Electrochemistry studies on the derivatives of graphene have been in the forefront of chemical research in recent years. The large specific surface area, high electrical conductivity, fast electron transfer rate and excellent biocompatibility to biomolecules constitute a few of the underlying reasons for the extensive application of graphene derivatives in modern electrochemistry and related technologies. Much interest in graphene derivatives has been driven by the ease of intentional functionalisation of the carbon backbone of graphene with dopants, such as nitrogen. Doping enhances the electrical conductivity and biocompatibility of nitrogen-doped graphene (NGr) nanomaterials and aids in their potential applications in electrochemical sensing and spectroelectrochemical devices. Despite the application of NGr in electrochemical sensing devices, the major challenge for reproducible industrial application still lies in the use of surfactants and binders and the limited knowledge on the correlation between the N-configurations and the electrocatalytic performance of these NGr-based electrodes. Therefore, the purpose of this short review article is to highlight some recent progress on the application of NGr derivatives for electrochemical detection of biomarkers such as uric acid and dopamine. The paper will also illustrate design parameters for new surfactant-free two-dimensional (2D) N-doped graphene based electrochemical sensors with variable N-functionalities for the detection of dopamine and uric acid.
To date, the world has been making a massive shift away from fossil fuels towards cleaner energy sources. For the past decade, polymer electrolyte membrane fuel cells (PEMFCs) powered by hydrogen have attracted much attention as a promising candidate for eco-friendly vehicles, i.e. fuel cell electric vehicles (FCEVs), owing to their high power density, high efficiency and zero emission features. Since the world’s first mass production of Tucson ix35 FCEV by Hyundai in 2013, global automotive original equipment manufacturers (OEMs) have focused on commercialising FCEVs. In 2018, Hyundai also unveiled the second generation of the mass-produced FCEV (i.e. Nexo) with improved performances and durability compared with its predecessor. Since then, the global market for PEMFCs for a variety of FCEV applications has been growing very rapidly in terms of both passenger vehicles and medium- and heavy-duty vehicles such as buses and trucks, which require much higher durability than passenger vehicles, i.e. 5000 h for passenger vehicles vs. 25,000 h for heavy-duty vehicles. In addition, PEMFCs are also in demand for other applications including fuel cell electric trains, trams, forklifts, power generators and vessels. We herein present recent advances in how hydrogen and PEMFCs will power the future in a wide range of applications and address key challenges to be resolved in the future.
To combat the global problem of carbon dioxide emissions, hydrogen is the desired energy vector for the transition to environmentally benign fuel cell power. Water electrolysis (WE) is the major technology for sustainable hydrogen production. Despite the use of renewable solar and wind power as sources of electricity, one of the main barriers for the widespread implementation of WE is the scarcity and high cost of platinum group metals (pgms) that are used to catalyse the cathodic hydrogen evolution reaction (HER) and the anodic oxygen evolution reaction (OER). Hence, the critical pgm-based catalysts must be replaced with more sustainable alternatives for WE technologies to become commercially viable. This critical review describes the state-of-the-art pgm-free materials used in the WE application, with a major focus on phosphides and borides. Several emerging classes of HER and OER catalysts are reviewed and detailed structure–property correlations are comprehensively summarised. The influence of the crystallographic and electronic structures, morphology and bulk and surface chemistry of the catalysts on the activity towards OER and HER is discussed.
In recent years, sodium-ion batteries (NIBs) have been explored as an alternative technology to lithium-ion batteries (LIBs) due to their cost-effectiveness and promise in mitigating the energy crisis we currently face. Similarities between both battery systems have enabled fast development of NIBs, however, their full commercialisation has been delayed due to the lack of an appropriate anode material. Hard carbons (HCs) arise as one of the most promising materials and are already used in the first generation of commercial NIBs. Although promising, HCs exhibit lower performance compared to commercial graphite used as an anode in LIBs in terms of reversible specific capacity, operating voltage, initial coulombic efficiency and cycling stability. Nevertheless, these properties vary greatly depending on the HC in question, for example surface area, porosity, degree of graphitisation and defect amount, which in turn are dependent on the synthesis method and precursor used. Optimisation of these properties will bring forward the widespread commercialisation of NIBs at a competitive level with current LIBs. This review aims to provide a brief overview of the current understanding of the underlying reaction mechanisms occurring in the state-of-the-art HC anode material as well as their structure-property interdependence. We expect to bring new insights into the engineering of HC materials to achieve optimal, or at least, comparable electrochemical performance to that of graphite in LIBs.
