Abstract Book CPCE

Abstract Book of Virtual National Conference on Catalysis and Photocatalysis for Clean Energy (CPCE) October 9-10, 2020 Organized by Department of Chemistry NIT Jamshedpur Jharkhand, India

Contents Sl Title of the Abstract Authors Page No. No. 1 Plasmon-induced interfacial electron transfer Akihiro FURUBE dynamics in Au/semiconductor nanosystems 1 2 Ligand Directed Catalysis by Nanomaterials Pramod P. Pillai 2-3 4-5 3 NanoCatalysis by Perfecting Imperfection and Black Vivek Polshettiwar Gold 4 Inorganic organic hybrid perovskite materials as Vivek Polshettiwar 6 photoelectrochemcial cell for water splitting application: Promise and challenges 5 Solar Hydrogen Generation Chinnakonda S. Gopinath 7 8 6 Polymer-Metal/Semiconductor Nanocomposite Thin T. P. 9 10 - 11 Film based Radhakrishnan 12 13 ‘Dip Catalysts’ for Chemical, Photo and 14 Electrocatalysis 15 7 Sustainable Approaches toward CO2 Conversion Joyanta Choudhury Catalysis 16 17 8 Solar light harvesting nanostructured photocatalyst for Vishnu Shanker dye degradation and H2-generation 9 Organic Cage Supported Metal Nanoparticles as Bijnaneswar Heterogeneous Photocatalyst in Organic Mondal Transformation 10 Visible light driven photocatalytic performance of Ag Abinash Dasa, modified ZnO Mathan Kumar Pb, nanorod through effective charge carrier separation Muthuraaman Bhagavathiacharib, Ranjith G. Nair 11 Photocatalytic activity of Mn(III) and Co(III) M. Shahnawaz complexes derived from 8-hydroxyquinoline Khan, Mohd Khalid 12 Noble metal-free multi-component equiatomic Mariappan Gd0.2La0.2Y0.2Hf0.2Zr0.2O2 and Anandkumara*, Gd0.2La0.2Ce0.2Hf0.2Zr0.2O2 oxide nanoparticles AjayLatheb, Anil as an alternate photocatlysts M.Palveb, and Atul SureshDeshpande 13 Biomass conversion to bio-fuels – An Overview Dr. Vijaya Kumari Nunna 14 Agrowaste Biomass a Green Catalyst for Biofuel Ghanshyam

Synthesis Barman 15 Unravelling the mechanistic insights for the Selective Ashish Kumar Kar 18 - 19 20 hydrogenolysis of lignin-derived and Rajendra 21 22 aryl ethers under mild reaction parameters Srivastava 23 24 16 Mesoporous Metal Phosphates Based Catalytic Abhinav Kumar 25 - 29 Materials for Biomass and Rajendra 30 Conversion into Chemicals and Fuels Srivastava 17 Cage to Framework: Potential Testbed for CO2 A. Giri, M. W. Fixation Hussain, and A. Patra 18 Highly stable M/NiO-MgO (M = Co, Cu and Fe) Yaddanapudi catalysts towards Varun, I. Sreedhar, CO2 methanation Satyapaul A. Singh 19 Role of Graphitic Carbon Nitride in CO2 Remediation via Mimicking Ankita Boruah Nature: A Doorway to Sustainaibility 20 Keggin POM Supported Cu(II) Coordination C. Singh, A. Haldar Complexes for Electrocatalytic and S. K. Das Hydrogen Evolution Reaction (HER) 21 RUTHENIUM (III) CATALYZED PERIODATE K.V.S.Koteswara OXIDATION OF PEG-400, AN Rao and R. Venkata ENCAPSULATING AGENT OF BIODIESEL Nadh PRODUCTION 22 Emplacement of Chemically Modified Screen-Printed Anurag Roy Graphene Oxide Coatings for Solar Thermal Management

Plasmon-induced interfacial electron transfer dynamics in Au/semiconductor nanosystems Akihiro FURUBE Department of Optical Science, Tokushima University, Tokushima, 770-8506, Japan E-mail: [email protected] Localized surface plasmon resonance (LSPR) of metal nanoparticles (NPs) and nanostructures has attracted wide attention because LSPR exhibits a strong near-field enhancement through interaction with visible light and provides many kinds of applications such as optical sensing of nano-environments and photo-fabrication of nanostructures. The oscillating electrons in the metal NP rapidly relax to generate hot electrons in femtosecond time scale, and they can transfer to contacting semiconductor material if the hybrid nanostructure is properly designed. This interfacial electron transfer generates charge- separated states that can be utilized for clean energy generation. Actually, many reports indicated plasmon-induced solar energy conversion to realize photovoltaic processes and photocatalytic reasons. The primary mechanism, however, is not understood very well. We have successfully utilized femtosecond transient absorption spectroscopy in a wide spectral region covering visible and infrared light to directly observe how electrons move in Au/semiconductor nanosystems. In this presentation three representative systems are selected to discuss the detailed mechanism: (i) Au NPs on TiO2 nanoparticles (Au/TiO2) as an essential part of plasmon-sensitized solar cells.1-3 (ii) (Au nanoparticle array) − (TiO2 film) − (Au film) sandwich structure as efficient light absorber for a wide wavelength range from UV to IR.4 (iii) Au nanorod-decorated hematite photoanode as a near-infrared sensitive solar fuel candidate.5 References: 1. Furube, Akihiro; Du, Luchao; Hara, Kohjiro; Katoh, Ryuzi; Tachiya, Masanori; Ultrafast plasmon-induced electron transfer from gold nanodots into TiO2 nanoparticles, J. Am. Chem. Soc., 129, 14852-14853, 2007 2. Du, Luchao; Furube, Akihiro; Yamamoto, Kazuhiro; Hara, Kohjiro; Katoh, Ryuzi; Tachiya, M.; Plasmon- induced charge separation and recombination dynamics in gold−TiO2 nanoparticle systems: dependence on TiO2 particle size, J. Phys. Chem. C, 113, 6454-6462, 2009 3. Du, Luchao; Furube, Akihiro; Hara, Kohjiro; Katoh, Ryuzi; Tachiya, Masanori; Ultrafast plasmon induced electron injection mechanism in gold-TiO2 nanoparticle system, J. Photochem. Photobio. C: Photochem. Reviews,15, 21-30, 2013 4. Yanagiya, Shin‐ichiro; Takahata, Toshihiko; Yoshitani, Yuki; Kawakami, Retsuo; Furube, Akihiro; Steady-State and Time‐Resolved Optical Properties of Multilayer Film of Titanium Dioxide Sandwiched by Gold Nanoparticles and Gold Thin Film, ChemNanoMat, 5, 1015-1020, 2019 5. Okazaki, Masahiro; Furube, Akihiro; Chen, Liang-Yih; Charge generation dynamics in hematite photoanodes decorated with gold nanostructures under near infrared excitation, J. Chem. Phys.,152, 41106, 2020 1

