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1.
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   

2.
Pt-based catalysts are still most attractive and could be the major driving force for facile electrochemical reactions in direct methanol fuel cells (DMFCs). In this work, a Pt3Mn nanowire network structures (NWNs) catalyst was successfully synthesized by a soft template (CTAB) method. The morphology and elemental composition of the Pt3Mn NWNs were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma-optical emission spectroscopy (ICP-OES). The electrocatalytic behavior of the synthesized Pt3Mn NWNs catalyst towards methanol oxidation reaction (MOR) was studied by cyclic voltammetry (CV) and chronoamperometry (CA). The results reveal that the Pt3Mn NWNs has superior MOR activity and durability compared to Pt NWNs and commercial Pt/C. The mass and specific activities of Pt3Mn NWNs are 0.843 A mg−1 and 1.8 mA cm−2 respectively, which are twice that of commercial Pt/C. Additionally, the results of CA test indicate that the Pt3Mn NWNs possesses better durability than Pt NWNs and commercial Pt/C catalysts in acidic media, which is expected to be a new alternative anode material in DMFCs.  相似文献   

3.
The key to direct methanol fuel cells (DMFCs) is the anode catalyst for methanol oxidation reaction (MOR) which has good catalytic activity and stability. Pt@CoOx@N-C catalysts were synthesized by compounding Pt nanoparticles and CoOx with nitrogen-doped porous carbon (N-C). Pt nanoparticles were prepared by solution plasma technique. CoOx@N-C are derived from zeolitic-imidazolate-framework-67 (ZIF-67) by heat treatment at 700 °C. For MOR, Pt@CoOx@N-C exhibits an outstanding electrocatalytic performance (mass activity of 2400 mA mgPt−1) and stability (70% remained after 300 cycles) under acidic condition, which owing to the synergistic effects among the Pt nanoparticles, CoOx and nitrogen-doped porous carbon. Pt@CoOx@N-C shows such mass activity superior to that of Pt/C (460 mA mgPt−1) due to the fact that CoO can adsorb –OH in the solution and then assist Pt to oxidize the CO-like intermediates to CO2 which improves the resistance to CO poisoning of Pt nanoparticles. Therefore, solution plasma method assisted with metal-organic frameworks have good development prospects on synthesis of highly efficient electrocatalysts.  相似文献   

4.
Factors as the Pt/C ratio of the catalyst, the binder content of the electrode and the catalyst deposition method were studied within the scope of ultra-low Pt loading electrodes for high temperature proton exchange membrane fuel cells (HT-PEMFCs). The Pt/C ratio of the catalyst allowed to tune the thickness of the catalytic layer and so to minimize the detrimental effect of the phosphoric acid flooding. A membrane electrode assembly (MEA) with 0.05 mgPtcm−2 at anode and 0.1 mgPtcm−2 at cathode (0.150 mgPtcm−2 in total) attained a peak power density of 346 mW cm−2. It was proven that including a binder in the catalytic layer of ultra-low Pt loading electrodes lowers its performance. Electrospraying-based MEAs with ultra-low Pt loaded electrodes (0.1 mgPtcm−2) rendered the best (peak power density of 400 mW cm−2) compared to conventional methods (spraying or ultrasonic spraying) but with the penalty of a low catalyst deposition rate.  相似文献   

5.
Developing the efficient and stable anode catalysts of direct methanol fuel cell has been a pivotal requirement for its extensive commercial application. Herein, we design the Fe-doped CoP nanotube heterostructure as the co-catalyst of Pt-based catalyst via combining a facile hydrothermal with phosphorization process, subsequently, the traditional NaBH4 reduction method is utilized to deposit Pt nanoparticles. As anticipated, Fe species have been successfully doped into CoP to generate the Fe-doped CoP nanotube heterostructure, and the involved characterizations identify that Pt–C/Fe2–CoP catalyst exhibits admirable mass activity (1237 mA·mg−1Pt) towards methanol oxidation reaction, which is approximately 2.04 and 3.66 times as high as the Pt–C/CoP (607 mA·mg−1Pt) and Pt–C–H (338 mA·mg−1Pt). After stability test, the decline ratio of mass activity for Pt–C/Fe2–CoP (83.43%) is markedly preferable to Pt–C/CoP (94.92%) and Pt–C–H (98.67%) catalysts. The enhanced catalytic activity and durability can be imputed to the formation of uniform Pt nanoparticles and co-catalysis effect of Fe-doped CoP nanotube heterostructure since the introduction of hetero-metal cations is able to effectively accelerate the charge transfer rate and adjust the electronic structure of material. Therefore, the fabrication of nanotube heterostructure and introduction of hetero-metal may provide a new direction to the development of other high-efficiency electrocatalysts.  相似文献   

