Virtual Conference on Materials for Energy Harvesting and...

Virtual Conference on "Materials for Energy Harvesting and Catalysis" Event Dates: May 1-3, 2020; Event Address: Virtual using Zoom

Convener: Prof. Vivek Polshettiwar (TIFR, Mumbai, [email protected]) and Prof. Sayan Bhattacharyya (IISER, Kolkata, [email protected])

S.No. Name Email Institute Supervisor Title

1st May 2020 Morning Session-1

11.00-11.30 am Inauguration

11.30 to 12.00 noon Manisha

Samanta

manisha.samanta001

@gmail.com

Jawaharlal Nehru Centre for

Advanced Scientific Research

(JNCASR), Bangalore

Prof. Kanishka

Biswas

Topological Quantum Materials for

Thermoelectric Energy Conversion

12.00 to 12.30 pm Ayan Maity withayan2011

@gmail.com

Tata Institute of Fundamental

Research (TIFR) Mumbai

Prof. Vivek

Polshettiwar

Amorphous ZeolitocNanosponges for Catalysis,

Plastic Degradation and CO2 to Fuel Conversion

1st May 2020 Afternoon Session-2

4.00 to 4.30 pm Amrita

Chakraborty

[email protected]

om

Indian Institute of Technology

(IIT) Chennai

Prof. T.

Pradeep

Atomically precise nanocluster assemblies

encapsulating plasmonic gold nanorods

4.30 to 5:00 pm Samim Hassan cyz148057@chemistr

y.iitd.ac.in


(IIT) Delhi

Prof. Sameer

Sapra

Molybdenum Diselenide based

Nanoheterostructures for Catalytic and

Optoelectronic Applications

5:00 to 5.30 pm Ajay Kumar lovechem9022@gm

ail.com


(IIT) Mandi

Prof. Venkata

Krishnan

Enhanced Photocatalytic Activity of Au

Nanostars Decorated on Two Dimensional

Carbonaceous Nanosheets: Role of Plasmon

Induced Hot Electron Generation

2nd May 2020 Morning Session-3

11.00-11.30 am Rahul Majee rahulmajee1991@gm

ail.com

Indian Institute of Science

Education and Research (IISER)

Kolkata

Prof. Sayan

Bhattacharyya

Flattening the Perovskite with Redox Flip-flop

Surface

11.30 to 12.00 noon Ritesh Kant

Gupta

ritesh110990@gmail.

com


(IIT) Guwahati

Prof.

Parameswar

Iyer

Engineering Polymer and Perovskite to Achieve

High Performance and Stable Solar Cells

12.00 to 12.30 pm Vikash Kumar Ravi

vikashkumar.ravi@st

udents.iiserpune.ac.i

n



Pune

Prof.

Angshuman

Nag

Stable Perovskite Semiconductors: From Halides

to Chalcogenides

2nd May 2020 Afternoon Session-4

mailto:[email protected]


Virtual Conference on "Materials for Energy Harvesting and Catalysis" Event Dates: May 1-3, 2020; Event Address: Virtual using Zoom

Convener: Prof. Vivek Polshettiwar (TIFR, Mumbai, [email protected]) and Prof. Sayan Bhattacharyya (IISER, Kolkata, [email protected])

4.00 to 4.30 pm Ranjith P. [email protected]

c.in



Thiruvananthapuram

Prof. M. M.

Shaijumon

Controllable Synthesis of Phosphorene

Nanostructures for Efficient Electrocatalysis

4.30 to 5:00 pm Palak [email protected] Indian Institute of Science


Bhopal

Prof. Amit Paul Functionalized graphene for different energy

applications

5:00 to 5.30 pm Anku Guha

[email protected]

m

Tata Institute of Fundamental

Research (TIFR) Hyderabad

Prof. T N

Narayanan

Role of 'Water-in-Salt' Type Electrolytes in

Tuning Hydrogen evolution reaction

3rd May 2020 Morning Session-5

11.00-11.30 am Jayeeta Saha [email protected]

om


(IIT) Bombay, Mumbai

Prof. C.

