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.     

Carbon-coated tungsten oxide nanowires supported Pt nanoparticles for oxygen reduction

Carbon-coated tungsten oxide nanowires were grown directly on carbon fiber of a carbon paper (C–W₁₈O₄₉ NWs/carbon paper) by chemical vapor deposition method and Pt nanoparticles were deposited on the nanowires (Pt/C–W₁₈O₄₉ NWs/carbon paper) to form the composite electrode. The microstructure and electrochemical behavior of the resultant Pt/C–W₁₈O₄₉ NWs/carbon paper composites are characterized by a transmission electron microscope (TEM) and cyclic voltammetry, respectively. The electrocatalytic activities of these composite electrodes for oxygen reduction reaction (ORR) were investigated and higher mass and specific activities in ORR were exhibited as compared to commercial Pt/C electrode.     

Development of tellurium-modified carbon catalysts for oxygen reduction reaction in PEM fuel cells

Tellurium (Te)-modified carbon catalyst for oxygen reduction reaction was prepared through chemical reduction of telluric acid followed by the pyrolysis process at elevated temperatures. The catalyst was found to be active for oxygen reduction reaction. High-temperature pyrolysis plays a crucial role in the formation of the active sites of the catalysts. When the pyrolysis was conducted at 1000 °C, the catalyst exhibited the onset potential for oxygen reduction as high as 0.78 V vs. NHE and generated less than 1% H₂O₂ during oxygen reduction. The performance of the membrane–electrode assembly prepared with the Te-modified carbon catalyst was also evaluated.     

Low-cost and durable catalyst support for fuel cells: Graphite submicronparticles

Low-cost graphite submicronparticles (GSP) are employed as a possible catalyst support for polymer electrolyte membrane (PEM) fuel cells. Platinum nanoparticles are deposited on Vulcan XC-72 carbon black (XC-72), carbon nanotubes (CNT), and GSP via ethylene glycol (EG) reduction method. The morphologies and the crystallinity of Pt/XC-72, Pt/CNT, and Pt/GSP are characterized with X-ray diffraction and transmission electron microscope, which shows that Pt nanoparticles (∼3.5 nm) are uniformly dispersed on supports. Pt/GSP exhibits the highest activity towards oxygen-reduction reactions. The durability study indicates that Pt/GSP is 2-3 times durable than Pt/CNT and Pt/XC-72. The enhanced durability of Pt/GSP catalyst is attributed to the higher corrosion resistance of graphite submicronparticles, which results from higher graphitization degree of GSP support. Considering its low production cost, graphite submicronparticles are promising electrocatalyst support for fuel cells.     

Fuel cell performance of Pt electrocatalysts supported on carbon nanocoils

Carbon nanocoils (CNCs) synthesized via the catalytic graphitization of resorcinol-formaldehyde gel were investigated as an electrocatalyst support in PEMFC anodes. Their textural and physical properties make them a highly efficient catalyst support for anodic hydrogen oxidation in low temperature PEMFC.     

CO tolerance and stability of PtRu and PtRuMo electrocatalysts supported on N-doped graphene nanoplatelets for polymer electrolyte membrane fuel cells

PtRu and PtRuMo electrocatalysts supported on N-doped graphene nanoplatelets (N-GNPs) were synthesized by a polyol method and utilized as anodes in polymer electrolyte membrane fuel cells (PEMFCs) to measure their CO tolerance and stability. A higher structural stability of the N-GNP supported catalysts, presenting a lower metal loss and a lower particle growth than PtRu/C was observed. Tests in PEMFCs indicated both a higher CO tolerance and a higher electrochemical stability of N-GNP supported PtRu and PtRuMo catalysts than a commercial conventional carbon black (CB) supported PtRu.     

