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1.
The durability and cost of fuel cell cathode catalysts are major technical barriers to the commercialization of fuel cells for vehicle applications. In this work, novel Pt and PtPd hybrid catalysts are developed that use a nitrogen-modified carbon composite (NMCC), which is itself active for the oxygen reduction reaction (ORR), instead of a conventional carbon black support. The fuel cell accelerated stress test (AST) for supports and catalysts demonstrated that the Pt3Pd1/NMCC and Pt/NMCC hybrid catalysts possess much higher stability than Pt/C catalysts in polymer electrolyte membrane (PEM) fuel cells. Moreover, the hybrid catalysts exhibit higher mass activity than the Pt/C catalysts. The origin of the hybrid catalysts’ improved performance relative to Pt/C is discussed in light of pore size distribution and surface area analysis, XRD, XPS, and TEM analyses and electrochemical measurements.  相似文献   

2.
Carbon-supported Pt-Co alloy nanoparticles of varying Pt:Co atomic ratios of 1:1, 2:1, 3:1 and 4:1 are prepared, characterized and tested in high temperature PEM fuel cell intend to reduce the Pt loading. These electrocatalysts are prepared by borohydride reduction method in the presence of citric acid as stabilizing agent. Face-centered cubic structure of Pt is evident from XRD. The positive shift of Pt diffraction peaks with increasing cobalt content in the PtxCoy/C catalysts indicated the solubility of Co in Pt lattice. The average crystallite size is found to be 6 nm in all the prepared catalysts. The electrochemical active surface area (EAS) of the catalysts from CO-stripping voltammetry is calculated to be 65.2, 51.4, 47.7, 41.5 and 38.3 m2 g−1 Pt for Pt/C, Pt-Co(4:1)/C, Pt-Co(3:1)/C, Pt-Co(2:1)/C and Pt-Co(1:1)/C, respectively. These catalysts are used as cathode in the fabrication of polybenzimidazole-based membrane electrode assembly (MEA) and the polarization curves are recorded at 160 and 180 °C. The results indicate the good performance of Pt-Co alloys than that of Pt under the PEM fuel cell conditions. Among the investigated electrocatalysts, Pt-Co(1:1)/C and Pt-Co(2:1)/C exhibited good fuel cell performance. Durability tests also indicated the good stability of Pt-Co(1:1)/C and Pt-Co(2:1)/C compared to Pt/C.  相似文献   

3.
A series of Platinum-Cobalt bimetallic catalyst supported on carbon (Vulcan XC-72R) were prepared by sequential deposition using an organic salt of cobalt for use as cathode in Phosphoric Acid Fuel Cell (PAFC). The atomic percent of non noble metal with respect to Pt in the alloy was varied from 5 to 100 and the composition of alloy catalyst was confirmed by chemical analysis and SEM - EDS spectra. Electrochemical performance of the catalyst was studied in half cell and unit cells. The exchange current densities for oxygen reduction reaction (ORR), for alloys with different concentration of non noble metal was evaluated from current-potential curves, which showed values close to 10−5 A/cm2 and the mass activity and specific activity, for the (ORR), were found to be higher for Pt-Co/C compared to that of 10% Pt/C catalysts. The catalyst was tested for its stability in unit cell for a period of 500 h using air as an oxidant which showed higher performance for Pt-Co/C containing 0.5 at% Co. The nature of hydrogen adsorption and dominant crystal plane was also evaluated from cyclic voltammetry. XPS analysis was carried out to determine the surface species present. Results show significant enhancement of electro catalytic activity of Pt by alloying with Co, with maximum activity at ca 0.5 at% Co.  相似文献   

