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1.
In this work, we investigated the effect of the carbon nanotubes (CNT) as alternative support of cathodes for oxygen reduction reaction (ORR) in alkaline medium. The Pt and Pt–Ag nanomaterials supported on CNT were synthesized by sonochemical method. The crystalline structure, morphology, particle size, dispersion, specific surface area, and composition were investigated by XRD, SEM-EDS, TEM, HR-TEM, N2 adsorption-desorption and XPS characterization. The electrochemical activity for ORR was evaluated by cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) in alkaline medium. The electrochemical stability was researched by an accelerated degradation test (ADT). Pt/CNT showed the better electrocatalytic activity towards ORR compared with Pt–Ag/CNT and Pt/C. Pt/CNT exhibited higher specific activity (1.12 mA cm?2 Pt) than Pt/C (0.25 mA cm?2 Pt) which can be attributed to smaller particle size, Pt-CNT interaction, and Pt load (5 wt%). The Pt monometallic samples supported on CNT and Vulcan showed higher electrochemical stability after ADT than Pt–Ag bimetallic. The ORR activity of all materials synthesized proceeded through a four-electron pathway. Furthermore, the EIS results showed that Pt/CNT exhibited the lower resistance to the transfer electron compared with conventional Pt/C and Pt–Ag/CNT.  相似文献   

2.
Carbon supported Pt3Y (Pt3Y/C) and PtY (PtY/C) were investigated as oxygen reduction reaction (ORR) catalysts. After synthesis via reduction by NaBH4, the alloy catalysts exhibited 10-20% higher mass activity (mA mgPt−1) than comparably synthesized Pt/C catalyst. The specific activity (μA cmPt−2) was 23 and 65% higher for the Pt3Y/C and PtY/C catalysts, respectively, compared to Pt/C. After annealing at 900 °C under a reducing atmosphere, Pt3Y/C-900 and PtY/C-900 catalysts showed improved ORR activity; the Pt/C and Pt/C-900 (Pt/C catalyst annealed at 900 °C) catalysts exhibited specific activities of 334 and 393 μA cmPt−2, respectively, while those of the Pt3Y/C-900 and PtY/C-900 catalysts were 492 and 1050 μA cmPt−2, respectively. X-ray diffraction results revealed that both the Pt3Y/C and PtY/C catalysts have a fcc Pt structure with slight Y doping. After annealing, XRD showed that more Y was incorporated into the Pt structure in the Pt3Y/C-900 catalyst, while the PtY/C-900 catalyst remained unchanged. Although these results suggested that the high ORR activity of the PtY/C-900 catalyst did not originate from Pt-Y alloy formation, it is clear that the Pt-Y system is a promising ORR catalyst which merits further investigation.  相似文献   

3.
The relatively low efficiency of the reaction of oxygen reduction (ORR) remains among the main obstacles for hydrogen fed proton exchange membrane fuel cells (H-PEMFCs) commercialization.In the present work, PtNiMo ternary alloy catalysts are obtained through reducing by NaBH4 and subsequent thermal annealing in NH3 at 1.0 atm. The as prepared catalysts are physico-chemically (XRD, TEM and XPS) characterized, exhibiting alloy nanostructure.From the electrochemical tests it is found that they exhibit high ORR activity in aqueous solutions saturated with O2 and acidified with HClO4. From the as synthesized catalysts, Pt3Ni3MoN/C shows the highest mass activity (539.41 mA mg1 Pt); 3.5 times greater than that observed over commercial Pt/C (154.46 mA mg1 Pt). Moreover, they show very good stability, while their ORR activity is only slightly altered after 5,000 cycles.These highly performing and low cost catalysts could thus open up new possibilities for the commercialization of hydrogen fed PEMFCs.  相似文献   

