Microbial fuel cell (MFC) research is a rapidly evolving field that lacks established terminology and methods for the analysis of system performance. This makes it difficult for researchers to compare devices on an equivalent basis. The construction and analysis of MFCs requires knowledge of different scientific and engineering fields, ranging from microbiology and electrochemistry to materials and environmental engineering. Describing MFC systems therefore involves an understanding of these different scientific and engineering principles. In this paper, we provide a review of the different materials and methods used to construct MFCs, techniques used to analyze system performance, and recommendations on what information to include in MFC studies and the most useful ways to present results.

Microbial Fuel Cells: Methodology and Technology†

The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non-precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non-precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%).

/pdf/high-performance-electrocatalysts-for-oxygen-reduction-3w5qtsq9yn.pdf

High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt

Fuel cell catalysts synthesized from abundant metals approach the performance and durability of platinum at lower cost. The prohibitive cost of platinum for catalyzing the cathodic oxygen reduction reaction (ORR) has hampered the widespread use of polymer electrolyte fuel cells. We describe a family of non–precious metal catalysts that approach the performance of platinum-based systems at a cost sustainable for high-power fuel cell applications, possibly including automotive power. The approach uses polyaniline as a precursor to a carbon-nitrogen template for high-temperature synthesis of catalysts incorporating iron and cobalt. The most active materials in the group catalyze the ORR at potentials within ~60 millivolts of that delivered by state-of-the-art carbon-supported platinum, combining their high activity with remarkable performance stability for non–precious metal catalysts (700 hours at a fuel cell voltage of 0.4 volts) as well as excellent four-electron selectivity (hydrogen peroxide yield <1.0%).

The recent advances in electrocatalysis for oxygen reduction reaction (ORR) for proton exchange membrane fuel cells (PEMFCs) are thoroughly reviewed. This comprehensive Review focuses on the low- and non-platinum electrocatalysts including advanced platinum alloys, core–shell structures, palladium-based catalysts, metal oxides and chalcogenides, carbon-based non-noble metal catalysts, and metal-free catalysts. The recent development of ORR electrocatalysts with novel structures and compositions is highlighted. The understandings of the correlation between the activity and the shape, size, composition, and synthesis method are summarized. For the carbon-based materials, their performance and stability in fuel cells and comparisons with those of platinum are documented. The research directions as well as perspectives on the further development of more active and less expensive electrocatalysts are provided.

http://repository.ust.hk/ir/bitstream/1783.1-77094/1/acs.chemrev.5b00462_withlink.pdf

Recent Advances in Electrocatalysts for Oxygen Reduction Reaction

First-generation glucose biosensors relied on the use of the natural oxygen cosubstrate and the production and detection of hydrogen peroxide and were much simpler, especially when miniaturized sensors are concerned. More sophisticated bioelectronic systems for enhancing the electrical response, based on patterned monolayer or multilayer assemblies and organized enzyme networks on solid electrodes, have been developed for contacting GOx with the electrode support. Electrochemical biosensors are well suited for satisfying the needs of personal (home) glucose testing, and the majority of personal blood glucose meters are based on disposable (screen-printed) enzyme electrode test strips, which are mass produced by the thick film (screen-printing) microfabrication technology. In the counter and an additional “baseline” working electrode, various membranes (mesh) are incorporated into the test strips along with surfactants, to provide a uniform sample coverage. Such devices offer considerable promise for obtaining the desired clinical information in a simpler, user-friendly, faster, and cheaper manner compared to traditional assays. Continuous ex-vivo monitoring of blood glucose was proposed in 1974 and the majority of glucose sensors used for in-vivo applications are based on the GOx-catalyzed oxidation of glucose by oxygen. The major factors that play a role in the development of clinically accurate in-vivo glucose sensors include issues related to biocompatibility, miniaturization, long-term stability of the enzyme and transducer, oxygen deficit, short stabilization times, in-vivo calibration, baseline drift, safety, and convenience.

