CN101455970A - Preparation method of carbon supported core-shell Ni-Pt particles for direct methanol fuel cells - Google Patents
Preparation method of carbon supported core-shell Ni-Pt particles for direct methanol fuel cells Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 19
- 229910052799 carbon Inorganic materials 0.000 title claims description 19
- 239000011258 core-shell material Substances 0.000 title claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title abstract description 30
- 239000000446 fuel Substances 0.000 title abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940078494 nickel acetate Drugs 0.000 claims abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 36
- 238000005119 centrifugation Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001488 sodium phosphate Substances 0.000 claims description 16
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 16
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 238000010792 warming Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 8
- 239000012279 sodium borohydride Substances 0.000 abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000003093 cationic surfactant Substances 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 abstract 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 abstract 2
- 239000001509 sodium citrate Substances 0.000 abstract 1
- 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 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 78
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 238000002484 cyclic voltammetry Methods 0.000 description 8
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- 238000002474 experimental method Methods 0.000 description 5
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
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- 239000002184 metal Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
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- 239000002356 single layer Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000004758 underpotential deposition Methods 0.000 description 2
- 229910002845 Pt–Ni Inorganic materials 0.000 description 1
- 229910002848 Pt–Ru Inorganic materials 0.000 description 1
- 229910018883 Pt—Cu Inorganic materials 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000010953 base metal Substances 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 231100000567 intoxicating Toxicity 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention provides a method for preparing carbon-supported nucleocapsid type Ni-Pt particles for direct methanol fuel cell catalysts, which belongs to a preparation process of direct methanol fuel cell catalysts. The method comprises the steps of adopting sodium citrate as a stabilizer, adopting cationic surfactant CTAB as dispersant, using sodium hypophosphite to reduce nickel acetate, generating a Ni kernel on the surface of Vulcan XC-72 or mesoporous carbon treated with sodium borohydride, washing superfluous sodium hypophosphite and generating a Pt shell on the surface of the Ni kernel through chemical replacement. The catalyst has a structure with the Ni kernel and the Pt shell, and has the advantages of low Pt support amount and high catalytic activity.
Description
Technical field
A kind of preparation method who is used for the carbon supported core-shell Ni-Pt particle of DMFC catalyst of this invention belongs to DMFC Preparation of catalysts technology.
Technical background
DMFC (DMFC) carbon commonly used carries platinum as the electrode electro Chemical catalyst for reaction.In early days, the Pt/C catalyst of U.S. E-TEK company exploitation is widely used in commercially producing owing to possessing excellent catalytic performance.Yet along with the aggravation of precious metals pt scarcity of resources, price is high, thereby has to reduce the application of Pt in fuel cell; On the other hand, the intermediate product of methanol oxidation, for example CO etc. easily makes the Pt catalyst poisoning.Therefore, reduce the Pt consumption, the anode catalyst that research and development high catalytic activity and anti-CO poison is a very important problem.At present, mostly the DMFC anode catalyst is based on the binary of Pt or ternary alloy three-partalloy catalyst, many research groups have reported the Pt based composite catalyst that performance is suitable with Pt/C (E-TEK), as Pt-Ru, Pt-Mn, Pt-Cu, Pt-Ni, Pt-Co, Pt-Cr and Pt-V etc., to the electro catalytic activity that improves methanol oxidation with prevent because the intoxicating phenomenon that the methanol oxidation intermediate product causes has better action.But common Pt content even surpassed 80% in the Pt alloy, high loadings Pt also can hinder the realization of commercially producing.
With respect to the conventional alloys component, nuclear shell type nano meter particle has special electronic structure and surface nature, not only kept the physical and chemical performance of original metal core, but also had the good metallic character of clad, thereby its application in fields such as catalysis comes into one's own day by day.For noble metals such as Pt, Pd, they are prepared as with the base metal is that the shell of examining also can significantly improve the noble metal utilization rate.R.Adzic group (J.Zhang, F.H.B.Lima, M.H.Shao, K.Sasaki, J.X.Wang, J.Hanson, R.R.Adzic, Platinum monolayer on nonnoble metal-noble metal core-shellnanoparticle electrocatalysts for O
2Reduction.J.Phys.Chem.B, 2005,109 (48): 22701-22704.) reported first the synthetic core-shell type eelctro-catalyst of employing electrochemical method, form UPD-Cu/M with underpotential deposition earlier, carry out chemical replacement with Pt, Pd etc. then and form the basic hud typed bianry alloy catalyst of Pt.Yet, owing to lack effective dispersant and stabilizing agent, make that its replacement process reaction is very fast, the big or small heterogeneity of Pt particle, wayward its particle diameter is difficult to prepare the high dispersancy nano particle as eelctro-catalyst; In addition, be underpotential deposition owing to what examine the metallic employing, make that nuclear metal limitation is big, the high energy consumption shortcoming of electrochemical method, so this method in addition is difficult to commercially produce on a large scale.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of easy Pt base nuclear shell type nano meter particle, prepare DMFC catalyst material with low Pt loading, high catalytic activity.
