- General Information
- Title of the Project and File No.
2. Principal Investigator and Co-principal Investigator
Principal Investigator:B.Viswanathan NCCR, IITM
Professor Rama Prabhu, Department of Physics IITM
Professor P Selvam, Department of Chemistry, IITM
Professor PrathapHaridass, Department of Materials and Metallurgical Engineering
DrK.S.Dhathatreyan, CFCT, ARCI, Chennai
Dr.Rajalakshmi, CFCT, ARCI, Chennai
DrPhani,
Co-Principal Investigator:
3. Implementing agency: IITMadras , Chennai, CFCT ARCI, NanoRam
4. Date of sanction of the project, duration and project completion date
(a)Date of sanction: 17.12.2009
(a)Duration: Five years
(c )Project completion date: 16.12.2014
(d) Total Budget 5.81 crores
1. Rs. 20000000 -17.12.2009 – 1stInstalment
2. Rs. 10856000 14/03/2012-II Instalment
3. Rs. 15000000 28/03/2013- III Instalment
(e) extensiongranted, if any: Nil
- Financial Information
5. Approved Objectives (as specified in the Sanction Order issued by the Ministry at the time of sanctioning of the project):
Broad Objectives: (i)Broad Objectives:
Research and development of hydrogen storage systems based on carbon based nanomaterials that will allow for storage capacity of about 4-5 wt%. In addition, technologies developed be coordinated with the hydrogen utilisation through fuel cell power packs.
(ii)Specific objectives:
The Specific Objective is to develop carbon based materials and evaluate them for the suitability to store hydrogen at ambient conditions. Carbon nano-materials can be prepared from a wide range of carbonaceous raw materials and high surface area can be obtained from controlled activation conditions like activation agent, activation temperature and heating ratio. The specific objectives during the course of the project could be to evaluate the following parameters:
(a)Synthesis of carbon nano-materials with various dopants fro molecular hydrogen absorption by multi layer sorption (if hydrogen absorbs on high surface area carbon as a single mono layer, the maximum storage is only 4.1 wt%. However, if multilayer adsorption is possible due to physisorption, then storage capacity can be increased.
(b)Develop materials for both physical and chemical adsorption on the surface at the same time. A layer of molecules may be physically adsorbed on top of an underline chemisorbed layer. The same surface can display physisorption at one temperature and chemisorption at a higher temperature, thereby increasing the storage capacity.
(c)Doping (Li, K, Ti and Ni) developed atom-scale metal centre interactions (not catalysis) to enhance hydrogen binding with carbon network, avoid forming nano clusters, blocking pores (for non dissociative adsorption, the increased hydrogen surface interactions will be developed by adding suitable dopants to facilitate storage at the target operational temperatures. The specific dopant is responsible for multi-layer adsorption.
(d)Target adsorbents need extremely high surface areas to approach the stated hydrogen storage target. Tailoring the target absorbents by increasing the specific surface area with small pore size (1 nm) and increased pore volume.
(e)Evolve strategies to mass production of the identified material. The evolved procedure should be adoptable by manufacturing agents.
(f)Examine methods for cost reduction for mass production of the identified storage material.
(g)Devise engineering components for suitable storage device that can be used in the applications like transport or stand alone power generation and other energy conversion devices.
(h)Development of novel carbon based nano-functional materials with hydrogen storage capacity of at least up to 4-5wt% hydrogen
(i) Development of graphene based systems and also heteroatom substituted systems for hydrogen storage applications
(j) Other new forms of carbon materials and storage capacity.
(k)Processing of carbon based nanostructured materials
(l) Dispersion of Pd metal nanoparticles on Boron/Nitrogen doped carbon based nanostructured materials
(m) Characterization of these materials by XRD, SEM, HRTEM, XPS
(n) Measurement of the hydrogen absorption/adsorption and kinetics of sorption using pressure reduction facility
(o) Development of novel low cost Carbon based materials with a hydrogen storage capacity of 4-5 wt% hydrogen at room temperature and moderate pressure
(i)Specific objectives
(ii)To achieve at least around 6 weight percent absorption of hydrogen in carbon materials and show its reproducibility.
(iii)To explore the possibility of generating this selected material in higher scale
(iv)To examine the commercialization possibilities of these materials and
(v)To establish the standards and other characteristics
6. Expected output of the project (as specified in the Sanction Order issued by the Ministry at the time of sanctioning of the project) :
To generate reproducible hydrogen storage capacity of around 6 weight percent in carbon materials.
a)Establishing re-producible hydrogen storage capacity at least to the tune of 5 wt% in carbon materials.
b)Durability of carbon materials – 1000 cycles
c)Ensuring the capacity to make these materials in sufficient quantities and exploring the viability for commercial production of these materials.
d)Demonstrating the use of these materials in viable devices including for transport applications and fuel cell packs
e)Patents
7. Project cost details (as provided in the Sanction Order) :
8.Revision in the project cost, if any NIL
9. Manpower sanctioned(as provided in the Sanction Order): at least 6 students for various investigators
10. Permanent equipment sanctioned (as per details given in Sanction Order) : High pressure absorption unit (Volumetric)
Thermogravimetricanalyzer
11. Project Cost Sharing: Internal and MNRE sanctions total fund to IIT M only
12. Funds released in the project so far (indicate for each financial year separately) :
1. Rs. 20000000 -17.12.2009 – 1stInstalment
2. Rs. 10856000 14/03/2012-2nd Instalment
3. Rs. 15000000 28/03/2013- 3rd Instalment
13. Amount utilized (indicate for each financial year separately based on Utilisation Certificates submitted to MNRE) :
All these documents are available with MNRE we shall attach a hard copy of the latest UC and financial statement as annexure to this document. This is being done and sent separately as soon as possible.
