Project:(File Number)NATIONAL CENTRE FOR CATALYSIS RESERACH-NCCR

Dr.Prof. P.SELVAM-Project In-chargeProf. B.VISWANATHAN-Co-Project In-Charge National Centre for Catalysis Research, Indian Institute of Technology, Madras, Chennai 600 036

Date of Start: (phase II)(29/07/2012)

Date of completion: (28/10/2016)Total cost of the project: Rs. (83,00,2965/-)

PROJECT OBJECTIVESTo establish a National Centre for Catalysis Research (NCCR) of international standing with the following objectives:(a) Generating man-power for Indian Industry and Academic Institutions(b) Collaborating with other academic and national laboratories and industrial

organizations to facilitate research, teaching and training in the area of Catalysis.

(c) Collaborate with industries (Indian and Global) to provide solutions to their problems and help in their search for new ventures and trouble shoots.

(d) Carrying out research work in frontier areas-Energy, New Materials, and Theoretical Studies in Catalysis, developing cutting edge technologies.

Figure1. Spheres of activities at NCCR

OVERALL PROJECT OUTCOMEEducation and Training A new PG Course, M.Tech-Chemical Engineering, with specialization in

Catalysis Technology, is being offered from 2009-10 onwards to specifically cater to the needs of academia and industry in the area of Catalysis. Six batches of students have so far completed the Course and are well-placed in the industry/academia

All these ten years NCCR has conducted the Orientation Course in Catalysis (OCC) for research scholars of this country and trained more than 400 research scholars. The feed-back on this Course (available with DST) has been consistently good and stresses the need for continuing such courses at national level.

Industry-Academia Collaboration

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NCCR

Basic

Researc

h

Applied Research

CSI activities

International cooperation

Education

1.Orientation programme

2.Capsule courses for industry, faculty and others

3.Regular course-post M.Sc.; M.Phil.; Ph.D.

4.Electives2.Trouble shooting1.Sponsored projects

3.Clearing house role4.Consultancy

3.Surface science2.Energy conversion process1.New materials

1.Research proposals

4.Societal roles3.Roadmap documents

2.Data base1.BCSI2.Exc

hange of students

3.Visiting positions

4.Joint workshops

4.Theoretical science

NCCR-Industry research collaboration has been another successful venture, with many national as well as international companies (Shell, P&G, GM, SABIC, Nissan, IOC, HPCL, CPCL, NFCL, Granules India), sponsoring projects (Total revenue Rs 469 lakhs). Novel catalysts and materials for specific processes/applications have been developed

NCCR has successfully completed six research projects sponsored by Government organizations like, DST, CSIR-NMITLI and MNRE. A project sponsored by DRDO on speciality grade fuel for strategic applications is in progress.

Established research collaborations with a number of national Universities/ Laboratories /Institutes. 8 Scholars from different Universities worked in NCCR and completed Ph.D Degree

Seven international collaborative research projects have been undertaken and completed successfully

Research Pursuing research work in the areas, like, energy conversion and renewable

energy, new materials and theoretical studies related to Catalysis. Salient features of research work are described below

SIGNIFICANT RESEARCH OUTCOME

A. Processes for Energy Conversion & Renewable energyFigure 2. Catalysts for trans-esterification of vegetable oils and deoxygenation of vegetable oils to diesel hydrocarbons A bench scale process for the trans-

esterification of vegetable oils withalcohols into bio-diesel

A process for catalytic conversion/deoxygenation of vegetable oils(including the non-edible jatropha oil into diesel hydrocarbons-(green diesel) using a novel zeolite based Ni-Mo-catalyst

Catalysts based on sulfided Ni-Mo containing micro and mesoporous materials for different diesel-hydrotreating reactions like desulfurization, denitogenation, demetallation and aromatic saturation.

A catalyst based on a modified high silica zeolite for reducing pour-point of diesel fuels and increase yield of diesel in refineries

Activated carbon prepared from natural sources for removing S to ultra-low levels (less than 10 ppm) from commercial diesel cuts.

A novel catalyst for light naphtha upgrading into high octane blend-stock for petrol

Catalyst and process for producing a high energy fuel (JP-10) for strategic applications is being developed in collaboration with CPCL and support from

GTRE/DRDO. Process to be scaled up to supply get 10 litres of the fuel to DRDO for engine testing in about a year.

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Figure 3. Photo catalysts for conversion of CO2 to solar fuels Modified Sodium tantalate (NaTaO3) and Strontium titanate (Sr3Ti2O7) based

catalysts (Fig.3) for reduction of CO2 under visible light to yield fuels and chemicals (Solar fuels) have been developed and national /international patents applied.