The present invention comprises following steps: (1), with powdered carbon and NaBH
4Join in the distilled water, magnetic agitation, centrifugation, vacuum drying, above-mentioned powdered carbon is Vulcan XC-72 or mesoporous carbon; (2), the powdered carbon of pre-treatment joins in deionized water and the isopropyl alcohol, magnetic agitation, add nickel acetate, natrium citricum and softex kw (CTAB) successively, stirring is warming up to 70～95 ℃, slowly adds inferior sodium phosphate, reaction 1～5h, wherein the ratio of the mole of nickel acetate, inferior sodium phosphate, natrium citricum and CTAB is 1:3～5:0.6～1:0.15～0.2, after being cooled to room temperature, centrifugation, fully washing is to remove excessive inferior sodium phosphate; (3), with the product of centrifugation, water and isopropyl alcohol disperse, and add the CTAB of 5mg, are warming up to 40～60 ℃, regulate pH value to 5～6 with HCl; (4), add H
2PtCl
6Solution, the ratio of the amount of substance of Pt and Ni is 1～5:1, the displacement reaction time is 1～5h, is cooled to room temperature, fully wash centrifugation after, vacuum drying.
This invention seeks to improve the solution of DMFC catalyst material performance from three aspects.At first, as catalyst carrier, this material has higher specific surface area and porosity, and is cheap, compares other material with carbon elements with Vulcan XC-72 or mesoporous carbon in the present invention, more helps satisfying the demand of commercially producing on a large scale.Secondly, this invention is used the method for chemical plating, generate the Ni nano particle of homogeneous, dispersion on the carbon carrier surface, as nuclear particle, by the method for simple chemical replacement, directly generate the Pt shell then on Ni nuclear surface, in the hope of when significantly reducing the Pt consumption, by special characteristic electron, surface nature and difunctional synergy between nuclear and the shell, make it have bigger electro-chemical activity area, thereby improve the catalytic performance of catalyst.Moreover this invention is easy to screen the nucleocapsid ratio with optimum catalytic performance by regulating the content of nuclear metal Ni and shell Pt.
This method prepares the Pt catalyst with nucleocapsid structure, and experimentation simply, does not need extra reducing agent, the shell spontaneous deposition; And adopt cationic surfactant CTAB in replacement process, effectively to control particle size, obtain the small-particle of size homogeneous, help the raising of material electrochemical performance; In significant reduction precious metals pt consumption, improved its catalytic performance.In addition, the present invention combines the nano material preparation technology with the Application and Development of electrode material, prepare Pt catalyst material with better dispersiveness and higher catalytic activity, technology is simple, to the research and development of DMFC Study of Catalyst and novel electrode material, played positive facilitation.
Description of drawings
Fig. 1 is the XRD figure spectrum of prepared Ni/C (1:0), Ni@Pt/C (3:1) and Pt/C (E-TEK).
Fig. 2 is the characteristic diffraction peak according to Pt among Fig. 1, provides the average grain diameter of different particles and the angle of different crystal face diffraction maximums.
Fig. 3 is the TEM photo of the prepared Ni@Pt/C of the present invention (3:1).
Fig. 4 is H
2PtCl
6Solution, Ni (Ac)
2The uv absorption spectra of solution, pure Pt and hud typed Ni@Pt (3:1) colloidal sol: (a) complex compound of Ni ion, (b) Ni@Pt (3:1) colloidal sol.
Fig. 5 is that the prepared Ni@Pt/C of the present invention (3:1), Ni/C (1:0) and Pt/C (0:1) catalyst are at 0.5mol/LNaClO
4Cyclic voltammetric comparison diagram in the solution, sweep speed are 50mV/s, 25 ℃.
Fig. 6 is that the Pt/C catalyst of the prepared Ni@Pt/C of the present invention (1:1), Ni@Pt/C (3:1) and Ni@Pt/C (5:1) catalyst and commercial E-TEK company is at 0.5mol/L H
2SO
4Cyclic voltammetry curve comparison diagram in the solution, sweep speed are 20mV/s, 25 ℃.
