Defective graphene foam : a platinum catalyst support for PEMFCs

Gram-scale synthesis of defective graphene foam from low-cost precursors is reported as a catalyst support material for platinum in fuel cell cathodes. The material was produced by combustion of sodium ethoxide, followed by washing and heat-treatment in various gases. The BET surface area is higher than 1500 m2/g. The defects in the material result in excellent distribution of platinum nanoparticles on the surface. The electrochemical performance is compared with platinum-decorated carbon black and commercially obtainable graphene using cyclic voltammetry, linear sweep voltammetry, and membrane electrode assemblies. Pt-decorated grapheme foam has larger electrochemical surface area (101 m2/g) and higher mass activity (176 A/gPt). However, durability and fuel cell power density still require improvements. This graphene foam is a potentially useful catalyst support, especially for use in polymer electrolyte membrane fuel cells

Lattice strain mapping of platinum nanoparticles on carbon and SnO2 supports

It is extremely important to understand the properties of supported metal nanoparticles at the atomic scale. In particular, visualizing the interaction between nanoparticle and support, as well as the strain distribution within the particle is highly desirable. Lattice strain can affect catalytic activity, and therefore strain engineering via e.g. synthesis of core-shell nanoparticles or compositional segregation has been intensively studied. However, substrate-induced lattice strain has yet to be visualized directly. In this study, platinum nanoparticles decorated on graphitized carbon or tin oxide supports are investigated using spherical aberration-corrected scanning transmission electron microscopy (Cs-corrected STEM) coupled with geometric phase analysis (GPA). Local changes in lattice parameter are observed within the Pt nanoparticles and the strain distribution is mapped. This reveals that Pt nanoparticles on SnO 2 are more highly strained than on carbon, especially in the region of atomic steps in the SnO 2 lattice. These substrate-induced strain effects are also reproduced in density functional theory simulations, and related to catalytic oxygen reduction reaction activity. This study suggests that tailoring the catalytic activity of electrocatalyst nanoparticles via the strong metal-support interaction (SMSI) is possible. This technique also provides an experimental platform for improving our understanding of nanoparticles at the atomic scale

Platinum-decorated tin oxide and niobium-doped tin oxide pefc electrocatalysts : oxygen reduction reaction activity

Using tin oxide (SnO2) and niobium-doped tin oxide (Nb-SnO2) as alternative electrocatalyst support materials can effectively solve the issue of carbon corrosion in polymer electrolyte fuel cell (PEFC) cathodes. Here, we systematically explore the effect of support surface area, Pt loading, and Pt nanoparticle size on the electrochemistry of these carbon-free electrocatalysts. Reducing the Pt loading leads to an increase in electrochemical surface area, but the specific activity decreases as previously observed in conventional carbon based electrocatalysts. Removing residual chlorine impurities by replacing the H2PtCl6 nanoparticle precursor with Pt(acac)2 increases the specific activity. Niobium-doping of the SnO2 support also results in an increase in specific activity, due to the increased electronic conductivity. Consequently, the oxygen reduction reaction activity of optimized Pt-decorated Nb-SnO2 is approaching to that of Pt-decorated carbon black, the current state-of-the-art PEFC electrocatalyst

In-situ ESEM and EELS observation of water uptake and ice formation in multilayer graphene oxide

Graphene oxide (GO) is hydrophilic and swells significantly when in contact with water. Here, we investigate the change in thickness of multilayer graphene oxide membranes due to intercalation of water, via humidity-controlled observation in an environmental scanning electron microscope (ESEM). The thickness increases reproducibly with increasing relative humidity. Electron energy loss spectroscopy (EELS) reveals the existence of water ice under cryogenic conditions, even in high vacuum environment. Additionally, we demonstrate that freezing then thawing water trapped in the multilayer graphene oxide membrane leads to the opening up of micron-scale inter-lamellar voids due to the expansion of ice crystals

Atomic-resolution analysis of degradation phenomena in SOFCS : a case study of SO2 poisoning in LSM cathodes

Solid oxide fuel cell (SOFC) degradation studies are often performed by scanning transmission electron microscopy (STEM), scanning electron microscopy (SEM), and X-ray diffraction (XRD). However, it is difficult to use these techniques to observe processes occurring at the smallest scales. Here, we study sulfur poisoning of La0.8Sr0.2MnO3−δ (LSM) cathodes as a model case for atomic resolution scanning transmission electron microscopy (STEM) analysis with energy dispersive X-ray diffraction (EDX). Significant SrSO4 nanoparticle formation is observed after SO2 exposure, especially at grain boundaries in the LSM. In addition, La2O3 formation inside the grain was also confirmed. The formation of SrSO4 is identified with irreversible SOFC degradation, in addition to simple SO2 adsorption, which is reversible

Development of Novel Optical Fiber System for Cathodoluminescence Detection in High Voltage Transmission Electron Microscope

We have installed a new system to observe cathodoluminescence (CL) in a high voltage transmission electron microscope (HVTEM). The system is constructed of a ball lens for collection of CL, an optical fiber and a multi-channel optical detector. The system can be operated without any disturbance of TEM observation. The system was proved to be very useful to observe CL in HVTEM and will be a powerful tool to investigate production mechanisms of luminescence centers by observing CL changes with incident electron energy and flux (displacement damage effect), and temperature, together with simultaneous TEM observations of microstructure changes

Nitrogen-Doped Carbon Foam as a Highly Durable Metal-Free Electrocatalyst for the Oxygen Reduction Reaction in Alkaline Solution

Nitrogen-doped carbon foam (CFN) with large surface area is synthesized via a template-free, scalable combustion technique using diethanolamine as a nitrogen source. The resulting macroporous, open-cell foam has micron-scale hollow cells, surrounded by thin, graphene-like walls. This material is applied as a metal-free electrocatalyst for the oxygen reduction reaction (ORR) in alkaline KOH solution. The activity of this metal-free electrocatalyst at the half-wave potential is just 43 mV lower than that of platinum-decorated carbon (Pt/CB), but 87 mV lower than a commercially available Fe-containing non-precious electrocatalyst (Pajarito Powder, PP), suggesting that iron is important in achieving the highest activities. In durability tests measured over 60,000 potential cycles, Pt/CB and PP undergo significant degradation, whilst the non-precious CFN electrocatalyst shows negligible change, indicating high stability of the electrochemical active sites compared with platinum or iron. Such metal-free catalysts therefore show great promise as electrocatalysts for specific alkaline ion exchange membrane fuel cell (AEMFC) applications where long lifetimes are most important.clos