6.
Pt is the ideal anode catalyst in fuel cells. In this paper, in order to increase the utilization of Pt, the PtAu nanowire networks (NWNs) with ultralow content of Pt are fabricated by a simple silicon monoxide (SiO) reduction method without any capping agent. PtAu NWNs supported on carbon black with Pt content of 1 wt% (Pt0.05Au NWNs) are employed as catalysts for formic acid oxidation (FAO) and methanol oxidation reaction (MOR), whose mass activities are as high as 4998.9 and 2282.3 mA∙mgPt−1, respectively. The network structure facilitates the electron transfer and increases the stability of the catalysts. The PtAu composite experiences compressive lattice strain as confirmed by X-ray powder diffraction (XRD). The Pt0.05Au NWNs catalyst with low Pt content results in the largest strain variation compared with PtAu composited of other ratios, which may downshift the d-band center of Pt and lead to the higher electrocatalytic activity in oxidation reaction.  相似文献   

7.
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   

8.
Three MnO2 samples with different well-defined morphologies including nanoplates, nanorods and corallines are prepared through a simple chemical precipitation method and used as the promoter/support for Pt electrocatalysts (denoted as Pt/MnO2P, Pt/MnO2-R and Pt/MnO2C, respectively). The morphology effects of MnO2 to the catalytic properties of Pt for methanol oxidation reaction (MOR) are intensively investigated. Results show that the catalytic properties of Pt are strongly dependent on the morphology of the promoter. Pt/MnO2-R with MnO2 nanorods as the promoter shows the highest catalytic properties among the MnO2-promoted catalysts. The mass-specific activity and intrinsic activity of Pt in Pt/MnO2-R catalyst is 0.51 A mg−1Pt and 11.54 A m−2Pt, which is ca. 1.89 and 2.18 times that of commercial Pt/C catalysts (0.27 A mg−1Pt and 5.29 A m−2Pt), respectively. Change in the electronic structure of Pt is responsible for the enhancement in the catalytic properties of Pt/MnO2-R.  相似文献   

9.
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   

10.
To achieve the practical application of direct methanol fuel cells, it is highly important to develop effective electrocatalyst with high activity and favorable durability. Herein, we report the successful preparation of PtCu bimetallic nanoparticles supported on ceria/multi-walled carbon nanotubes composite (PtCu–CeO2/MWCNTs) via microwave-assisted polyol reduction procedure. The composition and morphology of as-obtained composite catalysts were characterized by X-ray diffraction, Raman, X-ray photoelectron spectra, scanning electron microscopy and transmission electron microscopy. The synergistic effects combining PtCu bimetallic effect and oxygen vacancy effect in ceria of such composite catalysts provide abundant active surface area and enhanced conductivity for the effective charge transport during the methanol oxidation reaction (MOR) process. As a results, the PtCu–CeO2/MWCNTs with optimized Pt proportion achieve greatly enhanced MOR activity with mass activity of 1.28 A mg−1Pt and specific activity of 2.03 mA cm−2, superior CO tolerance and reliable stability in contrast to that of commercial Pt/C catalysts.  相似文献   

11.
In this work, the trimetallic PtPdCr nanoparticles with low platinum loading (~5 wt%) supported on Vulcan carbon (PtPdCr/C) were synthesized through a facile two-step co-reduction method and showed superior methanol oxidation activity. The particle size distribution, morphology and elemental composition of the PtPdCr/C were investigated by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. The electrochemical performance for methanol oxidation of the PtPdCr/C was found to be higher with the mass activity of 969 mA·mg−1Pt compared to Pt/C (581 mA·mg−1 Pt) and PtRu/C (725 mA·mg−1 Pt). Moreover, the stability studies confirmed the enhanced durability of PtPdCr/C over Pt/C and PtRu/C catalysts after the accelerated durability test (ADT) and chronoamperometry (CA) analysis. The increased methanol oxidation activity and durability of the trimetallic PtPdCr/C in acid medium can be attributed to the change in binding energy of Pt and the induced synergistic effect from Pd and Cr atoms to Pt, which demonstrated a promising strategy for the preparation and utilization of ternary alloy catalysts towards methanol electrooxidation.  相似文献   

12.
Developing catalysts with high performance and low cost for methanol oxidation reaction (MOR) is the key to promoting the industrialization of direct methanol fuel cells (DMFCs). In this work, multiwalled carbon nanotubes (MWCNTs) supported PtCo alloys catalysts with improved MOR properties and anti-CO poisoning ability are successfully prepared by integrating low temperature adsorption and high temperature reduction method. The Pt1Co3@NC/MWCNTs sample with moderate Co2+ feeding content (0.81 mA/ugPt) achieves a factor of 1.93 enhancement in MOR mass activity compared to the commercial Pt/C catalyst (0.42 mA/ugPt). In addition, the Pt1Co3@NC/MWCNTs sample displays a lower CO oxidation onset potential respect to pristine Pt/C catalyst (0.74 V vs. 0.82 V). Scuh improvement of MOR activity, durability and anti-CO poisoning ability of the Pt1Co3@NC/MWCNTs catalyst is ascribed to the moderate surface compositions, optimal electronic interaction between PtCo alloys and MWCNTs, and the protection of N-doped carbon (NC) shells. This study provides a new direction to decrease the utilization of platinum and improve the MOR activity, stability and anti-CO poisoning ability of electrocatalysts which will be potential in design and fabrication of the highly efficient electrocatalysts for DMFCs applications.  相似文献   