4.
A new strategy for fabricating atomically dispersed heteroatom-doped nanoporous carbon materials is reported. Through the self-assembly of dopamine, triblock copolymer F127, and metal ions, different three-dimensional atomic metal-N/S doped carbon catalysts are obtained after pyrolysis. Noble metal salts with ferrous sulfate induce the bimetallic monatomic FeM (M = Pd, Pt) N, S-doped carbon catalysts. Minute amounts of Pt or Pd single atoms in the catalysts greatly improve the oxygen reduction reaction (ORR) activity both in acidic and alkaline conditions. Typically, the obtained Fe, Pt–N/S co-doped carbon (FePt-NSC) catalyst exhibits superior ORR performance with positive half-wave potentials (E1/2) of 0.89 and 0.80 V in alkaline and acidic solutions, respectively. In addition, FePt-NSC displays dominant four electron catalytic process and excellent electrocatalytic stability. The high temperature proton exchange membrane fuel cell (HT-PEMFC) test (160 °C) illustrates that FePt-NSC reaches 0.67 V at 400 mA/cm2 and achieves the peak power density of 628 mW/cm2, better than most of the catalysts reported at the similar conditions. These results indicate the atomic metal-N/S doped porous carbon catalysts to be highly promising low-Pt catalysts for HT-PEMFC.  相似文献   

5.
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   

6.
Developing non-precious metal-based catalysts as the substitution of precious catalysts (Pt/C) in oxygen reduction reaction (ORR) is crucial for energy devices. Herein, a template and organic solvent-free method was adopted to synthesize Fe, B, and N doped nanoflake-like carbon materials (Fe/B/N–C) by pyrolysis of monoclinic ZIF-8 coated with iron precursors and boric acid. Benefiting from introducing B into Fe–N–C, the regulated electron cloud density of Fe-Nx sites enhance the charge transfer and promotes the ORR process. The as-synthesized Fe/B/N–C electrocatalyst shows excellent ORR activity of a half-wave potential (0.90 V vs 0.87 V of Pt/C), together with superior long-term stability (95.5% current density retention after 27 h) in alkaline media and is even comparable to the commercial Pt/C catalyst (with a half-wave potential of 0.74 V vs 0.82 V of Pt/C) in an acidic electrolyte. A Zn-air battery assembled with Fe/B/N–C as ORR catalyst delivers a higher open-circuit potential (1.47 V), specific capacity (759.9 mA h g?1Zn at 10 mA cm?2), peak power density (62 mW cm?2), as well as excellent durability (5 mA cm?2 for more than 160 h) compared to those with commercial Pt/C. This work provides an effective strategy to construct B doped Fe–N–C materials as nonprecious ORR catalyst. Theoretical calculations indicate that introduction of B could induce Fe-Nx species electronic configuration and is favorable for activation of OH1 intermediates to promote ORR process.  相似文献   

7.
Developing platinum-based nanoparticles on carbon catalysts with high activity and stability for oxygen reduction reaction (ORR) is of great significance for the practical application of fuel cells. Herein, a synchronous strategy of preparing nano-sized PtCo supported on atomic Co and N co-doped carbon nanorods (PtCo/Co–N–C NR) was developed to replace the conventional method of impregnating Pt sources into ready-made carbon materials, in which metal-organic frameworks (MOFs) with Co and Zn ions of rhombic dodecahedron were first prepared using 2-methylimidazole as building block and then their morphology was transformed into porous nanorods via the reduction of Co ions to Co–B–O complex in the MOFs by NaBH4; subsequently, Pt was deposited on the Co–Zn MOF nanorods through the displacement reaction of PtCl62- and metallic Co and coordination between MOF and PtCl62-; after pyrolysis and acid-leaching process, highly dispersed PtCo/Co–N–C NR was obtained. Attributed to its unique characteristics of hierarchical pore structure, uniform PtCo alloy nanoparticles with the average size of 7.0 nm and strong supporting interaction effect, the catalyst exhibits high ORR activity and stability with the mass activity of 577.0 mA mg?1Pt and specific activity of 1.4 mA cm?2 at 0.9 V vs RHE in 0.1 M HClO4, which is about 3.6 times and 3.5 times high than that of commercial Pt/C catalyst respectively. This strategy would provide a flexible route to develop highly active and stable ORR electrocatalysts with various morphologies for optimizing the exposure of active sites.  相似文献   

