Proton exchange membrane fuel cells (PEMFCs) and direct methanol fuel cells (DMFCs) are two types of low-temperature fuel cells (LTFCs) that operate at temperatures less than 100 °C and are appealing for portable, transportation, and stationary applications. However, commercialization has been hampered by several problems such as cost, efficiency, and durability. New electrocatalysts must be developed that have higher oxygen reduction reaction (ORR) activity, lower precious metal loadings, and improved durability to become commercially viable. This dissertation investigates the development and use of new electrocatalysts for the ORR. Core-shell (shell@core) Pt@Pd[subscript x]Cu[subscript y]/C electrocatalysts, with a range of initial compositions, were synthesized to result in a Pt-rich shell atop a Pd[subscript x]C[subscript y]-rich core. The interaction between core and shell resulted in a delay in the onset of Pt-OH formation, accounting in a 3.5-fold increase in Pt-mass activity compared to Pt/C. The methanol tolerance of the core-shell Pt@PdCu5/C was found to decrease with increasing Pt-shell coverage due to the negative potential shift in the CO oxidation peak. It was discovered that Cu leached out from the cathode has a detrimental effect on membrane-electrode assembly performance. A spray-assisted impregnation method was developed to reduce particle size and increase dispersion on the support in a consistent manner for a Pd88W12/C electrocatalyst. The spray-assisted method resulted in decreased particle size, improved dispersion and more uniform drying compared to a conventional method. These differences resulted in greater performance during operation of a single DMFC and PEMFC. Additionally, Pd88W12/C prepared by spray-assisted impregnation showed DMFC performance similar to Pt/C with similar particle size in the kinetic region while offering improved methanol tolerance. Pd88W12/C also showed comparable maximum power densities and activities normalized by cost in a PEMFC. Lastly, the activation of aluminum as an effective reducing agent for the wet- chemical synthesis of metallic particles by pitting corrosion was explored along with the control of particle morphology. It was found that atomic hydrogen, an intermediate, was the actual reducing agent, and a wide array of metals could be produced. The particle size and dispersion of Pd/C produced using Al was controlled using PVP and FeCl2 as stabilizers. The intermetallic Cu2Sb was similarly prepared with a 20 nm crystallite size for potential use in lithium-ion battery anodes. Lastly, it was found that the shape of Pd produced with Al as a reducing agent could be controlled to prepare 10 nm cubes enclosed by (100) facets with potentially high activity for the ORR.

Proton exchange membrane fuel cells (PEMFC) and direct methanol fuel cells (DMFC) are attractive power sources as they offer high conversion efficiencies with low or no pollution. However, the most commonly used platinum electrocatalyst is expensive and the world supply of Pt is limited. In addition, the slow oxygen reduction and methanol oxidation kinetics as well as the poisoning of the Pt catalyst at the cathode resulting from methanol permeation from the anode through the Nafion membrane to the cathode lead to significant performance loss. Also, the electrocatalyst utilization in the electrodes also needs to be improved to reduce the overall cost of the electrocatalysts and improve the fuel cell performance. This dissertation explores nanostructured Pt alloys with lower cost and higher catalytic activity than Pt for oxygen reduction in PEMFC to understand the effect of synthesis and structure on the catalytic activity, methanol tolerant Pt/TiOx nanocomposites for oxygen reduction in DMFC, nanostructured Pt-Ru alloys for methanol oxidation in DMFC, and improvement in the utilization of Pt by optimizing the membrane-electrode assembly (MEA) fabrication. From a systematic investigation of a series of Pt-M alloys (M = Fe, Co, Ni, and Cu), the catalytic activity of Pt-M alloys is correlated with the extent of atomic ordering. More ordered Pt alloys exhibit higher catalytic activity than disordered Pt alloys. The higher activity of the ordered Pt alloys is found to relate to various factors including the Pt-Pt distance, Pt: 5d orbital vacancy, {100} planar density and surface atomic configuration. The catalytic activity of the Pt alloys is also influenced by the synthesis method. Low temperature solution methods usually result in smaller particle size and higher surface area, while high temperature routes result in larger particle size and lower surface area but with a greater extent of alloying. Pt/TiOx/C nanocomposites exhibit higher performance than Pt for oxygen reduction in DMFC. The nanocomposites show higher electrchochemical surface area, lower charge transfer resistance, and higher methanol tolerance than Pt. Pt-Ru alloy synthesized by a reverse microemulsion method exhibits higher catalytic surface area than the commercial Pt-Ru. The higher catalytic activity is attributed to a better control of the particle size, crystallinity, and microstructure. Membrane-electrode assemblies (MEAs) fabricated by a modified thin film method exhibit much higher electrocatalyst utilization efficiency and performance than the conventional MEAs in PEMFC. Power densities of 715 and 610 mW/cm2 are obtained at a Pt loading of, respectively, 0.1 and 0.05 mg/cm2 and 90 oC. The higher electrocatalyst utilization is attributed to the thin catalyst layer and a better continuity of the membrane/catalysts layer interface compared to that in the conventional MEAs.

Global experts provide an authoritative source of information on the use of electrochemical fuel cells, and in particular discuss the use of nanomaterials to enhance the performance of existing energy systems. The book covers the state of the art in the design, preparation, and engineering of nanoscale functional materials as effective catalysts for fuel cell chemistry, highlights recent progress in electrocatalysis at both fuel cell anode and cathode, and details perspectives and challenges in future research.