Subramaniam

Magnetic tuning of electrocatalytic interface for

sustained kinetic enhancement of hydrogen

evolution

11.30 to 12.00 noon Sriram Kumar Bhabha Atomic Research

Centre (BARC), Mumbai

Dr. A. K. Satpati Kinetic Study of the photocharged Co-Bi

modified BiVO4 for PEC water oxidation

12.00 to 12.30 pm Gunjan Purohit gunjanp2503@gmail.

com

University of Delhi, India Prof. Diwan S.

Rawat

Sustainable synthesis of nanomaterial:

Application for one pot multicomponent

reactions.

3rd May 2020 Afternoon Session-6

4.00 to 4.30 pm Ajit Kumar kumarajitiitkgp@gm

ail.com


(IIT) Bombay, Mumbai

Prof. Sagar

Mitra

Room Temperature Sodium-Sulfur Batteries

4.30 to 5:00 pm Mukesh Kumar 2017cyz0004@iitrpr.

ac.in


(IIT) Ropor

Prof.

Tharamani C.N.

Poly(ionic liquid)–zinc polyoxometalate composite

as a cathode for high-performance

lithium–sulfur batteries

5:00 to 5.30 pm Tisita Das [email protected] Indian Institute of Technology

(IIT) Indore

Prof. Sudip

Chakraborty

Towards Efficient Inorganic Catalysis: A

Computational Roadmap

3rd May 2020 Award Session-7

6.30 to 7.30 pm Student Debate: “Is India Ready to Combat Climate Change: A Man made Virus? Why Research in Indian Labs are not Translated to

Industry? Why Research Students in India don’t Start-Up any Company?

7.30 to 7.45 pm Award Ceremony (top-5)



Topological Quantum Materials for Thermoelectric Energy Conversion

Manisha Samanta,1 Koushik Pal,2 Umesh V. Waghmare,2 and Kanishka Biswas1* 1New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Bangalore 560064, India. 2Theoretical Sciences Unit, Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Bangalore India. *Email: [email protected], [email protected]

Topological quantum materials, TQM (e.g. topological insulators, topological crystalline insulators and topological

semimetals), characterized by their nontrivial electronic surface states, have created a sensation in designing new

thermoelectric (TE) materials.1 Underlying reason for TQM being a source of potential candidates for TE is ascribed to the

fact that both TQM and TE materials demand similar material features such as the presence of heavy constituent elements,

narrow band gap and strong spin-orbit coupling (SOC). In our recent work, we have studied TE properties with detailed

understanding of structure property relationship of few intriguing TQM with layered hetero-structure from (Bi2)m(Bi2X3)n

(x = Se/Te; m,n - integer) homologous family (Figure 1a).2,3 We have reported realization of ultralow lattice thermal

conductivity, κlat and high n-type thermoelectric performance in BiSe, a weak topological insulator (WTI) from

(Bi2)m(Bi2Se3)n homologous family.4 Detailed investigations of various aspects of the structure and lattice dynamics through

measurements of low temperature heat capacity and first-principles density functional theoretical (DFT) calculations,

indicates localized vibrations of Bi-bilayer is responsible for the unusually low κlat of ~ 0.5 – 0.9 W/mK in BiSe (Figure

1b).4 Recently, we have demonstrated simultaneous occurrence of intrinsically low κlat of ~ 0.5-0.8 W/mK (Figure 1b) and

high carrier mobility, µ of ~ 500 -707 cm2/Vs in n-type BiTe, facilitated by its unique dual topological quantum phases.5

BiTe being a WTI hosts layered hetero-structure and hence it exhibits low κlat; while BiTe, being a TCI with metallic surface

states, possess high μ. This present results pave way to look for unconventional topological quantum materials for efficient

TE materials.5

Figure 1. (a) Crystal structure of BiX (X = Se/Te); cyan and yellow colour represents Bi atom of Bi2X3 and Bi2 layer respectively, violet colour represents chalcogen atoms. (b) κlat of BiSe and BiTe samples along different spark plasma sintering directions.

References

(1) Roychowdhury, S., Samanta, M., Banik, A. & Biswas, K. J. Solid State Chem. 275, 103 (2019). (2) Lind, H., Lidin, S. & Häussermann, U. Phys. Rev. B - Condens. Matter Mater. Phys. 72, 184101 (2005). (3) Sharma, P. A., Sharma, A. L. L., Medlin, D. L., Morales, A. M., Yang, N., Barney, M., He, J., Drymiotis, F., Turner, J. &

Tritt, T. M. Phys. Rev. B - Condens. Matter Mater. Phys. 83, 235209 (2011). (4) Samanta, M., Pal, K., Pal, P., Waghmare, U. V. & Biswas, K. J. Am. Chem. Soc. 140, 5866 (2018). (5) Samanta, M., Pal, K., Waghmare, U. V. & Biswas, K. Angew. Chemie - Int. Ed. 59, 4822 (2020).

