Application form for Joint Research Project
INDIA -TAIWAN PROGRAMME OF COOPERATION IN SCIENCE & TECHNOLOGY
Part 1: General information
1 Basic data
I herby confirm that all the information given in this application and the attachments is correct to the best of my knowledge.
Certified that the infrastructural facilities related to the project activity is available in this Institution including equipment, manpower and other facilities and all necessary administrative support will be extended for the project
2 Personal data
2.1 Indian Project coordinator
(Please insert additional tables into the document to list additional co-investigators)
The main objective of the proposal is to generate new nano materials by various synthetic procedures (methods to be employed are detailed in the proposal) for generating electrodes for fuel cell applications especially for Direct Methanol Fuel Cells (DMFC) and also for water splitting reaction. The essential components of the work are given as
(iii) Electrochemical Properties Measurement on one dimensional Group III-Nitride Semiconductors as water splitting electrode.
The objectives are as follows:
It is hoped that some of the objectives will be achieved by both the teams jointly or otherwise.
Liquid-fed Direct Methanol Fuel Cells (DMFCs), which are a type of PEFC, are promising as an alternative power source for the next generation of mobile devices and small stationary power applications because of their high energy density, the ease of fuel storage and delivery, and the ability to operate at, or near, ambient temperatures. Although several electro-catalysts have been employed for the oxidation of methanol [1-3], Pt and Pt-based alloys are the preferred anode catalysts due to their high electro-catalytic activity. However, the high cost of the catalyst has restricted the commercialization of DMFCs. Therefore, several studies have been focused on lowering the platinum loading in the PEFC electrodes.
The underlying concept of many such studies was to enhance catalyst utilization in the electrode by extending the three-phase boundary, because only the catalyst particles that keep contact with both electrolyte and reactant substance are electrochemically active. Although several efforts have been made to optimize this three-phase boundary structure, and various methods for producing it have been widely reported [4 – 11], a substantial amount of platinum in the catalyst layer may still not be fully utilized. In the general process of catalyst fabrication, nanometer-sized platinum catalysts were dispersed on the surface of 30–40 nm-sized carbon substrates to increase the platinum catalyst surface area. However, these small carbon particles tend to agglomerate via intermolecular interaction between their surfaces, thus the platinum inside the agglomerated carbon structure cannot be utilized in electrochemical reactions. This is because the perfluorosulfonate ionomer, which is generally added to the catalyst layer as a proton conducting agent during the electrode fabrication process, cannot penetrate into the smaller pores of the agglomerated carbon structure, and results in non uniform distribution throughout the catalyst layer and the catalyst particles not in contact with the electrolyte groups cannot be utilized for the electrochemical reactions.
Therefore, alternate electrode fabrication methods to achieve an ideal structure of the reaction field in the catalyst layer have been proposed and also various reduction technologies have been adopted. Essentially all these methods are based on reducing the Pt particle size to 3-4 nm with and without the use of capping or stabilizing agents and also to stabilize them in this size and shape. [12-31].
1.Increase of the three phase boundary of the catalyst particles with the proton conducting ionomer and the reactant molecule, by the introduction of molecular level proton conducting groups onto the carbon support before the catalyst particles are loaded onto it.
2. The stabilizing effect of the citrate and acetate anions on the dispersion of the Pt and Pt-Ru nano particles on the carbon support.
Following photo-electrochemical splitting of water (H2O) on n-type TiO2 electrodes (32), a range of semiconductor electrodes (33-35) has been tried and evaluated for the purpose. For efficient photo-splitting of water the semiconductor electrodes has to have the following properties, i) stable under photo-electrochemical environment, ii) the band edges have to straddle both the hydrogen and oxygen evolution potentials, and iii) be able to absorb a significant part of the solar spectrum. Nitride and oxide based materials looks attractive because of their wide band gap and high stability. In fact n-GaN has been studied extensively for the purpose (36-38), despite that there are reports of GaN being etched in certain electrolytic solutions. The photo-splitting efficiency is also a function of the carrier concentration in the material as demonstrated in Fig. 1 (36).
We believe that InxGa1-xN (x being the atomic percentage in composition) nanowires are unique for the photo-electrochemical splitting of water due to their tunable bandgap as a function of ‘x’, the polar nature of the compound surface, and high carrier concentration in nanowires. The change in the nature of electronic transport in nanowires below a critical diameter opens up the possibility of a higher photoconversion efficiency. However, the issue of surface etching can be avoided by i) choosing a proper electrolyte, or ii) by changing the bias voltage to the electrode or iii) by a proper surface treatment of the electrode.
Preliminary Studies (if any)
Preliminarily testing by a comparative measurement on thin film GaN and NWs. demonstrates that four fold increase in the photoelectric current was measured in GaN NWs compared to that in thin films at an illumination of 150 W (fig.2). The enhancement can be attributed to the enhanced light absorption, larger surface area for electrochemistry, or better carrier transport.
The preliminary results obtained are already better than some of the published reports shown below (Fig.3a, b)
Fig. 3: Time dependence of (a) current density and (b) gas volume generated at the Pt counter electrode in three different electrolytes. The n-GaN working photoelectrode was under illumination and in aqueous 1 mol/L HCl, NaCl and KOH. The applied bias (VCE) was +1.0 V for HCl and KOH, and +1.4V for NaCl. [Ref.37]
The advantage of using GaN NWs as against conventionally grown (metalorganic vapour phase epitaxy) supported (on sapphire) GaN thin film is evident. Most of the current density for the nanowires is generated due to their high surface area. Even if this is not in the nanowire form but still the etched film may have improved current densities compared to the as-grown thin film. Although the current-voltage profile for both the samples look similar in the dark, but under illuminated conditions the etched sample shows its superiority.
