Stability of platinum based alloy cathode catalysts in PEM fuel cells

Corrosion and surface area changes of platinum (Pt) based catalysts supported on carbon were evaluated using an accelerated durability test (ADT). The results obtained using the ADT were correlated to the performance of the Pt based catalysts in the fuel cell. The catalytic activity and dissolution rate of the alloying metal from the Pt-alloy catalysts were estimated in the same time domain. A strong correlation was observed between the amount of the alloying metal dissolved and the oxygen reduction reaction (ORR) activity of the Pt-alloy catalysts. The Pt catalyst exhibited loss of active surface area, and a resulting decrease in the ORR activity was observed. The Pt/C and Pt–Co/C catalysts showed similar behavior in both ADT and in the fuel cell testing. Cross-sectional studies by electron microprobe analysis of the membrane electrode assembly after fuel cell testing revealed cobalt dissolution followed by diffusion into the membrane.     

Boron doping induced electronic reconfiguration of Fe-Nx sites in N-doped carbon matrix for efficient oxygen reduction reaction in both alkaline and acidic media

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-N_x 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^?1_Zn 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-N_x species electronic configuration and is favorable for activation of OH1 intermediates to promote ORR process.     

Carbon supported Pt-Y electrocatalysts for the oxygen reduction reaction

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 mg_Pt⁻¹) than comparably synthesized Pt/C catalyst. The specific activity (μA cm_Pt⁻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 cm_Pt⁻², respectively, while those of the Pt₃Y/C-900 and PtY/C-900 catalysts were 492 and 1050 μA cm_Pt⁻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.     

Power source research at USC: Development of advanced electrocatalysts for polymer electrolyte membrane fuel cells

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.     

Enhancement of oxygen reduction activity with addition of carbon support for non-precious metal nitrogen doped carbon catalyst

An improved synthesis scheme of non-precious metal N-doped carbon catalysts for oxygen reduction reaction is reported. The non-precious metal N-doped carbon catalysts were prepared by pyrolysis of the mixture (phenol resin, Ketjen black carbon support and cobalt phenanthroline complex). The drastic improvement of distribution state of Ketjen black supported non-precious metal N-doped carbon catalysts was observed by means of transmission electron microscopy (TEM). In addition, the non-precious metal N-doped carbon catalyst synthesized with Ketjen black carbon support showed much higher oxygen reduction reaction (ORR) activity relative to unsupported non-precious metal N-doped carbon catalyst in O₂-saturated 0.5 mol l⁻¹ H₂SO₄ at 35 °C. Moreover, the highest ORR activity was obtained with addition of optimum amount of Ketjen black carbon support was thirtyfold compared to unsupported non-precious metal N-doped carbon catalyst at 0.7 V. Similarly, the performance of a polymer electrolyte fuel cell (PEFC) using the non-precious metal N-doped carbon catalyst as the cathode electrode catalyst was obviously better than that of the non-precious metal N-doped carbon catalyst before optimization. Microstructure, specific surface area and surface composition of the non-precious metal N-doped carbon catalysts were analyzed by XRD, XPS and BET measurement with nitrogen physisorption, respectively.     

Highly active and durable carbon support Pt-rare earth catalyst for proton exchange membrane fuel cell

Pt-rare earth catalysts are highly efficient novel electrocatalyst for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) due to their high stability and activity. In this study, we prepare Pt-YO_x/C catalysts using the traditional wet chemical reduction method. The optimal quantity of Y-oxides loaded onto the Pt/C surface is determined based on electrochemical performance using linear sweep voltammetry (LSV) and cyclic voltammetry (CV) methods. After accelerated durability tests (ADT), the remnant electrochemical surface area (ECSA) and mass active (MA) in Pt-YO_x/C catalyst are relatively higher compared to the commercial Pt/C (JM). In the single-cell test, the maximum mass power densities of the MEAs prepared by self-made Pt-YO_x/C and Pt/C (JM) catalysts in cathodes record at 1895 and 1371 mW mg_Pt⁻¹, respectively, which shows a successful increment in platinum utilization. These results indicate that Pt-YO_x/C catalyst can potentially improve the durability and lower the cost of PEMFCs.     