4.
High-performance platinum nanoparticle catalysts (Pt–NPCs) remain the most widespread applied electrocatalysts for oxygen reduction reaction (ORR). Here, cetyltrimethylammonium bromide (CTAB), a surface-controlling agent, is introduced to modulate the microstructure and size of Pt nanoparticles (NPs) via a microwave-assisted heating process. The Pt-NPC assisted by 5 wt% CTAB exhibits the highest mass activity (MA) of 0.072 A mgPt?1 and specific activity (SA) of 0.077 mA cm?2, higher than those of commercial Pt/C (0.023 A mgPt?1 and 0.035 mA cm?2). Transmission electron microscopy (TEM) results indicate that Pt NPs are uniformly dispersed onto carbon supports with an average size of 2.39 nm. When applied in membrane electrode assembly (MEA), it exhibits the highest power density of 1.142 W cm?2, which is about 1.24 times larger than that of commercial Pt/C.  相似文献   

5.
The development of highly active and efficient heterogeneous catalytic oxidation system has become an attractive research field. In this paper, a catalyst (RuCo/N-CNT@PEDOT-OH/Pt) from platinum nanoparticles (Pt NPs) supported on hydroxyl-grafted poly(3,4-ethylenedioxythiophene) (PEDOT–OH)-modified RuCo, N-tridoped bamboo-like carbon nanotubes (RuCo/N-CNT) are used for direct methanol fuel cell (DMFC). The electrocatalytic activity of RuCo/N-CNT@PEDOT-OH/Pt is systematically compared with RuCo/N-CNT/Pt (Pt NPs supported on RuCo/N-CNT without PEDOT-OH) in the methanol oxidation reaction (MOR). The growth mechanism of carbon nanotubes and the role of heteroatom doping in the electrocatalytic process is explored. The catalysts show excellent electrocatalytic performance with high stability for MOR. It is found that the mass activity (MA) of the RuCo/N-CNT@PEDOT-OH/Pt (1961.3 mA mg?1Pt) for MOR was higher than that of RuCo/N-CNT/Pt (1470.1 mA mg?1Pt) and the commercial Pt/C catalysts (281.0 mA mg?1Pt), indicating the positive effect of the PEDOT-OH in the electrocatalytic MOR. In addition, density functional theory (DFT) calculations verify the possible mechanism pathways of the obtained RuCo/N-CNT@PEDOT-OH/Pt catalyst. This presented catalyst offers new inspiration for designing efficient electrocatalysts for methanol oxidation.  相似文献   

6.
High cost and poor durability of Pt-based cathode catalysts for oxygen reduction reaction (ORR) severely hamper the popularization of proton exchange membrane fuel cells (PEMFCs). Tailoring carbon support is one of effective strategies for improving the performance of Pt-based catalysts. Herein, petroleum vacuum residue was used as carbon source, and nitrogen-doped porous carbon (N-PPC) was synthesized using a simple template-assisted and secondary calcination method. Small Pt nanoparticles (Pt NPs) with an average particles size of 1.8 nm were in-situ prepared and spread evenly on the N-PPC. Interestingly, the lattice compression (1.08%) of Pt NPs on the N-PPC (Pt/N-PPC) was clearly observed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), which was also verified by the shift of (111) crystal plane of Pt on N-PPC to higher angles. The X-ray photoelectron spectroscopy (XPS) results suggest that the N-PPC support had a strong effect on anchoring Pt NPs and endowing surface Pt NPs with lowered d band center. Thus, the Pt/N-PPC as a catalyst simultaneously boosted the ORR activity and durability. The specific activity (SA) and mass activity (MA) of the Pt/N-PPC at 0.9 V reached 0.83 mA cm−2 and 0.37 A mgPt−1, respectively, much higher than those of the commercial Pt/C (0.21 mA cm−2 and 0.11 A mgPt−1) in 0.1 M HClO4. The half-wave potential (E1/2) of Pt/N-PPC exhibited only a minimal negative shift of 7 mV after 30,000 accelerated durability tests (ADT) cycles. More importantly, an H2–O2 fuel cell with a Pt/N-PPC cathode achieved a power density of 866 mW cm−2, demonstrating that the prepared catalyst has a promising application potential in working environment of PEMFCs.  相似文献   

