduced form granule after; The DMSO molecule can be adsorbed in the granule surface; Stop its growing up further, thereby make that the tubular metal catalyst tube walls of preparation is thin and form, increased active area by smaller particles.
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 electrochemical window, high-k and the high viscosity of broad, thereby the electrochemical window of this broad has guaranteed that electrolyte under lower electrochemistry resultant voltage chemical reaction does not take place, has improved the speed of growth that is parallel to the sense of current; Secondly, high dielectric constant has avoided metal ion than electronegative potential the time, in solution, to discharge, and has guaranteed that metal ion still can be diffused on the electrode to discharge; Once more, high viscosity can reduce catalyst in the diffusion and the speed of growth perpendicular to the sense of current, helps the formation of tubulose; At last, because that DMSO and complexing of metal ion effect can form is sterically hindered, further reduced diffusion rate perpendicular to the sense of current.Therefore, the tubular metal catalyst tube walls that the present invention prepares as solvent with DMSO approaches and is made up 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
Carry out clear, intactly description in the face of the technical scheme in the embodiment of the invention down, 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 are not making the every other embodiment that is obtained under the creative work prerequisite, all belong to the scope of the present invention's protection.
The invention discloses a kind of tubular metal Preparation of catalysts method, comprising:
Step a) is with first slaine and sodium nitrate (NaNO
3) be dissolved in the dimethyl sulfoxide (DMSO) (DMSO), obtain mixed solution;
Step b) is a template with the aluminum oxide porous mould with nanoscale duct; Said mixed solution is carried out electrochemical deposition at place, said nanoscale duct; Obtaining the tubular metal catalyst after removing said template, the operating voltage of said electrochemical deposition is-0.8V～-1.8V.
Among the present invention, said 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, said first slaine is preferably precious metal salt, more preferably PtCl
2, PdCl
2, AuCl
3HCl4H
2O or AgNO
3During preparation multicomponent tubular metal catalyst, said first slaine is preferably PtCl
2, PdCl
2, AuCl
3HCl4H
2O, AgNO
3With among the CuBr several kinds.Wherein, PdCl
2Dissolving method in DMSO is preferably: in DMSO, add PdCl
2, leave standstill 0.8～2h after the stirring, preferably leave standstill 1h, wait not dissolve part and become white continued stirring, so repeatedly up to dissolving fully.
During preparation multicomponent tubular metal catalyst, the interpolation order of each component has certain influence to the solubility property of component, for example, said step a) can for: step a1) with PdCl
2Be dissolved among the DMSO, obtain PdCl
2Solution; Step a2) to said PdCl
2Solution adds AuCl
3HCl4H
2O, the dissolving back adds NaNO
3, obtaining mixed solution, this mixed solution can obtain PdAu tubular metal catalyst after step b).Perhaps, said step a) can for: step a1) CuBr is dissolved among the DMSO, obtains CuBr solution; Step a2) adds PdCl to said CuBr solution
2, the dissolving back adds NaNO
3, obtaining mixed solution, this mixed solution can obtain PdCu tubular metal catalyst after step b).In addition, said step a) can also for: step a1) successively with CuBr and PdCl
2Be dissolved among the DMSO, obtain premixed solution; Step a2) in said first solution, adds AuCl
3HCl4H
2O, the dissolving back adds NaNO
3, obtaining mixed solution, this mixed solution can obtain PdAuCu tubular metal catalyst after step b).Simultaneously, NaNO
3Be the supporting electrolyte in this preparation process, be beneficial to the generation of electrochemical reaction.The concrete steps of said step a) are not limited only to above-mentioned reactions step, and at first slaine that adopts not simultaneously, the interpolation of each component order can suitably be adjusted.
The DMSO that the present invention adopts contain the metal surface had a little less than adsorbing S group; After metal is reduced the formation granule; The DMSO molecule can be adsorbed in the granule surface; Stop its growing up further, make the tubular metal catalyst tube walls of preparation thin and form, thereby improved active surface area greatly by particle.And after synthetic the completion, the DMSO molecule is very easily removed through 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 electrochemical window, high-k and the high viscosity of broad; The electrochemical window of this broad has guaranteed that electrolyte under lower electrochemistry resultant voltage chemical reaction does not take place, has improved the speed of growth that is parallel to the sense of current; Secondly, high dielectric constant has avoided metal ion than electronegative potential the time, in solution, to discharge, and has guaranteed that metal ion still is diffused into electrode and discharges; Once more, high viscosity can reduce catalyst in the diffusion and the speed of growth perpendicular to the sense of current, helps the formation of tubular structure; At last, because that DMSO and complexing of metal ion effect can form is sterically hindered, further reduced 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 bigger, even tube wall, and draw ratio is high.