A melamine formaldehyderesin route to in situ encapsulate Co2O3 into carbon black for enhanced oxygen reduction in alkaline media

Enhancing the activity and stability of the non-precious metal catalyst (NPMC) for oxygen reduction reaction (ORR) is vital for the commercialization of fuel cells. Herein, we put forward a method in which the melamine formaldehyderesin was used as a precursor to encapsulate in situ Co₂O₃ into carbon black to form Co₂O₃@MF-C catalysts. The prepared catalysts were characterized by TEM, XRD, XPS, BET, and Raman spectroscopy. The electrocatalytic activity was measured by using rotating disk electrode (RDE) voltammetry. The Co₂O₃@MF-Cs shows outstanding electrocatalytic activity in alkaline solution compared with the commercial Pt/C catalyst. The 20%Co₂O₃@MF-C-650 shows the highest activity for ORR and its initial reduction potential and half-wave potential reach 1.01 V and 0.94 V, respectively, in 0.1 M KOH solution. The prepared catalysts also follow the 4-electron pathway ORR process both in alkaline and in acid conditions.     

Waste wine mash-derived doped carbon materials as an efficient electrocatalyst for oxygen reduction reaction

Oxygen reduction reaction (ORR) is a core reaction of fuel cell and metal-air cell. In recent years, it has been a hot topic to study non-precious metal catalysts for ORR. Herein, we have used waste wine mash-derived carbon, melamine and ferric chloride to prepare a Fe- and N- co-doped carbon catalyst. The specific surface area of the catalyst is up to 1066.6 m² g⁻¹. And its wave potential is 15 mV higher than that of commercial Pt/C catalyst. The ORR on our catalyst followed a four-electron pathway; and it has high stability and high impressive immunity to methanol. After continuous oxygen reduction of 30,000s, the retention rate is 90%.     

A novel 3D hybrid carbon-based conductive network constructed by bimetallic MOF-derived CNTs embedded nitrogen-doped carbon framework for oxygen reduction reaction

The rational design of novel non-precious oxygen reduction reaction (ORR) electrocatalysts with good catalytic activity for energy conversion devices is under the spotlight of current research. Herein, we designed and fabricated a novel 3D Co-derived CNTs embedded nitrogen-doped carbon framework (denoted as Co-CNTs@NCF_T, where T represents the pyrolysis temperature) as an efficient ORR catalyst by pyrolysis of the bimetallic metal-organic framework (MOF) in the presence of graphene oxide (GO). The optimized catalyst furnishes large specific surface area, outstanding electrical conductivity and rapid mass transport rates during reactions. Because of these synergistic advantages, the Co-CNTs@NCF₉₀₀ exhibits excellent ORR catalytic activity in terms of a high onset potential of 0.96 V and a half-wave potential of 0.84 V in alkaline electrolyte, outperforming the commercial Pt/C. Furthermore, the Co-CNTs@NCF₉₀₀ manifests good stability and methanol tolerance comparable to the commercial Pt/C catalyst. The presented strategy open up a new avenue for the synthesis of novel electrocatalysts derived from MOF materials for energy-related applications.     

Solving Nafion poisoning of ORR catalysts with an accessible layer: designing a nanostructured core-shell Pt/C catalyst via a one-step self-assembly for PEMFC

A core-shell Pt/C@NCL300 catalyst with an accessible layer was designed to recover lost ORR activity and was constructed via a one-step self-assembly process in this paper. A thin porous layer derived from Nafion was first formed on the surface of Pt/C catalyst to create a shell. This first coating successfully separated the Nafion and Pt particles in the catalysts and reducing the negative impact of Nafion on ORR activity and enhancing the fuel cell performance. The newly fabricated Pt/C@NCL300 catalyst exhibited much higher specific activity than the original Pt/C catalyst in RDE tests under the same conditions and were comparable to the activity of Pt/C electrode without Nafion poisoning. Moreover, the fuel cell with Pt/C@NCL300 catalyst exhibited a higher power density without an obvious increase in proton transport and O₂ transport resistance compared to that of a Pt/C fuel cell with a low Pt loading. This result indicates that coating the Pt/C catalyst with a layer accessible for oxygen and protons is a promising way to effectively promote Pt-based catalysts that work under normal operating conditions.     