Fig. 7 is that the prepared Ni/C of the present invention (1:0), Ni@Pt/C (3:1), Pt/C (0:1) and commercial Pt/C (E-TEK) catalyst are at 0.5mol/L H
2SO
4Cyclic voltammetry curve comparison diagram in the solution, sweep speed are 20mV/s, 25 ℃.
Fig. 8 inhales according to the hydrogen of Pt among Fig. 7 to take off the peak, deducts the influence of electric double layer electric current, has provided the electro-chemical activity area of different catalysts.
Fig. 9 is that the Pt/C catalyst of the prepared Ni@Pt/C of the present invention (3:1) catalyst and commercial E-TEK company is at 0.5mol/L H
2SO
4+ 1.0mol/L CH
3Cyclic voltammetry curve comparison diagram in the OH solution, sweep speed are 20mV/s, 25 ℃.
Figure 10 is bimodal according to methanol oxidation among Fig. 9, the characteristic parameter that provides.
The specific embodiment
Specific embodiment one:
(1) gets the XC-72 that the 40mg sodium borohydride is handled, add 20ml deionized water and 20ml isopropyl alcohol successively, ultrasonic 10min.
Under (2) 60 ℃ of magnetic agitation, add the Ni (Ac) of 0.1mol/L, 1.5ml successively
2, the natrium citricum of 0.1mol/L, 1.0ml and the CTAB of 10mg.
(3) stirring is warming up to 80 ℃, slowly adds the inferior sodium phosphate of 0.1mol/L, 4.5ml, reaction 1h.Be cooled to room temperature, centrifugation is fully washed 4 times with distilled water and acetone respectively, to remove excessive inferior sodium phosphate.The gained catalyst is designated as Ni@Pt/C (1:0).
By cyclic voltammetry experiment test, DMFC of the present invention is with carbon supported core-shell platinum catalyst Cai LiaoNi @Pt/C (1:0), to the oxidation of hydrogen catalytically inactive almost, promptly shows the character of pure Ni.
Specific embodiment two:
(1) gets the XC-72 that the 40mg sodium borohydride is handled, add 20ml deionized water and 20ml isopropyl alcohol successively, ultrasonic 10min.
Under (2) 60 ℃ of magnetic agitation, add the H of 0.038mol/L, 0.6ml successively
2PtCl
6, the natrium citricum of 0.1mol/L, 1.0ml and the CTAB of 10mg.
(3) stirring is warming up to 80 ℃, slowly adds the inferior sodium phosphate of 0.1mol/L, 4.5ml, reaction 1h.Be cooled to room temperature, centrifugation is fully washed 4 times with distilled water and acetone respectively, to remove excessive inferior sodium phosphate.The gained catalyst is designated as Ni@Pt/C (0:1).
By the cyclic voltammetry experiment test, DMFC of the present invention presents the electrochemical catalysis activity hardly with carbon supported core-shell platinum catalyst Cai LiaoNi @Pt/C (0:1), only shows the capacitive property of XC-72, illustrates that Pt generates by the reaction of replacing Ni.
Specific embodiment three:
(1) gets the XC-72 that the 40mg sodium borohydride is handled, add 20ml deionized water and 20ml isopropyl alcohol successively, ultrasonic 10min.
Under (2) 60 ℃ of magnetic agitation, add the Ni (Ac) of 0.1mol/L, 1.5ml successively
2, the natrium citricum of 0.1mol/L, 1.5ml and the CTAB of 10mg.
(3) stirring is warming up to 95 ℃, slowly adds the inferior sodium phosphate of 0.1mol/L, 7.5ml, reaction 5h.Be cooled to room temperature, centrifugation is fully washed 4 times with distilled water and acetone respectively, to remove excessive inferior sodium phosphate.
(4) with the product of centrifugation, water and isopropyl alcohol disperse, and add the CTAB of 5mg, are warming up to 60 ℃, stir 10min.
(5) HCl with 0.2mol/L regulates pH value to 5～6.
(6) H of adding 0.038mol/L, 0.35ml
2PtCl
6Solution is replaced, and the reaction time is 5h.Be cooled to room temperature, centrifugation and with acetone washing, 80 ℃ of following vacuum drying 12h.The gained catalyst is designated as Ni@Pt/C (5:1).