Highly stable nanocarbon supported Pt catalyst for fuel cell via a molten salt graphitization strategy

Proton exchange membrane fuel cells (PEMFCs) durability has been severely hindered by carbon support poor stability in the cathodic Pt-based catalyst. Herein, a high-surface-area nitrogen-doped graphitic nanocarbon (N-G-CA) with mesopores is developed as Pt support to address PEMFCs durability challenge. Resorcinol-formaldehyde aerogel pyrolyzed carbon aerogel is selected as N-G-CA raw material. Nitrogen atoms are introduced into carbon aerogel via NH₃ heat treatment. Then, nitrogen-doped carbon aerogel is transferred into N-G-CA via heating together with transition-metal salts (one of FeCl₃, FeCl₂, CoCl₂, or MnCl₂, etc.) at 1200 °C. As ORR catalyst, Pt/N-G-CA half-wave potential only lost 10 mV, after 30, 000 cycles accelerated aging test in the rotating-desk-electrode. Only 12 mV voltage loss at 1.5 A/cm2 is observed, after 5, 000 cycles for membrane electrode. Pt/N-G-CA exhibits superior durability and activity than commercial Pt/C. High durability of Pt/N-G-CA is due to N-G-CA high graphitization extent, as well as the interactions between doping nitrogen and Pt. N-G-CA is promising as stable support for durable Pt-based catalysts in PEMFCs, thanks to enhanced carbon corrosion resistance, uniformly dispersed Pt, and strong support-metals interaction.     

Ultrathin nitrogen doped carbon layer stabilized Pt electrocatalyst supported on N-doped carbon nanotubes

The enhancements in fuel cell performance and durability are crucial for the commercialization of polymer electrolyte fuel cells (PEFCs). Here, we deposit platinum nanoparticles on nitrogen doped carbon nanotubes (N-CNT) and continuously coat the electrocatalyst with nitrogen doped carbon (NC) layer derived from the carbonization of poly(vinyl pyrrolidone) (PVP). The NC-coated electrocatalyst shows stable electrochemical surface area (ECSA) during the potential cycling from 0.6 V to 1.0 V vs. RHE; while, the commercial and non-coated electrocatalysts lose 50% and 33% of initial ECSAs, respectively. Moreover, the NC-coated electrocatalyst shows higher oxygen reaction reduction (ORR) activity compared to non-coated electrocatalyst due to the additional nitrogen atoms in the electrocatalyst. The maximum power density of the coated electrocatalyst reaches 676 mW cm^?2 with Pt loading of 0.1 mg cm^?2, indicating that the mass power density of the electrocatalyst is one of the highest values in recently published literature. The NC layer is significantly important for simultaneous enhancements in durability and fuel cell performance.     

Development of high performance carbon composite catalyst for oxygen reduction reaction in PEM Proton Exchange Membrane fuel cells

Highly active and stable carbon composite catalysts for oxygen reduction in PEM fuel cells were developed through the high-temperature pyrolysis of Co–Fe–N chelate complex, followed by the chemical post-treatment. A metal-free carbon catalyst was used as the support. The carbon composite catalyst showed an onset potential for oxygen reduction as high as 0.87 V (NHE) in H₂SO₄ solution, and generated less than 1% H₂O₂. The PEM fuel cell exhibited a current density as high as 0.27 A cm⁻² at 0.6 V and 2.3 A cm⁻² at 0.2 V for a catalyst loading of 6.0 mg cm⁻². No significant performance degradation was observed over 480 h of continuous fuel cell operation with 2 mg cm⁻² catalyst under a load of 200 mA cm⁻² as evidenced by a resulting cell voltage of 0.32 V with a voltage decay rate of 80 μV h⁻¹. Materials characterization studies indicated that the metal–nitrogen chelate complexes decompose at high pyrolysis temperatures above 800 °C, resulting in the formation of the metallic species. During the pyrolysis, the transition metals facilitate the incorporation of pyridinic and graphitic nitrogen groups into the carbon matrix, and the carbon surface doped with nitrogen groups is catalytically active for oxygen reduction.     

