首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
Ruthenium-oxide nanosheet (RuO2ns) crystallites with thickness less than 1 nm were prepared via chemical exfoliation of a layered potassium ruthenate and deposited onto carbon supported platinum (Pt/C) as a potential co-catalyst for fuel cell anode catalysts. The electrocatalytic activity towards carbon monoxide and methanol oxidation was studied at various temperatures for different RuO2ns loadings. An increase in electrocatalytic activity was evidenced at temperatures above 40 °C, while little enhancement in activity was observed at room temperature. The RuO2ns modified Pt/C catalyst with composition of RuO2:Pt = 0.5:1 (molar ratio) exhibited the highest methanol oxidation activity. CO-stripping voltammetry revealed that RuO2ns promotes oxidation of adsorbed CO on Pt. In addition to the enhanced initial activity, the RuO2ns modified Pt/C catalyst exhibited improved stability compared to pristine Pt/C against consecutive potential cycling tests.  相似文献   

2.
Nafion stabilized inks of Vulcan XC-72 supported platinum (20 wt.%) nanoparticles (Pt/XC-72) were utilized to produce electrocatalytic films on glassy carbon. The catalysts were modified (activated) with phosphododecatungstic acid H3PW12O40 (PW12). Comparison was made to bare (PW12-free) electrocatalytic films. Electroreduction of dioxygen was studied at 25 °C in 0.5 mol dm−3 H2SO4 electrolyte using rotating disk voltammetry. For the same loading of platinum (≈95 μg cm−2) and for the approximately identical distribution of the catalyst, the reduction of oxygen at a glassy carbon electrode modified with the ink containing PW12 proceeded at ca. 30-60 mV more positive potential (depending on the PW12 content), and the system was characterized by a higher kinetic parameter (rate of heterogeneous electron transfer), when compared to the PW12-free electrocatalyst. Gas diffusion electrodes with Pt/XC-72 supported on carbon paper (Pt loading 1 mg cm−2) were also tested. Under the same experimental conditions, while the exchange current density and the total resistance contribution to polarization components, computed from the galvanostatic polarization curves were found to be clearly higher and lower, respectively, for the ink modified with PW12 relative to the unmodified system. The results demonstrate that addition of heteropolytungstatic acid (together with Nafion) enhances the electrocatalytic activity of platinum towards reduction of oxygen.  相似文献   

3.
Xuguang Li 《Electrochimica acta》2006,51(17):3477-3483
In this work, carbon supported PtxPd1−x (x = 0-1) nanocatalysts were investigated for formic acid oxidation. These catalysts were synthesized by a surfactant-stabilized method with 3-(N,N-dimethyldodecylammonio) propanesulfonate (SB12) as the stabilizer. They show better Pt/Pd dispersion and higher catalytic performance than the corresponding commercial catalysts. Furthermore, the electrocatalytic properties of PtxPd1−x/C were found to depend strongly on the Pt/Pd deposition sequence and on the Pt/Pd atomic ratio. At a lower potential, formic acid oxidation current on co-deposited PtxPd1−x/C catalysts increase with increasing Pd surface concentration. Nanoscale Pd/C is a promising formic acid oxidation catalyst candidate for the direct formic acid fuel cell.  相似文献   

4.
In this work, we study the preparation, structural characterization, and electrocatalytic analysis of robust Pt and Pd-containing catalyst structures for silicon-based formic acid micro fuel cells. The catalyst structures studied were prepared and incorporated into the silicon fuel cells by a post CMOS-compatible process of electrodeposition, as opposed to the more common introduction of nanoparticle-based catalyst by ink painting. Robust, high surface area, catalyst structures consisting of pure Pt, pure Pd, and Pt/Pd = 1:1 were obtained. In addition, Pt/Pd catalyst structures were obtained via spontaneous deposition on the electrodeposited pure Pt structure. The catalyst structures were characterized electrochemically using cyclic voltammetry and chronoamperometry. All Pd-containing catalyst structures facilitate formic acid oxidation at the lower potentials and deliver higher oxidation currents compared to pure Pt catalyst structures. Fuel cells of these catalyst structures show that pure Pd catalyst structures on the anode exhibit the highest peak power density, i.e. as high as 28.0 mW/cm2. The MEMS compatible way of catalyst electrodeposition and integration presented here has yielded catalyst structures that are highly active towards formic acid oxidation and are sufficiently robust to be compatible with post-CMOS processing.  相似文献   