Ligand Directed Catalysis by Nanomaterials Pramod P. Pillai Department of Chemistry and Centre for Energy Sciences, Indian Institute of Science Education and Research (IISER), Dr. Homi Bhabha Road, Pashan, Pune – 411 008, India E-mail: [email protected] Surface ligands are ubiquitous in colloidal nanoscience. They provide the colloidal stability to nanoparticles (NPs) as well as dictate most of their physicochemical properties.1,2 However in the area of catalysis, the ligands have a bad reputation of poisoning the catalyst, either by hindering the surface accessibility or by creating an insulating barrier for the movement of electrons/holes.2 So, how to overcome this challenge of 'ligand poisoning'? Traditional strategies include the deposition of NPs onto a support or use of ligand free NPs for catalysis.2 However, the available surface area and stability of NPs are often compromised during the course of catalysis. Thus, NPs and ligands are two inseparable entities, and strategies have to be developed to accomplish catalysis by retaining as well as utilizing the ligands on the NP surface. This talk will present a new strategy based on NP-reactant interaction (emanating from surface ligands) to address the so called 'ligand poisoning' effect. By tuning the NP- reactant interaction we were not only able to achieve efficient catalysis at low NP concentration, but also to regulate the catalytic property between completely 'ON' and 'OFF' states - rendering the same NP as a catalyst or a non-catalyst.4 Such interaction driven enhancement in catalytic performances can be prominent in the emerging area of ‘ligand directed product formation’ in NP catalysis. Precise catalyst – reactant interaction outplays ligand poisoning in NP (a) catalysis and (b) photocatalysis. References 1. (a) C. A. S. Batista, R. G. Larson, N. A. Kotov, Science 2015, 350, 1242477; (b) K. J. Bishop, C. E. Wilmer, S. Soh, B. A. Grzybowski, Small 2009, 5, 1600. 2. (a) G. Devatha, S. Roy, A. Rao, A. Mallick, S. Basu, P. P. Pillai, Chem. Sci. 2017, 8, 3879; (b) J. A. M. Xavier, G. Devatha, S. Roy, A. Rao, P. P. Pillai, J. Mater. Chem. A 2018, 6, 22248; (c) P. Roy, G. Devatha, S. Roy, A. Rao, P. P. Pillai, J. Phys. Chem. Lett. 2020, 11, 5354; (d) G. Devatha, A. Rao, S. Roy, P. P. Pillai, ACS Energy Lett. 2019, 4, 1710; (e) G. Devatha, P. Roy, A. Rao, S. Roy, P. P. Pillai, J. Phys. Chem. Lett. 2020, 11, 4099. 2

3. (a) Smith, J. G.; Jain, P. K. J. Am. Chem. Soc. 2016, 138, 6765; (b) Menumerov, E.; Hughes, R. A.; Neretina, S. Nano Lett. 2016, 16, 7791-7797. 4. (a) S. Roy, A. Rao, G. Devatha, P. P. Pillai, ACS. Catal. 2017, 7, 7141; (b) S. Roy, S. Roy, A. Rao, G. Devatha, P. P. Pillai, Chem. Mater. 2018, 30, 8415; (c) I. N. Chakraborty, S. Roy, G. Devatha, A. Rao, P. P. Pillai, Chem. Mater. 2019, 31, 2258; (d) S. Roy, V. Jain, R. K. Kashyap, A. Rao, P. P. Pillai, ACS. Catal. 2020, 10, 5522; (e) S. Shirin, S. Roy, A. Rao, P. P. Pillai, J. Phys. Chem. C 2020, 124, 19157. 3

NanoCatalysis by Perfecting Imperfection and Black Gold Vivek Polshettiwar* Nanocatalysis Laboratory, Department of Chemical Sciences, Tata Institute of Fundamental Research (TIFR), Mumbai, India. Email: [email protected], Web: www.nanocat.co.in Energy and environment are two of our critical societal challenges. The use of hybrid nanomaterials to harvest solar energy as well as capture and convert CO2 seems to be the best way combat climate change. We recently reported the synthesis of a new class of dendritic fibrous nano-silica (DFNS).1-13 Fibrous morphology observed in these nanospheres has not been seen before in silica materials. Uniqueness of DFNS is, its high surface area is by virtue of its fibrous structure instead of pores (unlike MCM-41 and SBA-15 silicas), and hence easily accessible. More than 150 groups worldwide is now using our patented DFNS for various applications such as catalysis, solar-energy harvesting, energy storage, self- cleaning antireflective coatings, surface plasmon resonance-based ultrasensitive sensors, CO2 capture, and biomedical applications.1 We showed successful utilization of DFNS for range of important catalytic applications such as metathesis, hydrogenolysis, oxidation, hydrogenation, coupling reactions etc2-8 as well as for CO2 capture.9 We have also developed a new method of fabricating active photocatalysts by TiO2 coating of DFNS.10 and plasmonic black gold.11 In this seminar, I will discuss these results on synthesis and application fibrous nano-silica (including black gold,11 amorphous zeolites13 and defected silica12) for fine chemical synthesis, solar energy harvesting, CO2 capture-conversion and waste plastic to chemicals. References 1) (a) V. Polshettiwar, D. Cha, X. Zhang, J. M. Basset, Angew. Chem. Int. Ed. 2010, 49, 9652; (b) A. Maity, V. Polshettiwar, ChemSusChem 2017, 10, 3866; (c) A. Maity, R. Belgamwar, V. Polshettiwar, Nature Protocol, 2019, 14,2177. 2) A. Fihri, M. Bouhrara, D. Cha, V. Polshettiwar, ChemSusChem 2012, 5, 85. 3) A. Fihri, M. Bouhrara, D. Cha, Y. Saih, U. Patil, V. Polshettiwar, ACS Catal. 2012, 2, 1425. 4

4) (a) M. Dhiman, B. Chalke, V. Polshettiwar, J. Mat. Chem. A. 2017, 5, 1935; (b) M. Dhiman, V. Polshettiwar, J. Mat. Chem. A. 2016, 4, 12416. 5) V. Polshettiwar, T. C. Jean, M. Taoufik, F. Stoffelbach, S. Norsic, J. M. Basset, Angew. Chem. Int. Ed. 2011, 50, 2747. 6) M. Bouhrara, C. Ranga, A. Fihri, R. R. Shaikh, P. Sarawade, A. Emwas, M. N. Hedhili, V. Polshettiwar, ACS Sustain. Chem. Eng. 2013, 1, 1192. 7) A. S. L Thankamony, C. Lion, F. Pourpoint, B. Singh, A. J. P. Linde, D. Carnevale, G. Bodenhausen, H. Vezin, O. Lafon, V. Polshettiwar, Angew. Chem. Int. Ed. 2015, 54, 2190. 8) B. Singh, K. R. Mote, C. S. Gopinath, P. K. Madhu, V. Polshettiwar, Angew. Chem. Int. Ed. 2015, 54, 5985. 9) (a) B. Singh, V. Polshettiwar, J. Mat. Chem. A. 2016, 4, 7005; (b) U. Patil, A. Fihri, A. H. Emwas, V. Polshettiwar, Chem. Sci. 2012, 3, 2224. 10) (a) R. Singh, R. Bapat, L. Qin, H. Feng, V. Polshettiwar, ACS Catalysis 2016, 6, 2770; (b) N. Bayal, R. Singh, V. Polshettiwar, ChemSusChem, 2017, 10, 2182, (c) R. Singh, N. Bayal, A. Maity, D. Jeiyendira Pradeep, J.Trébosc, P. K. Madhu, P. Lafon, V. Polshettiwar, ChemNanoMat, 2018, 4, 1231, (d) S. Kundu, V. Polshettiwar, ChemPhotoChem 2018, 2, 796. 11) V. Polshettiwar, et al. Chemical Science 2019, 10, 6694. 12) Mishra, A. K.; Belgamwar, R.; Jana, R.; Datta, A.; Polshettiwar, V. Proc. Natl. Acad. Sci. U.S.A 2020, 117, 6383-639. 13) Maity, A. Chaudhari, S.; Titman, J. J.; Polshettiwar, V. Nature Comm. 2020, 11, 3828. 5

