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1.
The nanostructured platinum–bismuth catalysts supported on carbon (Pt3Bi/C, PtBi/C and PtBi3/C) were synthesised by reducing the aqueous metal ions using sodium borohydride (NaBH4) in presence of a microemulsion. The amount of metal loading on carbon support was found to be 10 wt.‐%. The catalyst materials were characterised by X‐ray diffraction (XRD), X‐ray fluorescence (XRF), transmission electron microscope (TEM) and electroanalytical techniques. The Pt3Bi/C, PtBi/C and PtBi3/C catalysts showed higher methanol tolerance, catalytic activity for oxygen reduction reaction (ORR) than Pt/C of same metal loading. The electrochemical stability of these nano‐sized catalyst materials for methanol tolerance was investigated by repetitive cycling in the potential range of –250 to 150 mVMSE. Bi presents an interesting system to have a control over the activity of the surface for MOR and ORR. All Pt–Bi/C catalysts exhibited higher mass activities for oxygen reduction (1–1.5 times) than Pt/C. It was found that PtBi/C catalyst exhibits better methanol‐tolerance than the other catalysts. 相似文献
2.
RuO2‐MnO2 complex supported by multi‐wall carbon nanotubes (CNTs) was firstly synthesised by the oxidation–reduction precipitation of RuCl3 and KMnO4 in one step. Then Pt was loaded onto the obtained RuO2‐MnO2/CNTs to fabricate a novel anodic catalyst Pt/RuO2‐MnO2/CNTs for direct methanol fuel cells (DMFCs). The catalyst was characterised by transmission electron microscopy (TEM), X‐ray diffraction (XRD), temperature programmed reduction (TPR), X‐ray photoelectron spectroscopy (XPS) and BET specific surface areas (BET). Pt nanoparticles were found uniformly dispersed on the surface of CNTs, with the average diameter of about 2.0 nm. The activities of methanol and CO electrocatalytic oxidation were analysed, and the reaction mechanism of methanol electro‐oxidation on Pt/RuO2‐MnO2/CNTs catalyst was discussed. The MnO2 in the catalysts improves the proton conductivity and electrochemical active surface area (EAS) for the catalysts. RuO2 improves the CO oxidation activity and Pt dispersion. CNTs provide effectively electron channels. Thus, the Pt/RuO2‐MnO2/CNTs catalyst has high utilisation of the noble metal Pt, high CO oxidation ability and excellent methanol electro‐oxidation activity, being an outstanding anode catalyst for DMFC. 相似文献
3.
Molybdenum carbide (MoC) and tungsten carbide (WC) are synthesized by direct carbonization method. Pt–Ru catalysts supported on MoC, WC, and Vulcan XC‐72R are prepared, and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, and transmission electron microscopy in conjunction with electrochemistry. Electrochemical activities for the catalysts towards methanol electro‐oxidation are studied by cyclic voltammetry. All the electro‐catalysts are subjected to accelerated durability test (ADT). The electrochemical activity of carbide‐supported electro‐catalysts towards methanol electro‐oxidation is found to be higher than carbon‐supported catalysts before and after ADT. The study suggests that Pt–Ru/MoC and Pt–Ru/WC catalysts are more durable than Pt–Ru/C. Direct methanol fuel cells (DMFCs) with Pt–Ru/MoC and Pt–Ru/WC anodes also exhibit higher performance than the DMFC with Pt–Ru/C anode. 相似文献
4.
Pt nanoparticles supported on Vulcan XC‐72 carbon black have been synthesized by a facile solvothermal method. The obtained Pt/C catalysts are characterized by X‐ray diffraction (XRD), energy dispersive X‐ray analysis (EDAX), and transmission electron microscopy (TEM) analysis to identify Pt mean size and Pt content. The results of electrochemical measurements demonstrate that the Pt/C catalyst prepared at the reaction temperature of 140 °C and the reaction time of 2 h shows the biggest initial electrochemical area with an initial electrochemically active specific surface area (ESA) of 70.6 m2gPt−1, the highest electrocatalytic stability with an ESA loss of 48.7% after 1,000 CV cycles, and the best electrocatalytic activity and stability toward methanol oxidation reaction (MOR) with a specific activity of 0.6 mA cm−2 and a retention rate (the ratio of the final current density to the maximum current density) after 3,600 s of 42.8%. Moreover, the electrochemical performance of homemade Pt/C catalyst is superior to that of commercial Pt/C catalyst, suggesting that the solvothermal synthesis is a promising method for preparing Pt based catalyst. 相似文献
5.