- Project and progress related information
14. Background information about the project (in about 500 words indicating the project aims and methodology to be adopted).
Hydrogen absorption in carbon materials has been pursued ever since in 1999 67 weight percent storage was reported in USA. Since then various groups all over the world have attempted to reproduce this result and also formulate material which will have desirable capacity of storage. In these 15 years the storage capacity has been only decreasing and a typical set of data collected from literature is shown in Fig.1.
It has been shown in the literature that carbon materials suitably modified and also dimensionally regulated (like graphene) can be good candidates for hydrogen storage applications. Taking this clue from literature, in this study it has been attempted to examine the storage capacity of carbon materials in various configurations and exotic architectures have been examined from the point of view of hydrogen storage capacity. The available literature in this area are effectively summarised in the Fig.1 above.
The methodology adopted is to device methods for architecting carbon materials and decorating them with additives like noble metals (example Pd) and evaluate hydrogen sorption capacity near ambient conditions. Various attempts and permutations and combinations have been examined and the results show the breadth to which these studies have been carried out.
15.Status of submission of Progress Report for the Project as on 31.12.2013
The reports have been already submitted to MNRE at various stages of the project
16. Present Status of the project (in about 1000 words from inception of the project till 31st December, 2013)
The present status of the project is still at the development stage but promising materials have been identified and various modifications of these carbon materials have been synthesized and their storage capacity has been evaluated.
Reproducibility of the hydrogen sorption which is one of the important lacuna in the reported literature has been given due attention and reproducibility has been established in the materials that have been proposed and attempted in this project.
It is still needed to push the storage capacity to 5-6 weight percent in which direction the research efforts are being focussed.
Detailed report given in various other columns will testify these statements
17. Achievements of the project vis-à-vis its objectives and deliverables/outputs
Hydrogen Adsorption study on carbon nanohorns synthesized using arc discharge technique
Figure: H2 adsorption isotherms at 25oC, 50oC and 100oC
Hydrogen adsorption experiments were carried out on carbon nanohorns produced at 10 rpm cathode wheel speed using arc discharge technique. The adsorption was carried out using a high pressure Sievert’s Apparatus operating between 1-4 MPa. The H2 adsorption increased as the pressure increased for all temperatures. The CNHs adsorbed a maximum of 2.3 % (wt. %) of H2 at room temperature. While keeping in mind the fact that the CNHs were synthesized in open atmosphere, this is the highest that has been observed at room temperature adsorption experiments. The H2 weight % adsorbed shows an increasing trend as the temperature of adsorption decreases at all pressures. The isotherms at all the three temperatures show Langmuir type behavior. The isotherm at 25oC levels off at around 2 MPa thus exhibiting the formation of a monolayer of H2 at low pressures. The exponential rise in adsorption at high pressures results out of multiple layers of H2 being physisorped onto the carbon nanohorns. The H2isotherms at 50oC and 100oC do not form the small bump at low pressures and hence show a direct formation of multiple layers of H2 without a monolayer formation. This can be attributed to the fact that the thermal vibrations in the CNHs at higher temperatures are enough to overcome the Ea for a monolayer formation.
Many activated carbon materials from various precursors viz., corn cobs, coffee beans, lemon wastes, tamarind seeds, cotton, jute, papaya seeds, Date seeds have been prepared and activated using KOH with different concentration and temperature to increase the surface area and microporous volume. The samples were characterized for their morphology, pore structure, surface area etc.,
It has been observed that the tamarind seeds and corn cobs showed a high surface area of 1700 m2/g and a micropore volume of 0.9c m3/g. The hydrogen storage capacity for all these samples were measured and are tabulated in the following table.
Sample / SA (m2/g) / MPV (cm3/g) / H capacity wt %TSC-1 / 353 / 0.14 / 0.27
TSC-2 / 672 / 0.27 / ~
TSC-3 / 785 / 0.31 / ~
TSC-P / 775 / 0.08 / ~
2%Pd-TSC-1 / 280 / 0.1
PSC-1-600 / 672 / 0.28 / 1.47
PSC-3-600 / 1356 / 0.56 / 1.67
PSC-P / 750 / 0.04 / 1.43
MWTSC-50 / 0.67
MWTSC-75 / 1.19
MWTSC-100 / 1.36
TSC-3-700 / 1770 / 0.59 / 4.12
Jute-700-1hr / 382 / 0.16 / 0.53
Jute-700-1hr(1:1) / 894 / 0.35 / 0.82
Jute-700-1hr(1:3) / 1224 / 0.43 / 1.2
Jute-700-1hr (1:5) / 1141 / 0.42 / 0.97
Cotton-600-2hr / 444 / 0.19 / 1.2
Cotton-700-2hr / 526 / 0.21 / 1.5
Cotton-800-2hr / 1279 / 0.46 / 4.2
Activated carbons from Tamarind seeds and cotton show promising hydrogen storage capacity of about 4.2 weight % at RT and 4 MPa., which is about 80% 0f the USDOE target. Tamarind seed samples were prepared batch-wise and show repeatability and cyclic stability was also found to be promising. Cotton samples will also be prepared batchwise and will be tested.