Efficient synthesis of Pt3Co/NC alloy catalysts with enhanced durability and activity for the oxygen reduction reaction

Lack of catalytic performance, short life, and high cost are three main problems related to JM-Pt/C catalysts for proton exchange membrane fuel cells. The introduction of cheap transition metals improves catalytic performance while significantly reducing the cost of the catalysts. Here, we report the synthesis of Pt₃Co/NC alloy catalysts via coating and pyrolysis treatment. The agglomeration of nanoparticles during the high-temperature alloying process is significantly inhibited by coating with PANI. Remarkably, the obtained Pt₃Co/NC alloy catalysts exhibit excellent ORR catalytic performance and structural stability in 0.1 mol/L HClO₄. After 30,000 potential cycles, the mass activity and area-specific activity of Pt₃Co/NC alloy catalysts are 1.949 and 3.936 times higher, respectively, than that of JM-Pt/C with negligible performance loss. The strong metal-support interaction between N and Pt and the Pt-rich surface restrict the dissolution of Pt and Co, resulting in excellent stability. This synthesis approach provides an effective way to develop active and stable Pt alloy catalysts.     

Highly active Pt decorated Pd/C nanocatalysts for oxygen reduction reaction

This article describes findings of the correlation between the atomic scale surface structure and the electrocatalytic performance of nanoengineered Pt-Pd/C catalysts for oxygen reduction reaction (ORR), aiming at providing a new fundamental insight into the role of the detailed atomic decorated structure of the catalysts in fuel cell reactions. Carbon-supported Pt decorated Pd nanoparticles (donated as Pt-Pd/C), with Pt coverage close to a monolayer, were prepared from a simple galvanic replacement reaction between Pd/C particles and PtCl₄^2? at room temperature. The decorated architecture was confirmed by extensive microstructural characterization techniques, including TEM, XRD, XPS, HAADF-STEM, ICP and HS-LEIS. The catalysts were also examined for their intrinsic kinetic activities towards oxygen reduction reaction. The results have shown that the Pt-Pd/C catalysts are highly active towards molecular oxygen electrocatalytic reduction. These findings have profound implications to the design and nanoengineering of decorated surfaces of catalysts for oxygen reduction reaction.     

An effective electrocatalyst based on platinum nanoparticles supported with graphene nanoplatelets and carbon black hybrid for PEM fuel cells

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⁻¹_Pt for Pt/GNP and 55 m² g⁻¹_Pt for Pt/CB-GNP compared to 10 m² g⁻¹_Pt 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.     

Pt-Pd nanodendrites as oxygen reduction catalyst in polymer-electrolyte-membrane fuel cell

Platinum-palladium (Pt-Pd) bimetallic alloys have shown prospect as electrocatalyst for the oxygen reduction reaction (ORR) in the cathode of polymer-electrolyte-membrane (PEM) fuel cells. This article reports a facile solvothermal synthesis of Pt-Pd bimetallic nanodendrites (Pt-Pd NDs). The characterization with a variety of spectroscopic techniques indicates that the Pt-Pd NDs possess a three-dimensional (3-D) porous structure consisting of interconnected branches of highly alloyed Pt-Pd nanorods (NR). The measurements using rotating disk electrode in electrolyte solution show that the catalyst of Pt-Pd NDs supported on carbon (Pt-Pd NDs/C) possesses a Pt mass activity for ORR that is more than 3 times higher than that of the state-of-the-art Pt/C catalyst, as well as the significantly improved stability due to the branched porous structure. The measurements using membrane-electrode-assembly (MEA) in a single PEM fuel cell indicate the 3-D interconnected dendrite structures make the Pt-Pd NDs/C catalyst significantly advantageous over the nanoparticle Pt/C catalyst in reducing the mass transport and ohmic polarization which would become significant at high current density in MEA.     

