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DECORE Report Summary

Project ID: 309741
Funded under: FP7-NMP
Country: Italy

Periodic Report Summary 2 - DECORE (Direct ElectroChemical Oxidation Reaction of Ethanol: optimization of the catalyst/support assembly for high temperature operation (DECORE))

Project Context and Objectives:
Project Context
Bioethanol is an attractive alternative energy carrier, especially when it is not produced at the expense of food production, e.g. by fermentation of lignocellulose which uses crop or wood as precursors. The process furnishes an end product that is generally about 95% EOH and 5% water. Bioethanol is currently used as a valid alternative to standard gasoline (e.g. Brazil), even if the rough bioethanol cannot be directly used as a fuel for standard engines because of the water fraction, which has to be removed with the consequent costs. On the contrary, no water removal would be needed for the direct use of bioethanol as energy carrier for fuel cells.
Ethanol has a number of advantages over conventional fuels:
• it comes from a renewable and not from a finite resource, such as crops;
• the energy density (8 kW kg-1) is higher than that of hydrogen and comparable to gasoline;
• is a liquid at room temperature and relatively non-toxic, which allows for a simple storage and use.
The main general goal of DECORE is to achieve the fundamental knowledge needed for the development of a fuel cell (FC) electrode, which can operate efficiently (both in terms of activity and selectivity) as the anode of a direct ethanol fuel cell (DEFC) in the temperature range between 150-200 °C (intermediate-T) based on bioethanol. The intermediate-T is required for an efficient and selective total conversion of ethanol to CO2, so exploiting the maximum number of electrons in the DEFC. Such a technology is still lacking in the market.

Project Objectives
DECORE is exploring the use of fully innovative supports (based on titanium oxycarbide, TiOxCy) and nano-catalysts (based on group 6 metal carbides, MCx, M=Mo,W), which have never been tested in literature as components for DEFCs anodes. The new support is expected to be more durable than standard carbon supports at the targeted temperature. The innovative nano-catalysts are noble-metal free, so reducing Europe’s reliance on imported precious metals. To tailor the needed materials, both the support and nano-catalyst are studied by a physico-chemical approach aiming at understanding their structure/property relationships. Demonstrating an activity of such nano-catalyst/support assembly at intermediate-T would open a novel horizon where DEFCs with strongly reduced production costs would have an impact on a fast industrialisation. The power range for the envisioned application is of the order of hundreds of Watts, i.e. the so called distributed generation, having an impact for devices such as weather stations, medical devices, signal units, auxiliary power units, gas sensors and security cameras. By the end of the project, a bench-top single DEFC operating at intermediate-T will be built and tested.
DECORE duration is 48 months. Basically, the first two years have been devoted to develop the basic knowledge on the new materials (both the support and catalysts) and on developing the tools that are needed to accomplish the screening of the different MCx/TiOxCy assemblies. Starting from the third year the validation process has entered in the operative stage, which will eventually take to the best choice of the materials in terms of efficiency, selectivity and duration. The fourth year will be devoted to the development of the final anode to be implemented in a bench-top single DEFC operating at the target temperature.
The main original objectives of DECORE are :
• complete electro-oxidation of ethanol (EOR) to CO2 at intermediate-T (150-200 °C)
• development of innovative TiOxCy and MCx (M= Mo, W) supports specifically tailored to avoid degradation of the active catalyst and corrosion of the support at intermediate-T, and having sufficient electrical conductivity and porosity
• development of precious metal-free anode catalysts based on group 6 metal carbides (MCx, M=Mo,W)
• full characterization of the MCx/TiOxCy assembly
• development of tools for determining the electrochemical activity at intermediate-T in half-cells
• laboratory-scale validation of the nano-catalyst/support assembly compared to state-of-the-art benchmarks
• testing the nano-catalyst/support assembly using industrial standards in a existing test rigs of high-T FCs using hydrogen or synthethic reformate as energy carrier at the anode and air at the cathode
• development and tests of a bench-top single DEFC operating at intermediate-T
• develop a route for a fast industrialization of the results

Project Results:
At the end of the second Reporting Period (M36) the following main achievements were obtained:
• Thanks to the advancement of the work on model systems (WP2 and WP3), the intrinsic stability of TiOxCy and of MCx particles (M=Mo,W) toward oxidation has been derived in (a) UHV, (b) ambient conditions (i.e. in presence of oxygen) and (c) electrochemical conditions (i.e. in water solution).
• TiOxCy nanopowders were synthesized with a new procedure developed within the project (WP4). They are characterized by a nano crystalline morphology, have grain sizes of less than ~30 nm and surface areas of the order of hundreds of m2/g, and their electrochemical characterization at 25°C and 150°C in conc. H3PO4 has been carried out.
• Electrochemical half-cells for intermediate-T characterization were designed, built and distributed among the Consortium partners (WP6).
• A suitable atomic-scale methodology (IL-SEM) for mechanistic degradation studies at intermediate-T was developed (WP6).
• A standardized protocol for EC half-cell tests at intermediate-T was developed (WP6).
• It has been demonstrated that the TiOxCy powders have the needed properties to replace standard carbon supports at the intermediate-T regime. Its use also in HT-PEMFCs working with reformate fuel is now investigated and the data so far achieved are highly promising.
• Preparation of MCx (M=Mo,W) particles with sizes below 20 nm has been achieved following two different procedures (WP5).
• It has been demonstrated that the activity toward ethanol oxidation of the prepared MCx (M=Mo,W) particles is not enough to reach the targets of DECORE so that the incorporation of small amounts of precious metals as co-catalysts is now explored, as already considered by the contingency plans of DECORE.
• Several new M’/MCx/TiOxCy, M’/MCx and M’/TiOxCy (M’=alloyed Pt, Au, Sn; M=Mo,W) systems are now under test for their ethanol oxidation and reformate oxidation activities both at low T and at intermediate-T (WP4-6).
• A Technology Implementation Plan is under development to exploit both the TiOxCy support and the M’/MCx/TiOxCy , M’/MCx and M’/TiOxCy innovative catalysts.
• 14 papers with the DECORE acknowledgments have been published in relevant Journals of the field.
• At least 10 more papers are under development.

Potential Impact:
The results so far accumulated are strengthening the original ideas behind DECORE. After the experiments in the second Reporting Period, it seems that it is now demonstrated that switching from ambient to intermediate-T gives a very large boost to ethanol oxidation. The innovative support, TiOxCy, alternative to standard carbon-based ones, can withstand the required temperature of exercise and present interesting properties, also for reformate based HT-PEMFCs, an already existing market where the industrial partner ELCOR is active. This will allow a direct and quick exploitation of part of the results of DECORE. As to the nano-catalyst/support assemblies active with respect to ethanol oxidation, after a long testing we proved that for reaching a satisfactory activity, some small quantity of noble metals as co-catalysts must be added. Such a new redirection of DECORE is now under testing with a bench-top single DEFC operating at intermediate-T. If the test will fulfil the expectations, we will be in front of innovative Fuel Cells running on ethanol derived from a renewable source (i.e. bioethanol), which would result in a neutral carbon footprint, i.e. the carbon dioxide (CO2) emitted during its use is offset by the absorption from the atmosphere during the growth of the vegetal components to be used for the bioethanol production. So an important impact on the environmental issues is expected.

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Anna Modenato, (Administrative Officer)
Tel.: +39 049 8275115
Fax: +39 049 8275135
Record Number: 183796 / Last updated on: 2016-06-14
Information source: SESAM
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