A combinatorial library containing 645 different compositions was synthesised and characterised for methanol tolerant oxygen electro‐reduction reaction (ORR) catalytic performance. The library was composed of compositions involving between 1 and 4 metals among Pt, Ru, Fe, Mo and Se. In an optical screening test, Pt(50)Ru(10)Fe(20)Se(10) composition exhibited the highest ORR activity in the presence of methanol. This composition was further investigated by synthesis and characterisation of a powder version catalyst [Pt(50)Ru(10)Fe(20)Se(10)/C]. At 0.85 V [vs. reversible hydrogen electrode (RHE)] in the absence of methanol, the Pt/C catalyst exhibited higher ORR current (0.0990 mA) than the Pt(50)Ru(10)Fe(20)Se(10)/C catalyst (0.0902 mA). But much higher specific activity (12.7 μA cmpt–2) was observed in the Pt(50)Ru(10)Fe(20)Se(10)/C catalyst than for the Pt/C catalyst 6.51 μA cmpt–2). In the presence of methanol, the ORR current decreased by 0.0343 and 0.247 mA for the Pt(50)Ru(10)Fe(20)Se(10)/C and Pt/C catalysts, respectively, which proved the excellent methanol tolerance of the Pt(50)Ru(10)Fe(20)Se(10)/C catalyst. 相似文献
6.
C. Coutanceau A.F. Rakotondrainibé A. Lima E. Garnier S. Pronier J-M. Léger C. Lamy 《Journal of Applied Electrochemistry》2004,34(1):61-66
The electrodeposition of platinum and ruthenium was carried out on carbon electrodes to prepare methanol anodes with different Pt/Ru atomic ratios using a galvanostatic pulse technique. Characterizations by XRD, TEM, EDX and atomic absorption spectroscopy indicated that most of the electrocatalytic anodes consisted of 2 mg cm–2 of Pt–Ru alloy particles with the desired composition and with particle sizes ranging from 5 to 8 nm. Electrochemical tests in a single DMFC show that these electrodes are very active for methanol oxidation and that the best Pt/Ru atomic ratio in the temperature range used (50–110 °C) is 80:20. The influence of the relaxation time t
off was also studied and it appeared that a low t
off led to smaller particle sizes and higher performances in terms of current density and power density. 相似文献
7.
H. Bnnemann U. Endruschat J. Hormes G. Khl S. Kruse H. Modrow R. Mrtel K. S. Nagabhushana 《Fuel Cells》2004,4(4):297-308
The activation of platinum‐ruthenium (Pt‐Ru) fuel cell catalysts, which were made by supporting nanoscopic colloidal precursors on conductive carbon (Vulcan XC72) is brought about by reactive annealing (“conditioning process”) at 250–300 °C, in a particular set‐up. The tetraalkylammonium (A) or triorganoaluminium (B) protecting shell is cleaved from the Pt‐Ru metal surface in three mandatory steps under flowing argon, oxygen, and hydrogen (30 min each). Ex‐situ TEM micrographs were used to monitor changes in particle size during this conditioning process. Additionally, in‐situ X‐ray absorption spectroscopic measurements on the Pt LIII‐edge provided insight into the processes occurring in the metallic core of the particles. While a small increase in size is found with conditioning, the dominant structural change in both catalyst types (A and B) is a reduction in the disorder inside the metallic particles, particularly in those having organoaluminium‐protected nanoparticles (B). During oxidation under flowing oxygen, platinum atoms only undergo oxidation in the bimetallic Pt‐Ru catalyst type (B) while the platinum atoms in the bimetallic Pt‐Ru catalyst (A) remain strictly zerovalent. This difference may be attributed to differences in the internal structure of the as prepared colloidal particles (A and B) as evidenced from Pt LIII EXAFS‐data and XANES spectra. 相似文献
8.