Soybean powder enables the synthesis of Fe–N–C catalysts with high ORR activities in microbial fuel cell applications

The development of microbial fuel cells (MFCs) into a new type of carbon-neutral wastewater treatment technology requires efficient and low-cost oxygen reduction reaction catalysts in air cathodes. The use of raw soybean powder was investigated for synthesizing Fe–N–C ORR catalysts in a sacrificial SiO₂ support method. ZnCl₂ etching in the synthesis was found to facilitate the formation of hierarchical porous structures of Fe–N–C catalysts. Fe–N–C(1-1) catalyst synthesized with an optimal soybean/ZnCl₂ mass ratio of 1:1 exhibited the highest ORR activity in air cathodes. The use of the obtained Fe–N–C(1-1) catalyst enables a maximum power production of ~0.480 mW cm⁻² in MFCs, higher than commercial Pt/C (0.438 mW cm⁻²) with the same catalyst loading of 2 mg cm⁻². Long-term MFC operations demonstrated that the Fe–N–C synthesized from raw soybean have high stability and toxic tolerance, indicating that abundant low cost soybean biomass is a potential material for ORR catalyst development in MFC applications.     

ZrO2 anchored core-shell Pt–Co alloy particles through direct pyrolysis of mixed Pt–Co–Zr salts for improving activity and durability in proton exchange membrane fuel cells

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 mg_Pt^?1, which is ～6.6-fold higher than that of the commercial Pt/C (238 mA mg_Pt^?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.     

H2-induced thermal treatment significantly influences the development of a high performance low-platinum core-shell PtNi/C alloyed oxygen reduction catalyst

In the purpose of maximizing the utilization of noble metal Pt in oxygen reduction catalysts, we illustrate a synthesis method of preparing the low-platinum PtNi/C alloyed oxygen reduction reaction (ORR) catalyst, which is developed through the H₂-induced treatment to a glucose reduced PtNi/C alloy. After post-treatment with H₂/N₂ mixture gases, this catalyst displays excellent ORR catalytic activity and durability for the synergetic influences of electronic and geometry effects on catalysts during the alloying. Specifically, the as-prepared PtNi/C (350°C-6 h) sample delivers preponderant ORR activity with only 53.5% Pt usage than the commercial Pt/C. The specific activity and mass activity are corresponding 7.49 times and 3.5 times to the commercial Pt/C. This catalyst exhibits excellent ORR catalytic activity after 10 000 potential cycles in acid, which benefits from the well alloyed core-shell structure of PtNi/C. H₂-induced thermal treatment has significant effects on the development of high performance low-platinum PtNi/C alloy catalyst, and plays the significant role in the formation of well-alloyed core-shell structures. The lowered d-band center is believed to facilitate ORR catalysis through weakening the adsorption of intermediate oxygen species on the alloyed Pt surface. Therefore, PtNi/C(350°C-6 h) alloyed catalyst possesses outstanding ORR catalytic activity with much lower Pt loading.     

Stability of Pt-Ni/C (1:1) and Pt/C electrocatalysts as cathode materials for polymer electrolyte fuel cells: Effect of ageing tests