5.
铂微粒修饰聚苯胺膜电极对甲酸电催化氧化的研究   总被引:1,自引:0,他引:1  
采用循环伏安法研究Pt盘电极 (Pt)、铂微粒修饰Pt盘电极 [Pt(Pt) ]和Pt微粒修饰聚苯胺膜电极 [PAN(Pt) ]对甲酸电催化氧化行为的影响 ,比较了它们对甲酸电催化氧化的活性 ,发现PAN(Pt)电极对甲酸电催化氧化的表观电流密度为 3 79× 10 2 mA·cm-2 ,分别比Pt、Pt(Pt)和Pt-PDMA/Pt电极约高 2 35、2 5和 6 3倍。峰电位比Pt PDMA/Pt电极约低 0 16V。  相似文献   

6.
Zhan Lin 《Electrochimica acta》2009,54(27):7042-9377
Pt/carbon composite nanofibers were prepared by electrodepositing Pt nanoparticles directly onto electrospun carbon nanofibers. The morphology and size of Pt nanoparticles were controlled by the electrodeposition time. The resulting Pt/carbon composite nanofibers were characterized by running cyclic voltammograms in 0.20 M H2SO4 and 5.0 mM K4[Fe(CN)6] + 0.10 M KCl solutions. The electrocatalytic activities of Pt/carbon composite nanofibers were measured by the oxidation of methanol. Results show that Pt/carbon composite nanofibers possess the properties of high active surface area and fast electron transfer rate, which lead to a good performance towards the electrocatalytic oxidation of methanol. It is also found that the Pt/carbon nanofiber electrode with a Pt loading of 0.170 mg cm−2 has the highest activity.  相似文献   

7.
In this work, formic acid oxidation on Pt nanoelectrodes modified by irreversible adsorption of Bi is presented. The coverage of Bi, as measured by voltammetry and X-ray photoelectron spectroscopy, was controlled from 0.05 to 0.25. Chronoamperometric measurement of the catalytic activities of the Bi-modified Pt nanoelectrodes revealed that the catalytic enhancement depended on oxidation potential and Bi coverage: elemental Bi in the potential range from −0.1 V to 0.6 V enhanced formic acid oxidation by factor of 4, while partially oxidized Bi in the potential range from 0.3 V to 0.7 V increased by factor of 8. The enhancement in the latter potential range was effective only when the Bi coverage was more than 0.18. Single cell performance of the Pt nanoelectrodes modified by Bi increased by factor of 2-3, depending on operation conditions such as formic acid concentration, temperature, and humidity in the feeding gas into cathode. When the Bi coverage was more than 0.18, the single cell performances were nearly identical. Based on measurement of adsorbed CO and catalytic poison from formic acid, an oxidation path not involving catalytic poison in the potential range from 0.5 V to 0.7 V is discussed in detail.  相似文献   

8.
John L. Haan 《Electrochimica acta》2009,54(16):4073-19418
We found for the first time that solution pH makes a significant difference in the rate of a prototypical electrocatalytic reaction, formic acid electrooxidation, under conditions where H+ and OH do not adsorb strongly on the surface, and we demonstrate that the results can be explained using the Marcus model. We changed the pH of formic acid solutions and found enhanced oxidation on Pd and Pt black catalysts with increased pH. The interpolated current density for the oxidation of 1 M HCOOH in 0.1 M perchlorate electrolyte after 2 min at 0.22 V vs. SHE on Pt increased 30-fold from 0.005 to 0.17 mA cm−2 as the pH was increased from 1 to 5, while for Pd there was a 4-fold increase from 0.12 to 0.53 mA cm−2. The data was also interpolated at a current density of 0.1 mA cm−2, and the potential required to reach this current shifted negative 62 mV per pH on palladium and 56 mV per pH on platinum. A 24 h experiment compared two solution pH, in which the higher pH demonstrated remarkably stronger performance. In addition, the potential for oxidation of surface CO shifts negative on both catalysts, as much as ∼57 mV per pH on Pd.  相似文献   