(a)

(b)

-40 -20 0 20 40

0

50

100

150

200

Phase (

o)

dc bias (V)

25V

30V

35V

(c)

Amorphous Zeolitic Nanosponges for Catalysis, Plastic Degradation and CO2 to Fuel

Conversion

Ayan Maity,1 Sachin Chaudhari,2 Jeremy J. Titman,2 and Vivek Polshettiwar1* 1Department of Chemical Sciences, Tata Institute of Fundamental Research (TIFR), Mumbai, India 2School of Chemistry, University Park, University of Nottingham, Nottingham NG7 2RD, UK Email: [email protected], [email protected]

The synthesis of solid acids with strong zeolite-like acidity and textural properties like amorphous aluminosilicates (ASAs)

is still a challenge.1 In this work, we report the synthesis and application of a new class of material, called “Acidic

Amorphous Aluminosilicates (AmZe)”, which possesses Brønsted acidic sites like in zeolites and textural properties like

ASAs. This was achieved by controlling the hydrolysis and condensation reaction kinetics between silica (tetraethyl

orthosilicate) and alumina (aluminum acetylacetonate) precursors in a bicontinuous microemulsion template2-5. The synergy

between strong acidity and accessibility was reflected in the fact that AmZe catalyzed eight different catalytic processes

(styrene oxide ring-opening, vesidryl synthesis, Friedel−Crafts alkylation, jasminaldehyde synthesis, m-Xylene

isomerization and cumene cracking) which all require strong acidic sites and larger pore sizes, with better performance than

state-of-the-art zeolites and amorphous aluminosilicates. Notably, AmZe efficiently converted a range of waste plastics to

hydrocarbons at significantly lower temperatures. A Cu-Zn-Al/AmZe hybrid showed excellent performance for CO2 to fuel

conversion with 79% selectivity for dimethyl ether. The catalytic activity and selectivity of AmZe was then investigated by

conventional and DNP-enhanced solid-state NMR to provide molecular-level understanding of the distinctive Brønsted

acidic sites of these materials.

References

1. Corma, A., Iborra, S. & Velty, A. Chem. Rev. 107, 2411–2502 (2007). 2. Maity, A., Belgamwar, R. & Polshettiwar, V. Nature Prot. 14, 2177−2204 (2019). 3. Maity, A. & Polshettiwar, V. ChemSusChem 10, 3866−3913 (2017). 4. Choi, M., Cho, H. S., Srivastava, R., Venkatesan, C., Choi, D. & Ryoo, R. Nat. Mater. 5, 718–723 (2006). 5. Maity, A., Das, A., Sen, D., Mazumder, S. & Polshettiwar, V. Langmuir 33, 13774−13782 (2017).


Atomically Precise Nanocluster Assemblies Encapsulating Plasmonic Gold Nanorods

Amrita Chakraborty,1 Ann Candice Fernandez,1 Anirban Som,1 Biswajit Mondal,1 Ganapati Natarajan,1 Ganesan Paramasivam,1 Tanja Lahtinen,2 Hannu Häkkinen,2 Nonappa,3* and Thalappil Pradeep1*

1DST Unit of Nanoscience and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India. 2Nanoscience Centre, University of Jyväskylä, Survontie 9, FI-40014, Jyväskylä, Finland. 3Departments of Applied Physics and Bioproducts & Biosystems, Aalto University, Puumiehenkuja 2, P.O. Box 15100, FI-00076, Aalto, Finland. Email: [email protected], [email protected]

We present the self-assembled structures of atomically precise, ligand-protected noble metal nanoclusters leading to

encapsulation of plasmonic gold nanorods (GNRs). Unlike highly sophisticated DNA nanotechnology, our approach

demonstrates a strategically simple hydrogen bonding-directed self-assembly of nanoclusters leading to octahedral

nanocrystals encapsulating GNRs. Specifically, we use the p-mercaptobenzoic acid (pMBA) protected atomically precise

nanocluster, Na4[Ag44(pMBA)30] and pMBA functionalized GNRs. High resolution transmission and scanning transmission

electron tomographic reconstructions suggest that the geometry of the GNR surface is responsible for directing the assembly

of silver nanoclusters via H-bonding leading to octahedral symmetry. Further, use of water dispersible gold nanoclusters,

Au~250(pMBA)n and Au102(pMBA)44 also formed layered shells encapsulating GNRs. Such cluster assemblies on colloidal

particles present a new category of precision hybrids with diverse possibilities.