Carbon supported Pt and Pt-Ni (1:1) nanoparticles were prepared by reduction of metal precursors with NaBH₄. XRD analysis indicated that only a small amount of Ni alloyed with Pt (Ni atomic fraction in the alloy about 0.05). The as-prepared catalysts were submitted to chronoamperometry (CA) measurements to evaluate their activity for the oxygen reduction reaction (ORR). CA measurements showed that the ORR activity of the as-prepared Ni-containing catalyst was higher than that of pure Pt. Then, their stability was studied by submitting these catalysts to durability tests involving either 30 h of constant potential (CP, 0.8 V vs. RHE) operation or repetitive potential cycling (RPC, 1000 cycles) between 0.5 and 1.0 V vs. RHE at 20 mV s⁻¹. After 30 h of CP operation at 0.8 V vs. RHE, loss of all non-alloyed Ni, partial dissolution of the Pt-Ni alloy and an increase of the crystallite size was observed for the Pt-Ni/C catalyst. The ORR activity of the Pt-Ni/C catalyst was almost stable, whereas the ORR activity of Pt/C slightly decreased with respect to the as-prepared catalyst. Loss of all non-alloyed and part of alloyed Ni was observed for the Pt-Ni/C catalyst following repetitive potential cycling. Conversely to the results of 30 h of CP operation at 0.8 V vs. RHE, after RPC the ORR activity of Pt-Ni/C was lower than that of both as-prepared Pt-Ni/C and cycled Pt/C. This result was explained in terms of Pt surface enrichment and crystallite size increase for the Pt-Ni/C catalyst.     

Varying N content and N/C ratio of the nitrogen precursor to synthesize highly active Co-Nx/C non-precious metal catalyst

The most promising non-precious metal oxygen reduction catalysts are M-Nx/C (M = Fe and/or Co) materials. Moreover, N-containing precursor is one of the important factors that affect oxygen reduction reaction (ORR) activity of M-Nx/C materials. In this paper, we want to study nitrogen precursor effects on ORR activity of Co-Nx/C catalysts by varying N content and N/C ratio of the nitrogen precursor. In this regard, three Co-Nx/C catalysts were synthesized using a solvent-milling method followed by high temperature treatment. The results showed that the increase in N content and N/C ratio did not necessarily cause the improvement of ORR activity of the Co-Nx/C catalyst. The most active catalyst, Co-HQ/C-800 (heat treatment of carbon supported Co-HQ complex at 800 °C for 2 h), was obtained using 8-hydroxyquinoline (8-HQ) as the nitrogen precursor. XPS analysis demonstrated that more graphitic N and Co-Nx active sites were responsible for better ORR activity of the Co-HQ/C-800 catalyst. The electrochemical property of the three Co-Nx/C catalysts was evaluated by linear sweep voltammetry (LSV), chronoamperometric measurements, accelerated durability tests (ADT) and H₂/O₂ alkaline fuel cell (AFC) tests.     

Sponge tofu-like graphene-carbon hybrid supporting Pt–Co nanocrystals for efficient oxygen reduction reaction and Zn-Air battery

Developing highly efficient electro-catalysts for oxygen reduction reaction (ORR) by an economic and green manner is vital for the practical application of fuel cells and metal-air batteries. Herein, inspired by the manufacturing process of sponge tofu (Chinese Food), we develop a sponge tofu-like graphene-carbon hybrid supporting Pt–Co nanoparticles catalyst (denoted as Pt–Co/CB + RGO-3D) by a cheap and environment-friendly freeze-drying technology using ice as the template. The electrochemical tests show that Pt–Co/CB + RGO-3D exhibits approximately 16-fold higher ORR activity and better stability compared with Pt/C. Its excellent performance could be attributed to the high mass transfer efficiency and enhanced electron transfer capacity, which roots in its unique structure. Furthermore, the Pt–Co/CB + RGO-3D-based Zn-air battery exhibits superior performance, corroborating its commercial application potential. This work not only provides a prospective method to fabricate catalysts with porous structure but also offers an effective strategy to design highly efficient electrocatalysts with special structure.     

Carbon supported nano-sized Pt–Pd and Pt–Co electrocatalysts for proton exchange membrane fuel cells