9.
The behaviours of irreversible adsorption (IRA) of Sn adatoms on Pt(1 0 0), Pt(1 1 1) and Pt(1 1 0) electrodes were characterized using cyclic voltammetry. It has revealed that Sn can adsorb irreversibly on Pt(1 0 0) and Pt(1 1 1), while not significantly on Pt(1 1 0) electrode. Quantitative analysis of the relationship between 1 − θH and θSn suggests that Sn adatoms may adsorb preferably on hollow sites of Pt(1 1 1) (threefold) and Pt(1 0 0) (fourfold) planes, which is in accordance respectively with the values 0.31 and 0.21 of coverage of IRA Sn adatoms in saturation adsorption determined on these electrodes. The IRA Sn adatoms on different basal planes of Pt single crystal yield different impact on the electrocatalytic oxidation of ethanol. It has revealed that the IRA Sn adatoms on Pt(1 0 0) electrode have declined the activity for ethanol oxidation, while IRA Sn adatoms on Pt(1 1 1) have enhanced remarkably the electrocatalytic activity with Sn coverage θSn between 0.09 and 0.18. The oxidation peak potential Ep and the current density jp of ethanol oxidation on Pt(1 1 1)/Sn were varied with θSn, and the highest jp (1258 μA cm−2) as well as the lowest Ep (0.20 V) were measured simultaneously at θSn around 0.14. In comparison with the data obtained on a bare Pt(1 1 1), the Ep was shifted negatively by 65 mV and the jp has been enhanced to about 1.7 times on the Pt(1 1 1)/Sn (θSn = 0.14), which is ascribed to hydroxyl species adsorption at relatively low potentials on Pt(1 1 1)/Sn surfaces. The current study is of importance in revealing the fundamental aspects of modification of the basal planes of Pt single crystal using Sn adatoms, and the impact of this modification on electrocatalytic activity towards ethanol oxidation.  相似文献   

10.
We reported that various compositions of AuPt nanoparticles synthesized as an anode material for formic acid fuel cell were investigated. Its surface characteristics were systematically analyzed using XRD and TEM and anodic electrocatalytic activity was studied using a linear sweep voltammetry technique in 0.5 M H2SO4 + 1 M HCOOH. In addition, the voltage-current curve and power density of home-made AuPt-based membrane-electrode-assembly (MEA) and commercial Pt0.5Ru0.5-based MEA was measured at 60 °C in 9 M formic acid. The maximum power density of Au0.6Pt0.4-based MEA was 30% higher than that of PtRu-based MEA which were 200 mW cm−2 and 155 mW cm−2, respectively.  相似文献   

11.
In the present work, a variety of Pt-based bimetallic nanostructured materials including nanoporous Pt, Pt-Ru, Pt-Ir, Pt-Pd and Pt-Pb networks have been directly grown on titanium substrates via a facile hydrothermal method. The as-fabricated electrodes were characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and electrochemical methods. The active surface areas of these nanoporous Pt-based alloy catalysts are increased by over 68 (Pt-Pd), 69 (Pt-Ru) and 113 (Pt-Ir) fold compared to a polycrystalline Pt electrode. All these synthesized nanoporous electrodes exhibit superb electrocatalytic performance towards electrochemical oxidation of methanol and formic acid. Among the five nanoporous Pt-based electrodes, the Pt-Ir shows the highest peak current density at +0.50 V, with 68 times of enhancement compared to the polycrystalline Pt for methanol oxidation, and with 86 times of enhancement in formic acid oxidation; whereas the catalytic activity of the nanoporous Pt-Pb electrode outperforms the other materials in formic acid oxidation at the low potential regions, delivering an enhanced current density by 280-fold compared to the polycrystalline Pt at +0.15 V. The new approach described in this study is suitable for synthesizing a wide range of bi-metallic and tri-metallic nanoporous materials, desirable for electrochemical sensor design and potential application in fuel cells.  相似文献   

