Low Cost High Performance Novel Catalysts for Direct Alcohol Alkaline Fuel Cells using anion exchange membrane and bio-fuels

Lead Research Organisation: Queen's University Belfast
Department Name: Sch of Chemistry and Chemical Eng

Abstract

This UK-China (QUB-DICP) joint project will aim to provide low cost high performance Portable Power Fuel Cell technology capable of operating on alcohol containing fuels with an emphasis on use of biofuels such as bio-ethanol and glycerol, from bio-feedstocks. The collaborative research seeks to seize the initiative in low temperature fuel cell research and development by capitalising upon extremely promising results on Direct Alcohol Alkaline Anion Exchange Membrane Fuel Cell (DA-AAEM-FC) development by both China and UK teams, and exciting data in the literature on anode and cathode catalysts for alcohol-fuelled alkaline fuel cells. The electro-catalytic oxidation of alcohols under alkaline conditions is relatively unexplored, but with some extremely promising reports in the literature on low cost but highly active and selective non-Pt catalysts. Our main strategy is to extend the range of potential fuels, ultimately to side products, waste and (cheap) products from sustainable bio-refining. The broadening of fuel cell fuels from hydrogen and methanol, fuels generally produced from fossil fuels, to bio-feedstocks, e.g. bioethanol, will greatly decrease reliance on fossil fuels for portable power generation. In addition, the use of direct biofeedstock fuel cells as power sources for portable devices as compared to Li-ion rechargeable, will reduced reliance of fossil fuels on electricity generation. In addition, the diversification of feedstock will allow higher energy density fuels to be employed, for example ethanol provides 24 MJ l-1 compared with methanol at 16 MJ l-1. In addition, the safety aspects can be tailored for the application, for example methanol is toxic and this prevents wider deployment of portable fuel cell systems into areas and environments where this is a concern, e.g. in aircraft cabins. The time scale of benefit will be dependent on the continuing introduction of portable power devices based on fuel cells. Flexibility in the form of the fuel used and its purity without having a detrimental effect on the fuel cell lifetime will provide a significant opportunity and impact in future years. The development of an efficient, durable alkaline fuel cell, utilising cheaper catalysts and accessing a wider range of fuels will have a major impact on a number of aspects of power/energy technology. The UK and China teams have strong and complementary skills relevant to the proposed work. Both teams have demonstrated individual achievements and are trying to develop the strength-plus-strength cooperation on electro-catalysis and fuel cell R&D, through this novel and challenging joint project, with a continue two-way transfer of knowledge throughout the project. The joint project will timely provide an excellent platform for the UK and China teams to establish a long-term win-win partnership for working together on the clean sustainable energy technology which will bring great benefits to both countries.

Planned Impact

This UK-China (QUB-DICP) joint project aims to provide low cost high performance Portable Power Fuel Cell technology capable of operating on alcohol containing fuels with an emphasis on use of biofuels such as bio-ethanol and glycerol, from bio-feedstocks. The collaborative research seeks to seize the initiative in low temperature fuel cell research and development by capitalising upon extremely promising results on Direct Alcohol Alkaline Anion Exchange Membrane Fuel Cell (DA-AAEM-FC) development by both China and UK teams, and exciting data in the literature on anode and cathode catalysts for alcohol-fuelled alkaline fuel cells. The electro-catalytic oxidation of alcohols under alkaline conditions is relatively unexplored, but with some extremely promising reports in the literature on low cost but highly active and selective non-Pt catalysts. Our main strategy is to extend the range of potential fuels, ultimately to side products, waste and (cheap) products from sustainable bio-refining. The broadening of fuel cell fuels from hydrogen and methanol, fuels generally produced from fossil fuels, to bio-feedstocks, e.g. bioethanol, will greatly decrease reliance on fossil fuels for portable power generation. In addition, the use of direct biofeedstock fuel cells as power sources for portable devices as compared to Li-ion rechargeable, will reduced reliance of fossil fuels on electricity generation. In addition, the diversification of feedstock will allow higher energy density fuels to be employed, for example ethanol provides 24 MJ l-1 compared with methanol at 16 MJ l-1. In addition, the safety aspects can be tailored for the application, for example methanol is toxic and this prevents wider deployment of portable fuel cell systems into areas and environments where this is a concern, e.g. in aircraft cabins. The timescale of benefit will be dependent on the continuing introduction of portable power devices based on fuel cells. Flexibility in the form of the fuel used and its purity without having a detrimental effect on the fuel cell lifetime will provide a significant oppurtunity and impact in future years. The development of an efficient, durable alkaline fuel cell, utilising cheaper catalysts and accessing a wider range of fuels will have a major impact on a number of aspects of power/energy technology.

Publications

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Chen ZY (2013) WC@meso-Pt core-shell nanostructures for fuel cells. in Chemical communications (Cambridge, England)

 
Description We have discovered a high performance low cost nanocatalyst based on platinum (Pt) shell@tungsten carbide (WC) core for methanol fuel cell applications. We have discovered a new class of high performance low cost palladium (Pd) based nanocatalysts for ethanol, ethylene glycol and other high alcohols electrooxidation for direct alcohol fuel cells applications. The electrocatalysis of the Pd based catalysts towards various fuel oxidation in alkaline media has been revealed at the atomic and molecular levels by combined studies of electrochemical in-situ spectroscopy and density functional theory calculations.