7.
A simple, rapid and energy-saving method has been used to synthesize nanostructured tungsten carbide on graphitized carbon (WC/gC) materials. The procedures include the ion exchange of the ion-exchange resin as original precursor with targeting ions and heat treatment by an intermittent microwave heating (IMH) method. The resulting product was loaded by Pt nanoparticles to form a uniformly dispersed nanocomposite (Pt-WC/gC). The samples are characterized by physical and electrochemical methods. The Pt-WC/gC as electrocatalyst for oxygen reduction reaction shows high activity proved by the Pt-mass activity of 207.4 mA mg−1Pt which is much higher than that of 107.4 mA mg−1Pt on Pt/C at 0.9 V. The onset potential for methanol oxidation is 100 mV more negative than that on Pt/C electrocatalyst. The synthesis of other types of nanomaterials based on this method is current under way to demonstrate the general suitability.  相似文献   

8.
Designing oxygen reduction reaction (ORR) catalysts with high activity and long durability is significant for the development of proton exchange membrane fuel cells. Herein, the optimized platinum nanowires are used as templates for inducing growth of cobalt-containing metal-organic framework, deriving uniform nanofibers. After the calcination, the metal ions are transferred into the nitrogen-rich porous carbon, and wrapped by the carbon skeleton to form the PtCo bimetal incorporated nanofibers as high-performance ORR electrocatalyst. The Pt4Co@NC-900 catalyst yields high specific activity (1.37 mA cm−2) in comparison to Pt/C (0.38 mA cm−2). The mass activity (MA) of Pt4Co@NC-900 catalyst is approximately 3.8-fold higher than that of the commercial Pt/C under acidic conditions. After the accelerated durability tests, the Pt4Co@NC-900 catalyst presents only 16% loss in MA, while Pt/C catalyst retains 73.0% of the initial MA. The improved ORR performance can be ascribed to the synergistic interaction between Co and Pt.  相似文献   

9.
Synthesis of Pt-based catalysts with high activity and durability for oxygen reduction reaction (ORR) remains a very challenging task in the field of fuel cells. Here, Co-doped Pt nanoparticles (NP) with surface-defect ZrO2 are supported on the multi-walled carbon nanotubes (MWCNTs) (denoted as Pt–Co + ZrO2/MWCNTs). The Pt–Co + ZrO2/MWCNTs displays an ORR mass activity of 0.98 A mgPt?1 at 0.9 V, which is 4.1-fold higher than that of the commercial Pt/C (0.238 A mgPt?1). Further durability test shows that the Pt–Co + ZrO2/MWCNTs remains nearly unchanged ORR mass activity after 50000 accelerated durability testings (ADTs). Based on the mass performance and surface performance, the fuel cell with Pt–Co + ZrO2/MWCNTs cathode has far better power performance than that with commercial Pt/C. Moreover, the fuel cell with Pt–Co + ZrO2/MWCNTs cathode undergo only a 6.1% maximum power loss after 50000 ADTs. However, that with commercial Pt/C cathode after 30000 ADTs has 39.6% maxinum power loss. More impressively, compared to the 220 mV loss of Pt/C after 30000 ADTs, the Pt–Co + ZrO2/MWCNTs cathode also displays only 20 mV loss at 0.8 A/cm2 after 50000 ADTs. The enhanced intrinsic activity of Pt–Co + ZrO2/MWCNTs may be attributed to the Co-doped Pt NPs and interface effect of Co-doped Pt NPs and surface defect-rich ZrO2.  相似文献   

10.
We report the use of nitrogen-doped three-dimensional carbon frameworks (N-MCF) to promote the catalytic performance of nano-sized Pt electrocatalyst for the catalysis of oxygen reduction reaction (ORR). The N-MCF, obtained by pyrolysis of zeolitic imidazolate framework, provides abundant edges, defects, and heteroatom-doped sites to anchor Pt nanoparticles, leading to strong Pt-support interaction and excellent particle dispersion within its three-dimensional mass transport channels. Electrochemical results show only 8 mV degradation in the half-wave potential after accelerated durability test for the N-MCF supported Pt catalysts. Meanwhile, the mass activity and specific activity of Pt/N-MFC could reach 246 mA mg−1Pt and 0.276 mA cm−2 at 0.90 VRHE, which is better than that of commercial Pt/C. Moreover, the high Pt utilization of Pt/N-MFC (186 mg Pt kW−1) could reach 1.9 times than that of fuel cell fabricated with commercial Pt/C cathode.  相似文献   