8.
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   

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.
The single molybdenum oxide (MoO2) crystals down to 5 nm in diameter on carbon (denoted as C-MoO2) are synthesized based on ion-exchange principle for the first time. The structures, morphologies, chemical and electrocatalytic performances of as-synthesized nanomaterials are characterized by physical, chemical and electrochemical methods. The results indicate that electrocatalysts made with Pt nanoparticles supporting on C-MoO2 (denoted as Pt/C-MoO2) are highly active and stable for oxygen reduction reaction (ORR) in fuel cells. A mass activity of 187.4 mA mg−1Pt at 0.9 V is obtained for ORR, which is much higher than that on commercial Pt/C (TKK) electrocatalyst (98.4 mA mg−1Pt). Furthermore, the electrochemical stability of Pt/C-MoO2 is more excellent than that of Pt/C (TKK). The origin of the improvement in catalytic activity can be attributed to the synergistic or promotion effect of MoO2 on Pt. The improvement in electrochemical stability is due to the strong interaction force between Pt and MoO2.  相似文献   

11.
Pt/TiO2/C catalysts are employed as the cathode catalysts for proton exchange membrane fuel cell (PEMFC). The comparative studies on the Pt/C and Pt/TiO2/C catalysts are conducted with the physical and electrochemical techniques.After the accelerating aging test (AAT), the remaining electrochemical active surface area (EAS) of the Pt/TiO2/C catalysts is 75.6%, which is larger than that of the Pt/C catalysts (42.6%). The apparent exchange current density () of the oxygen reduction reaction (ORR) at the Pt/C catalysts decreases from 3.02 × 10−9 to 1.32 × 10−11 A cm−2 after the AAT. And the value of of the ORR at the Pt/TiO2/C catalysts is 2.88 × 10−9 A cm−2 before the AAT and 2.51 × 10−9 A cm−2 after the AAT. Furthermore, the output performance degradation of the PEMFC using the Pt/TiO2/C cathode catalysts is also less than that using the Pt/C catalysts. The particle size of the Pt/C catalysts increases significantly from 5.3 to 26.5 nm after the AAT. The mean particle size of the Pt/TiO2/C catalysts is 7.3 nm before the AAT and 9.2 nm after the AAT. It can be concluded that the long-term durability of the Pt/TiO2/C catalysts in a PEMFC is much better than that of the Pt/C catalysts.  相似文献   

12.
Developing non-precious metal catalysts for oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) is crucial for proton exchange membrane fuel cell (PEMFC), metal-air batteries and water splitting. Here, we report a in-situ simple approach to synthesize ultra-small sized transition metal carbides (TMCs) nanoparticles coupled with nitrogen-doped carbon hybrids (TMCs/NC, including WC/NC, V8C7/NC and Mo2C/NC). The TMCs/NC exhibit excellent ORR and HER performances in acidic electrolyte as bi-functional catalysts. The potential of WC/NC at the current density of 3.0 mA cm?2 for ORR is 0.814 V (vs. reversible hydrogen electrode (RHE)), which is very close to Pt/C (0.827 V), making it one of the best TMCs based ORR catalysts in acidic electrolyte. Besides, the TMCs/NC exhibit excellent performances toward HER, the Mo2C/NC only need an overpotential of 80 mV to drive the current density of 10 mA cm?2, which is very close to Pt/C (37 mV), making it the competitive alternative candidate among the reported non-precious metal HER catalysts.  相似文献   