Electro catalytic and photo electro catalytic routes for sustainable production of solar fuels from CO2 using sun light are being explored

B. Novel materials / Catalysts

Ruthenium based multi-metallic catalysts for condensation of bio-ethanol with >80% selectivity towards butanol and higher alcohols have been developed.

Successful field trials conducted with Urea based multi-metallic micro-nutrients, synthesized and scaled up in the laboratory.

Synthesis, characterization (Fig.4) & application of shape and size controlled Pd and Ni based bi-metallic nano size catalysts for selective hydrogenation of alkynes and α-β unsaturated aldehydes have been developed

Morphology controlled ZSM-12 Zeolite composite catalysts for hydro-isomerization of long chain paraffins for fuel quality improvement

Developing preparation protocols for coating active phase as thin layer on metallic grids with good adherence, for application in high throughput catalyst evaluation

Synthesis, characterization and application of novel ordered meso porous carbon for fuel cell electrode, hydrogen storage and meso porous alumina for alkylation of phenol (Figs. 5 & 6)

Gold supported on meso porous carbon as catalysts for selective oxidation of glycerol

Ordered meso porous titania for photo catalytic hydrogen production, CO2 reduction and removal of pollutants

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Bimetallic nanoparticles with Hetero junctions

Figure.4. Ni based bimetallic nano particles

Figure 5. Novel meso prous carbon materials

Figure 6.Novel synthesis routes for meso porous alumina

In addition to the conventional inter-metallics, heteroatom incorporated one dimensional carbon materials have been developed in the laboratory scale, to achieve hydrogen storage capacity of 1-4% with good reproducibility. Preparation on large scale is in progress. (Fig.7)

Figure 7. Hydrogen sorption at 298 K on Phosphorus substituted carbon (left) and unsubstituted carbon (right) treated at 600 and 8000 C

C. Theoretical studies Theoretical studies for catalyst

development: Employing Density Functional Theory (DFT) and other modern theories for condensed matter applications, like: Methanol formation by catalytic

hydrogenation of CO2 on a nitrogen doped zinc oxide surface: an evaluative study on the mechanistic pathway

Studies on tetra ammine platinum (II) complex encapsulated in various zeolites(Fig.8)

Studies on Zeolite Y encapsulated Copper (II) Salen Complexes

Figure 8. Schematics for HOMO and LUMO level of the neat and the encapsulated platinum complexes

SUMMARY OF CONTRIBUTIONSa. Publications, patents and books

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Output2006-2011

2011-2013

2013-2014

2014-2015

2015-2016

Total

Papers published in refereed journals

118 46 32 58 25 279

Presentations in Conferences 178 50 20 19 10 277

Patents 7 2 2 1 4 16

Books 16 1 3 - 2 22

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Sr. No

Level No

1 M.Tech and PG students ~1002 Ph.D-completed 293 Ph.D- in progress 204 PDF on rolls and trained 5+75 Research Associates 156 Orientation Course- in last 10

years400+

7 Summer course – in last 10 years

150+

8 Capsule Courses for Industry 5

PROJECT PROPOSALIt is proposed to reposition NCCR to enhance its capacity for human resource development, training and re-orient itself towards research areas of relevance, wherein the future focus of Indian research in Catalysis should be. The deliberations in the recently concluded COP21 and India’s INDC document guaranteeing the reduction of emissions by 33 – 35 % by 2030 mandate the focusing of research in alternate sources of energy, transportation fuels and chemicals. Thus the major goal of NCCR’s future research will be on the development of catalysts/electro/photo-catalysts for splitting of water CO2 and di-nitrogen reduction under mild conditions and processes for the conversion of biomass and algae into transportation fuels and chemicals.

ANNEXURESelected List of Publications/Books/Patents (filed/awarded)a. Publications

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1. P. Selvam and B. Kuppan, Synthesis, characterization and electro-catalytic properties of nano-platinum-supported mesoporous carbon molecular sieves, Pt/NCCR-41, Catalysis Today, 198, 85-91 (2012).

2. P. Selvam, V.M. Ravat, V. Krishna, Selective oxidation of alkenes over uranyl-anchored mesoporous MCM-41 molecular sieves, J. Phys. Chem. C, 115 (2011) 1922-1931.