PtRuMo/C catalyst was prepared by impregnation reduction method and characterised. Comparison is made between a home‐made PtRu/C prepared by similar method and Pt/C (E‐Tek Co., Pt/C‐ET) catalysts. One glassy carbon disc electrode for ternary alloy catalyst was used to evaluate the catalytic performances by cyclic voltammetric, chronoamperometric, amperometric i–t curves, and electrochemical impedance spectra (EIS). The electrochemical measurement results indicated that the performance of PtRuMo/C with a molar ratio of 6:3:1 was the highest among 15 PtxRuyMo10–x–y/C catalysts with different molar ratios. The composition, particle size, lattice parameter and morphology of the PtRuMo(6:3:1)/C catalyst were determined by means of X‐ray energy dispersive analysis, X‐ray diffraction (XRD) and transmission electron micrographs (TEM). The result of XRD analysis exhibits that PtRuMo(6:3:1)/C has the fcc structure with the smaller lattice parameter than the home‐made PtRu/C and Pt/C‐ET. Its typical particle sizes is only about 5 nm. With respect to the catalytic activity and stability, the PtRuMo(6:3:1)/C catalyst is superior to PtRu/C despite their comparable active areas. Though the electrochemically active surface area of Pt/C‐ET is the biggest, its performance is the lowest. EIS results also indicate that the reaction resistances for methanol electrooxidation on the PtRuMo(6:3:1)/C catalyst are smaller than those of PtRu/C at different polarisation potentials. 相似文献
9.
PtRu/C catalysts with different mean particle sizes have been synthesised by microwave‐assisted polyol process at various pH values and characterised by transmission electron microscopy (TEM), energy dispersive analysis of X‐ray (EDAX) and X‐ray diffraction (XRD). Their electrochemical performances have been tested by cyclic voltammetry, amperomeric i–t, and CO‐stripping techniques. The effects of pH values on performances of the PtRu/C catalysts have been mainly investigated. It has been found that the particle size, composition and catalytic activity of the PtRu/C catalyst are very sensitive to the pH value of reducing solution, and the PtRu/C catalyst prepared at the pH value of 8 exhibits the better performance for methanol electrooxidation than the other samples. The size of the nanoparticles decreases as the pH value increases from 0.2 to 10 with the largest size of 4.4 nm and the smallest one of 2.1 nm. The two metal elements distribute uniformly in the catalyst and their metal loadings are similar to the theoretical value. 相似文献
10.
In this work, Pt nanoparticles are deposited on NbO2‐modified carbon composites and evaluated as promising direct methanol fuel cell (DMFC) electrocatalysts. Transmission electron microscopy (TEM) and X‐ray diffraction (XRD) indicate that Pt nanoparticles (about 2.5 nm) are uniformly dispersed on NbO2‐modified carbon composites. Electrochemical measurements show that the mass activity toward methanol electrooxidation on Pt/NbO2‐C is as high as 3.0 times that of conventional Pt/C. Meanwhile, the onset potential of CO oxidation is negatively shifted by about 46 mV as compared with that of Pt/C, which means that the synergistic effect between NbO2 and Pt facilitates the feasible removal of poisoning intermediate CO during methanol electrooxidation. X‐ray photoelectron spectroscopy (XPS) characterizations reveal the electron transfer from Nb to Pt, which suppress the poisoning CO adsorption on Pt nanoparticles and facilitate methanol electrooxidation. NbO2 nanoparticles facilitate methanol electrooxidation on Pt/C catalyst by synergistic effect and electronic effect, which represents a step in the right direction for the development of excellent fuel cell anode electrocatalysts. 相似文献
11.