The Hydrogen South Africa (HySA) programme is based upon the beneficiation of South Africa's large platinum group metal (pgm) resources. The present article summarises some of the progress by HySA Systems, one of the three Competence Centres under the HySA Programme, since 2008. Work has been carried out on membrane electrode assembly and stack development for high-temperature proton exchange membrane fuel cells (HT-PEMFCs) for use in combined heat and power (CHP) supplied by natural gas and hydrogen fuelled vehicle (HFV) applications. The emphasis is on improved carbon monoxide tolerance and simplified heat and humidity management, allowing simpler fuel cell systems to be designed. Metal hydrides modified with palladium are being explored as poisoning-tolerant hydrogen storage materials for stationary and special mobile applications, and metal organic frameworks (MOFs) modified with platinum as light-weight hydrogen storage with a high hydrogen storage capacity. Lastly research into hydrogen purification using Pd membrane reactors is focused on membrane support synthesis, hollow fibre seeding and development of the plating procedure.
Recently lithium-ion batteries have started to be used in a number of automotive passenger car applications. This paper will review these applications and compare the requirements of the applications with the capabilities of the lithium-ion chemistries that are actually being used. The gaps between these requirements and capabilities will be highlighted and future developments that may be able to fill these gaps will be discussed. It is concluded that while improvements to the lithium-ion cell chemistry will help reduce the weight of battery packs for electric vehicle applications the largest weight gains will come from the pack design.
The Ulm Electrochemical Talks are held annually in Ulm, Germany. The 14th meeting, held from 23rd–26th June, 2014, focused on the topic of “Next Generation Electrochemical Energy Technologies”. Fuel cells and batteries are described as the dominant technologies to deliver the e-mobility vision within the next few decades. This selective review will focus on battery technologies and supercapacitors; although there was also plenty of material on the equally important topic of fuel cells which is not covered here.
Introduction “Electrochemistry: Volume 14” is a collated book of five papers edited by Craig Banks (Manchester Metropolitan University, UK) and Steven McIntosh (Lehigh University, Bethlehem PA, USA), both of whom are well established in the field with research interests covering the topics in the book. The book is one of a series which aims to collate and summarise the key topics receiving...
Historically, Johnson Matthey has had a long association with electrochemistry, and perhaps this was inevitable because of the importance of the platinum group metals (pgm) to Johnson Matthey’s early development. Platinum, in particular, has been incredibly useful in the field, because of its exceptional electrocatalytic activity and impressive inertness in most environments. Famously,...
Rechargeable metal-oxygen cells could exceed the stored energy of today’s most advanced lithium-ion cells. However challenges exist that must be overcome to bring this technology into practical application. These challenges include, among others, the recharge and cyclability efficiency, materials development and improvements in fundamental understanding of the electrochemistry and chemistry inside the cell. The common challenges for the anode, including corrosion, passivation and dendrite formation and those for the air cathode and the electrolyte are summarised in this review for cells based on magnesium, calcium, aluminium, silicon, zinc and iron.
Chemically regenerative redox cathode (CRRC) polymer electrolyte fuel cells (PEFCs) are attracting more interest as a platinum-free PEFC technology. These fuel cells utilise a liquid catalyst or catholyte, to perform the indirect reduction of oxygen, eliminating the major degradation mechanisms that plague PEFC durability. A key component of a CRRC PEFC system is the catholyte. This article reports a thorough study of the effect of catholyte concentration and temperature on CRRC PEFC system performance for H7PV4Mo8O40 and Na4H3PV4Mo8O40, two promising polyoxometalate (POM)-based catholytes. The results suggest 80°C and a catholyte concentration of 0.3 M provide the optimum performance for both H7PV4Mo8O40 and Na4H3PV4Mo8O40 (for ambient pressure operation).
Introduction The third UK Energy Storage Conference (UKES2016) was held at the Edgbaston campus of the University of Birmingham, UK, from midday on Wednesday 30th November to midday on Friday 2nd December 2016. The aim of the conference, organised by the Energy Storage Research Network on behalf of the UK Research Council funded Energy SuperStore Hub and chaired by Professor Nigel Brandon...
Introduction The Royal Society of Chemistry Faraday Discussions are a series of meetings focusing on rapidly developing areas of physical chemistry. Contrary to typical conferences, Faraday Discussions rely on the active participation of speakers and audience alike. Topics for each session are based on new research papers submitted specifically for the meeting. Audience participation is...
Bismuth vanadate (BiVO4) is proven to be a promising photocatalyst for water splitting. However, the effect of materials syntheses, electrode preparation and size of photoelectrode on the photocurrent output of BiVO4 photoanodes needs further investigations. In this study, three different BiVO4 nanoparticle synthesis were employed, namely hydrothermal (HT), HT in the presence of ethylene glycol (EG) and HT with the addition of hydrazine hydrate (HH). In addition, two molecular inks (Triton-X and ethyl‐methyl‐imidazole, EMI), were compared for the preparation of BiVO4 photoanodes using a simple doctor-blade technique followed by calcination at 450°C. The photoanodes (9 cm2 active surface) were then compared for their photocurrent density at AM1.5G illumination and 1.2 V (vs . standard hydrogen electrode (SHE)) bias in a specifically designed, three-dimensional (3D)-printed electrochemical cell. The highest photocurrent 0.13 ± 0.1 mA cm–2 was obtained with the EMI ink, whereas tenfold lower photocurrent was obtained with Triton-X due to the higher charge transfer resistance, measured by electric impedance spectroscopy (EIS). The photoresponse was reproducible and relatively stable, with only 8% decrease in five consecutive illumination periods of 1 min.