In addition; The adjustable components of tubular metal catalyst provided by the invention; Promptly in DMSO solution; It is no longer practical that electrode potential under the aqueous environment will become, and reduction potential no longer receives the constraint of electrode potential, each components in proportions of the tubular metal catalyst that can prepare through the operating voltage control of regulating electrolyte ratio and electrochemical deposition.
In step a), the concentration of first slaine is preferably 10～70mM in the said mixed solution, more preferably 20～60mM, more preferably 30～50mM; NaNO in the said mixed solution
3Concentration be preferably 80～120mM, more preferably 90～110mM, more preferably 100mM.The concentration of first slaine in the mixed solution and supporting electrolyte NaNO
3Concentration be two performance indications that influence 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 taken place in first slaine and DMSO, and time of repose is preferably 6～20h, more preferably 8～15h, more preferably 10～12h.
In step b), said electrochemical deposition adopts three-electrode system, and auxiliary electrode is a platinum electrode; Reference electrode is silver/silver chloride electrode; Working electrode is the gold-plated alumina formwork of single face, preferably according to following method preparation: said alumina formwork single face is steamed gold, preferred; This single face steams golden thickness and is preferably 30～50nm, more preferably 40nm; The operating voltage of said 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 according to the 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,, can guarantee that equally the tubular metal catalyst for preparing has thin, the uniform characteristics of tube wall through adjusting its operating voltage within the specific limits.
Adopt the tubular metal catalyst of method for preparing to be made up of the particle less than 8nm, active high, active surface area is big, and still can keep good tubulose pattern through sonicated.Through 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 solution 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; Describe just to further specifying feature and advantage of the present invention but should be appreciated that these, 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
At volume is to add 0.177g PdCl in the beaker of 100mL
2With 50mL DMSO (Shanghai traditional Chinese medicines group), with mechanical agitation dissolving part PdCl
2Sealing was later on placed one hour, treated undissolved PdCl
2Change the later stirring and dissolving once more of white into, so repeatedly, up to whole PdCl
2The NaNO that adds 100mM/L after the dissolving fully
3Supporting electrolyte obtains first mixed solution after sealing and standing is spent the night;
One side of the alumina formwork that commercial Britain Whatman company is produced steam go up 40nm thickness the gold layer to form the annular substrates electrode, it is the duct that (is obtained by sem test) about 300nm that said alumina formwork has diameter;
As electrolytic cell, is template with above-mentioned alumina formwork with the 100mL beaker, and said first mixed solution is carried out the constant potential electrochemical deposition at the place, duct of said alumina formwork; Electrochemical deposition adopts three-electrode system; As working electrode, platinum electrode is an auxiliary electrode with said gold layer, and silver/silver chloride electrode is a reference electrode; The operating voltage of electrochemical deposition is-1.0V that the electrochemical deposition time is set to 1h;
Template after the said electrochemical deposition completion is removed the DMSO solution of remained on surface with a spot of alcohol flushing; Drying at room temperature, the gold layer of cleaning on the template fully to be steamed with the alumina particle of diameter 50nm～1 μ m is then put into about the sodium hydroxide solution 1h of 1M/L and is dissolved said template and ultrasonic dispersion; Obtain second mixed solution; Said 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 a tubular structure.The transmission electron microscope picture of Fig. 2, the tubular metal catalyst for present embodiment preparation shown in Figure 3 is observed the tube wall of tubular metal catalyst through transmission electron microscope and to be shown that the tube wall of this tubular metal catalyst is made up of the bead of 20～50nm.Like Fig. 4, shown in Figure 5, the observed result that obtains through further amplification shows that the nanometer bead is made up of the particle of 3～6nm.
Embodiment 2～4
Utilize the preparation method identical, respectively with PtCl with embodiment 1
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 one pack system Pt tubular metal catalyst, Au tubular metal catalyst and Ag tubular metal catalyst respectively.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 like Fig. 6, Fig. 7 and shown in Figure 8.