12.
Novel carbon supported Pt/SnOx/C catalysts with Pt:Sn atomic ratios of 5:5, 6:4, 7:3 and 8:2 were prepared by a modified polyol method and characterized with respect to their structural properties (X-ray diffraction (XRD) and transmission electron microscopy (TEM)), chemical composition (XPS), their electrochemical properties (base voltammetry, COad stripping) and their electrocatalytic activity and selectivity for ethanol oxidation (ethanol oxidation reaction (EOR)). The data show that the Pt/SnOx/C catalysts are composed of Pt and tin oxide nanoparticles with an average Pt particle diameter of about 2 nm. The steady-state activity of the Pt/SnOx/C catalysts towards the EOR decreases with tin content at room temperature, but increases at 80 °C. On all Pt/SnOx/C catalysts, acetic acid and acetaldehyde represent dominant products, CO2 formation contributes 1-3% for both potentiostatic and potentiodynamic reaction conditions. With increasing potential, the acetaldehyde yield decreases and the acetic acid yield increases. The apparent activation energies of the EOR increase with tin content (19-29 kJ mol−1), but are lower than on Pt/C (32 kJ mol−1). The somewhat better performance of the Pt/SnOx/C catalysts compared to alloyed PtSnx/C catalysts is attributed to the presence of both sufficiently large Pt ensembles for ethanol dehydrogenation and C-C bond splitting and of tin oxide for OH generation. Fuel cell measurements performed for comparison largely confirm the results obtained in model studies.  相似文献   

13.
Tungsten and nickel tungsten carbides were evaluated as the anode catalysts of a polymer electrolyte fuel cell (PEFC). These catalysts were prepared by the temperature-programmed carburization of tungsten and nickel tungsten oxides from 573 to 873-1073 K in a stream of 20% CH4/H2 and kept at temperature for 3 h. The 30% tungsten and nickel tungsten carbides mixed with Ketjen carbon (KC) were evaluated by cyclic voltammetry and linear sweep voltammetry using a rotating disk electrode and electrocatalytic activity (I-V performance) using a single cell. The W1023/KC catalyst achieved a power density of 6.4 mW/cm2 (current density: 15.2 mA/cm2) which corresponded to 5.7% of that achieved by a commercial 20% Pt/C catalyst in a single cell (20% Pt/C: 111.7 mW/cm2) using our setup. From the XRD data, α-W2C together with a small amount of WC was active during the anodic oxidation. The maximum power density of the 30 wt% 873 K-carburized NiW/KC was 8.2 mW/cm2 at the current density of 19.0 mA/cm2 which was 7.3% of the 20 wt% Pt/C.  相似文献   

14.
Pb and Sb modified Pt/C catalysts for direct formic acid fuel cells   总被引:1,自引:0,他引:1  
Xingwen Yu 《Electrochimica acta》2010,55(24):7354-7361
PtPb/C and PtSb/C bi-metallic catalysts were synthesized by chemical deposition of Pb or Sb on a commercial 40% Pt/C catalyst. The performances of catalysts with a range of compositions were compared in a multi-anode direct formic acid fuel cell in order to optimize compositions and evaluate the statistical significance of differences between catalysts. The catalytic activity for formic acid oxidation increased approximately linearly with adatom coverage for both PtPb/C and PtSb/C, to maxima at fractional coverages of ca. 0.7. At a cell voltage of 0.5 V, the currents at the optimum Pb or Sb coverages were ca. 8 times higher than at unmodified Pt/C. CO-stripping results indicate that the presence of Pb or Sb facilitates the oxidation of adsorbed CO. In addition, both metals appear to produce electronic effects that inhibit poison formation on the modified Pt surface.  相似文献   