The effect of the surface area or other specific effects, such as electrical conductivity, in enhancing the water splitting process in the nanowire geometry is the subject of research and will be studied extensively.
The bandgap and electrical transport of these materials can be controlled by its dimensions. In short the photoelectrochemical properties become tailorable not only by the choice of the material but also by its dimensions. It has already been demonstrated in our laboratory that a surface conduction mechanism dominates the carrier transport in group III-nitride nanowires when their diameters are below a certain critical value. We would like to put this idea to test the efficiency of photosplitting of water with nanowires of controlled dimensions. We propose to use low dimensional, specifically one dimensional, GaN and InxGa1-xN nanowires, of controlled diameters and carrier concentrations, as electrodes for photosplitting of water. For this purpose, GaN and InxGa1-xN nanowires of different diameters and carrier concentrations would be used to study the photo and dark current density as a function of applied potential. This study will translate into the photoconversion efficiency for the nanowire based semiconductor electrodes as a function of the applied voltage.
We hope to demonstrate superior photoconversion efficiency at a lower applied bias voltage for our one dimensional InxGa1-xN nanowire based electrodes.
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-To demonstrate superior photoconversion efficiency at a lower applied bias voltage for nanostructured electrodes (in general).
To demonstrate superior photoconversion efficiency at a lower applied bias voltage for one dimensional III-V (such as GaN, InxGa1-xN) nanowire based electrodes (in particular).
In this proposal the expertise in the catalysis field of the Indian side is going to complement the expertise in nano-synthesis and characterization of the Taiwanese side. Both aspects of this proposal are related to the global issue of energy shortage, the answer to which is the relevance of this proposal. Initial studies already underway in Academia Sinica, Taiwan, as described above clearly shows promise of this proposal. Use of nanostructured GaN has shown to enhance the photoelectrochemical conversion efficiency. Several high-impact publications (1-7) in the nano-synthesis field and several publications (8-10) in the fuel cell field of research support the claimed expertise of the Taiwanese side. Indian Institute of Technology, Chennai, and Academia Sinica, Taiwan, are major seats of research activities in the respective countries and are capable of delivering the objectives mentioned in this proposal. Evidently, most of the facilities required for this proposal are currently available with the partner institutions and support in the form of manpower exchange is sought.
The Indian Centre for Catalysis Research has built up all facilities and also have been working on various types of semiconductors including anionic substitution in TiO2. It is our hope that complimentary nature of the two teams will synergise the efforts and can bear fruit.
Methodology and Advantages
With the advent of nanomaterials, a whole new gamut of materials now becomes available which are suitable for the purpose.(11-15). The bandgap and electrical transport of these materials can be controlled by its dimensions. In short the photoelectrochemical properties become tailorable not only by the choice of the material but also by its dimensions. As in many applications, such as sensors, the low dimensional materials have proven to be better suited than the thin film or bulk counterparts, here should be no exception. It has already been demonstrated in our laboratory that a surface conduction mechanism dominates the carrier transport in group III-nitride nanowires when their diameters are below a certain critical value (1). We would like to put this idea to test the efficiency of photosplitting of water with nanowires of controlled dimensions. We propose to use low dimensional, specifically one dimensional, GaN and InxGa1-xN nanowires, of controlled diameters and carrier concentrations, as electrodes for photosplitting of water.
For this purpose, GaN and InxGa1-xN nanowires of different diameters and carrier concentrations (to be synthesized by Taiwan partner) would be used to study the photo and dark current density as a function of applied potential with and without illumination. The MOCVD and Thermal CVD processes to be used for the synthesis are available with the Taiwan partner. Metal catalysed conventional chemical vapour deposition routes will be taken for the nanowire fabrication (1-12). The current-voltage measurement facility is also available with the Taiwan partner (1). This study will translate into the photoconversion efficiency for the nanowire based semiconductor electrodes as a function of the applied voltage. We propose to carry out the electrical measurements in solutions using the electrochemical techniques (to be performed in Taiwan). That is, using an electrolyte as one of the contacts. A schematic of the proposed measurement cell is shown in Fig.2 where the working electrode will host the nitride or oxide nanomaterials. The electrochemical measurement set-up is currently existing and working with the Taiwan partner.
12) X. Sun et al., Appl. Catal. 327, 114 (2007).
13) K. Maeda et al., Bull. Chem. Soc. Jpn. 80, 1004 (2007).
14) K. Maeda et al., J. Catal. 243, 303 (2006).
15) K. Maeda et al., Nature 440, 295 (2006).
6. List of on-going and/or recent research projects between applicants: NIL
In addition, please provide for all applicants:
Part 3 - Requested funding
3.1 Indian side
4. Research requiring authorizations or notifications
Indicate whether the proposed research includes:
Please note that research on humans, human embryonic stem cells, vertebrates, decapods, cepaholpods, pathogens and genetically modified organisms needs authorization and/or notification.
2. Infrastructure available/required to implement the project:
3. Certified that the following Indian scientists SRF/JRF, Post-Docs are presently affiliated with the University/Institute and will be the official project participants for the entire duration of the project:
5. Please mention Name/Address/Contact details including email address/ area of specialisation of
3 possible peer-reviewers of the project proposal.
Signature of the Indian PI
(NOTE- This project summary should not exceed more then one page in any case)
1. Programme/Scheme applied for - Indo Taiwan Progamme of cooperation in S and T
2. Project Title - Design and studies on electrode materials for fuel cells and water splitting
3. Project Participants -
4. Broad objectives of the Project-
5. Methodology to be adopted-
6. Likely out-puts of the project-
7. Are any IPR/Security-sensitivity/GMO/ transfer of biological material aspects involved in the project proposal-?
8. Justification/ need for foreign collaboration-
9. Break-up of financial support asked for –
(Signature of the Indian PI)