13.
Polybenzimidazole (PBI) was studied as an ionomer binder at varying ratios (1–7) in a 20–40 wt% Pt–Pd/C cathode-coupled catalyst layer for the oxygen reduction reaction (ORR) in a high-temperature proton exchange membrane fuel cell (HT-PEMFC). Catalytic activity was examined by CV and LSV, while the properties of the catalysts were characterized by FESEM-EDX, N2 adsorption–desorption, XRD and FTIR. The results showed that the distribution of metals on the carbon surface, carbon wall thickness and the interaction between ionomer and coupled catalysts affected the ORR performance. The fabricated membrane electrode assembly with 5:95 PBI: 30 wt% Pt–Pd/C catalyst ratio exhibited the best performance and highest durability for HT-PEMFC at 170 °C, yielding a power density of 1.30 Wcm−2 with 0.02 mgPt/cm Pt loading. This performance of ultra-low metal loading of coupled Pt–Pd/C electrocatalyst with PBI binder was comparable to those reported by other studies, highlighting a promising catalyst for fuel cell application.  相似文献   

14.
Morphology of carbon nanofibers significantly effects Pt nanoparticles dispersion and specific interaction with the support, which is an important aspect in the fuel cell performance of the electrocatalysts. This study emphasizes, the defects creation and structural evolution comprised due to N–F co-doping on graphitic carbon nanofibers (GNFs) of different morphologies, viz. GNF-linearly aligned platelets (L), antlers (A), herringbone (H), and their specific interaction with Pt nanoparticle in enhancing the oxygen reduction reaction (ORR). GNFs–NF–Pt catalysts exhibit better ORR electrocatalytic activity, superior durability that is solely ascribed to the morphological evolution and the doped N–F heteroatoms, prompting the charge density variations in the resultant carbon fiber matrices. Amongst, H–NF–Pt catalyst performed outstanding ORR activity with exceptional electrochemical stability, which shows only 20 mV loss in the half-wave potential whilst 100 mV loss for Pt/C catalyst on 20,000 potential cycling. The PEMFC comprising H–NF–Pt as cathode catalyst with minimum loading of 0.10 mg cm?2, delivers power density of 0.942 W cm?2 at current density of 2.50 A cm?2 without backpressures in H2–O2 feeds. The H–NF–Pt catalyst owing to its hierarchical architectures, performs well in PEMFC at the minimized catalyst loading with outstanding stability that can significantly decrease total price for the fuel cell.  相似文献   

15.
Developing non-noble metal oxygen reduction reaction (ORR) electrocatalysts with high performance, excellent stability, and low-cost is crucial for the industrialization of fuel cells. Herein, trace level Co modified 3D hybrid titanium carbonitride MXene and boron-carbon-nitrogen nanotubes catalyst (TiCN–BCN–Co) is fabricated by spray-lyophilization and high-temperature pyrolysis. This strategy not only avoids the oxidation of Ti3C2Tx MXene, but also introduces nitrogen atoms into the titanium carbide lattice to form a more electrocatalytically active TiCN crystal phase. The obtained TiCN–BCN–Co exhibits superior ORR catalytic activity with a positive half-wave potential of 0.83 V vs. RHE and outperforms commercial Pt/C in terms of stability and methanol tolerance. Impressively, the Zn-air battery with TiCN–BCN–Co cathode achieves a superior specific capacity of 791 mAh g?1 and long-term stability of 200 h.  相似文献   

