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    Production of Clean Hydrogen by Electrochemical Reforming of Oxygenated Organic Compounds
    Production of Clean Hydrogen by Electrochemical Reforming of Oxygenated Organic Compounds
    Production of Clean Hydrogen by Electrochemical Reforming of Oxygenated Organic Compounds
    Ebook229 pages1 hour

    Production of Clean Hydrogen by Electrochemical Reforming of Oxygenated Organic Compounds

    By Claude Lamy, Christophe Coutanceau and Steve Baranton

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    About this ebook

    Production of Clean Hydrogen by Electrochemical Reforming of Oxygenated Organic Compounds provides a comprehensive overview of the thermodynamics and experimental results that allow the decomposition process of organic compounds leading to hydrogen to be carried out at working cell voltages much lower than those encountered in water electrolysis. The authors review different methods of synthesis and characterization of the catalysts needed to activate the electro-oxidation reaction and describe different electrolysis experiments that produce hydrogen in a Proton Exchange Membrane Electrolysis Cell (PEMEC). Other sections investigate the effect of the nature of the reactive molecules, the nature and structure of the catalysts, and more.

    By exploring the link between organic oxidation/conversion to hydrogen production, this book fills a gap in the existing literature and provides researchers in the field with an authoritative and comprehensive reference they can use when developing new sustainable processes and systems for hydrogen production.

    • Explores, in detail, the decomposition process of organic compounds leading to hydrogen
    • Presents foundational information, practical insights and pathways for future work in the development of proton exchange membrane electrolysis cell systems
    • Includes results, experimental data and interpretations using different organic compounds, such as methanol, formic acid, ethanol, glycerol and biomass
    LanguageEnglish
    PublisherAcademic Press
    Release dateNov 27, 2019
    ISBN9780128215012
    Production of Clean Hydrogen by Electrochemical Reforming of Oxygenated Organic Compounds
    Author

    Claude Lamy

    Claude Lamy is a Professor at the European Institute of Membranes of Montepellier University. Before taking on his current position, Professor Lamy was a research scientist in CNRS (Laboratoire d'Electrochimie Interfaciale) and full Professor at the University of Poitiers. His main research interests include interfacial electrochemistry, mechanisms of reactions, electrocatalysis, electro-synthesis in aqueous media from biomass compounds and hydrogen production by electrochemical reforming of alcohols. His research activity has led to more than 250 published original papers (among them about 220 in International Journals with Referee), 65 papers in proceedings, 18 chapters in scientific books, 80 invited lectures and more than 300 oral presentations. He has also received the Christian Schönbein Prize at the European Fuel Cell Forum, Lucerne (Switzerland) and is a Fellow of the International Society of Electrochemistry.

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      Production of Clean Hydrogen by Electrochemical Reforming of Oxygenated Organic Compounds - Claude Lamy

      diffraction

      Chapter one

      Introduction

      Abstract

      The introduction section explains first the important role of hydrogen as energy vector for fuel cells and as reactant for chemical industries. It points out that more than 95 % of hydrogen used worldwide is currently produced from fossil resources, mainly by methane and hydrocarbon steam reforming. Electrolysis is proposed as an alternative process for greener production of pure hydrogen, using either water splitting or electrochemical reforming of organic compounds, first formic acid as a proof of concept, then methanol (being the simplest alcohol) and ethanol, and at last bio-sourced polyols and sugars.

      Keywords

      Hydrogen; steam methane reforming; energy production; electrolysis; PEMFC

      Contents

      Outline

      References 4

      In the near future, hydrogen is considered as a key compound for energy production and storage, besides its use in chemical industries. Its implication as an energy career is expected to deal with the environmental issues to respond to the growing energy demand and, at the same time, to allow economic expansion. Hydrogen is widely used for the production of fertilizers and chemicals; more recently, one of the main applications for hydrogen energy concerns feeding fuel cells [1]. These systems display very high energy efficiencies compared with internal combustion engines [2], and more and more car manufacturers are already proposing or will be proposing fuel-cell electric vehicles on the market in the next years. Therefore, the hydrogen demand will inevitably increase, and the development of methods for delivering hydrogen safely is becoming of paramount importance. Currently, 96% of the hydrogen is produced from fossil sources, mainly from natural gas by steam methane reforming. Indeed, the delivery of hydrogen mainly leans on processes such as reforming of natural gas (c.48%), oil (c.30%), and gasification or reforming of coal (c.18%) [3]. Such processes based on fossil resources obviously make hydrogen production not yet green or at least not yet sustainable.