The electrochemistry of embodiment 5 bi-component PdAu tubular metal catalyst is synthetic
At volume is to add 0.0885g PdCl in the beaker of 100mL
2With 40mL DMSO (Shanghai traditional Chinese medicines group), with mechanical agitation dissolving part PdCl
2Sealing was later on placed 1 hour, treated undissolved PdCl
2Change the later stirring and dissolving once more of white into, so repeatedly, up to whole PdCl
2The NaNO that adds 100mM/L after the dissolving fully
3Supporting electrolyte obtains first mixed solution after sealing and standing is spent the night;
One side of the alumina formwork that commercial Britain Whatman company is produced steam go up 40nm thickness the gold layer to form the annular substrates electrode, said alumina formwork has the duct that diameter is (sem test acquisition) about 300nm;
The AuCl that in said first mixed solution, adds 1mL
3HCl4H
2O solution and constant volume obtain second mixed solution to 50ml; As electrolytic cell, is template with above-mentioned alumina formwork with the 100mL beaker, and said second mixed solution is carried out the constant potential electrochemical deposition at the place, duct of said alumina formwork; Electrochemical deposition adopts three-electrode system; As working electrode, platinum electrode is an auxiliary electrode with said gold layer, and silver/silver chloride electrode is a reference electrode; The operating voltage of electrochemical deposition is-1.3V that the electrochemical deposition time is set to 0.1～2h;
Template after the said electrochemical deposition completion is removed the DMSO solution of remained on surface with a spot of alcohol flushing; Drying at room temperature, the gold layer of cleaning on the template fully to be steamed with the alumina particle of diameter 50nm～1 μ m is then put into about the sodium hydroxide solution 1h of 1M/L and is dissolved said template and ultrasonic dispersion; Obtain the 3rd mixed solution; Said 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, like 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, through transmission electron microscope the tube wall of tubular metal catalyst is observed to show that this tubular metal catalyst tube wall thickness is even.In addition, Pd and Au element evenly disperse in first vegetarian noodles distribution results demonstration tubular structure of this tubular metal catalyst.
Embodiment 6～8
Utilize the preparation method identical, the AuCl of adding 2mL, 4mL, 6mL with embodiment 5
3HCl4H
2O solution, operating voltage is respectively-1.4V ,-1.5V and-1.6V, prepare bi-component PdAu tubular metal catalyst respectively.
Bi-component PdAu tubular metal catalyst to embodiment 5～8 preparations carries out the photoelectric table analysis, and the result is shown in figure 12, and 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
At volume is to add 0.0715g CuBr (Shanghai traditional Chinese medicines group) and 40mLDMSO (Shanghai traditional Chinese medicines group) in the beaker of 100mL, treats to dissolve fully back adding 0.0885g PdCl
2, with mechanical agitation dissolving part PdCl
21h is placed in sealing later on, treats undissolved PdCl
2Change the later stirring and dissolving once more of white into, so repeatedly, up to whole PdCl
2The NaNO that adds 100mM/L after the dissolving fully
3Supporting electrolyte obtains first mixed solution after sealing and standing is spent the night;
One side of the alumina formwork that commercial Britain Whatman company is produced steam go up 40nm thickness the gold layer to form the annular substrates electrode, said alumina formwork has the duct that diameter is (sem test acquisition) about 300nm;
The AuCl that in said first mixed solution, adds 2mL
3HCl4H
2O solution and constant volume obtain second mixed solution to 50ml; As electrolytic cell, is template with above-mentioned alumina formwork with the 100mL beaker, and said second mixed solution is carried out the constant potential electrochemical deposition at the place, duct of said alumina formwork; Electrochemical deposition adopts three-electrode system; As working electrode, platinum electrode is an auxiliary electrode with said gold layer, and silver/silver chloride electrode is a reference electrode; The operating voltage of electrochemical deposition is-1.5V that the electrochemical deposition time is set to 0.1～2h;
Template after the said electrochemical deposition completion is removed the DMSO solution of remained on surface with a spot of alcohol flushing; Drying at room temperature; The gold layer of cleaning on the template fully to be steamed with the alumina particle of diameter 50nm～1 μ m is then put into about the sodium hydroxide solution 1h of 1M/L and is dissolved said template and ultrasonic dispersion, obtains the 3rd mixed solution; Said second mixed solution centrifugation, distilled water are cleaned 3 times; Clean 3 times with ethanol, 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, shown in figure 13, this tubular metal catalyst is a tubular structure.Shown in figure 14, be the transmission electron microscope picture of the tubular metal catalyst of present embodiment preparation, through transmission electron microscope the tube wall of tubular metal catalyst is observed and shown that this tubular metal catalyst tube wall thickness is even, is made up of the particle about 5nm; In addition, first vegetarian noodles distribution results of this tubular metal catalyst shows that Pd, Au and Cu element evenly disperse in the tubular structure.