16.
Hierarchically porous materials are promising as catalyst supports in fuel cells and batteries as they increase overall mass transfer and active site density. In this work, a hierarchically porous catalyst support for oxygen reduction reaction (ORR) in acidic media has been developed by a bottom-up approach. Graphene oxide (GO) was introduced during synthesis conditions of zeolitic imidazolate framework-8 (ZIF-8) to produce hybrid material of ZIF-8/GO. Successful nanocomposite formation was realized by preserved crystallinity and chemical interaction between species as revealed by X-ray diffraction and Fourier transform infrared spectroscopy. Introduction of GO and pyrolysis of resulting hybrid structure causes emergence of disordered meso/macropores with an accompanying increase in pore volume as revealed by N2 sorption experiments. Pt nanoparticle deposition on pyrolyzed hybrid material by polyol method results in electrocatalyst Pt/NC-1, which shows greatly improved mass activity (182 vs 86 A g−1Pt) and specific activity (467 vs 186 μA g−1Pt) at 0.8 V for ORR against reference electrocatalyst Pt/r-GO and improved specific activity against Pt/C.  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.
Nano-structured Pt-WO3/C, Pt-WO3-TiO2/C and Pt/C catalysts are synthesized by chemical reduction method using sodium borohydride as reducing agent. The catalysts thus prepared are characterized and compared with commercial Pt/C catalyst. The electrochemical performances are characterized by single cell test evaluation, long term stability test and cyclic voltammetry measurement. The chemical compositions, physical and morphological characterizations are investigated by various techniques such X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM). XRD analysis shows that, all prepared catalysts exhibited face-centered cubic structures. XRD results confirm that, the Pt-WO3/C and Pt-WO3-TiO2/C catalysts are smaller in particle size and larger in surface area calculated from line broadening. The amount of Pt reduced from1.76 mg cm−2 (10% Pt/C) to 1.056 mg cm−2 and 0.704 mg cm−2 in the case of Pt-WO3/C and Pt-WO3-TiO2/C respectively. Both the tungstate and titanate based electrocatalysts have exhibited higher performance in single cell tests than lone Pt catalysts.  相似文献   

19.
Iron-chelated electrocatalysts for the oxygen reduction reaction (ORR) in a microbial fuel cell (MFC) were prepared from sodium ferric ethylenediamine-N,N′-bis(2-hydroxyphenylacetic acid) (FeE), sodium ferric diethylene triamine pentaacetic acid (FeD) supported on carbon Vulcan XC-72R carbon black and multi-walled carbon nanotubes (CNTs). Catalyst morphology was investigated by TEM; and the total surfaces areas as well as the pore volumes of catalysts were examined by nitrogen physisorption characterization. The catalytic activity of the iron based catalysts towards ORR was studied by cyclic voltammetry, showing the higher electrochemical activity of FeE in comparison with FeD and the superior performance of catalysts supported on CNT rather than on Vulcan XC-72R carbon black. FeE/CNT was used as cathodic catalyst in a microbial fuel cell (MFC) using domestic wastewater as fuel. The maximum current density and power density recorded are 110 (mA m−2) and 127 ± 0.9 (mW m−2), respectively. These values are comparable with those obtained using platinum on carbon Vulcan (0.13 mA m−2 and 226 ± 0.2 mW m−2), demonstrating that these catalysts can be used as substitutes for commercial Pt/C.  相似文献   

20.
A facile synthesis at room temperature and at solid-state directly on the support yielded small, homogeneous and well-dispersed Pt nanoparticles (NPs) on CB-carbon black, GNP-graphene nanoplatelets, and CB-GNP-50:50 hybrid support. Synthesized Pt/CB, Pt/GNP and Pt/CB:GNP NPs were used as electrocatalysts for polymer electrolyte membrane fuel cell (PEMFC) reactions. HRTEM results displayed very small, homogeneous and well-dispersed NPs with 1.7, 2.0 and 4.2 nm mean-diameters for the Pt/CB-GNP, Pt/GNP and Pt/CB electrocatalysts, respectively. Electrocatalysts were also characterized by RAMAN, XRD, BET and CV techniques. ECSA values indicated better activity for graphene-based supports with 19 m2 g−1Pt for Pt/GNP and 55 m2 g−1Pt for Pt/CB-GNP compared to 10 m2 g−1Pt for Pt/CB. Oxygen reduction reaction (ORR) studies and fuel cell tests were in parallel with these results where highest maximum power density of 377 mW cm−2 was achieved with Pt/CB-GNP hybrid electrocatalyst. Both fuel cell and ORR studies for Pt/CB-GNP indicated better dispersion of NPs on the support and efficient fuel cell performance that is believed to be due to the prevention of restacking of GNP by CB. To the best of our knowledge, Pt/GNP and Pt/CB-GNP electrocatalysts are the first in literature to be synthesized with the organometallic mild synthesis method using Pt(dba)3 precursor for the PEMFC applications.  相似文献   

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