Inorganic organic hybrid perovskite materials as photoelectrochemcial cell for water splitting application: Promise and challenges Monojit Bag, Indian Institute of Technology Roorkee, Dept. of Physics Email: [email protected] Abstract: Inorganic organic hybrid materials have shown great promise in optoelectronic device application due to superior properties in these materials, starting from photovoltaic cells to light emitting diodes; perovskites are widely used even in other application such as sensors, detectors and memristors. Very recently perovskites have been used in liquid junction photoelectrochemical cells and it has shown great promise for photoelectrochemical water splitting application as well. However, there are some major problems in perovskite materials despite their wide use in solar cells. These materials are highly unstable under light and humidity due to photoinduced ion migration and hydrated compound formation. In this talk I will discuss about the challenges currently the whole community is facing for commercializing perovskite based optoelectronic devices especially when the charge transport is modulated due to the ion kinetics in these devices. There will be special emphasis on how these materials could be utilized in photoelectrochemical cells and what the challenges one has to address to use them as stable photoelectrode. I will also discuss about what are the strategies to implement these materials as efficient photoanode or photocathode in photoelectrochemical cells for water splitting application. At the end I will discuss some interesting observations in spectroelectrochemistry when these perovskite materials form semiconductor/electrolyte junctions. Reference: 1. Bag et. al. J. Am. Chem. Soc. 2015, 137(40), 13130-13137. 2. Smith et. al. J. Phys. Chem. C. 2018, 122(25), 13986-13994. 3. Srivastava et. al. ACS Applied Energy Mater. 2018, 1(9), 4420-4425 4. Srivastava et. al. Phys. Chem. Chem. Phys. 2020, 22, 11062-11074. 5. Kumar et. al. ACS Appl. Mater. Interfaces, 2020, 12(30), 34265-34273. 6

Solar Hydrogen Generation Chinnakonda S. Gopinath Catalysis and Inorganic Chemistry Division, CSIR - National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411 008 [email protected] Solar hydrogen production by water splitting is one of the “holy grail” of chemistry listed in a special issue published by the Accounts of Chemical Research1 on 1995 by Allan Bard et al. Water splitting to hydrogen is yet to be exploited, in spite of the large amount of research work in the past five decades. It is also true that photocatalysis measurements are not carried out in the right manner, to maximize the light absorption to hydrogen yield. In the talk to be delivered, let me explain some of the common mistakes researchers do and how to overcome those. We also reported few photocatalytic devices based on the artificial leaf concept and wireless approach, and they will be explained.2-3 A simple comparison of solar hydrogen generation from thin film and powder based catalyst, demonstrates the former to outweigh the latter.4 There is a very good possibility that this device can be scaled to bigger sizes to produce large amount of hydrogen. However, many more challenges are ahead and some of them will be discussed. References 1. A. J. Bard, G. M. Whitesides, R. N. Zare, F. W. McLafferty, Acc. Chem. Res. 1995, 28, Issue 3. 2. K. K. Patra, B. D. Bhuskute, C. S. Gopinath, Sci. Rep. 2017, 7, 6516. 3. K. K. Patra, P. A. Bharad, V. Jain, C. S. Gopinath, J. Mater. Chem. A 2019, 7, 3179. 4. N. Nalajala, K. K. Patra, P. A. Bharad, C. S. Gopinath, RSC. Adv., 2019, 7, 6094. 7

Polymer-Metal/Semiconductor Nanocomposite Thin Film based ‘Dip Catalysts’ for Chemical, Photo and Electrocatalysis T. P. Radhakrishnan School of Chemistry, University of Hyderabad, Hyderabad – 500 046 Email: [email protected] Web: http://chemistry.uohyd.ac.in/~tpr/ Several nanomaterials serve as superior catalysts, thanks to the high surface-to-volume ratios and selected surface structures at the nanoscale. Harmonization of the high efficiency of homogeneous catalysts with the extensive reusability of heterogeneous catalysts is key to the promise of nano catalysts. Polymer-metal nanocomposite thin films are versatile materials that combine the unique characteristics of the components, and manifest mutualistic effects. The soft-chemical in situ methodology developed in our laboratory for the fabrication of metal, alloy and semiconductor nanostructures will be described.1- 4 The ‘dip catalyst’ paradigm will be demonstrated through examples of hydrogenation and carbon- carbon coupling reactions,5 as well as photocatalytic applications.3 Recent studies demonstrate the counter-intuitive utility of insulating polymer – semiconductor nanocomposite thin film based electrodes in electrocatalytic water splitting.4,6 Ease of fabrication of the catalyst thin films, their high efficiency and facility of reuse, and the feasibility of monitoring through the usage cycles will be highlighted. References 1. G. V. Ramesh, S. Porel, T. P. Radhakrishnan, Chem. Soc. Rev. 2009, 38, 2646; E. Hariprasad, T. P. Radhakrishnan, in Nanocomposites: In Situ Synthesis of Polymer-Embedded Nanostructures, Eds. G. Carotenuto and L. Nicolais, John Wiley and Sons, 2013, p.129. 2. V. K. Rao, T. P. Radhakrishnan, J. Mater. Chem. A 2013, 1, 13612. 3. V. K. Rao, T. P. Radhakrishnan, Mater. Res. Bull. 2017, 87, 193. 4. U. Divya Madhuri, T. P. Radhakrishnan, ChemElectroChem 2019, 6, 1984. 5. E. Hariprasad, T. P. Radhakrishnan, Chem. Eur. J. 2010, 16, 14378; E. Hariprasad, T. P. Radhakrishnan, ACS Catal. 2012, 2, 1179. 6. U. Divya Madhuri, T. P. Radhakrishnan, J. Phys. Chem. C 2020, 124, 44. 8

Sustainable Approaches toward CO2 Conversion Catalysis Joyanta Choudhury Organometallics & Smart Materials Laboratory, Department of Chemistry, IISER Bhopal, Bhopal 462 066, India Email: [email protected] Abstract: “Methanol Economy” and “Hydrogen Economy” have been proposed as potential solution for much- demanding carbon-neutral energy cycle. Chemical hydrogen storage (CHS) within CO2 through catalytic hydrogenation and as-required delivery of hydrogen through a reverse catalytic dehydrogenation process is an interesting concept in this context. However, a sustainable catalytic protocol is the primary requirement in this prospective technology. One major research program in our laboratory is focused on this issue. With the help of recently-developed “Switchable Catalysis” approach,1 we have demonstrated our initial efforts in this area by devising an ambient-pressure H2-storage and low-temperature H2-release with CO2/HCO2H couple catalysed by a pH-responsive “Ir-NHC” complex.2 The developed concept triggered to discover the first ever atmospheric-pressure CO2-conversion strategy which does not require H2 gas and instead uses renewable hydride donors.3 The later approach is currently being upgraded in our laboratory to achieve a sustainable CO2-conversion protocol.4 In a parallel programme in our laboratory, recently we developed half-sandwich Co complexes as potential electrocatalysts for selective CO2-to- CO conversion processes.5 References 1. (a) Semwal, S.; Choudhury, J. ACS Catal. 2016, 6, 2424−2428; (b) Semwal, S.; Choudhury, J. Angew. Chem. Int. Ed. 2017, 56, 5556–5560, and https://www.chemistryworld.com/news/ruthenium-complex- catalyses-complimentary-reactions/3007136.article; (c) Maji, B.; Choudhury, J. Chem. Commun. 2019, 55, 4574–4577. 2. Semwal, S.; Kumar, A.; Choudhury, J. Catal. Sci. Technol. 2018, 8, 6137–6142. 3. Kumar, A.; Semwal, S.; Choudhury, J. ACS Catal. 2019, 9, 2164–2168; and https://www.chemistryworld.com/news/taking-the-pressure-off-catalytic-carbon-dioxide-conversion- /3010094.article. 4. Unpublished results. 5. Pandey, I.K.; Kumar, A.; Choudhury, J. Chem Asian J. 2020, 15, 904-909. This article appeared in: Hot Topic: Carbon Dioxide The 2nd International Conference on Organometallics and Catalysis (ICOC-2020) 9