15.
A cuprous oxide (Cu2O) nanoparticles modified Pt rotating ring-disk electrode (RRDE) was successfully fabricated, and the electrocatalytic determination of p-nitrophenol (PNP) using this electrode was developed. Cu2O nanoparticles were obtained by reducing the copper-citrate complex with hydrazine hydrate (N2H4·H2O) in a template-free process. The hydrodynamic differential pulse voltammetry (HDPV) technique was applied for in situ monitor the photoelectrochemical behavior of PNP under visible light using nano-Cu2O modified Pt RRDE as working electrode. PNP undergoes photoelectrocatalytic degradation on nano-Cu2O modified disk to give electroactive p-hydroxylamino phenol species which is compulsive transported and can only be detected at ring electrode at around 0.05 V with oxidation signal. The effects of illumination time, applied bias potential, rotation rates and pH of the reaction medium have been discussed. Under optimized conditions for electrocatalytic determination, the anodic current is linear with PNP concentration in the range of 1.0 × 10−5 to 1.0 × 10−3 M, with a detection limit of 1.0 × 10−7 M and good precision (RSD = 2.8%, n = 10). The detection limit could be improved to 1.0 × 10−8 M by given illumination time. The proposed nano-Cu2O modified RRDE can be potentially applied for electrochemical detection of p-nitrophenol. And it also indicated that modified RRDE technique is a promising way for photoelecrocatalytic degradation and mechanism analysis of organic pollutants.  相似文献   

16.
Qian Cheng 《Electrochimica acta》2010,55(27):8273-8279
Pt tetrahexahedral (Pt-THH) nanocrystals enclosed with 24 {h k 0} facets, Pt nanothorns (Pt-Thorn) with a high surface density of atomic steps, and congeries of Pt nanoparticles (Pt-NP) were prepared and served as catalysts to study the electrocatalytic reduction of both adsorbed and solution nitric oxide. The structure sensitivity for the reduction of a saturated NO adlayer on the Pt nanocrystals (NCs) of different shape was studied by cyclic voltammetry (CV) and in situ FTIR spectroscopy in sulphuric acid solutions. The results revealed that two types of NO adsorbates can be reduced independently at separated potentials, i.e. the reduction of linear bonded NO (NOL) on the Pt-NP electrode gives rise to a current peak at −0.01 V (vs. SCE), while the bridge adsorbed NO (NOB) yields a current peak at −0.08 V. The in situ SNIFTIRS results confirmed the assignment of NO adsorbates, i.e. the NOB species yielding a IR absorption bipolar band with its negative-going peak at 1636 cm−1 and positive-going peak around 1610 cm−1, and the NOL species giving rise to a bipolar band with its negative-going peak at 1809 cm−1 and positive-going peak around 1720 cm−1. It has determined that the NOL species can be preferentially formed on the Pt NCs with open surface structure, i.e. the more open the surface structure of the Pt NCs, the larger the relative quantity of NOL versus NOB. It has also revealed that the Pt NCs with a high surface density of atomic steps exhibit superior electrocatalytic activity for the reduction of solution NO species. The steady-state current density of NO reduction on Pt-THH NCs is 7.5-12 times as large as that on Pt-NP, and that on Pt-Thorn is 2.5-4 times of that on Pt-NP in the reduction potential region of electrochemical dynamic control.  相似文献   

17.
Sudip Chakraborty 《Carbon》2010,48(11):3242-3249
We describe a simple approach for the synthesis of nanosized Pd particles supported on multiwall carbon nanotubes (MWCNTs) and their electrocatalytic performance in the oxidation of formic acid and the reduction of oxygen. The metal precursors are pre-organized on poly(diallyldimethylammonium) chloride-wrapped MWCNTs by electrostatic interaction and chemically reduced to obtain Pd nanoparticles. The MWCNT-supported nanoparticles are characterized by UV-visible spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy and electrochemical measurements. MWCNTs are uniformly decorated with closely packed array of nanoparticles. The nanoparticles on the MWCNTs have spherical and rod-like shapes with size ranging from 5 to 10 nm. XRD and selected area electron diffraction measurements of the nanoparticles show (1 1 1), (2 0 0) and (2 2 0) reflections of the Pd lattice. The electrocatalytic activity of the nanoparticles towards oxidation of formic acid and reduction of oxygen is examined in acidic solution. The MWCNT-supported particles exhibit excellent electrocatalytic activity. The electrocatalytic reduction of oxygen follows the peroxide pathway. Surface morphology and coverage of particles on the nanotubes control the electrocatalytic activity. The large surface area and high catalytic activity of the MWCNT-supported nanoparticles facilitate the electrocatalytic reactions at a favorable potential.  相似文献   