Novel osmium-based electrocatalysts for oxygen reduction and hydrogen oxidation in acid conditions

In this work, novel osmium electrocatalysts for oxygen reduction and hydrogen oxidation in 0.5 M H₂SO₄, have been developed. The syntheses were performed by thermolysis of Os₃(CO)₁₂ and Os₃(CO)₁₂/Vulcan^®, in two reaction media, N₂ (in the absence of solvents) and n-octane, in order to evaluate the effect of these parameters on the electrocatalytic activity of the new materials. In the solvent-free pathway, different reaction temperatures (in the 120–320 °C range) and times (5, 7 and 10 h) were explored; the syntheses in n-octane were done at reflux temperature, for 30 and 72 h. The products were characterized structurally by FT-IR spectroscopy, X-ray diffraction and scanning electron microscopy, and electrochemically by room temperature rotating disk electrode measurements, using cyclic and linear sweep voltammetry. Some materials prepared in both reaction media can efficiently perform the hydrogen oxidation and/or oxygen reduction reaction, i.e. those prepared by pyrolysis of Os₃(CO)₁₂/Vulcan^® in N₂, at 180 °C/7 h, 320 °C/5 h, 320 °C/7 h and 320 °C/10 h, as well as the materials synthesized in n-octane (from both Os precursors); the latter, in addition, have the important property of being tolerant to carbon monoxide to some extent, in contrast to platinum, which is easily deactivated even by traces of CO.     

Graphene and carbon nanotube structures supported on mesoporous xerogel carbon as catalysts for oxygen reduction reaction in proton-exchange-membrane fuel cells

Non-precious metal catalysts for the oxygen reduction reaction (ORR) in proton-exchange-membrane fuel cells (PEMFCs) were obtained by pyrolysis of iron citrate and polyacrylonitrile on mesoporous xerogel carbon support. Chemical-physical characterizations, electrochemical studies by the rotating disc electrode, and electrochemical tests in a PEMFC configuration demonstrated that the porosity of the pristine carbon promotes the formation of graphene and carbon nanotube structures featuring ORR catalytic activity.     

Enhancement of the electrocatalytic activity for the oxygen reduction reaction of boron-doped reduced graphene oxide via ultrasonic treatment

Commercial polymer electrolyte membrane fuel cells have relied on scares Platinum to catalyse the kinetically sluggish oxygen reduction reaction occurring at their anodes. Over the last decade organic materials, frequently based on graphitic structures have been demonstrated as promising alternative electrocatalysts to the noble metals. Researchers typically utilize ultrasonic treatment as part of the synthesis procedure to achieve homogeneous dispersion of graphitic carbon prior to. Herein we investigate the implications of the structural and compositional changes induced by the ultrasonication treatment on boron-doped reduced graphene oxide for oxygen reduction reaction. It is shown that ultrasonication pre-treatment prior to the boron doping and reduction of graphene oxide via hydrothermal process step leads to the increase of both substitutional B and electrocatalytic surface area, with associated reduction of average pore size diameter, leading to a significant improvement in the oxygen reduction reaction performance, with respect to the non-ultrasonicated material. It is proposed that the higher degree of substitutional doping of boron is a result of formation of the additional epoxy functionalities on graphitic planes, which act as a doping site for boric acid.     

Efficient electrocatalysts for the oxygen reduction reaction,based on mixed carbonyl-phosphine clusters of iridium

This work reports the synthesis and characterization of two novel electrocatalysts for the oxygen reduction reaction based on iridium clusters containing carbonyl (CO) and phosphine (PPh₃ or PPh(OMe)₂) ligands. The study of the complexes by FTIR, XRD, EDS, XPS, MS, as well as ¹H, ¹³C and ³¹P NMR shows that they preserve the nuclearity of the iridium cluster used as precursor (Ir₄(CO)₁₂), while several of the carbonyl groups were substituted by the corresponding phosphine-type ligands and solvent (o-dichlorobenzene) molecules. The electrochemical characterization by rotating disk electrode measurements in an acid medium (0.5 mol L^?1 H₂SO₄), from which the kinetic parameters could be obtained, indicates that both clusters exhibit an important catalytic activity for the oxygen electroreduction, even in the presence of methanol in concentrations as high as 2.0 mol L^?1. According to these results, the new electrocatalysts are good potential candidates to be evaluated as cathodes in PEMFCs and DMFCs.     