Nano-sized Pt–Pd/C and Pt–Co/C electrocatalysts have been synthesized and characterized by an alcohol-reduction process using ethylene glycol as the solvent and Vulcan XC-72R as the supporting material. While the Pt–Pd/C electrodes were compared with Pt/C (20 wt.% E-TEK) in terms of electrocatalytic activity towards oxidation of H₂, CO and H₂–CO mixtures, the Pt–Co/C electrodes were evaluated towards oxygen reduction reaction (ORR) and compared with Pt/C (20 wt.% E-TEK) and Pt–Co/C (20 wt.% E-TEK) and Pt/C (46 wt.% TKK) in a single cell. In addition, the Pt–Pd/C and Pt–Co/C electrocatalyst samples were characterized by XRD, XPS, TEM and electroanalytical methods. The TEM images of the carbon supported platinum alloy electrocatalysts show homogenous catalyst distribution with a particle size of about 3–4 nm. It was found that while the Pt–Pd/C electrocatalyst has superior CO tolerance compared to commercial catalyst, Pt–Co/C synthesized by polyol method has shown better activity and stability up to 60 °C compared to commercial catalysts. Single cell tests using the alloy catalysts coated on Nafion-212 membranes with H₂ and O₂ gases showed that the fuel cell performance in the activation and the ohmic regions are almost similar comparing conventional electrodes to Pt–Pd anode electrodes. However, conventional electrodes give a better performance in the ohmic region comparing to Pt–Co cathode. It is worth mentioning that these catalysts are less expensive compared to the commercial catalysts if only the platinum contents were considered.     

Highly efficient and ORR active platinum-scandium alloy-partially exfoliated carbon nanotubes electrocatalyst for Proton Exchange Membrane Fuel Cell

Oxygen reduction reaction (ORR) in Proton Exchange Membrane Fuel Cell (PEMFC) is the most sluggish reaction, which impedes the performance and commercialization of PEMFC. Platinum-based alloys show higher ORR activity than Pt and it is suggested by density functional theory calculations that Pt₃Sc alloy has high stability and higher ORR activity due to filling the metal d-bands and lowers binding energy of the oxygen species respectively. Herein, we report Pt₃Sc alloy nanoparticles (NPs) dispersed over partially exfoliated carbon nanotubes (PECNTs) as a cathode catalyst for single-cell measurements of PEMFC where Pt₃Sc alloy shows a lower binding energy towards oxygen and facilitates ORR with much faster kinetics. The ORR activity of Pt₃Sc/PECNTs electrocatalyst, investigated by cyclic voltammetry, Rotating Disk electrode (RDE) and Rotating Ring Disk electrode (RRDE), shows the higher mass activity and lower H₂O₂ formation than the commercial catalyst Pt/C-TKK. Accelerated Durability Tests (ADT) was performed to evaluate the stability of catalysts in acidic medium. In single-cell measurements, Pt₃Sc/PECNTs cathode catalyst exhibits a power density of 760 mW cm⁻² at 60 °C. Our study gives an important insight into the design of a novel ORR electrocatalyst with an excellent stability and high power density of PEMFC.     

Facile synthesis and characterization of highly dispersed platinum nanoparticles for fuel cells

We report a facile synthesis and characterization of highly-dispersed platinum nanoparticles supported on Ketjen carbon black (Pt/C) as electrocatalysts for polymer electrolyte membrane fuel fells (PEMFCs). Pt particles with size of ∼ 2.6 nm were synthesized through adsorption of Pt acetylacetonate on carbon supports and subsequently thermal decomposition. A comparative characterization analysis, including X-ray diffraction (XRD), high resolution transmission electron microscope (HR-TEM), cyclic voltammetry (CV), and hydrodynamic voltammetry measurements, was performed on the synthesized and commercial TKK catalysts. It revealed the details of Pt dispersion on the carbon support, particle size and distribution, electrochemical surface area (ECSA), and oxygen reduction reaction (ORR) activity of the catalysts. It was found that the synthesized Pt/C has similar particle size to that of the TKK catalyst (2.6 nm and 2.7 nm, respectively), but narrower particle size distribution. Accelerated durability tests under potential cycles were performed to study electrochemical degradation of the catalysts in corrosive environments. The synthesized Pt/C displayed significant losses in ECSA and activities after 20 k potential cycles, especially from 5 k to 20 k cycles, though with higher initial values (43% and 79% higher in ECSA and mass activity, respectively).     

Pt and Pt–Ag nanoparticles supported on carbon nanotubes (CNT) for oxygen reduction reaction in alkaline medium

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.