The {[PdPW11O39]5–/Pt/PAMAM}n multilayer composites constructed from G4.0 Amino‐terminated poly (amidoamine) dendrimer (PAMAM), Pt and Keggin‐type palladium(II)‐substituted polyoxometalates anion ([PdPW11O39]5–) were prepared via layer by layer electro‐depositing technique. The X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction (XRD), and field emission scanning electron microscope (FE‐SEM) characterization indicate that the Pt nanoparticles have been anchored on the as‐prepared nanocomposites. And the morphologies of Pt nanoparticles are influenced by deposition potential, the number of layers of {[PdPW11O39]5–/Pt/PAMAM}n multilayer nanocomposites, and the existence of PAMAM. The electrocatalytic properties and stability of {[PdPW11O39]5–/Pt/PAMAM}n multilayer nanocomposites were investigated by cyclic voltammetry. Experimental investigation results reveal that PAMAM is a good support for Pt nanoparticle growth due to its interior cavity structure and high stability. [PdPW11O39]5– play an important role to prevent intermediate product (mainly as CO) in the methanol oxidation from poisoning the as‐prepared catalyst. The {[PdPW11O39]5–/Pt/PAMAM}3/GC shows better electrocatalytic properties, stability, and CO tolerance ability than Pt/GC and {Pt/PAMAM}3/GC fabricated by similar electrodeposition processes. 相似文献
12.
Nano‐sized Pt colloids were prepared using the polyol method and supported on Ketjen black EC 600J (KB), Vulcan XC‐72 (VC) and high surface area graphite 300 (HG). The effects of the Nafion ionomer content, and the Pt loading of the cathode catalyst layer as well as the Pt loading on the support on the performance of direct methanol fuel cells (DMFCs), were studied. The membrane electrode assemblies (MEAs) were analysed using current–voltage curves, cyclic voltammetry, electrochemical impedance spectroscopy (EIS) and adsorbed CO stripping voltammetry. Optimum Nafion to carbon (N/C) ratios (N/C being defined as the weight ratio of the Nafion ionomer to the carbon) were determined. The optimum N/C ratios were found to depend on the support as follows, 1.4, 0.7 and 0.5 for Pt/KB, Pt/VC and Pt/HG, respectively and to be independent of the Pt/C loading range of 20–80 wt% tested in this work. The highest DMFC performances, as well as the highest electrochemical active surface areas, and improved gas diffusivities, were achieved using these ratios. For the catalysts prepared in this work, the average Pt crystallite size was found to decrease with increasing surface area of the support for a particular Pt loading. MEAs made using KB as support and the optimal N/C ratio of 1.4 showed the best performances, i.e. higher than the VC and HG supports for any N/C ratio. The highest DMFC performance was observed using 60 wt% Pt on KB cathode electrodes of 1 mg Pt cm–2 loading and an N/C value of 1.4. For all three supports studied, the 60 wt% Pt on carbon loading resulted in the best DMFC performance. This may be linked to the Pt particle size and catalyst preparation method used in this work. In comparison to literature results, high DMFC performances were achieved using relatively ‘low' Pt and Ru loadings. For example, a maximum power density of >100 mW cm–2 at 60 °C was observed using a 1 mg Pt cm–2 cathode loading and a 2 mg PtRu cm–2 anode loading. 相似文献
13.
Novel submicrometer‐scale flat carbon fibers (SFCF) have been synthesized by catalytic chemical vapor deposition of acetylene over an Ni‐Al layered double hydroxide (NiAl‐LDH) compound, and the electrochemical activity of Pt supported on as‐synthesized SFCF for methanol oxidation has been investigated. The materials were characterized by power X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectra, and cyclic voltammetry tests. The results reveal that the active crystal facets of the NiAl2O4 spinel phase derived from NiAl‐LDH can deposit carbon atoms to grow SFCF, and that the co‐growing Ni nanoparticles are not catalytically active for the formation of SFCF. Furthermore, after support with Pt, the resultant Pt/SFCF electrocatalyst shows much higher activity for methanol oxidation than the Pt/C one in both acid and alkaline media, which is attributed to the combined beneficial effects of the microstructure of the SFCF support, improved electrical conductivity originating from the NiAl2O4 spinel catalyst embedded in SFCF, and improved dispersion of Pt particles through exposed Ni nanoparticles adhering intimately to the SFCF. 相似文献
14.