11.
A series of Pt-Ir thin films envisaged for application as fuel cell cathodic catalysts are deposited by dc co-sputtering from pure metal targets. To achieve different metal ratios, the sputtering power applied on the iridium target (PIr) is varied in the range 0-100 W at constant power of the Pt target (PPt). The influence of the sputtering power on the film composition, morphology, and surface structure is analysed by energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The catalytic activity towards oxygen reduction reaction (ORR) is evaluated in sulphuric acid solutions applying the methods of cyclic voltammetry and potentiodynamic polarization curves. The performed morphological and electrochemical investigations reveal that catalytic efficiency of the co-sputtered Pt-Ir films is superior compared to pure Pt. The ORR is most intensive on the sample deposited at power ratio PPt:PIr = 100:30 W containing 11 at.% Ir that has also the most developed active surface. The ORR current density for this film achieved at 0.825 V in acid solution (4.1 mA cm−2) is about 6 times higher than for pure Pt (0.67 mA cm−2). The improved activity of the thin co-sputtered Pt-Ir over Pt allows for essential reduction of the catalyst loading at preserved performance.  相似文献   

12.
13.
Electrochemical reactions such as the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and methanol oxidation reaction (MOR) are essential for energy conversion applications such as water electrolysis and fuel cells. Furthermore, Pt or Ir-related materials have been extensively utilized as electrocatalysts for the OER, ORR, and MOR. To reduce the utilization of precious metals, innovative catalyst structures should be proposed. Herein, we report a bi-metallic phosphide (Ni2P and PdP2) structure surrounded by graphitic carbon (Ni–Pd–P/C) with an enhanced electrochemical activity as compared to conventional electrocatalysts. Despite the low Pd content of 3 at%, Ni–Pd–P/C exhibits a low overpotential of 330 mV at 10 mA cm?2 in the OER, high specific activity (2.82 mA cm?2 at 0.8 V) for the ORR, and a high current density of 1.101 A mg?1 for the MOR. The superior electrochemical performance of Ni–Pd–P/C may be attributed to the synergistic effect of the bi-metallic phosphide structure and core-shell structure formed by graphitic carbon.  相似文献   

14.
The objective of this study was to fabricate an efficient structural catalyst electrode of Pt/C consisting of double catalyst layers (DCL) with catalyst-ink spray and electrophoresis deposition (EPD) methods. The prepared Pt/C DCL electrode with Pt-dispersed and Pt-concentrated catalyst layers demonstrated better electrochemical properties than individual Pt/C single catalyst layer (SCL) electrodes. An S1E1 DCL electrode with Pt loading weight ratio of 1:1 between the Pt-dispersed and Pt-concentrated layers exhibited a higher electrochemical surface area (ECSA, 57.2 m2/gPt) and lower internal resistance (20 Ω) than an individual Pt-dispersed SCL electrode prepared with only the spray method (S1E0, 31.9 m2/gPt and 132 Ω) and an individual Pt-concentrated SCL electrode prepared with only the EPD method (S0E1, 34.1 m2/gPt and 120 Ω). The S1E1 DCL electrode exhibited 2.1 and 1.7 times higher mass activity for methanol oxidation reaction (MOR) than S1E0 and S0E1 SCL electrodes, respectively (1,230 mA/mgPt for S1E1 vs. 595 mA/mgPt for S1E0 and 715 mA/mgPt for S0E1). In addition, the S1E1 DCL electrode demonstrated high MOR durability after 1,000 sequential cycles while losing 30% activity. Meanwhile, S0E1 and S1E0 SCL electrodes rapidly lost 52% and 55% activity, respectively. These improved electrochemical performances of DCL electrode were owing to the advantages of separating Pt catalysts into two layers, which provides more Pt catalytic active sites to the electrolyte than those in SCL electrodes. Our observation may aid in minimizing the usage amount of Pt catalysts (~0.16 mgPt/cm2) compared to those in present commercial Pt/C composites (~0.3 mgPt/cm2) as well as maximize efficient Pt utilization. More importantly, with regard to proton exchange membrane fuel cell (PEMFC) activity as a crucial in-situ characterization of a catalyst, a membrane electrode assembly (MEA) containing S1E1 as the anode electrode could generate mass maximum power density of 3.84 W/mgPt, 3.6 times higher than the present commercial one (1.07 W/mgPt).  相似文献   