Main results
Graphene and GNP were chemically modified by acid functionalization and nitrogen doping for the dispersion of 3d transition metal nanoparticles.
Nitrogen doping provides high dispersion, small particle size and strengthened interaction of catalyst metal nanoparticles over the support.
Pd nanoparticles decorated Boron doped graphene gives an hydrogen storage capacity of 5.0 weight % at room temperature and 3.2 MPa pressure.
Enhancement in hydrogen storage capacity of Pd-Graphene nano-composite is due to heteroatom doping and spillover mechanism
a)Achievements vis-à-vis objectives
S.No. / Approved objectives of the project / Achievements of the project so far1
2.
3.
4. / Development of various carbon forms
Hydrogen storage capacity of new materials have to be evaluated.
Bulk material preparation and testing in field trials
Commercial possibility / Hetero atom substituted carbons and noble metal decorated graphene architectures have been successfully developed
Measurements have been made on various carbon materials and the measurements are going on.
Yet to be done
To be explored
b)Achievements vis-à-vis deliverables/outputs
S.No. / Approved deliverables/outputs of the project / Achievements of the project so far1. / Carbon material with storage capacity of at least 6 weight percent / Not yet but the results are tending towards this figure
18.Whether the approved objectives and deliverables can be achieved within the approved duration of the project? If not, what are the constraints and extension required, if any.
It is envisaged that the approved objectives and deliverables may require one more extension with additional fellowship grant. In addition, some validation experiments have to be carried out for global acceptance and MNRE must establish two independent centres for this purpose. IITM will be willing in coordinating this endeavour on behalf of MNRE.
19.Year wise (a) publications in international journals, and (b) patent applications filed
Publications/ Paper
1. Activated carbons derived from Tamarind seeds- T.Rameshkumar, N.Rajalakshmi and K.S.Dhathathreyan, Communicated (2013)
2. Pt loaded on carbon derived from corn cobs for hydrogen storage - R.Karthikeyan, N.Rajalakshmi and K.S.Dhathathreyan Communicated (2013)
3. Jute fibres based activated carbons for Hydrogen storage , M. Vivekanandan, T.Rameshkumar, N.Rajalakshmi and K.S.Dhathathreyan - Communicated (2013)
4. Carbon from Cotton as hydrogen storage medium– T.Rameshkumar, N.Rajalakshmi and K.S.Dhathathreyan, In preparation (2014)
5. Hydrogen storage from composites based on Mg and activated carbon derived from tamarind seeds, ( in preparation 2014).
6. Hetero Atom Substituted Carbon—PotentialHydrogen Storage Materials, BalasubramanianViswanathan, SankaranMurugesan, ArjunanAriharan, and Kripal Singh Lakhi, Advanced Porous Materials, 1.122-128 (2013)
7.Vinayan B P., Rupali Nagar, K. Sethupathi and S. Ramaprabhu, The Journal of Physical Chemistry C, 115, 15679, (2011).
8. Vinayan B P, K. Sethupathi and S. Ramaprabhu, Transactions of the Indian Institute of Metals, 64, 169, (2011).
9.Vinayan B P, K.Sethupathi and S.Ramaprabhu, Journal of Nanoscience and Nanotechnology, 12, 1, (2012)
10.Vinayan B P, Rupali Nagar, and S. Ramaprabhu, Langmuir,28,7826, (2012).
11.Transition metal - graphene based hydrogen storage nanomaterial (Indian patent) filed (2012).
12.Chemically modified- carbon based hydrogen storage material (patent) to be filed (2014).
13. B.Viswanathan, Hydrogen storage in carbon materials An Appraisal, Bulletin of the Catalysis Society of India, 12, 84-86 (2013).
14. B.Viswanathan, Hydrogen storage in carbon materials An Appraisal, Part 11, Bulletin of the Catalysis Society of India, (in press)
Conferences:
1. T. Ramesh, G.Subashini, N.Rajalakshmi and K .S.Dhathathreyan , Activated Carbon from Tamarind Seeds- Promising Hydrogen storage material , Paper presented at the National conference on Advanced materials , NCAMA-2013 at NIT, Trichy during 4th and 5th April 2013
20.Requirement of funds during 2014-15
Balance of the grant may kindly be released. In addition we may require some contingency grant and also for one year extension we need the fellowship grant.
21.Any other issue from the project implementing institution/organisation
Nothing specifically