A direct methanol fuel cell using a mixture of O2 and CO2 at the cathode was evaluated using anion exchange materials and cathode catalysts of Pt and a non‐Pt catalyst. The MEA based on non‐noble metal catalyst Acta 4020 showed superior performance than Pt/C based MEA in terms of open circuit potential and power density in carbonate environment. The fuel cell performance was improved by applying anion exchange ionomer in the catalyst layer. A maximum power density of 4.5 mW cm–2 was achieved at 50 °C using 6.0 M methanol and 2.0 M K2CO3. 相似文献
15.
Chanho Pak Seung Jae Lee Seol-Ah Lee Hyuk Chang 《Korean Journal of Chemical Engineering》2005,22(2):214-218
To reduce the effect of methanol permeated from the anode, the structure of the cathode was modified from a single layer with
Pt black catalyst to two-layer with PtRh black and Pt black catalysts, respectively. The current density of the direct methanol
fuel cell (DMFC) using the two-layer cathode was improved to 228 mA/cm-2 compared to that (180 mA/cm-2) of the DMFC using the single layer cathode at 0.3 V and 303 K. From the cyclic voltammograms (CVs), it is indicated that
the amount of adsorbates on the metal catalyst in the two-layer cathode is less than that of adsorbates in the single layer
cathode after methanol test. In addition, the adsorbates were removed very rapidly by electrochemical oxidation from the two-layer
cathode. It is suggested fromex situ X-ray absorption near edge structure analysis that the d-electron vacancy of Pt atom in the two-layer cathode is not changed
by the methanol test. Thus, Pt is not covered with the adsorbates, which agrees well with the results of CV. 相似文献
16.
Pt-Ru catalysts prepared by high energy ball-milling for PEMFC and DMFC: Influence of the synthesis conditions 总被引:1,自引:0,他引:1
High energy ball-milling was used to prepare several unsupported Pt-Ru anode catalysts for PEM- and direct methanol fuel cells. Pt and Ru with a 50:50 nominal Pt/Ru ratio were ball-milled at various ball-to-powder weight ratios (from 4/1 to 12/1) and with various Pt:Ru:MgH2 proportions (from 1:1:2 to 1:1:10), where MgH2 is a leacheable dispersive agent. The presence of MgH2 is necessary to obtain unsupported catalysts with a specific surface area of between 50 and 75 m2 g−1. The ball-milling parameters greatly affected the relative proportions of the three phases constituting the catalysts. These phases are: Pt(Ru) alloy nanocrystallites, unalloyed Ru crystallites and nanocrystallites. The best CO tolerant catalyst is obtained by using a 12/1 ball-to-powder ratio and a 1:1:8 Pt:Ru:MgH2 proportion of dispersive agent. It is made of 57 at.% of a nanocrystalline (3 nm) Pt80Ru20 alloy, 42 at.% of a nanocrystalline (3 nm) Ru phase and 1 at.% of a crystalline (∼40 nm) Ru phase. This catalyst has the lowest Pt/Ru surface ratio (0.9), the highest content in nanocrystalline Ru, and the highest ratio of oxidized/metallic Ru (3.3). Both Pt-Ru alloy and nanocrystalline Ru participate to the CO tolerance. The best CO tolerant catalyst is, however, not the best catalyst in DMFC. The latter is obtained by using a 4/1 ball-to-powder ratio and a 1:1:6 Pt:Ru:MgH2 proportion. Within the starting 50:50 Pt-Ru nominal atomic ratio, no specific correlation was found between catalyst performance in DMFC and atomic surface Pt/Ru ratio, nor nanocrystalline Ru content, nor oxidized/metallic Ru ratio. Performances of the best ball-milled catalysts are compared to those of commercial unsupported catalysts in PEMFC and DMFC. 相似文献
17.