References

1. I. Chakraborty, T. Pradeep, Chem.Rev. 117, 8208–8271 (2017). 2. Nonappa, T. Lahtinen, J. S. Haataja, T. R. Tero, H. Häkkinen, O. Ikkala, Angew.Chem.Int.Ed. 55, 16035–16038

(2016). 3. L. Zhao, T. Ming, H. Chen, Y. Liang, J. Wang, Nanoscale 3, 3849 (2011). 4. D. Nepal, L. F. Drummy, S. Biswas, K. Park, R. A. Vaia, ACS Nano 7(10), 9064–9074 (2013). 5. A. Som, I. Chakraborty, T. A. Maark, S. Bhat, T. Pradeep, Adv.Mater.28, 2827–2833 (2016).



Molybdenum Diselenide based Nanoheterostructures for Catalytic and Optoelectronic Applications Md. Samim Hassan,1 Pooja Basera,2 Susnata Bera,1 Soniya Gahalawat,1 Pravin P. Ingole,1 Samit Kumar Ray,3 Saswata Bhattacharya,2 Sameer Sapra1* 1Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, 110016 2Department of Physics, Indian Institute of Technology Delhi, Hauz Khas, New Delhi, 110016 3Department of Physics, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal,

721302

Email: [email protected], [email protected]

Two dimensional transition metal dichalcogenides have made a smooth entry into the elite class of materials due to the perfect amalgamation of unique and tunable material properties such as quantum-well structures with broad range of indirect to direct band gap crossover, thickness dependent band transitions, in-plane charge carrier mobility, high specific surface area, and enhanced spin-orbit coupling. We have synthesized defect-rich MoSe2 nanosheets and used them as electrocatalyst in hydrogen evolution reaction and counter electrode in dye-sensitized solar cells. We have utilized these defects for designing nanoheterostructures with different materials for catalytic and photonic device applications. Lattice matched heterostructures have been grown epitaxially and also it has been possible to combine materials with completely different lattice structures by means of bifunctional ligands. Defect-passivated synthetic route was developed for the design of MoSe2−Cu2S nanoheterostructures, where Cu2S islands grow vertically on top of the defect sites present on the MoSe2 surface, thereby forming a vertical p−n junction having plasmonic characteristics. A number of applications such as oxygen evolution reaction, hydrogen evolution reaction, quantum-dot sensitized solar cell, and photodetector have been attempted with this nanoheterostructures. MoSe2−CsPbBr3 nanoheterostructures have been synthesized using a bifunctional ligand, i.e., 4-aminothiophenol. Due to the formation of a donor-bridge-acceptor system, an efficient shuttling of charge carriers is occurred at the interfaces, which is also reflected in photocurrent measurement in photodiode configuration.


References:

1. Hassan, M.S., Basera, P., Bera, S., Mittal M., Ray, S.K., Bhattacharya, S., Sapra, S. ACS Appl. Mater. Interfaces 12, 7317−7325 (2020)

2. Hassan, M.S., Sapra, S. Materials Today Proceeding (10.1016/j.matpr.2020.03.170) (2020) 3. Hassan, M.S., Bera S., Gupta, D., Ray, S.K., Sapra, S. ACS Appl. Mater. Interfaces 11, 4074–4083

(2019). 4. Hassan, M. S., Jana, A., Gahlawat, S., Bhandary, N., Bera, S., Ingole, P. P., Sapra, S. Bull. Mater.

Sci. 42, 74 (2019).