Catalysts in the electrodes of polymer exchange membrane fuel cells (PEMFCs) serve a critical function in reactions which can be used to generate electrical energy from chemical fuels. Pt nanoparticles are commonly dispersed on a conductive support and used as electrode materials in these devices because of their exceptional catalytic activity and electrochemical active surface area. The performance and stability of these electrodes strongly depend on the characteristics of the support. Catalysts supported on high surface area carbon black are widely used in low-temperature fuel cells. In PEMFCs, these catalyst materials can be exposed to high potential and low pH values, resulting in irreversible loss of activity that will limit the useful lifetime of the cell, ultimately leading to its failure. Pt is a noble metal which has good intrinsic stability, but carbon is not thermodynamically stable resulting in the corrosion of the catalyst support under these conditions. The design of more resilient platinum catalyst supports to carry out the successful reaction in a fuel cell's catalyst layer is required to extend the lifetime of PEMFCs degradation. In this thesis, two approaches were used to synthesize robust catalyst support materials for fuel cell applications. In the first case, carbon surfaces were functionalised to enhance their interactions with the catalyst and secondly, stable metal oxide was combined with modified carbon substrates, to maximise contacts within the composite electrocatalysts and to prevent carbon corrosion of a single phase carbon support catalyst. TiO2 NPs, were first chemically bonded to the surfaces of Vulcan carbon to help anchor the Pt catalyst nanoparticles through strong metal-support interactions. Validation of a dual phase catalyst support is an important goal of this research. Each material phase offers a unique advantage that can only be recognized by the preparation of a composite electrocatalyst. Pristine Vulcan (PV) was functionalised with glucose hydroxyl functional groups that react with the base titanium metal alkoxide in a sol-gel reaction and then calcined to form a more chemically crystalline surface. This is followed by impregnation reduction process to deposit the nanostructured Pt catalyst. Material characterization data of synthesized materials were used to correlate the effects of support structure and composition on resilient performance. Advantages from the TiO2/C supports toward performance and durability were contrasted against a set of control samples and demonstrated ex situ. The prepared composite catalysts showed substantial enhancements toward oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) as well as improved stability of the Pt-TiO2 heterogeneous interface formed between catalyst and support. The enhanced performance and durability of these composite catalysts is improved by applying the science of materials and interfaces to the synthesis of composite supports, thus serving as an example for further progress and optimization. Irradiation of these composite catalysts with UV-visible light also showed ~ 171 % photo enhanced activity for MOR, which clearly demonstrates a synergistic effect between the photo- and electrocatalysts. The comparison between the prepared catalysts indicates that there is an appropriate ratio of carbon and TiO2 to obtain the best performance of these photoelectroactive materials. These results demonstrate that methanol oxidation is achieved by electro- and photoelectrocatalysis using a simple and affordable method. This procedure can be conveniently exploited to enhance the response of direct methanol fuel cell electrodes.

Exhibiting both homogeneous and heterogeneous catalytic properties, nanocatalysts allow for rapid and selective chemical transformations, with the benefits of excellent product yield and ease of catalyst separation and recovery. This book reviews the catalytic performance and the synthesis and characterization of nanocatalysts, examining the current state of the art and pointing the way towards new avenues of research. Moreover, the authors discuss new and emerging applications of nanocatalysts and nanocatalysis, from pharmaceuticals to fine chemicals to renewable energy to biotransformations. Nanocatalysis features contributions from leading research groups around the world. These contributions reflect a thorough review of the current literature as well as the authors’ first-hand experience designing and synthesizing nanocatalysts and developing new applications for them. The book’s nineteen chapters offer a broad perspective, covering: Nanocatalysis for carbon-carbon and carbon-heteroatom coupling reactions Nanocatalysis for various organic transformations in fine chemical synthesis Nanocatalysis for oxidation, hydrogenation, and other related reactions Nanomaterial-based photocatalysis and biocatalysis Nanocatalysts to produce non-conventional energy such as hydrogen and biofuels Nanocatalysts and nano-biocatalysts in the chemical industry Readers will also learn about the latest spectroscopic and microscopy tools used in advanced characterization methods that shed new light on nanocatalysts and nanocatalysis. Moreover, the authors offer expert advice to help readers develop strategies to improve catalytic performance. Summarizing and reviewing all the most important advances in nanocatalysis over the last two decades, this book explains the many advantages of nanocatalysts over conventional homogeneous and heterogeneous catalysts, providing the information and guidance needed for designing green, sustainable catalytic processes.

Abstract: Fuel cell, as an alternative green power source for automobiles and portable electronics, has attracted worldwide attention due to its desirable properties such as high energy density and low greenhouse gas emission. Despite great progress in the past decades, several challenges still remain as obstacles for the large-scale commercialization. Among them, the high cost of Pt-based electrode material is considered as a major barrier, while the life span or stability of electrode catalysts is another concern since the electrocatalysts can be easily poisoned during the fuel cell operation. In order to overcome these issues, nanostructured carbon materials, especially carbon nanotubes (CNTs), are studied as catalyst support. In addition, recent research also suggests that the coupling of a second metal element with Pt can effectively protect the electrocatalysts from being poisoned and thus improve their long-term durability. The objective of the present work was to demonstrate an efficient synthetic method for the preparation of CNTs supported binary PtM (M=Ru, Sn) electrocatalysts. In this project, a polymer wrapping technique along with an in-situ polyol reduction strategy was adopted to decorate well-dispersed binary PtM nanoparticles on the surface of modified-CNTs. The unique nanostructures as well as the excellent catalytic activities of the as-prepared nanohybirds were investigated through a diversity of physiochemical and electrochemical characterization techniques. This fabrication method provided a simple and convenient route to assemble Pt-based catalyst on carbon substrates, which is useful for the further development of high-performance fuel cell catalysts.