Wentao Ma Jingjie Wu Chunhui Shen Haolin Tang Mu Pan 《Journal of Applied Electrochemistry》2008,38(6):875-879
This paper describes an investigation of the role of nickel phthalocyanine-tetrasulfonic acid (NiPcTs) for methanol electro-oxidation
on a Pt/C catalyst. Cyclic voltammetry (CV) revealed that NiPcTs has no catalytic activity in methanol or CO electro-oxidation.
However, methanol electro-oxidation occurs faster on a Pt/C catalyst modified with NiPcTs than on the original Pt/C catalyst.
CO stripping results demonstrated that NiPcTs promotes electro-oxidation of adsorbed CO (COads) on the Pt/C catalyst, which is likely to be responsible for the enhancement of the methanol electro-oxidation rate. The
promotion effect of NiPcTs is attributable to its ability to modify the electron density of the Pt surface. The electron deficiency
of Pt0 in the NiPcTs-Pt/C catalyst is shown by the shift of the Pt0
4f peak to higher binding energies in the X-ray photoelectron spectrum. 相似文献
18.
A novel PtPd/C nanocrystals catalyst with truncated‐octahedral structure has been successfully prepared by ethylene glycol reduction to induce anisotropic growth in an isotropic medium by adding a small amount of Fe3+ species. Its structure, composition, and morphology are characterized by X‐ray diffraction, transmission electron microscopy, and scanning transmission electron microscopy‐energy dispersive spectroscopy elemental maps, respectively. The electrochemical measurements demonstrate that the highly dispersed and uniform PtPd/C nanocrystals have excellent poisoning tolerance, significantly higher electrocatalytic activity and durability for the methanol oxidation, as compared to solid solution PtPd/C and Pt/C catalysts. This may be ascribed to the stepped atoms and dangling bonds, which served as active sites for breaking chemical bonds during oxidation–reduction reaction; the high density of preferred crystal planes of (111) facets greatly enhanced the oxidation of poisonous residues during reaction. 相似文献
19.
We have prepared carbon‐supported nanoparticles with the heterogeneous structure of a PdPt shell on a PdCo core which are effective for the oxygen reduction reaction (ORR) in the presence of methanol. The preparation was based on the galvanic replacement reaction between PdCo/C nanoparticles and PtCl42–, a method of general utility which can be extended to the preparation of other core‐shell electrocatalysts. The heterogeneous PdCo‐core and PtPd‐shell architecture was confirmed by multiple techniques including high resolution transmission electron microscopy, energy dispersive X‐ray spectroscopy, powder X‐ray diffraction and X‐ray photoelectron spectroscopy. The activity of the PdCo@PdPt/C catalyst in ORR was evaluated in acidic solutions both with and without methanol (0.1 M). The results showed four to sixfold increases in activity over a standard Pt/C catalyst with no apparent loss of catalyst stability. It is inferred that the strain effect from the lattice mismatch between the shell and core components is the major contributor for the enhancement of ORR activity and selectivity. 相似文献
20.
Phosphomolybdic acid (H3PMo12O40, POM) was attempted to be used as the energy‐storage agent in this paper to avoid some problems of the direct methanol fuel cell (DMFC), such as catalyst poisoning and methanol permeation. Catalytic oxidation of methanol by aqueous POM on Al2O3 supported catalysts with Pt and Ru active metal was evaluated in the presence of liquid water. The process takes advantage of the high catalytic activities of platinum for methanol oxidation. The effects of temperature, reaction time, and methanol concentration on activity were observed. The catalytic activity of Pt/Al2O3 is better than that of Ru/Al2O3 for the oxidation of methanol by POM. The methanol conversion rate reached 93.55% on the Pt/Al2O3 at 80 °C after reaction for 1 h. The electrochemical experiments indicate that POM shows a larger current density in redox processes on an Au electrode than methanol. The redox process of reduced POM is a reversible multi‐electron transfer process. 相似文献