15.
The development of electrocatalysts with high activity and durability for oxygen reduction reaction (ORR) in acidic electrolyte environments remains a serious challenge for clean and efficient energy conversion. Synergistic effects between Pt and inexpensive metals, the d band center of Pt and catalyst morphology could adjust the adsorption and desorption of oxygen intermediates by the Pt. All the factors affect the catalytic performance of Pt-based nanocrystals. Here, we prepared Cu@PtCu3 NWs with an average diameter of 74.9 nm for Cu and about 10 nm PtCu3 layer. After etching, the Cu@PtCu3 nanowires is transformed into PtCu nanotube structure, due to the removal of copper from the surface and interior. PtCu NTs for ORR shows excellent activities and durability due to the integration of structural advantages and synergistic effects. Notably, the mass activity and specific activity of PtCu NTs (0.105 A mg?1Pt and 0.230 mA cm?2Pt) are 2.0 and 3.8 times higher than that of commercial Pt/C (0.053 A mg?1Pt and 0.06 mA cm?2Pt). The etching process to change the morphology of the catalyst and alter the electronic structure of the catalyst is expected to be useful for the design of future structured Pt-based alloy nanocatalysts.  相似文献   

16.
Highly active and durable Pt-based catalysts for oxygen reduction reaction (ORR) are very important and necessary for the proton exchange membrane fuel cells (PEMFCs). In this paper, we report the preparation and performance study of ORR catalysts composed of core-shell Pt–Co alloy nanoparticles (NPs) on multi-walled carbon nanotubes (MWCNTs) anchored with ZrO2 NPs (denoted as Pt–Co–ZrO2/MWCNTs). Thanks to the unique three-phase structure, the mass activity of Pt–Co–ZrO2/MWCNTs for ORR at 0.9 V versus reversible hydrogen electrode (RHE) is1577 mA mgPt?1, which is ~6.6-fold higher than that of the commercial Pt/C (238 mA mgPt?1). After 50,000 cycles for durability test, the mass activity of Pt–Co–ZrO2/MWCNTs for ORR remained 88% of its initial value. In stark contrast, that of Pt/C kept only about 56.3% of its initial value. More importantly, its catalytic performance was fully observed/verified in a H2-air PEMFC single cell test. When the Pt loading of Pt–Co–ZrO2/MWCNTs loaded cathode was one fourth of that with commercial Pt/C as the cathode catalyst, comparable cell performance was achieved. More impressively, the MEA with Pt–Co–ZrO2/MWCNTs underwent only 24.5% degradation in maximum power density after 30,000 accelerated durability tests (ADTs). However, the MEA with Pt/C after 30,000 ADTs exhibited 39.6% performance loss in maximum power density. The enhanced mass activity and catalytic durability of Pt–Co–ZrO2/MWCNTs could be attributed to the core-shell Pt–Co alloy NPs with Pt-rich surface and the interface effect between Pt–Co alloy NPs and oxygen vacancy-rich ZrO2 NPs. In addition, this research also provided a solution to the durability issue of cathodes without sacrificing ORR mass activity, which would promote practical application of PEMFCs.  相似文献   

17.
A peerless inexpensive electrochemical engineering of spherical Pt nanoparticles (nano-Pt: ca. 100 nm in average diameter) was achieved with intersected ferric oxyhydroxide nanotubes (α-FeOOH (goethite): ca. 20 nm in average diameter). The FeOOH@Pt catalyst exhibited ca. 2.5 and 1.94-times increases in the catalytic activity and poisoning tolerance, respectively, of the formic acid electro?oxidation (FAO) – the anodic reaction in the direct formic acid fuel cells (DFAFCs). Surprisingly, with a post-activation of the FeOOH@Pt catalyst at 0.48 V vs. reversible hydrogen electrode (RHE) in 0.2 mol L?1 NaOH, a favorable Fe2+/Fe3+ transformation succeeded to eliminate the permanent CO poisoning of Pt that impaired the catalytic performance of DFAFCs. This was synchronized (relatively to nano-Pt) with a four-fold increase in the catalytic efficiency, ca. ?174 mV shift in the onset potential, and eightfold enhancement in the catalyst's durability for FAO. The activated FeOOH@Pt catalyst also showed a mass activity of 296 mA mg?1Pt (at 0.8 V), which was ca. nine times higher than that (34 mA mg?1Pt) of the commercial Pt/C catalyst. The ascertained improvement in the electron transfer at the FeOOH@Pt surface foresees quick industrialization for DFAFCs.  相似文献   