Solar light harvesting nanostructured photocatalyst for dye degradation and H2-generation Vishnu Shanker Department of Chemistry, National Institute of Technology Warangal, Telangana, INDIA Email: [email protected] In order to meet increasing demand of energy and reduce environmental deterioration attracted present generation of the researcher to design and develop possible technologies to address these problems. One of the most attractive possible technology to address these problems is photocatalysis. The photocatalysis is able to convert solar energy into chemical energy i.e; evolution of H2 through water splitting process, and remove organic pollutants form water body with the help of semiconductor-based nanostructured photocatalysts. Recent development of a new class of metal-free organic semiconductor, especially graphitic carbon nitride (g-C3N4), is considered to be a breakthrough in the field of visible light active photocatalyst due to its novel properties such as visible light responsive wide band gap, high chemical and physical stability, low cost and nontoxicity.1,2 However, the practical applications of g-C3N4 are still limited due to the short life-span of photogenerated electron-hole pairs, low specific surface area and poor quantum yield.3 To overcome this problem, many attempts have been made to improve the performance of g-C3N4, such as doping with foreign elements, and coupling with other semiconductors or noble metals.4-8 The coupled semiconductors significantly enhance the photocatalytic efficiency by decreasing the recombination rate of photogenerated electron-hole pairs and exhibit potential applications for water splitting, organic decomposition, and photovoltaic devices. The other observation revealed that the ternary nanocomposite system LaFeO3/CdS/carbon quantum dots can be a potential photocatalyst for H2 evaluation from water splitting with a high rate of 25,302 mmolh-1gcat.-1 by using a small amount of photocatalyst (5 mg) from glycerol-water solution.9 Figure 1a shows the Photocatalytic dye degradation in aqueous solution over g-C3N4, Ag3PO4 and g-C3N4/Ag3PO4 nanocomposite and Figure 1b shows the H2 evolution rates of ternary LaFeO3/CdS/carbon quantum dots photocatalysts under solar light irradiation (a) (bb)) 10

References 1. X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J. M. Carlsson, K. Domen and M. Antonietti, Nat. Mater., 8, 76 (2009). 2. Thomas, A. Fischer, F. Goettmann, M. Antonietti, J. O. Müller, R. Schlögl and J. M. Carlsson, J. Mater. Chem., 18, 4893 (2008). 3. K. Maeda, X. Wang, Y. Nishihara, D. Lu, M. Antonietti and K. Domen, J. Phys. Chem. C, 113, 4940 (2009). 4. S. Kumar, T. Surendar, A. Baruah and V. Shanker, J. Mater. Chem. A, 1, 5333 (2013). 5. S. Kumar, T. Surendar, B. Kumar, A. Baruah, V. Shanker, J. Phys. Chem. C, 117, 26135 (2013). 6. T. Surendar, S. Kumar, V. Shanker, Phys. Chem. Chem. Phys., 16, 728 (2014). 7. Surendar Tonda, Santosh Kumar, Syam Kandula and Vishnu Shanker, J. Mater. Chem. A, 2, 6772 (2014). 8. S Tonda, S Kumar, V Shanker, Journal of Environmental Chemical Engineering, 3 (2), 852 (2015). 9. Saikumar Manchala, Ambedkar Gandamalla, Navakoteswara Rao Vempuluru, Shankar Muthukonda Venkatakrishnan, Vishnu Shanker, Journal of Colloid and Interface Science 583, 255 (2021). 11

Organic Cage Supported Metal Nanoparticles as Heterogeneous Photocatalyst in Organic Transformation Bijnaneswar Mondal Department of Chemistry, Guru Ghasidas University, Bilaspur, Chhattisgarh 495009 [email protected] Abstract: From a chemist’s viewpoint, both dynamic covalent chemistry (DCC) and supramolecular chemistry have resemblance in terms of reversibility. However, unlike supramolecular chemistry, DCC provides the additional advantage of generating relatively stable molecules due to the formation of covalent bonds. Notably, imine condensation that is known to chemists for more than a century, has recently been well explored to construct self-assembled organic cages of different size and shape. In this fact, covalent organic cages have received much appreciation as a porous material for gas adsorption and separation.1,2 Barring porosity, their use as a template for metal nanoparticles (MNPs) synthesis and as a material for the detection of harmful organic pollutants 3 are certainty two most promising applications that have been explored in recent times. Now, it has been well recognized that organic cages with suitable metal binding sites and stable aromatic backbone provide the ideal platform to foster control growth and stabilization of ultrafine MNPs. Also, owing to their solution processability, chemical, and thermal stability, cage supported MNPs serve as an excellent material for catalysis. Recently, we have revealed using two discrete nanoscopic organic cages of different size and shape, proper size tuning of palladium nanoparticles (Pd@CC1r and Pd@CC2r) could be engineered.4 Furthermore, cage impregnated Pd-NPs acts as an excellent heterogeneous catalyst in the cyanation of aryl halides for several cycles. In another report, we have shown organic cage encapsulated gold nanoparticles (Au@OC1R) acts as a heterogeneous photocatalyst for facile and selective reduction of nitroarenes to its corresponding azo compounds.5 Recently, we have reported organic cage supported silver nanoparticles (Ag@OB4R) acts as efficient heterogeneous photocatalyst for additive free Ullmann type coupling reaction of various poly-aromatic haloarenes at room temeperature.6 Organic cage supported AgNPs as heterogeneous photocatalyst in Ullmann type coupling reaction References: 1. Hasell, T.; Cooper, A. I. Nat. Rev. Mater. 2016, 1, 16053- 16066. 2. Mastalerz, M. Acc. Chem. Res. 2018, 51, 2411- 2422. 3. Acharyya, K.; Mukherjee, P. S. Chem. Commun. 2014, 50, 15788- 15791. 4. Mondal, B.; Acharyya, K.; Howlader, P.; Mukherjee, P. S. J. Am. Chem. Soc. 2016, 138, 1709- 1716. 5. Mondal, B.; Mukherjee, P. S. J. Am. Chem. Soc. 2018, 140, 12592- 12601. 6. Mondal, B.; Bhandari. P.; Mukherjee, P. S. Chem.-Eur. J. 2020, 10.1002/chem.202003390 12