Electrochemical Glucose Biosensors

Introduction Technology for electrical power generation using enzyme catalysts, established four decades ago, has recently received increased attention associated with demand for micro-scale and implantable power supplies. The main challenges, namely the fragility of enzyme molecules, characteristic low current density, and poor fundamental understanding of redox biocatalysis, are currently being addressed from a variety of research perspectives, to take advantage of enzyme selectivity, low temperature and moderate pH activity, and manufacturability in small-scale devices. Such an effort benefits from four decades of multidisciplinary research in biosensors and related bioelectrochemical fields. This review paper summarizes the current state of enzymatic biofuel cell research in the context of foreseeable applications and assesses the future prospects of the technology. Emphasis is placed on device performance and engineering aspects, with a view toward practical portable power devices based on enzymatic biofuel cells. Research in biocatalytically modified electrodes, particularly for sensor applications, has provided a significant technological underpinning for current biofuel cell development. There exists significant overlap in technical requirements between sensors and biofuel cells, including chemical and mechanical stability, selectivity, and cost of materials. However, these two technologies diverge in the areas of current density, cell potential and stability. There exists extensive review literature in the area of biological fuel cells. Notably, Palmore and Whitesides summarized biological fuel cell concepts and performance up until about 1992. More recently, Katz and Willner discussed recent progress in novel electrode chemistries for both microbial and enzymatic fuel cells. We do not duplicate these valuable contributions, but instead focus on the strengths and weaknesses of state-of-art materials in the context of specific classes of applications, and point to areas where additional knowledge is currently needed to exploit biological fuel cells. With some exceptions, we focus on contributions made after 1992. Biofuel cells have traditionally been classified according to whether the catalytic enzymes were located inside or outside of living cells. If living cells are involved the system is considered to be microbial, and if not it is considered enzymatic. Although microbial fuel cells posses unique features unmatched by enzymatic cells, such as long-term stability and fuel efficiency, the power densities associated with such devices are typically much lower owing to resistance to mass transfer across cell membranes. Thus, microbial fuel cells are expected to find limited application in smallscale electronic devices. This review will focus on enzymatic biofuel cells. While such cells typically demonstrate reduced stability due to the limited lifetime of extracellular enzymes, and are typically unable to fully oxidize fuels, they allow for substantial concentration of catalysts and removal of mass transfer barriers and provide higher current and power densities, approaching the range of applicability to microand mini-scale electronics applications. Applications and Requirements The range of possible applications for biofuel cells may be broken down into three main subclasses: 1. Implantable power, such as micro-scale cells implanted in human or animal tissue, or larger cells implanted in blood vessels. 2. Power derived from ambient fuels or oxidants, mainly plant saps and juices, but extending to sewage and other waste streams. 3. Power derived from conventional fuels including hydrogen, methanol or higher alcohols. Classes 1 and 2 are closely related. The fuels available for implantable power, such as blood borne glucose or lactate, are ambient in the sense that they are present in a physiological environment in the absence of a fuel cell device. One major distinction between these two classes is that the ambient-fueled cell need not be implanted, and focuses on plantor waste-derived fuels, whereas the implantable cell focuses on animal-derived fuels and is present within the physiological system. Class 3 is unique in that this class competes with well-established conventional fuel cell technology. To a greater or lesser extent, all three classes share the fundamental technical requirements of high power density and high activity.

Enzymatic biofuel cells for implantable and microscale devices.

A miniature biofuel cell.

Millions of years of evolution have produced biological systems capable of efficient one-pot multi-step catalysis. The underlying mechanisms that facilitate these reaction processes are increasingly providing inspiration in synthetic chemistry. Substrate channelling, where intermediates between enzymatic steps are not in equilibrium with the bulk solution, enables increased efficiencies and yields in reaction and diffusion processes. Here, we review different mechanisms of substrate channelling found in nature and provide an overview of the analytical methods used to quantify these effects. The incorporation of substrate channelling into synthetic cascades is a rapidly developing concept, and recent examples of the fabrication of cascades with controlled diffusion and flux of intermediates are presented.

Substrate channelling as an approach to cascade reactions.

We report on the synthesis of thin, transparent, and highly catalytic carbon nanotube films. Nanotubes catalyze the reduction of triiodide, a reaction that is important for the dye-sensitized solar cell, with a charge-transfer resistance as measured by electrochemical impedance spectroscopy that decreases with increasing film thickness. Moreover, the catalytic activity can be significantly enhanced by exposing the nanotubes to ozone in order to introduce defects. Ozone-treated, defective nanotube films could serve as catalytic, transparent, and conducting electrodes for the dye-sensitized solar cell. Other possible applications include batteries, fuel cells, and electroanalytical devices.

http://trancik.scripts.mit.edu/home/wp-content/uploads/2012/09/TrancikNanoLett2008.pdf

Scott Calabrese Barton

Papers

Enzymatic biofuel cells for implantable and microscale devices.

A miniature biofuel cell.

Substrate channelling as an approach to cascade reactions.

Transparent and Catalytic Carbon Nanotube Films

Spectroscopic insights into the nature of active sites in iron–nitrogen–carbon electrocatalysts for oxygen reduction in acid