Development of Integrated Technologies for Conversion of Industrial waste

CO2 to MeOH & other Value-added chemicals via Thermochemical Route:

Translation from Academic to Industry

Arjun Cherevotan,1,2 Jithu Raj1,2 and Sebastian C. Peter1,2*

1New Chemistry Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur,

Bangalore-560064 2School of Advanced Materials, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur,

Bangalore-560064

E-mail: [email protected], [email protected]

Two most imminent scientific and technological problems that the mankind is facing now, is that of

energy and climate. The energy production and utilization in modern society is mostly based on the

combustion of carbonaceous fuels like coal, petroleum and natural gas the combustion of which

produces CO2, which alters earth’s carbon cycle. 30 billion of tons of CO2 per year get emitted globally

as waste from the carbonaceous fuel burning and industrial sector, which if converted to valuable

chemicals have the potential to change the economy of the world. We, in our lab are trying to address

both issues and are keen upon translating our innovative technologies from the lab to the industrial and

commercial scale. We are capturing CO2 from industrial flue stream (of any composition) and

thermo-catalytically converting it to value added chemicals/fuels methanol, carbon-monoxide, methane,

dimethyl ether, C2-C5 & C5-C11 gasoline hydrocarbons. The end to end technology comprises

innovations in catalyst synthesis, reactor designs, hydrogen generation and product purification. MeOH

is one of the most attractive conversion product in the thermo-catalytic pathway which could not be

commercially realized yet due to problems of low catalytic conversion, limited conversion, energy

efficiency of the technology and most importantly high cost of hydrogen. Catalyst design is at the heart

of all these technologies and we are developing customized catalysts and reactor systems for targeted

product conversions as per the need of different industries. The catalysts have been synthesized through

extensive structure property relation study corroborating with 1st Principle DFT calculations. Advanced

CFD calculations are used to design energy efficient reactor systems. Nano structuring in the group 13

elements doped CZZ systems showed highly enhanced conversion and methanol selectivity. At present

we are scaling up the end-to-end process, the success of which might lead to opening of new directions

in CO2 conversion technology.

References 1. Peter, S. C. ACS Energy Lett. 3, 1557-1561 (2018).

2. Roy, S. Cherevotan, A. Peter & S. C. ACS Energy Lett. 3, 1938-1966 (2018).


Enhanced Photocatalytic Activity of Au Nanostars Decorated on Two Dimensional

Carbonaceous Nanosheets: Role of Plasmon Induced Hot Electron Generation

Ajay Kumar, Priyanka Choudhary, Kamlesh Kumar, Ashish Kumar and Venkata Krishnan*

School of Basic Sciences and Advanced Materials Research Center, Indian Institute of Technology Mandi, Kamand, Mandi

175075, Himachal Pradesh, India.

Email: [email protected]

For efficient utilization of solar energy in photocatalytic application, rational design and development of photocatalysts is

of paramount importance. The conventional problem of low light absorption, poor charge carrier separation and their

transfer in photocatalytic materials is the main bottleneck of this process.1-3 However, plasmonic energy conversion has

emerged as an attractive alternative to address these issues. The generation of hot electrons in plasmonic nanostructures

can play an important role in boosting the photocatalytic performance of semiconductor materials. In this work, Au

nanostars (Au NST) have been decorated on the surface of graphitic carbon nitride (GCN) and reduced graphene oxide

(RGO) 2D-2D nanosheets and their photocatalytic activity towards the degradation of organic pollutants and organic

reactions has been demonstrated under visible light illumination.4 The enhanced photocatalytic activity of the synthesized

nanocomposites towards both the applications could be attributed to surface plasmon resonance of Au NST and efficient

promotion of charge carriers’ separation and transfer due to the formation of Au NST-GCN-RGO interfacial contacts.

Finally, plausible mechanisms to explain the role of the photocatalyst for both the applications has been proposed. This

work could provide physical insights for future development of plasmon-enhanced photocatalysts.

References

1. Kumar, A., Reddy, K.L., Kumar, S., Kumar, A., Sharma, V., Krishnan, V., ACS Appl. Mater. Interfaces 10, 15565-15581

(2018).