18.
Highly active Pt-decorated Au nanoparticles on carbon support with Pt:Au mole ratio ranging from 1:10 to 1:2 was successfully synthesized based on successive reduction strategy. The successful formation of this structure was suggested by transmission electron microscopy, UV-vis and voltammetry analyses. The electrocatalytic activity of this decorated structure toward formic acid oxidation surprisingly increases despite the low amount of Pt being used. At 0.1 V, the specific activity of PtAu/C with Pt/Au mole ratio 1:8 was more than one order of magnitude higher than the conventional Pt/C. The enhancement was attributed to the less Pt ensemble sites that the decorated structure possesses (ensemble effect) and the increase in the Pt atom reactivity on Au nanocrystal. The formic acid oxidation mechanism on this decorated structure was also elucidated using electrochemical impedance spectroscopy technique. It is proposed that besides the dehydrogenation reaction pathway happening on clean Pt sites, the reactive intermediate i.e. formate species could also be oxidized by the adsorbed water species on Pt at higher potential.  相似文献   

19.
Carbon supported nanoparticle catalysts of PdxPt1−x (0 ≥ x ≥ 1) were synthesized using a modified polyol method and poly(N-vinyl-2-pyrrolidone) (PVP) as a stabilizer. Resulting nanoparticles were characterized by X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and chronoamperommetry (CA) study for formic acid electro-oxidation. Surface composition of the synthesized nanoparticles found from XPS revealed the Pt surface segregation even for the Pd-rich compositions. It is suggested that the surface segregation behavior in PdPt nanoparticles supported on carbon may be influenced, in addition to the difference in Pd and Pt surface energies, by particle size and particle interaction with the support. According to CA, the carbon supported Pd nanoparticles show the highest initial activity towards formic acid electro-oxidation at the potential of 0.3 V (RHE), due to the promotion of the direct dehydrogenation mechanism. However its stability is quite poor resulting in the fast deactivation of the Pd surface. Addition of Pt considerably improves the steady-state activity of Pd in 12 h CA experiment. CA measurements show that the most active catalyst is Pd0.5Pt0.5 of 4 nm size, which displays narrow size distribution and Pd to Pt surface atomic ratio of 27-73.  相似文献   

20.
Behaviors of irreversibly adsorbed Sb adatoms on Pt(100), Pt(110), Pt(320) and Pt(331) single crystal surfaces and electrocatalytic properties of the modified electrodes towards formic acid oxidation were investigated. It was determined that Sb adatoms are stable at potentials below 0.45 V (SCE) on Pt(100) and Pt(110), below 0.40 V on Pt(320), and below 0.35 V on Pt(331). Different coverage of Sbad was obtained conveniently by partially stripping Sbad from saturation coverage of Sbad. It has demonstrated that the redox behaviors of Sb adatoms and the coadsorption properties of Sbad with Had depend strongly on the orientations of the Pt single crystal electrode. Significant catalytic effects towards HCOOH oxidation were observed on Pt single crystal electrodes modified with Sb adatoms, which consist of (1) the inhibition of dissociative adsorption of HCOOH, (2) the enhancement of oxidation current, and (3) the negative shift of oxidation potential that was measured about 220 mV on Pt(110)/Sb, 110 mV on (110) sites of Pt(320)/Sb, and 100 mV on Pt(331)/Sb electrode. Neither enhancement of oxidation current nor negative shift of oxidation potential can be observed on Pt(100)/Sb electrode. The results suggested that electronic effect is the main effect presented on Pt(110), Pt(320) and Pt(331) surface upon Sb modification, while geometric effect is considered to the major effect on Pt(100) electrode.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号