We review recent research into oxides of platinum group metals (pgms), in particular those of ruthenium and iridium, for use as electrocatalysts for the oxygen evolution reaction (OER). These are used in membrane electrode assemblies (MEAs) in devices such as electrolysers, for water splitting to generate hydrogen as fuel, and in fuel cells where they provide a buffer against carbon corrosion. In these situations, proton exchange membrane (PEM) layers are used, and highly acid-resilient electrocatalyst materials are required. The range of structure types investigated includes perovskites, pyrochlores and hexagonal perovskite-like phases, where the pgm is partnered by base metals in complex chemical compositions. The role of chemical synthesis in the discovery of new oxide compositions is emphasised, particularly to yield powders for processing into MEAs. Part I introduces the electrocatalytic splitting of water to oxygen and hydrogen and provides a survey of ruthenium and iridium oxide structures for oxygen evolution reaction catalysis.
It is imperative to develop novel processes that rely on cheap, sustainable and abundant resources whilst providing carbon circularity. Microbial electrochemical technologies (MET) offer unique opportunities to facilitate the conversion of chemicals to electrical energy or vice versa by harnessing the metabolic processes of bacteria to valorise a range of waste products including greenhouse gases (GHGs). Part I (1) introduced the EET pathways, their limitations and applications. Here in Part II, we outline the strategies researchers have used to modulate microbial electron transfer, through synthetic biology and biohybrid approaches and present the conclusions and future directions.
This is a focused review of recent highlights in the literature in cathode development for low temperature electrochemical carbon dioxide and carbon monoxide reduction to multi-carbon (C2+) products. The major goals for the field are to increase Faradaic efficiency (FE) for specific C2+ products, lower cell voltage for industrially relevant current densities and increase cell lifetime. A key to achieving these goals is the rational design of cathodes through increased understanding of structure-selectivity and structure-activity relationships for catalysts and the influence of catalyst binders and gas diffusion layers (GDLs) on the catalyst microenvironment and subsequent performance.
We continue our review of recent research into oxides of platinum group metals (pgms), in particular those of ruthenium and iridium, for use as electrocatalysts for the oxygen evolution reaction (OER). In Part I (1), the electrocatalytic splitting of water to oxygen and hydrogen was introduced as a key process in developing future devices for various energy-related applications. A survey of ruthenium and iridium oxide structures for oxygen evolution reaction catalysis was presented. Part II discusses mechanistic details and acid stability of pgm oxides and presents the conclusions and outlook. We highlight emerging work that shows how leaching of the base metals from the multinary compositions occurs during operation to yield active pgm-oxide phases, and how attempts to correlate stability with crystal structure have been made. Implications of these discoveries for the balance of activity and stability needed for effective electrocatalysis in real devices are discussed.
Traditional microbial synthesis of chemicals and fuels often rely on energy-rich feedstocks such as glucose, raising ethical concerns as they are directly competing with the food supply. Therefore, it is imperative to develop novel processes that rely on cheap, sustainable and abundant resources whilst providing carbon circularity. Microbial electrochemical technologies (MET) offer unique opportunities to facilitate the conversion of chemicals to electrical energy or vice versa, by harnessing the metabolic processes of bacteria to valorise a range of waste products, including greenhouse gases (GHGs). However, the strict growth and nutrient requirements of industrially relevant bacteria, combined with low efficiencies of native extracellular electron transfer (EET) mechanisms, reduce the potential for industrial scalability. In this two-part work, we review the most significant advancements in techniques aimed at improving and modulating the efficiency of microbial EET, giving an objective and balanced view of current controversies surrounding the physiology of microbial electron transfer, alongside the methods used to wire microbial redox centres with the electrodes of bioelectrochemical systems via conductive nanomaterials.
“Electrolytes for Lithium and Lithium-Ion Batteries”, published in 2014 by Springer, is Volume 58 in the Modern Aspects of Electrochemistry series. The volume is edited by T. Richard Jow, Kang Xu, Oleg Borodin and Makoto Ue. In the preface the Editors set out their purpose in compiling this volume, which was to provide a comprehensive overview of electrolytes for lithium-ion batteries. It covers electrolyte research and development in the last ten years and may be used as a foundation for future work and directions. The volume succeeds in covering the multifaceted area of electrolytes in a logical and highly comprehensive manner.
Chapter topics include lithium salts, advances in solvents, additives and ionic liquids, then progressing to understanding of the cathode and anode interphases, reviewing various characterisation approaches, a discussion of modelling approaches and finally future technologies such as lithium air batteries.