3. A.Suzuki,  P. Bonnaud,  M.C. Williams,  P. Selvam, N. Aoki,  M. Miyano,  A. Miyamoto,  J.-I. Saito,  K. Ara, Effect of the Titanium Nanoparticle on the Quantum Chemical Characterization of the Liquid Sodium Nanofluid, J. Phys. Chem. B, 120 (2016) 3527-3539

4. A. Milev, L. George, S. Khan, P. Selvam and G.S.K. Kannangara, Li-ion Kinetics in LiFePO4/Carbon Nanocomposite Prepared by a Two-step Process:  The Role of Phase Composition.  Electrochim. Acta,  209 (2016) 565-573

5. F. Benyettou, J.A.O. Flores, F. Ravaux, R. Rezgui, M.Jouiad, S.I. Nehme, R.K.Parsapur, J.-C. Olsen, P. Selvam, A.Trabolsi- F108-Gated Mesoporousγ-Iron Oxide Nanoparticles for Magnetically Triggered Doxorubicin Delivery and Hyperthermia-, Chem. Eur. J., 22, 2016 (in press)

6. N.V.Krishna and P.Selvam, Architecting ordered mesoporousaluminosilicates under acidic condition via intrinsic hydrolysis method – Dalton Trans. 45 2016 in press

7.  C. M. Janet, B. Viswanathan, R. P. Viswanath, T. K. Varadarajan, Characterization and Photoluminescence Properties of MgOMicrotubes Synthesized from Hydromagnesite Flowers, Journal of Physical Chemistry C 28(2007) 10267-10272.

8. N.Kakati, J.Maiti, S.H.Lee, S.H.Jee, B. Viswanathan and Y.S.Yoon, Anode catalystsfor direct methanol fuel cells in acidic media: do we have any alternative for Pt?, Chemical reviews, 114, 12397-12429 (2014).

9. Ch.VenkateswaraRao and B.Viswanathan, RuxSey/C Electrodes for Oxygen Reduction ? A Reverse Microemulsion Method of Fabrication of Electrode Material, Journal of Physical Chemistry C 111(44), (2007) 16538-16543.

10.Ch.VenkateswaraRao and B.Viswanathan, ORR Activity and direct ethanol fuel cell performance of carbon supported Pt-M (M=Fe,Co and Cr) alloys prepared by polyol reduction method,J of Physical Chemistry C,   Volume: 113   Issue: 43(2009)   Pages: 18907-18913.

11.P. Satyananda Kishore B.Viswanathan, and T K Varadarajan, Silico tungstic Acid Based Carbon Supported Noble Metal Electrodes for Energy Conversion Application, J Physical Chemistry C , 113 (29)(2009), pp 12918-12925.

12.C. M Janet, S.Navaladian, B.Viswanathan, R.P.Viswanath and T K Varadarajan, Heterogeneous Wet Chemical Synthesis of Superlattice-Type Hierarchical ZnO Architectures for Concurrent H-2 Production and N-2 Reduction, Journal of Physical Chemistry C,   Volume: 114,   Issue: 6 (2010) , Pages: 2622-2632

13.G. Deepa, T.M. Sankaranarayanan, K. Shanthi and B. Viswanathan, Hydrodenitrogenation of model N-compounds over NiO-MoO3 supported on mesoporous materials, Catalysis Today 198, 252-262 (2012).

14. M. Banu, P. Venuvanalingam, R. Shanmugam, B. Viswanathan, S. Sivasanker, Sorbitol hydrogenolysis over Ni, Pt and Ru supported on Na-Y, Topics in Catalysis, 55 (2012) 897-907.  

15.Sankaranarayanan, T.M., M. Banu, Pandurangan and S. Sivasanker, Trans-esterification of sun flower oil over a solid catalyst, MoO3 supported on alumina, Appl. Catal., A., 409-410,239-247 (2011)

16.M. Banu, S. Sivasanker, T.M. Sankaranarayanan, P. Venuvanalingam, Hydrogenolysis of sorbitol over Ni and Pt loaded on NaY, Catal. Commun. 12 (2011) 673.

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17.S. Narayanan, J. Judith Vijaya, S. Sivasanker, MahboobAlam, P. Tamizhdurai, L. John Kennedy, Characterization and catalytic reactivity of mordenite – Investigation of selective oxidation of benzyl alcohol, Polyhedron, 89 (2015) 289–296.

18.R.VijayaShanthi, T.M. Sankaranarayanan, R. Mahalakshmy and S. Sivasanker, Fly ash based Ni catalyst for conversion of sorbitol into glycols, Journal of Environmental Chemical Engg. 3 (2015) 1752–1757.