2. Reddy, K.L., Kumar, S., Kumar, A., Krishnan, V., J. Hazard. Mater. 367, 694-705 (2019).

3. A., Kumar, K., Krishnan, V., Mater. Lett. 245, 45-48 (2019).

4. Kumar, A., Choudhary, P., Kumar, K., Ashish, K., and Krishnan, V., Manuscript submitted (2020).


Flattening the Perovskite with Redox Flip-flop Surface Rahul Majee, Quazi Arif Islam, Surajit Mondal and Sayan Bhattacharyya*

Department of Chemical Sciences, and Centre for Advanced Functional Materials, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur - 741246, India *Email for correspondence: [email protected] Flattening any ABO3 type perovskite into atomically thin two-dimensional nanosheets is an arduous task and in

this line A-site ordered BaPrMn1.75Co0.25O5+ (BPMC-0.25, = 0.06-0.17) double perovskite oxide has been

chemically metamorphosed into 4.1 nm thick nanosheets (NSs) with 5 unit cells stacked along c-axis. Secondly

the precise reversible alterations of the catalyst structure during redox processes is seldom observed and often

overlooked. By X-ray diffraction and transmission electron microscopy we have demonstrated such a flip-flop

structural reversibility at this NS surface while catalyzing the successive oxygen evolution and reduction

reactions (OER/ORR). The overall approach has larger implications as a bifunctional electrocatalyst at the air-

electrode of metal-air batteries and fuel cells. Our studies show that the oxygen deficient PrOx terminated layer

at the NS surface has flexible oxygen coordination of Pr3+ ions that promotes the redox processes. Under small

reversible electrochemical bias, PrO1.8 phase appear and disappear reciprocally at the NS surface, due to the

intake and release of oxygen, respectively. Although the underlying B-site cations are well-known active sites,

this is the first demonstration of A(Pr3+)-site cation influencing the activity by reversibly altering its oxygen

coordination. Furthermore to alleviate the limitations of electronic conductivity, the p-type BPMC-0.25 NSs are

engineered at room temperature with n-type nitrogen doped multi-walled carbon nanotube (NCNT) that show

significant enhancement in bifunctional oxygen electrocatalytic activity. The optimization of donor level by

charge transfer from the perovskite to NCNT is demonstrated to be a prodigious approach to facilitate the redox

oxygen activation. Proof of concept rechargeable Zn-air battery with BPMC containing 10wt% NCNT cathode

demonstrates the highest specific discharge capacity of 789.2 mA.h/gZn and cyclic stability for at least 85h at

current density of 5 mA/cm2.

Figure 1: (Left to right) TEM image of BPMC-0.25 NSs; Crystal structure representation of the structural

reversibility; Spatially connected NS/NCNT p-n heterojunction; Charge transfer to facilitate the redox oxygen

activation.


Engineering Polymer and Perovskite to Achieve High Performance and Stable

Solar Cells

Ritesh Kant Gupta1, Rabindranath Garai,2 Mohammad Adil Afroz,2 Parameswar Krishnan Iyer,1,2* 1Centre for Nanotechnology, Indian Institute of Technology Guwahati, Assam, India 2Department of Chemistry, Indian Institute of Technology Guwahati, Assam, India


Abstract: There has been an enormous increase in energy demand and use of the conventional energy

sources escalate environmental pollution further. This has increased the mandate for the exploration of

renewable energy sources. Solar energy is one of the most promising sources for the obvious fact that it

will be available for generations. Materials for absorbing the wavelength near infrared regions have already

been developed. Now the challenge remains to produce these materials in large scale at a very low cost and

thereafter large area stable devices for photovoltaic application has to be developed. Here, the microwave

synthesis of conjugated polymers for achieving high performance solar cell will be covered. Using this

technique large scale polymers can be synthesized with negligible batch to batch variation in few minutes.

Later, this material was further used to enhance the performance of the solar cell by a newly developed

device engineering with efficiency > 9%.

Nowadays, perovskite materials have also grown potential in the field of photovoltaics as the efficiency has

crossed 25%. Still, stability of the solar cell developed using perovskite materials remains a big challenge.

The reason for low stability of such devices are ion migration and moisture sensitivity which leads to trap

states. Here, the trap states passivation will be conveyed which not only increased the solar cell stability,

but also displayed enhanced performance of ~ 19%.


Stable Perovskite Semiconductors: From Halides to Chalcogenides

Vikash Kumar Ravi,1 Sajid Saikia,1 Shivam Yadav,1 Vaibhav Nawale,1 Parikshit Rajput,1 Seong

Hoon Yu,2 Dae Sung Chung2 and Angshuman Nag1*

1Department of Chemistry, Indian Institute of Science Education and Research (IISER Pune), Pune,

India. 2Department of Chemical Engineering, Pohang University of Science and Technology (POSTECH),

Pohang, Korea.