Visible light driven photocatalytic performance of Ag modified ZnO nanorod through effective charge carrier separation Abinash Dasa, Mathan Kumar Pb, Muthuraaman Bhagavathiacharib, Ranjith G. Naira1 a. Solar Energy Materials Research & Testing Laboratory (SMaRT lab), Department of Physics, National Institute of Technology Silchar, Silchar, Assam-788010 (India) b. Department of Energy, School of Chemical Sciences, University of Madras, Guindy Campus, Chennai- 600025 (India) Over the past few decades, a lot of interest has been generated among the researchers to use ZnO based photocatalyst for energy and environmental applications. However, most of the work suggests that the effectiveness of implementing bare ZnO is limited due to several inherent shortcomings of the photocatalyst. Considering the same, current study has shown that the modification of ZnO with silver (Ag) can significantly improve the visible light driven photocatalytic activity through suitable modification in physicochemical properties. Highly active silver modified ZnO has been prepared using modified hydrothermal method. The structural, morphological, elemental and optical properties were characterised using XRD, TEM, FESEM, EDS, FTIR, UV-Vis and photoluminescence (PL) spectroscopy. The visible light driven photocatalytic performance of Ag doped ZnO was studied for the degradation of methylene blue (MB), and it is found that silver modified ZnO shows approximately seven times higher performance in terms of rate constant than the pristine ZnO. The improved performance of Ag modified ZnO was further supported by the photoelectrochemical (PEC) study, indicating the reduced charge transfer resistance of Ag doped ZnO. The PEC study emphasizes on the role of Ag in obstructing the recombination pathway of photogenerated charge carriers. 1 Corresponding author. E-mail address: [email protected] (R.G. Nair). 13

Photocatalytic activity of Mn(III) and Co(III) complexes derived from 8-hydroxyquinoline M. Shahnawaz Khana, Mohd Khalida*, aDepartment of Chemistry, Aligarh Muslim University, Aligarh 202002 Email: [email protected] Abstract We have synthesized two mononuclear complexes, Mn-hq and Co-hq to serve as sustainable catalysts for degrading dyes from organic pollutant. The two complexes have been characterized by various spectroscopic tools and with the assistance of single-crystal X-ray diffraction data, their molecular structures were established. The present complexes exploited for the catalytic activity i.e., photocatalytic property. Mn-hq and Co-hq demonstrated remarkable photocatalytic activity for the degradation of methylene blue (MB) in the aqueous medium beneath visible- light. Co-hq shows excellent stability and recyclability towards MB. Further, trapping experiment along with degradation pathways is also explored. Thus the present research throws light on the excellent photocatalytic properties of simply designed complexes and this activity can be tuned for desired efficiencies in future prospects. References [1] E. Bizani, K. Fytianos, I. Poulios, V.T. Siridis, J. Hazardous Mater. 136, 85 (2006). [2] J. Hou, C. Yang, Z. Wang, S. Jiao, H. Zhu, Appl. Catal. B Environ. 129, 333 (2013). 14

Noble metal-free multi-component equiatomic Gd0.2La0.2Y0.2Hf0.2Zr0.2O2 and Gd0.2La0.2Ce0.2Hf0.2Zr0.2O2 oxide nanoparticles as an alternate photocatlysts Mariappan Anandkumara*, AjayLatheb, Anil M.Palveb, and Atul SureshDeshpandea aDepartment of Materials Science and Metallurgical Engineering, Indian Institute of Technology Hyderabad, Kandi, Sangareddy, 502285, India bDepartment of Chemistry, Mahatma Phule Arts, Science and Commerce College, Panvel, Navi-Mumbai, 410206, India *[email protected] Abstract High entropy alloys have recently gained widespread interest as a consequence of their high configurational entropy, as five or more equiatomic elements form a solid solution regardless of the number of phases. High entropy alloys have outstanding properties, such as good strength and hardness, due to their high entropy effect. The recent field of research into high entropy ceramics was an extrapolation of alloy structures that have characteristics similar to that of an alloy system. Oxides, diborides, carbides, and nitrides are a different class of ceramics people have been explored. Oxides are of particular importance compared to other types of ceramics with a number of functional properties such as catalysts, batteries, lithium superconductors, etc. We report for the first time the use of noble metal-free multi-component equiatomic oxide as photocatalysts with excellent performance for natural sunlight driven degradation of Cr(VI) and methylene blue dye. The multi-component oxide nanoparticles with a composition Gd0.2La0.2Ce0.2Hf0.2Zr0.2O2 and Gd0.2La0.2Y0.2Hf0.2Zr0.2O2 were synthesized by simple co- precipitation followed by peptization in acid to obtain nanoparticle sol and calcined at 500 °C. The nanopowders were characterized by x-ray diffraction (XRD), UV–Visible spectroscopy (UV–Vis), and high-resolution transmission electron microscopy (HRTEM). The complete (∼100%) reduction of Cr(VI) to Cr(III) was observed after 90 and 100 min for the calcined Gd0.2La0.2Ce0.2Hf0.2Zr0.2O2 and Gd0.2La0.2Y0.2Hf0.2Zr0.2O2 respectively, under exposure to natural sunlight. In addition, 70% degradation of methylene blue is observed in 180 min. The effective photocatalytic activity of multi-component oxides can be attributed to their unique composition containing five components in equimolar amounts. The role of oxygen vacancies in photocatalytic reduction of Cr(VI) is also discussed. 15

Biomass conversion to bio-fuels – An Overview Dr. Vijaya Kumari Nunna Mahatma Gandhi National Council of Rural Education Hyderabad, Telangana E-mail: [email protected] ABSTRACT Fossil fuels like coal, oil, and gas are practical convenient sources of energy, and they meet the energy demands of society very effectively. However, there is one major problem, fossil fuel resources are finite and not renewable. Thus use of fossil fuel is not sustainable. Biomass, on the other hand, grows and hence this resource is renewable and its use is sustainable. Biomass provides more than 10 % global energy use. Biomass is plant or animal material used for energy production namely, electricity or heat, and is also used in various industrial processes as raw substance for a range of products. Biomass conversion technologies are normally classified as 1st, 2nd, or 3rd generation, according to the type of feedstock. Biomass conversion is proving to be an important option for several applications including energy and chemical production. Biomass conversion to bio-fuels has significant environmental, socio-economical and renewability benefits as well as carbon sequestration potential. Keywords: Renewable energy source, Biomass, Conversion, Bio-fuels, Benefits, Sustainability 16

Agrowaste Biomass a Green Catalyst for Biofuel Synthesis Ghanshyam Barman CGPIT, Uka Tarsadia University, Bardoli, Gujarat, India [email protected] Abstract Conventional disposal of waste generated from agriculture by burning is an ineffective method. It is a potential hazard for human being and major threat for environment. Agricultural waste can be utilised as catalyst for biofuel synthesis. The low cost, biocompatible, ecofriendly and wide availability, makes it attractive and widely acceptable to be used. The agrowaste is used as catalyst for biofuel preparation requires less time and it is easy to process. It can be processed under anaerobic pyrolysis process at optimised condition of temperature and pressure. The optimised blend of different types of plants and agrowaste improves the quality of biofuel. The obtained biofuel has high calorific value and high H:C ratio. The conversion of waste in to high commercial value product, saves millions of dollars and have low carbon footprint, and results into conservation of environment. Key words: Agro waste, biofuel, pyrolysis, carbon footprint, environment 17