19.K.R .Krishnamurthy, Sunil Mehla, Shivanand Pai; Mathew Jhon. Kishore Kumar; Yogesh Niwate and Bharat L Newalkar, n-Hexadecane Hydro isomerization over BTMACl / TEABr / MTEABr templated ZSM-12,Microporous &Mesoporous Materials, 177, 120-126 (2013)

20.Murthiyamma Gengatharan Prakash, Rajaram Mahalakshmy, Konda Ramaswamy Krishnamurthy and Balasubramanian Viswanathan, Selective hydrogenation of cinnamaldehyde on nickel nano particles supported on titania: role of catalyst preparation methods, Catal. Sci. Technol., 2015,,5, 3313-3321.

21.V. Jeyalakshmi, R. Mahalakshmy, K. Ramesh, P.V.C.Rao, N.V.Choudhary, G. Sri Ganesh, K.Thirunavukkarasu, K.R.Krishnamurthy and B.Viswanathan, Visible light driven reduction of carbon dioxide with water on modified Sr3Ti2O7 catalysts, RSC Adv.,5, 5958-5966 (2015).

22.Velu Jeyalakshmi, Rajaram Mahalakshmy, K. R. Krishnamurthy and Balasubramanian Viswanathan, Photo catalytic reduction of carbon dioxide by alkaline water on La modified sodium tantalate with different co-catalysts under UV-Visible radiation, Catalysis Today, 266,160-167,2016

23.M G Prakash, R.Mahalakshmy, K.R.Krishnamurthy, B.Viswanathan, Studies on Ni-M (M=Cu, Ag, Au) bimetallic catalysts for selective hydrogenation of Cinnamaldehyde, Catalysis Today, 263,105-111, 2016

24.V. Jeyalakshmi, S. Tamilmani, R. Mahalakshmy, P. Byrappa, K. R. Krishnamurthy and B. Viswanathan, Sensitization of La modified NaTaO3with cobalt tetra phenyl porphyrin for photo catalytic reduction of CO2by water with UV–visible light, Journal of Molecular Catalysis A: Chemical, 420 (2016) 200–207.

b. Books/Book Chapters1. D.K.Chakrabarty and B.Viswanathan, Heterogeneous Catalysis, New Age International (September) (2007). and International Edition 2008, TN1 1YS UK November 20082. B.Viswanathan, Energy Sources, Fundamentals of Chemical Conversion Processes and Applications, Elsevier (2016).3. P.Selvam and B.Kuppan, Micro- and Nano-Engineering of Fuel Cells (Ed. Dennis Leung), 2015, Chapter 5, CRC Press, pp.131-157.  Ordered Mesoporous Carbon-supported Nano-Platinum Catalysts:  Application in Direct Methanol Fuel Cells.4. V. Jeyalakshmi, , R. Mahalakshmy, K. R. Krishnamurthy and B. Viswanathan , Photo catalytic reduction of carbon dioxide by water: A step towards sustainable fuels andChemicals, in “ Materials Science Forum” Vol. 734 (2013) pp 1-62 (2013) Trans Tech Publications, Switzerland, doi:10.4028/www.scientific.net/MSF.734.1

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c. Patents

1. P.Selvam, B.Viswanathan and K.Suthagar, Selective conversion of glycerol to 1,2 and 1,3 propan-diol, Indian Patent Appln. No. 956/CHE/2010.

2. , V. Jeyalakshmi, K. R. Krishnamurthy, B. Viswanathan, K. Ramesh, P.V.C.Rao, N.V. Choudary and G. Sriganesh., “Catalyst composition for photo catalytic reduction of carbon dioxide” PCT/IN2013/000521 27th August, 2013

3. P. Selvam, B. Viswanatha, T. Nithya, K.P. Raju, S. Mahendran, An improved process for producing g-alumina with high surface area, narrow and wider pores, Indian Patent Appln. No. 6162/CHE/2014.

4. V. Jeyalakshmi, K. R. Krishnamurthy, B. Viswanathan, K. Ramesh, P.V.C.Rao, N.V. Choudary and G. Sriganesh, Layered oxide catalyst composites for photo catalytic reduction of CO2, Indian Patent Appl- Provisional- 100/MUM/2014, 10th January, 2014Complete patent specifications filed in January, 2015

5. V. Jeyalakshmi, K. R. Krishnamurthy, B. Viswanathan, K. Ramesh, P.V.C. Rao, N.V. Choudary and G. Sriganesh, Catalyst composition for photocatalytic reduction of carbon dioxide, US patent, Pub. No. US 2016/0129427A1, Pub. Date May 12, 2016.

6. P. Selvam and N.V. Krishna, An improved process for the acid-mediated synthesis of ordered meso porous aluminosilicates and the product thereof, , Indian Patent Appln. No. 201641027469 (2016).

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