By cyclic voltammetry experiment test, DMFC of the present invention is with carbon supported core-shell platinum catalyst Cai LiaoNi @Pt/C (5:1), its catalytic activity a little more than the Pt/C commercial catalysts of E-TEK company (Natick, MA.20% Pt supported onVulcan XC-72,
Http:// www.etek-inc.com/home.php).
Specific embodiment four:
(1) gets the XC-72 that the 40mg sodium borohydride is handled, add 20ml deionized water and 20ml isopropyl alcohol successively, ultrasonic 10min.
Under (2) 60 ℃ of magnetic agitation, add the Ni (Ac) of 0.1mol/L, 1.5ml successively
2, the natrium citricum of 0.1mol/L, 1.0ml and the CTAB of 10mg.
(3) stirring is warming up to 80 ℃, slowly adds the inferior sodium phosphate of 0.1mol/L, 4.5ml, reaction 3h.Be cooled to room temperature, centrifugation is fully washed 4 times with distilled water and acetone respectively, to remove excessive inferior sodium phosphate.
(4) with the product of centrifugation, water and isopropyl alcohol disperse, and add the CTAB of 5mg, are warming up to 50 ℃, stir 10min.
(5) HCl with 0.2mol/L regulates pH value to 5～6.
(6) H of adding 0.038mol/L, 0.6ml
2PtCl
6Solution is replaced, and the reaction time is 3h.Be cooled to room temperature, centrifugation and with acetone washing, 80 ℃ of following vacuum drying 12h.The gained catalyst is Ni@Pt/C (3:1) successively.
Test by cyclic voltammetry experiment, DMFC of the present invention carbon supported core-shell platinum catalyst Cai LiaoNi @Pt/C (3:1), not only catalytic activity is significantly higher than Ni@Pt/C (5:1), and has a Pt/C commercial catalysts (Natick than E-TEK company, MA.20% Pt supported on Vulcan XC-72) bigger catalytic activity, reduce under 60% condition at the Pt loading, the electro-chemical activity area reaches 100.1m
2g
-1, be 1.2 times of Pt/C (E-TEK); Methanol oxidation is shown excellent catalytic performance, and its catalytic activity is 3.5 times of Pt/C (E-TEK), has great application prospect.
Specific embodiment five:
(1) gets the XC-72 that the 40mg sodium borohydride is handled, add 20ml deionized water and 20ml isopropyl alcohol successively, ultrasonic 10min.
Under (2) 60 ℃ of magnetic agitation, add the Ni (Ac) of 0.1mol/L, 1.5ml successively
2, the natrium citricum of 0.1mol/L, 1.0ml and the CTAB of 8mg.
(3) stirring is warming up to 70 ℃, slowly adds the inferior sodium phosphate of 0.1mol/L, 4.5ml, reaction 1h.Be cooled to room temperature, centrifugation is fully washed 4 times with distilled water and acetone respectively, to remove excessive inferior sodium phosphate.
(4) with the product of centrifugation, water and isopropyl alcohol disperse, and add the CTAB of 5mg, are warming up to 40 ℃, stir 10min.
(5) HCl with 0.2mol/L regulates pH value to 5～6.
(6) H of adding 0.038mol/L, 0.9ml
2PtCl
6Solution is replaced, and the reaction time is 1h.Be cooled to room temperature, centrifugation and with acetone washing, 80 ℃ of following vacuum drying 12h.The gained catalyst is designated as Ni@Pt/C (1:1).
Test by cyclic voltammetry experiment, DMFC of the present invention carbon supported core-shell platinum catalyst Cai LiaoNi @Pt/C (1:1), its catalytic activity significantly descends than Ni@Pt/C (5:1) and Ni@Pt/C (3:1), Pt/C commercial catalysts (Natick a little less than E-TEK company, MA.20% Pt supported on Vulcan XC-72), illustrate that ratio has reached the upper limit between nucleocapsid this moment, shell is blocked up, electronics benefit special between nuclear and shell weakens, and catalytic activity descends.
Fig. 1 shows, compare Pt/C, skew has taken place to big angular direction respectively in (111) of Ni@Pt/C, (200), (220), (311) characteristic diffraction peak, degrees of offset is seen Fig. 2, this shows that it has formed the binary bimetal structure, this is because internal layer Ni nuclear has supported the Pt shell, thereby causes the variation of Pt lattice parameter.The diffraction maximum of contrast Ni@Pt/C and Ni/C does not have the oxide characteristic peak of tangible Ni or Ni as can be seen on Ni@Pt/C, illustrate that Pt has been coated on Ni nuclear surface fully.Among Fig. 1, the diffraction maximum broad of Ni@Pt/C this means that the particle diameter of particle is less, and according to the Scherrer formula, the average grain diameter of calculating the Ni@Pt particle from (220) diffraction maximum is 3.2nm, and the Pt average grain diameter of commercial E-TEK company is 3.4nm.