Abstract Unravelling the mechanistic insights for the Selective hydrogenolysis of lignin-derived aryl ethers under mild reaction parameters Ashish Kumar Kar and Rajendra Srivastava Department of Chemistry, Indian Institute of Technology Ropar, India, 140001 Presenter (Ashish Kumar Kar, Research Scholar, Indian Institute of Technology Ropar, India) Short Description of presentation (The title of my presentation is “unravelling the mechanistic insights for the Selective hydrogenolysis of lignin-derived aryl ethers under mild reaction parameters. This presentation brings attention for the importance of hydrogenolysis of lignin and its derivatives which is an important milestone to be achieved to fulfill the future fuel demands from abundantly available biomass resources. Moreover, in this presentation, it is extensively discussed how the selective hydrogenolysis requires precise modulation of surface reactivity of the catalyst to obtain the desired reactivity and selectivity. In this study, the selective hydrogenolysis of benzyl phenyl ether to phenol and toluene is achieved in methanol or water medium at very low temperature (353 K) and H2 pressure (2 bar) over Pd nanoparticles decorated Ce-MOF. The activity of the developed catalyst is 3 times higher to that of Pd decorated CeO2. Structure-activity relation is established using, catalytic measurements, X-ray photoelectron spectroscopy, and transmission electron microscopy. A detailed mechanism of hydrogenolysis of aryl ethers and the reasons behind the superior activity of Pd/Ce-BTC than Pd/CeO2 are investigated using the density functional theoretical (DFT) calculations. Spectroscopic measurements and DFT calculations suggest that the higher Pd0/Pd2+ ratio and higher adsorption of benzyl phenyl ether over Pd/Ce-BTC and higher adsorption of phenol over Pd/CeO2 are factors responsible for the higher activity of Pd/Ce-BTC than Pd/CeO2. Efficient recyclability and hot filtration test shows that the catalyst exhibits no significant loss in the activity even after five recycles. The catalyst exhibits very high turnover frequency and low activation energy which are very attractive from the academic and industrial points of view.) What will the audience take away from your presentation? • This presentation will address the importance of the lignin obtained from biomass and its unique characteristics for the replacement to fossil fuel. 18

• This presentation will motivate the researchers and industrialists for the importance of selective hydrogenolysis of lignin and its model derivatives. • This presentation will discuss the design and development of the simple and highly efficient heterogeneous catalyst for the selective hydrogenolysis of lignin and other bimass derived compounds. Research interests (Selective hydrogenolysis of biomass derived compunds into fine chemicals using heterogeneous catalyst.) No. of published articles and Journals information 1. A. K. Kar, and R. Srivastava, New J Chem, 2018, 42, 9557 – 9567. 2. A. K. Kar, and R. Srivastava, Inorg. Chem. Front., 2019, 6, 576–589. 3. A. K. Kar and R. Srivastava, ACS Sustainable Chem. Eng. 2019, 7, 13136−13147. 4. A. K. Kar and R. Srivastava, Catal. Sci. Technol., (DOI: 10.1039/d0cy01279c). Author Details: Full Name: Ashish Kumar Kar Contact Number: +91 8196954514 Country: India Category: Oral Presentation Email: [email protected] 19

Mesoporous Metal Phosphates Based Catalytic Materials for Biomass Conversion into Chemicals and Fuels Abhinav Kumar and Rajendra Srivastava* Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar-140001, India ABSTRACT Fossil fuels providing more than 90 % of our energy needs and feedstock to the chemical industry in combination with the emission of major greenhouse gas CO2 is one of the most pressing challenges throughout the world.1 Biomass provides an alternative path to fossil fuels and CO2 emission. Biomass-derived carbohydrates are considered as a cheap, sustainable, and green source of energy and are produced in a large scale in every part of the world. Several groups have reported many heterogeneous, homogeneous, and bio- catalytic systems for the conversion of carbohydrates into fine chemicals. Heterogeneous catalysts have good tolerance and a longer lifetime than homogeneous and biocatalysts. Simple cerium phosphate (CePO4) is presented for the efficient conversion of various carbohydrates (fructose, glucose, sucrose, and starch) into 5-hydroxymethylfurfural (HMF) in water-diglyme solvent mixture.2 To improve the catalytic activity, especially for glucose and starch, CePO4 was supported on the surface of H-Beta zeolite. Moreover, CePO4 also exhibited good activity for the selective oxidation of HMF at atmospheric pressure under the flow of oxygen gas.2 The catalytic activity of CePO4 was further explored for fuels and chemicals synthesis by using 2-propanol as the hydrogen source.3 In addition to this, another important simple zirconium phosphate (ZrPO4) could be applied for the efficient production of various value-added chemicals from biomass- derived furan-aldehydes via hydrogenation and condensation.4 Details of synthesis and characterization of metal phosphates and their catalytic activity data in biomass conversion shall be presented during the conference. Keywords: metal phosphates, H-Beta, HMF, DFF, MPV reduction, hydrogenation, Knoevenagel & Biginelli condensation. *Corresponding Author: Rajendra Srivastava, Email: [email protected] Reference: 1. D. Gielen, F. Boshell, D. Saygin, M. D. Bazilian, N. Wagner, R. Gorini, Energy Strateg. Rev., 2019, 24, 38–50. 2. A. Kumar and R. Srivastava, Sustainable Energy Fuels, 2019, 3, 2475–2489. 3. F. Li, L. J. France, Z. Cai, Y. Li, S. Liu, H. Lou, J. Long and X. Li, Appl. Catal. B Environ., 2017, 214, 67–77. 4. A. Kumar and R. Srivastava, ACS Sustainable Chem. Eng., 2020, 8, 9497 – 9506. 20

Catalysis and Photocatalysis for Clean Energy (CPCE-2020), NIT Jamshedpur Cage to Framework: Potential Testbed for CO2 Fixation A. Giri, M. W. Hussain, and A. Patra* Indian Institute of Science Education and Research Bhopal, Bhopal, Madhya Pradesh, India E-mail: [email protected]  [email protected] Abstract Enhancing the activity, selectivity, and the ease of recyclability of the heterogeneous catalysts along with the energy-economic, waste-free catalytic methodologies are the keys to the industrial revolution and sustainable future. All-organic nanoporous materials, e.g., organic cages, cavitands, porous organic polymers (POPs), have attracted significant attention in the last few years for their potential applications in heterogeneous catalysis due to the lightweight, customizable structures, high porosity, and outstanding hydrothermal stability.1 Catalytic fixation of CO2 with epoxide for the synthesis of cyclic carbonates has drawn a great deal of interest because it provides a viable route to minimize the production cost of various materials derived from cyclic carbonates using easily available, renewable raw material, CO2, as a one-carbon building block.2 The high atom economy, as well as the versatile utility of the cyclic organic carbonates, make the conversion of CO2 to cyclic carbonates an industrially relevant reaction.2 A plethora of organic, inorganic, and organometallic catalysts have emerged in the last decade.2 In this scenario, our group has focused on the importance of the ‘nanoconfinement’ effect in the aforementioned catalytic process.3 In this talk, I shall discuss the nanoporous organic imine/amine cages as homogeneous catalytic platform for CO2 fixation.4a Addressing the recyclability issue and milder reaction conditions, I will switch to the heterogeneous catalytic platform discussing the use of recently developed cavitand-based POPs,4b and N-rich triaminoguanidinium-based ionic frameworks for the efficient CO2 fixation into cyclic organic carbonates.4c Figure: Pictorial representation depicting the nanoporous catalysts from cage to frameworks for catalytic fixation of CO2 to cyclic carbonates. References: 1. Slater, A. G.; Cooper, A. I. Science 2015, 348, 6238. 2. Shaikh, R. R.; Pornpraprom, S.; D’Elia, V. ACS Catal. 2018, 8, 419. 3. Grommet, A. B.; Feller, M.; Klajn, R. Nat. Nanotechnol. 2020, 15, 256. 4. (a) Hussain, M. W.; Giri, A.; Patra, A. Sustainable Energy Fuels 2019, 3, 2567; (b) Giri, A.; Hussain, M. W.; Sk., B.; Patra, A. Chem. Mater. 2019, 31, 8440; (c) Hussain, M. W.; Bhardwaj, V.; Giri, A.; Chande, A; Patra, A. Chem. Sci. 2020, 11, 7910. 21