13.
In this work, a facile Fe- and N-containing porous carbon derived from sewage sludge was prepared and served as the support of Pt nanoparticles for the electrooxidation of methanol. Both the sludge-derived carbon (denoted as SC) and the resultant Pt/SC catalyst was physically characterized by scanning electron microscope (SEM), transmission electron microscope (TEM) and X-ray diffraction (XRD). The electrocatalytic performance for methanol oxidation reaction (MOR) of the Pt/SC was examined by cyclic voltammetry (CV) and chronoamperometric method. The results showed that the Pt/SC possessed slightly larger Pt particle size (5.5 nm) and lower electrochemical active surface area (ECA) compared to common Pt/C catalyst. However, the mass activity of Pt/SC for MOR was up to 201 mA mg−1, which was much higher than that of Pt/C (93 mA mg−1), indicating the synergistic effect of the sewage sludge-derived carbon with Fe and N species on methanol electrooxidation. Furthermore, Pt/SC showed enhanced durability towards MOR compared to common Pt/C, implying its potential for using in direct methanol fuel cell (DMFC) for energy conversion, which also demonstrated a promising solution for the utilization of sewage sludge resources.  相似文献   

14.
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   

15.
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   

16.
The effect of carbon monoxide (CO) on the reduction of Pt ion to metallic Pt is studied. The modified GC electrode with platinum metal synthesized in the presence of CO shows excellent activity for hydrogen evolution reaction (HER). Despite the decrease in the loading of platinum (4.5 × 10−4 mg cm−2) a substantial increase in its electrocatalytic activity towards HER is observed in a sulfuric acid environment. The observed electrocatalytic activity is comparable to available commercial catalysts like Pt/C. Tafel slope was obtained to be 34 mV.dec−1, and the overpotential was acquired to be 31 mV at the mass activity of 10 mA mg−1 were observed which was very close to kinetic parameters of Pt/C catalyst.  相似文献   

17.
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   

18.
Platinum (Pt) is considered as the preferred metal catalyst for methanol oxidation reactions. However, the application prospects of Pt catalysts are limited due to the inherent scarcity and cost. Enabling a trace amount of Pt to exert satisfactory catalytic activity and durability has become a key issue in designing electrocatalysts. Here, Ru-doped PtSn alloy nanoplates (PtSn@Ru NP) with an average particle size of less than 5 nm were controllably synthesized by adjusting the Pt–Sn atomic ratio. Compared with Ru-doped PtSn alloy nanospheres (PtSn@Ru NS/C, 714.7 mA/mgPt), PtSn bimetallic nanoplates (PtSn NP/C, 880.2 mA/mgPt) and commercial Pt/C (299.6 mA/mgPt), the prepared PtSn@Ru NP/C (1105.1 mA/mgPt) exhibited an extraordinary methanol oxidation mass activity. Furthermore, the peak oxidation current retention of PtSn@Ru NP/C was as high as at 87.5% after 1000 accelerated durability tests. The significantly enhanced catalytic performance and durability were attributed to the synergistic effect of the alloy components and morphological advantages. This work has led us to think more deeply about the constitutive relationship between structure and performance.  相似文献   

19.
The commonly used Pt/C catalyst has low durability for oxygen reduction reaction (ORR). In this work, CNT-supported TiO2 nanoparticles, which synergistically combines the merits of TiO2 (high stability and strong interactions with the supported Pt nanoparticles) and CNT (high specific surface area and large electrical conductivity), are prepared by a sol-gel process coupled with an annealing process and used as the support for Pt nanoparticles, which are anchored around TiO2 nanoparticles by a photodeposition technique. The as-synthesized Pt/TiO2@CNT catalyst exhibits a mass activity 5.3 times as large as that of the commercial Pt/C catalyst (0.358 A mgPt−1 vs. 0.067 A mgPt−1 at 0.9 V) and an excellent stability (no activity loss after 10000 potential cycles) for ORR, which can be mainly attributed to the lower oxygen adsorption energy of Pt, resulting from the strong metal-support interaction induced by the deposition of Pt nanoparticles around the well-dispersed TiO2 nanoparticles on CNT.  相似文献   

20.
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   

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