Embodiment 10～11
Utilize the preparation method identical, add the AuCl of 4mL and 6mL respectively with embodiment 9
3HCl4H
2O solution, operating voltage is respectively-1.6V and-1.7V, prepare the PdAuCu atomic ratio respectively and be 35/13/52 tubular metal catalyst and PdAuCu atomic ratio and be 21/21/58 tubular metal catalyst.
Utilize SEM that embodiment 10 is observed with the tubular metal catalyst of embodiment 11 preparations, Figure 15 is the surface sweeping Electronic Speculum picture of the tubular metal catalyst of embodiment 10 preparations, and this tubular metal catalyst is a tubular structure.Shown in figure 16, be the transmission electron microscope picture of the tubular metal catalyst of embodiment 10 preparation, through transmission electron microscope the tube wall of tubular metal catalyst is observed and shown that this tubular metal catalyst tube wall thickness is even, is made up of the particle about 5nm; In addition, first vegetarian noodles distribution results of this tubular metal catalyst shows that Pd, Au and Cu element evenly disperse in the tubular structure.
Figure 17 sweeps the Electronic Speculum picture for the tubular metal catalyst of embodiment 11 preparation, and this tubular metal catalyst is a tubular structure.Shown in figure 18, be the transmission electron microscope picture of the tubular metal catalyst of embodiment 11 preparation, through transmission electron microscope the tube wall of tubular metal catalyst is observed and shown that this tubular metal catalyst tube wall thickness is even, is made up of the particle about 5nm; In addition, first vegetarian noodles distribution results of this tubular metal catalyst shows that Pd, Au and Cu element evenly disperse in the tubular structure.
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 conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. tubular metal Preparation of catalysts method comprises:
Step a) is dissolved in first slaine and sodium nitrate in the dimethyl sulfoxide (DMSO), obtains mixed solution;
Step b) is a template with the aluminum oxide porous mould with nanoscale duct; Said mixed solution is carried out electrochemical deposition at place, said nanoscale duct; Obtaining the tubular metal catalyst after removing said template, the operating voltage of said electrochemical deposition is-0.8V～-1.8V.
2. preparation method according to claim 1 is characterized in that, said first slaine is one or more in the inferior platinum of dichloride, palladium chloride, gold chloride, silver nitrate and the cuprous bromide.
3. preparation method according to claim 1 is characterized in that, the concentration of first slaine is 10～70mM in the said mixed solution.
4. preparation method according to claim 1 is characterized in that, the concentration of sodium nitrate is 100mM in the said mixed solution.
5. preparation method according to claim 1; It is characterized in that said electrochemical deposition adopts three-electrode system, auxiliary electrode is a platinum electrode; Reference electrode is silver/silver chloride electrode, and working electrode prepares according to following method: said alumina formwork single face is steamed gold.
6. preparation method according to claim 1 is characterized in that, the operating voltage of said electrochemical deposition is-and 1V～-1.5V.
7. preparation method according to claim 6 is characterized in that, the operating voltage of said electrochemical deposition is-and 1.2V～-1.5V.
8. preparation method according to claim 1 is characterized in that, the time of electrochemical deposition is 0.1～10h.
9. preparation method according to claim 1 is characterized in that, said step a) is specially:
Step a1) palladium chloride is dissolved in the dimethyl sulfoxide (DMSO), obtains palladium chloride solution;
Step a2) add gold chloride to said palladium chloride solution, the dissolving back adds sodium nitrate, obtains mixed solution.
10. preparation method according to claim 1 is characterized in that, said 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 said first solution, add gold chloride, the dissolving back adds sodium nitrate, obtains mixed solution.
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| CN106191941A (en) * | 2016-07-14 | 2016-12-07 | 东南大学 | A kind of preparation method and applications of gas-solid-liquid three phase boundary |
| CN106191941B (en) * | 2016-07-14 | 2018-02-02 | 东南大学 | A kind of preparation method and applications of gas-solid-liquid three phase boundary |
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