Highly stable M/NiO-MgO (M = Co, Cu and Fe) catalysts towards CO2 methanation Yaddanapudi Varun, I. Sreedhar, Satyapaul A. Singh* Department of Chemical Engineering, Birla Institute of Technology and Science (BITS) Pilani, Hyderabad Campus, Jawahar Nagar, Kapra Mandal, Hyderabad-500 078, India. ABSTRACT NiO-MgO nanocomposites are synthesized using solution combustion, sonochemical, and co- precipitation synthesis to understand the catalytic activity of CO2 methanation. Excellent particle size distribution was noticed with the sonochemical routed synthesis method, and the CO2 conversions are found to be better with the same synthesis protocol. Surface modifications in NiO-MgO composite were incorporated by doping M (M = Co, Fe, and Cu). The active catalysts are characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to understand physical, structural properties and surface morphology of the nanocomposites. All catalysts showed excellent catalytic activity for the conversion of CO2 to methane and selectivity towards methane to be higher than 85%. However, 2%Co/NiO-MgO showed the lowest activation energy of about 43 ± 2 kJ mol-1 among other synthesized catalysts. The mechanism of CO2 methanation was investigated with the inputs from temperature programming reduction with H2 (H2-TPR), and temperature programming desorption with CO2 (CO2-TPD) studies. Detailed reaction mechanism and kinetics are investigated for all doped catalysts. M/NiO-MgO offered excellent stability up to 50 h reaction time with high CO2 conversions and CH4 selectivities. Keywords: NiO-MgO nanocomposites; Sonochemical synthesis; Reaction mechanism; CO2 methanation; Co, Fe, and Cu doping 22

Role of Graphitic Carbon Nitride in CO2 Remediation via Mimicking Nature: A Doorway to Sustainaibility Ankita Boruah, Cotton University With rapid industralisation and urbanization, a threat has been imposed on the existing energy sources to meet the neccessary demands.Moreover,the consumption of fossil fuels have invigorated growing awareness owing to environmental concerns in the past few decades. Hence,the development of sustainable energy and advanced technologies to mitigate energy shortages and environmental pollution has become vital. In this aspect, semiconductor photocatalysis is a promising technology that can directly convert solar energy to chemical energy and is extensively used for its environmentally-benign properties.In the field of photocatalysis, graphitic carbon nitride (g-C3N4) as a fascinating conjugated polymer has attracted huge attention. Due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature, it has become a promising metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This work summarizes how g-C3N4 has been successfully employed as an effective photocatalyst to facilitate the photocatalytic CO2 reduction over the years. The latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites like elemental doping of g-C3N4, copolymerization, constructing isotype g-C3N4/ g-C3N4 heterojunctions , carbon-g-C3N4 (C-CN) heterojunctions , CNT/g-C3N4 hybrid heterostructures , graphene/g-C3N4 hybrid heterostructures are discussed.The different modifications brought on bare g-C3N4 in order to enhance its photocatalytic activity and lesssen electron hole recombination rate along with the different routes undertaken using a plethora of precursors is a prime focus of the work. A comparative study is carried out showing the improvements that has been observed in the performance subjected to functionalization.The importance of different parameters leading to subsequent increase in the photoredox efficiency is discussed with an attempt to provide a clear illustration of how the mechanism works.On the basis of this finding, a charge transfer mechanism is proposed. Focus is given on proposing green facile synthetic routes for obtaining g-C3N4 based photocatalysts which are cost effective and eco-friendly thereby supporting an easy and effective method of CO2 remediation by mimicking natural photosynthesis.The band structures, electronic properties, optical absorption, and interfacial charge transfer of g-C3N4-based heterostructured nanohybrids will also be theoretically discussed based on the first-principles density functional theory (DFT) calculations to provide insightful outlooks on the charge carrier dynamics.Lastly,this comprehensive review will conclude with a summary and some invigorating perspectives on the challenges and future prospects at the forefront of this budding research area. It is anticipated that this review will provide new inroads on the development of metal-free heterostructured photocatalysts composed by inexpensive, nontoxicity and earth abundant elements for artificial photosynthesis thus upgrading the performances of g-C3N4-based photocatalyst by harnessing their startling properties and thereby fostering sustainablility. 23

Keggin POM Supported Cu(II) Coordination Complexes for Electrocatalytic Hydrogen Evolution Reaction (HER) C. Singh, A. Haldar and S. K. Das* School of chemistry, University of Hyderabad, Telangana, India [email protected] Polyoxometalate (POM) belongs to the oldest chemistry topic, which is still evolving in diverse areas of chemistry. One such applicative approach of using POM is to synthesize inorganic- organic hybrid structure, where mere incorporation of metal-organic moieties leads to effective structural modification. In this work, we have synthesized a new inorganic-organic hybrid compound, [{CoW12O37[(O-CuII(2,2′-bipy)(H2O))]2[(O-CuII(2,2′-bipy)(H2O)2)]}]•2H2O (compound 1). This compound is characterized by various spectroscopic techniques and unambiguously by single-crystal X-ray crystallography. The compounds act as electrocatalyst for hydrogen evolution reaction, at near-neutral pH (pH= 4.8). The Compound 1 catalyzes HER reaction with a faradic efficiency of 85% and has an overpotential of 0.52 mV with a TOF of 17.17 102 [mol H2 (mol Cu)-1s-1] at a current density of 1 mA/cm2. An extensive study has been carried out to understand the mechanism and true nature of this catalysis. 0.00004 Compound 1 Epa2 Epa1 0.00002 Epa4 Epa3 0.00000 I (A) -0.00002 Epc1 Epc2 -0.00004 -0.00006 Epc1 -0.00008 Initial direction of scan -0.00010 Onset potential -0.00012 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 E(V vs. Ag/AgCl) Figure: 1. Crystal structure of compound 1 2. CV of compound 1 in 0.1 M acetate buffer, pH= 4.8 Keywords: Polyoxometalate/ Hybrid Compound/ Electrochemistry/ Water Reduction/ Electrocatalyst 24

RUTHENIUM (III) CATALYZED PERIODATE OXIDATION OF PEG-400, AN ENCAPSULATING AGENT OF BIODIESEL PRODUCTION K.V.S.Koteswara Rao1* and R. Venkata Nadh2 1* Department of Chemistry, GVSM Government Degree College, Ulavapadu-523292 Email: [email protected]; Mobile: 8985432683 2GITAM University, Bengaluru Campus, Karnaataka - 561203 email: [email protected]; Mobile: +91-9902632733 Abstract Poly Ethylene Glycol - 400 is used in the preparation of encapsulated heterogeneous catalysts of Biodiesel production. The kinetics of ruthenium(III) catalyzed periodate PEG-400 was studied in aqueous alkaline medium. The kinetic rates with respect to oxidant, substrate and alkali were determined. Effect of salts on the rate of reactions was studied. The effect of temperature on reaction rates was studied and Arrhenius parameters were calculated. The observations were rationalized by suitable mechanistic pathway and rate law. Key words: Kinetics, oxidation, PEG-400, alkaline medium, ruthenium(III). 1 25