Highly uniform platinum nanoparticles supported on graphite nanoplatelets as a catalyst for proton exchange membrane fuel cells

Graphite nanoplatelets (GNPs), which consist of layers of graphene, are an ideal electrocatalyst support due to their high electrical and thermal conductivity, excellent chemical stability, and easy availability. However, GNPs are somewhat chemically inert, which makes the even deposition of catalytic metal nanoparticles on their surface difficult. In this paper, we present a facile method to prepare highly uniform Pt nanoparticles on GNPs, which are decorated with 1-pyrenecarboxylic acid (PCA). When the hydrophobic pyrene group of the PCA is adsorbed on the surface of GNPs via π–π interaction, its carboxylic group can serve as an anchor for the Pt deposition. This decoration facilitates a narrow size profile, which is centered at approximately 2–3 nm, and an even spatial distribution on the GNPs surface for the Pt nanoparticles. The resultant Pt/GNPs catalyst exhibits a noticeably higher durability and electrochemical activity than the commonly used Pt/C catalyst and is therefore a promising cathodic catalyst for proton exchange membrane fuel cells.     

Highly efficient CO2 bubble removal on carbon nanotube supported nanocatalysts for direct methanol fuel cell

In this paper, we investigate the CO₂ microbubble removal on carbon nanotube (CNT)-supported Pt catalysts in direct methanol fuel cells (DMFCs). The experiments involve the incorporation of near-catalyst-layer bubble visualization and simultaneous electrochemical measurements in a DMFC anodic half cell system, in which CH₃OH electro-oxidation generate carbon dioxide (CO₂) microbubbles. We observe rapid removal of smaller CO₂ bubble sizes and less bubble accumulation on a Pt-coated CNT/CC (Pt/CNT/CC, CC means carbon cloth) electrode. The improved half cell performances of the high CO₂ microbubble removal efficiency on the CNT-modified electrode (Pt/CNT/CC) were 34% and 32% higher than on Pt/CC and Pt/CP electrodes, respectively.     

Manganese dioxide-coated carbon nanotubes as an improved cathodic catalyst for oxygen reduction in a microbial fuel cell

To develop an efficient and cost-effective cathodic electrocatalyst for microbial fuel cells (MFCs), carbon nanotubes (CNTs) coated with manganese dioxide using an in situ hydrothermal method (in situ MnO₂/CNTs) have been investigated for electrochemical oxygen reduction reaction (ORR). Examination by transmission electron microscopy shows that MnO₂ is sufficiently and uniformly dispersed over the surfaces of the CNTs. Using linear sweep voltammetry, we determine that the in situ MnO₂/CNTs are a better catalyst for the ORR than CNTs that are simply mechanically mixed with MnO₂ powder, suggesting that the surface coating of MnO₂ onto CNTs enhances their catalytic activity. Additionally, a maximum power density of 210 mW m⁻² produced from the MFC with in situ MnO₂/CNTs cathode is 2.3 times of that produced from the MFC using mechanically mixed MnO₂/CNTs (93 mW m⁻²), and comparable to that of the MFC with a conventional Pt/C cathode (229 mW m⁻²). Electrochemical impedance spectroscopy analysis indicates that the uniform surface dispersion of MnO₂ on the CNTs enhanced electron transfer of the ORR, resulting in higher MFC power output. The results of this study demonstrate that CNTs are an ideal catalyst support for MnO₂ and that in situ MnO₂/CNTs offer a good alternative to Pt/C for practical MFC applications.