18.
This paper provides an overview on the development of advanced fuel cell cathode catalysts at University of South Carolina (USC) with the emphasis on the stability of non-precious metal and Pt alloy catalysts. Nitrogen-modified carbon composite (NMCC) catalysts were developed for the oxygen reduction reaction (ORR) through the pyrolysis of cobalt (iron)-nitrogen chelate followed by the treatment combination of pyrolysis, acid leaching, and re-pyrolysis. A promising stability was observed for 1050 h fuel cell operation under current density of 200 mA cm−2 as evidenced by a potential decay rate as low as 40 μV h−1. The performance degradation mechanism of the NMCC-based fuel cell is discussed. Pt and PtPd hybrid catalysts are developed that use a NMCC, which is itself active for the ORR, instead of a conventional carbon black support. The stability test at 1 A cm−2 indicated that the Pt/NMCC hybrid catalyst (new Pt-Co/C) is more stable than the conventional Pt-Co/C without the Co leaching out. The PEM fuel cell accelerated stress test (AST) for supports and catalysts demonstrated that their stability changes in the order: Pt3Pd1/NMCC hybrid catalyst > Pt/NMCC hybrid catalyst > conventional Pt/C catalyst. Moreover, the hybrid catalysts exhibit higher mass activity than the Pt/C catalysts.  相似文献   

19.
A facile synthesis method has been developed for preparing porous hexadecyltrimethylammonium-coated Pt-Ag nanosponges using ascorbic acid. As determined via electron diffraction and mapping element measurements, the nanosponges feature fcc and mixed-alloy structures. The nanosponges were successfully deposited on the sidewalls of sodium dodecyl sulfate-micelle-functionalized herringbone graphite nanofibers (Pt-Ag/GN) using an electrostatic attraction. Further, as supported by in situ analyses, the mass activity and electrochemical kinetics of the Pt-Ag/GN nanocomposite toward the electrocatalysis of the oxygen reduction reaction (ORR) were studied. The results demonstrate that the mass activity of Pt-Ag/GN is 5.59 × 10−3 mA μgpt−1 and greater than 3.91 × 10−3 mA μgpt−1, the commercial Pt/C (at −0.15 V vs. Ag/AgCl). The numbers of ORR transfer electrons on the new composites reached 3.44 (at −0.15 V vs. Ag/AgCl), which shows that the ORR occurred quickly.  相似文献   

20.
Subjected to CO poisoning and weak catalytic performance, there are still large barriers to the effective use of direct methanol fuel cells. Therefore, bimetallic FeNi2P/C hybrid is synthesized by a facile hydrothermal method and low temperature phosphorization process. Subsequently, the as-synthesized FeNi2P/C is employed as catalytic support to load Pt nanoparticles. Due to the existence of phosphorus and the difunctional effects of Fe and Ni, electrochemical results demonstrate that the prepared Pt–FeNi2P/C compound exhibits an outstanding catalytic activity of 1125 mA·mg-1 Pt during methanol oxidation in acid solution, tower over that of Pt–FeP4/C (721 mA·mg-1Pt), Pt–Ni2P/C (588 mA·mg-1Pt) and Pt/C-JM (284 mA·mg-1Pt), separately. Significantly, bimetallic Pt–FeNi2P/C hybrid shows the optimal anti poisoning tolerance, which onset potential is negatively shifted 0.2 eV in comparison of Pt/C-JM. Hence, Pt-based catalyst decorated by bimetallic phosphides with excellent anti poisoning tolerance would be a superb material to flourish the catalytic field.  相似文献   

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