INTRODUCTION Polyethyleneglycol (PEG) is a water soluble polymer with low toxicity, used in many consumer products such as tooth pastes, laxatives, and cosmetics. PEG is used in medicinal formulations, and has even been attached to protein medications through its hydroxyl end groups, referred to as PEGlycation of proteins, as a way to modify the biological uptake of the protein. In formulations, PEG is used to modify the absorption of ingested medications. In these applications, any degradation of PEG can have an adverse effect on the shelf life or potency of the medication. The present study is proposed to gain insight into the identity of oxidative degradation of PEG and to observe any effect of substrate inhibition. EXPERIMENTAL All the reagents used in these experiments were of analytical reagent grade. Requisite volumes of oxidant and substrate solutions were thermostated at the required temperature to attain equilibrium. After rapid mixing an equal volume of oxidant solution to the substrate solution, progress of the reaction was followed by assaying aliquots of the reaction mixture for periodate, iodometrically using starch as an indicator after suitable time intervals. In these oxidations, one oxygen loss or two electrons transfer per periodate molecule was observed i.e., oxidation capacity of oxidant was observed till the conversion of periodate into iodate. This was also confirmed by non oxidation of these polyglycols by iodate. RESULTS AND DISCUSSION The kinetic studies were carried out under pseudo first order conditions with the concentration of the substrate in large excess compared to that of the oxidant. The pseudo first order with respect to [periodate] was almost constant in the concentration range. The reaction orders of substrate(s) were 2 26

determined from the slope of logk1vs. log [variant] plots while maintaining all other concentrations and conditions constant. Substrate Inhibition A decrease in k values was observed at higher PEG concentrations and an inverse fractional with respect to substrate was found. Much attention was not paid by the earlier workers who observed similar effects with hexacyano ferrate (III) oxidation of carbohydrates (Singh et al, 1975) and ceric sulphate oxidation of alcohols (Littler and Waters, 1960). Olusanya and Odebunmi studied copper (II) inhibition in the oxidation of maltose and xylose by hexacyanoferrate (III) in alkaline medium and reported that the order of reaction in sugar decreased from one to zero at higher sugar concentration, but actually, their data shows that a 12% decrease in rate of reaction at higher concentration of maltose can be observed (Olusanya and Odebunmi, 2011). Substrate inhibition, i.e., a decrease in rate of reaction with an increase in substrate concentration can be contributed to the formation of periodate – PEG complex which resists oxidation. The inert complexes must contain a higher proportion of substrate molecules, which take part in the oxidation. Similar substrate inhibition was reported by us in the oxidation of myoinositol / Sorbitol and Mannitol by periodate in alkaline medium (Lakshman Kumar, 2012 and 2014). 3 27

S.No Variant Conc K 0x 107 K1 x 104 min-1 M moles/lit/min PEG-400 PEG-300 PEG-600 1 0.00025 PEG-200 20.78 12.25 5.12 12.98 18.68 16.99 5.54 2 0.0005 18.08 13.5 12.03 4.16 PERIODATE 25.67 9.67 2.52 53.1 15.77 7.8 5.69 3 0.001 18.1 17.99 20.45 4.26 15.8 13.72 18.64 5.3 4 0.002 22.6 18.15 14.9 5.35 25.7 14.94 20.43 5.43 5 0.1 21.5 12.97 21.08 6.97 14.1 16.2 12.3 7.13 6 0.05 23.4 16.42 18.55 4.81 22.5 11.36 17.61 4.81 7 Substrate 0.025 14.9 7.74 14.58 3.34 9.4 15.4 10.4 5.58 8 0.0125 21.5 12.8 19.72 3.72 13.84 25.71 18.47 13.27 9 0.0025 16.6 4.29 30.22 5.78 16 3.04 5.29 10 0.025 1.427/1.44 16.47 18.9 19.22 11 0.05 18.8 15.43 12 ALKALI 0.1 14.91 17.8 15.8 13 0.2 20.1 18.6 18.1 35.63 14 0.5 23.5 55.27 34.246 64.86 15 0 51.62 69.7 16 KCl 17 Salt Effect KBr 18 KI 19 KNO3 20 0 18.25 5.21 21 Boric Acid 0.01 14.13 4.91 22 0.025 13.46 5.33 23 0.05 16.9 5.51 24 14.9 5.19 25 35 23.08 11.01 40 34.77 15.09 TEMPERATURE 45 49.55 15.84 26 50 27 4 28

CONCLUSION Substrate inhibition was observed in the oxidation of PEG in alkaline medium due to stable complex formation between the substrate and periodate. REFERENCES Lakshman Kumar Y, Venkata Nadh R, and Radhakrishnamurti PS, Kinetics of oxidation of myo-inositol by potassium periodate in alkaline medium, Asian Journal of Chemistry, 24(12) (2012) 5869-5872. Lakshman Kumar Y, Venkata Nadh R, and Radhakrishnamurti PS, Substrate Inhibition: Oxidation of Sorbitol and Mannitol by Potassium periodate in Alkaline Medium, Russian Journal of Physical Chemistry-A, 88(5) (2014) 774-778. Littler J. S. and W. A. Waters, J. Chem. Soc., p. 2767 (1960). Mitewa M., P. Bontchev, Coord. Chem. Rev. 1985, 61, 241. Olusanya S. O. and E. O. Odebunmi, Pacif. J. Sci. Tech. 12, 328 (2011). Shalk Sandu, Bangalore Sethuram and Tangea Navaneeth Reo ; Transition Metal Chemistry, , 15 No. 1, 78-80,(1990). Sharma J.P., R.N.P. Singh, A.K. Singh And Bharat Singh, Kinetics and Mechanism of Ru(III) Catalysed Oxidation of Some Polyhydric Alcohols by N-Bromosuccinimide in Acidic Media, Tetrahedron 42(10) (1986) 2739–2747. Sheila Srivastava ; Trans. Met. Chem., 24, 683-685,(1999). Singh M. P., H. S. Singh, M. C. Ganwar, P. Thakur, and A. K. Singh, Proc. Ind. Nat. Sci. Acad., Part A 41, 178 (1975). 5 29

Emplacement of Chemically Modified Screen-Printed Graphene Oxide Coatings for Solar Thermal Management Anurag Roy Postdoctoral Researcher Environment and Sustainability Institute, University of Exeter, Penryn Campus, Cornwall TR10 9FE, U.K. Email: [email protected] ABSTRACT A novel graphene oxide coating (GOC) has been developed by screen-printing technique, which plays a crucial role in improving the thermal resistant and thermal stability along with the water-resistance performance (Figure 1). The basic concept consists of the integration of the GOC as a flat absorber on the top of a low iron glass or aluminum-based substrate connecting through a phase change material in contact with direct sun exposure. Using GOC on Al sheet resulted in a maximum temperature difference (ΔT) of ~50oC, while GOC on glass substrate offered the maximum ΔT increment to ~30oC. Besides, the reduced temperature maintenance extensively sustains for a more extended period compared to the outside temperature. The experimental results show good behavior of the proposed thermal comfort solution. Despite that, to thoroughly exploit the GOCs as a pre-illumination cooling technique for a solar cell, we experimentally characterized GOC further chemically and optically to observe the attenuation of light across a wide wavelength range with different graphene thicknesses coated on low iron-glass. The thermal and electrical characterizations followed to observe the performance of a polycrystalline Si solar cell. Based on these, the concept of utilizing GOC as a neutral density filter for focal spot concentrated photovoltaic systems has successively reduced the cell temperature significantly with no external cooling power. Figure 1. Flexible graphene oxide coating for various solar thermal applications and its relative heat dispersive mechanism. 30