      One alternative for producing pure hydrogen is the electrolysis of water. The splitting of the water molecule into low-temperature electrolysis cells (such as a proton exchange membrane electrolysis cell [PEMEC] or an alkaline electrolysis cell) leading to oxygen at the anode and hydrogen at the cathode is indeed currently extensively studied [4,5]. Historically alkaline technology was the most studied and developed process because the environment is less corrosive than an acidic one [6]. However, the development of highly active Ir- or Ru-based dimensionally stable anodes allowed the proton exchange membrane electrolysis technology reaching higher efficiency than the alkaline technology [4,7]. Furthermore, in this case, renewable intermittent primary energy sources, such as wind, solar, tidal, and so on, can be used to make this technology greener. However, one of the major problems of these technologies comes from the high electrical energy needed to dissociate the water molecule (ΔΗ⁰=285.8 kJ mol−1 and ΔG⁰=236.8 kJ mol−1), which leads to a very high standard cell voltage of 1.23 V. Moreover, the oxygen evolution reaction occurs with a very low kinetics, so that high overvoltages are necessary to reach acceptable current densities of at least 1 A cm−2 (i.e., to obtain a high hydrogen production rate at the cathode). Thus, cell voltages of 1.8–2.0 V are generally required for the significant hydrogen production. These overvoltages are responsible for the high cost of hydrogen production via the water electrolysis process, not only in terms of electrical energy required but also in terms of materials for the anode, for example, Ru- and Ir-based catalysts and corrosion-resistant support based on titanium.

      Liquid alcohols, polyols, and sugars from the biomass could serve as a bridge between hydrocarbon sources and gaseous H2. They own high energy densities and can be easily stored and distributed through the existing gasoline infrastructure. It has also been claimed that alcohols are the next liquid fuels to use after the depletion of petroleum resources [8]. Alcohols can be used to produce electricity in direct fuel cells or mechanical energy in internal combustion engines, such as in the ProAlcohol Plan developed in Brazil. However, the performances, between a few tens and a few hundreds of mW cm−2, of a direct alcohol fuel cell (DAFC) remain relatively low [9,10], compared with those obtained by a hydrogen proton exchange membrane fuel cell (PEMFC) reaching more than 1 W cm−2. The DAFC performances are low due to the low kinetics of the electrooxidation reaction of organic molecules and to the poisoning of the catalyst surface by adsorbed intermediate species at low potentials [11,12]. Moreover, the difficulty to activate alcohol oxidation at low temperatures, below 100°C, necessitates high loadings of catalysts, for example, several mg cm−2, at the anode of the fuel cell in order to achieve acceptable performances.

      Furthermore, very clean hydrogen is required to feed a PEMFC. Indeed, the platinum-based catalysts used at the anode of the fuel cell can be easily poisoned through the strong adsorption of poisons, such as CO, sulfur, and others, which leads to a rapid and drastic decrease in performances [13,14]. Clean H2 can be produced from alcohol by its oxidation in an electrochemical reformer or electrolyzer and can be used in different devices such as fuel cells, resulting in an improvement in the overall system performance. Electrochemical reforming or electrolysis is a process in which an organic compound such as alcohol is electro-oxidized to form H2. Electrical power is required to split the chemically bonded species. In a PEMEC, the electrochemical reformer consists of two electrodes separated by an ion-exchange membrane, which form the so-called membrane electrode assembly (MEA). The role of the membrane will be to ensure the ionic conductivity between both anodic and cathodic compartments and to separate the reaction products (H2 at the cathode and CO2 and organic oxidation products at the anode), leading to the production of clean hydrogen. According to thermodynamic data (see Section 2.1), the oxidation of many alcohols needs smaller electrical energy (ΔG+) than that of water splitting and leads to very low standard potentials, which is close to that of hydrogen. Their oxidation at the catalytic anode of an electrolysis cell is expected to occur at lower overvoltages, thus decreasing the working cell voltage, compared with that of a water electrolysis cell, and further to save energy for the production of clean

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