Among Fig. 4 as can be seen, Ni (Ac)
2Present absworption peak at the 350nm place, after reduction, 350nm place absworption peak still exists, to the high band direction skew has taken place just, this is owing to due to the formed complex compound of Ni ion that is not reduced, because pure Ni does not have absworption peak, illustrate not have excessive reducing agent in the solution.H
2PtCl
6About 260nm, located obvious absorption peaks, and pure Pt does not have absworption peak, adding H
2PtCl
6After, the absworption peak at 260nm place disappears, and this surperficial Pt has generated shell by displacement reaction on Ni nuclear surface.
As can be seen, than Ni/C, the characteristic peak of the last Ni of Ni@Pt/C disappears among Fig. 5, shows that Ni nuclear is coated by the Pt shell fully; Ni@Pt/C presents the oxidation/reduction peak similar with Pt/C, illustrates that Ni@Pt shows the electrochemical properties on typical pure Pt surface.Yet characteristic peak and the Pt/C of Ni@Pt/C still there are differences, and to the high potential district skew have taken place respectively, and this shows that formed Pt shell and pure Pt surface are different, may be because kernel Ni has supported the cause of shell Pt.
As can be seen, Ni/C does not possess catalytic activity among Fig. 7, and the Pt/C catalytic activity is also less; About forward voltage 0.5V, show as the reduction peak of oxide species adsorbed on the Pt nano particle among the figure.Than pure Pt, hud typed Ni@Pt particle is the oxidation peak value height of hydrogen not only, and oxide reduction peak value is shuffled about 50mV, the energy of adsorption that oxygenated species is described reduces, corresponding therewith, hydrogen reduction activity on the Ni@Pt significantly improves, and this may be the character of the Pt monolayer surface of Ni support, is because Ni examines due to the effects such as lattice contraction that make shell Pt.
The forward scan peak current among employing Fig. 9 and the ratio (i of reverse scan peak current
f/ i
b) and starting resistor characterize the performance of catalyst to methanol oxidation, parameter is seen Figure 10.The starting resistor of Ni@Pt/C is littler than Pt/C (E-TEK), and the district has been offset 5mV to electronegative potential, shows that its reactivity improves greatly; And Ni@Pt/C has bigger i
f/ i
bValue illustrate that the anti-CO poisoning capability of Ni@Pt/C is better than Pt/C (E-TEK), and the catalyst activity of calculating gained Ni@Pt/C unit loading is 3.5 times of Pt/C of commercial E-TEK company, has shown the catalytic performance to the methyl alcohol excellence.
Claims (2)
1, a kind of preparation method who is used for the carbon supported core-shell Ni-Pt particle of DMFC catalyst is characterized in that comprising following steps:
(1), with powdered carbon and NaBH
4Join in the distilled water, magnetic agitation, centrifugation, vacuum drying, above-mentioned powdered carbon is Vulcan XC-72 or mesoporous carbon;
(2), the powdered carbon of pre-treatment joins in deionized water and the isopropyl alcohol, magnetic agitation, add nickel acetate, natrium citricum and softex kw (CTAB) successively, stirring is warming up to 70～95 ℃, slowly adds inferior sodium phosphate, reaction 1～5h, wherein the ratio of the mole of nickel acetate, inferior sodium phosphate, natrium citricum and CTAB is 1: 3～5: 0.6～1: 0.15～0.2, after being cooled to room temperature, centrifugation, fully washing is to remove excessive inferior sodium phosphate;
(3), with the product of centrifugation, water and isopropyl alcohol disperse, and add the CTAB of 5mg, are warming up to 40～60 ℃, regulate pH value to 5～6 with HC1;
(4), add H
2PtC1
6Solution, the ratio of the amount of substance of Pt and Ni is 1～5:1, the displacement reaction time is 1～5h, is cooled to room temperature, fully wash centrifugation after, vacuum drying.
2, the preparation method who is used for the carbon supported core-shell Ni-Pt particle of DMFC catalyst according to claim 1 is characterized in that: the ratio of the amount of substance of Pt and Ni is 3:1 described in (4) step.
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