We have developed an effective model catalyst through the nano-engineering of the well-defined facets of nanocrystals with continuously tunable surface structure. This strategy is in significant contrast to the conventional wisdom of using well-defined bulk single-crystal planes as model catalysts, as our studies on ethanol oxidation exemplified the effectiveness of the nanocrystals but not the bulk single-crystals. Only the nanocrystals can reveal the key roles conferred by the edge sites of real/practical catalysts, enabling us to study the structure-reactivity effectively at atomic and molecular lever and to realize the rational design of improved catalysts, this study will have a far-reaching impact on both catalysis and surface sciences communities.

Inspired by the neural-network structure of the brain, we constructed a bionic catalytic network for the oxygen reduction reaction (ORR), via setting up Pt-organic ligands-Co2+-organic ligands-Pt connections and then thermally transforming them into a metal-organic-framework (MOF)-like matrix in which hollow PtCo alloy nanoparticles (NPs) with an average particle size of 4.4 nm are bridged together by carbon nanotubes (PtCo@CNTs-MOF). The bionic catalytic network provides highly e?cient linkages of various species-transport channels to active sites; as a result, an order of magnitude improvement is achieved in mass transfer e?ciency as compared to the traditional Pt/C catalytic layer. Besides, the hollow PtCo alloy derived from Pt NPs shows a high initial mass activity of 852 mA mgPt-1 @ 0.90 V and an undetectable decay in an accelerated aging test. Accordingly, a remarkable Pt utilization e?ciency of 58 mgPt kW-1 in the fuel cell cathode and 98 mgPt kW-1 in both the anode and cathode was eventually achieved, respectively. The latter is almost 3 times higher than that of the traditional catalytic layer. Moreover, no decay was detected during continuous operation for 130 hours from the bionic catalytic network-based fuel cell. This strategy o?ers a new concept for designing an ultra-low Pt loading yet highly active and durable catalytic layer for fuel cell applications and even wider catalytic reactions for energy and environmental engineering.
Exploitation Route The high performance catalysts we have discovered can be scaled up for fit-for-purpose fuel cell systems for portable, automotive and stationary applications. The new understanding of the fuel cell catalysis would be useful for further catalyst innovation.

Catalysts and catalysis processes play an extremely important role in enhancing the quality of our modern life, including clean energy production such as fuel cells, environmental protection such as catalytic converters fit in the modern cars, and modern industry including highly efficient production of commodities for every-day life. As much as 90% of chemicals and materials manufactured throughout the world depends on catalysis. In order to rationally design high-performance catalysts, we need to understand the catalysis processes at atomic and molecular level, in other words, we need to probe the secrets of reactions occurring on metal catalysts, which is not straightforward. The real catalysts are far too complicated for fundamental studies. How to effectively study the catalysis processes at the most fundamental level is extremely challenging if not impossible. This grand challenge motivated us to develop an effective model catalyst through the nano-engineering of the well-defined facets of nanocrystals with continuously tunable surface structure. This strategy is in significant contrast to the conventional wisdom of using well-defined bulk single-crystal planes as model catalysts, as our studies on ethanol oxidation exemplified the effectiveness of the nanocrystals but not the bulk single-crystals. Only the nanocrystals can reveal the key roles conferred by the edge sites of real/practical catalysts, enabling us to study the structure-reactivity effectively at atomic and molecular lever and to realize the rational design of improved catalysts, this study will have a far-reaching impact on both catalysis and surface sciences communities.
Sectors Aerospace

Defence and Marine

Chemicals

Education

Electronics

Energy

Environment

Manufacturing

including Industrial Biotechology

Transport

 
Description A patent on the catalysts we developed for fuel cell applications has been granted in the USA: US patent: US-2015-0018199-A1, 2015. C. A. Ma, Z. Y. Chen, W. F. Lin, Y. Q. Chu. WC/CNT, WC/CNT/Pt Composite Material and Preparation Process Therefor and Use Thereof. China patent: CN103357408 A, 2013. International patent: PCT/CN2012/086627, 2013. US patent: US-2015-0018199-A1, 2015.
First Year Of Impact 2013
Sector Chemicals,Energy,Environment,Manufacturing, including Industrial Biotechology,Transport
Impact Types Economic

 
Title WC/CNT, WC/CNT/Pt Composite Material and Preparation Process Therefor and Use Thereof 
Description Disclosed are WC/CNT, WC/CNT/Pt composite material and preparation process therefor and use thereof. The WC/CNT/Pt composite material comprises mesoporous spherical tungsten carbide with diameter of 1-5 microns, carbon nanotubes and platinum nanoparticles, with the carbon nanotubes growing on the surface of the mesoporous spherical tungsten carbide and expanding outward, and the platinum nanoparticles growing on the surfaces of the mesoporous spherical tungsten carbide and carbon nanotubes. The WC/CNT composite material comprises mesoporous spherical tungsten carbide with diameter of 1-5 microns, and carbon nanotubes growing on the surface of the mesoporous spherical tungsten carbide and expanding outward. The WC/CNT/Pt composite material can be used as an electro-catalyst in a methanol flue battery, significantly improving the catalytic conversion rate and the service life of the catalyst. The WC/CNT composite material can be used as an electro-catalyst in the electro-reduction of a nitro aromatic compound, significantly improving the efficiency of organic electro-synthesis. 
IP Reference US2015018199 
Protection Patent granted
Year Protection Granted 2015
Licensed No
Impact Not yet.