Lead halide perovskites have attracted tremendous research interest because of their extraordinary

optoelectronic properties. However, intrinsic instability of lead halide perovskites because of their ionic

nature still remains a major problem that needs to be tackled. Here, I will first discuss about how we

stabilized the CsPbBr3 nanocrystals against external environment by having a shell of ZnS around it.

The CsPbBr3/ZnS core/shell nanocrystals shows about 15 times increase in luminescence lifetime along

with ehnanced water and photostability. These types of core/shell structure will find its application for

more stable LEDs and photocatalysis.

Secondly, I will discuss about the chalcogenide perovskites, which are inherently more stable than its

halide counterparts. We have explored one such BaZrS3 chalcogenide perovskite nanocrystals having a

direct bandgap of 1.9 eV. These nanocrystals were synthesized by solid state synthesis having size of

around 50 to 60 nm and shows enhanced water and thermal stability. One problem that hindered the use

of these chalcogenide perovskites in thin film device fabrication is the lack of solution processability.

We have modified the surface of BaZrS3 nanocrystals to obtain colloidal dispersion, which was then

used for making field effect transistors (FET). The FET shows ambipolar properties with hole mobility

0.048 cm2V-1s-1 and electron mobility 0.017 cm2V-1s-1. This first report of solution processed

chalcogenide perovskite thin film with reasonable carrier mobility and strong optical absorption and

emission, is expected to pave the way for future optoelectronic devices of chalcogenide perovskites.

Halide perovskite:

Stability by surface modificationChalcogenide perovskite:

Inherently stable


Controllable Synthesis of Phosphorene Nanostructures for Efficient

Electrocatalysis Ranjith Prasannachandran,1 T. V. Vineesh1 and M. M. Shaijumon*1

1School of Physics, IISER Thiruvananthapuram, Maruthamala PO, Thiruvananthapuram, Kerala,

695551, India

E-mail: [email protected], [email protected]

Black phosphorus (BP), a unique 2D layered material, has generated considerable excitement in the rapidly

emerging field of 2D layered materials.[1] With its interesting physico-chemical properties, few-layered

black phosphorus has recently been explored as a promising electrocatalyst for hydrogen evolution reaction

(HER) and oxygen evolution reaction (OER). Controllable synthesis of mono/few-layered phosphorene

nanostructures with large number of electrocatalytically active sites and exposed surface area is important

to achieve significant enhancement in their electrocatalytic activity. Further, engineering BP through

various strategies such as functionalization, making heterostructures with transition metal dichalcogenides,

etc, have been shown to improve the electrocatalytic activity towards overall water splitting process. In this

work, we demonstrate a novel strategy for controlled synthesis and in situ surface functionalization of

phosphorene quantum dots (PQDs) using a single step electrochemical exfoliation process. The presence

of nitrogen containing groups enhances electro-catalytic activity for OER with exceptional stability.[2]

Further, we attempt to design strategies to fabricate 0D/2D heterostructures of few-layered phosphorene

and MoS2 nanosheets, under ambient condition, which exhibit bifunctional electrocatalytic activity for HER

and OER. The obtained results clearly illustrate the advantages of our unique approach, which will be

discussed along with some of the challenges faced in terms of material stability and scalability towards

realizing an overall water splitting system.

References

[1] A. Carvalho, M. Wang, X. Zhu, A. S. Rodin, H. Su, A. H. Castro Neto, Nat. Rev. Mater. 2016, 1, 16061.

[2] R. Prasannachandran, T. V. Vineesh, A. Anil, B. M. Krishna, M. M. Shaijumon, ACS Nano 2018, 12, 11511–11519.

Functionalized graphene for different energy applications

Palak,1 Chanderpratap Singh, Irin Cherian, Midhula Wilson and Amit Paul* 1Department of Chemistry, Indian Institute of Science Education and Research (IISER), Bhopal, India Email: [email protected], [email protected] Graphene has been extensively investigated in the field of energy storage and conversion because of its excellent electrical,

mechanical, and thermal properties. This “Wonder Material” exhibits high surface area, mesoporous characteristics along

with high intrinsic mobility and excellent electrical conductivity which makes graphene a promising material for adsorption,

fuel cell, battery and supercapacitor applications.1,2 The horizon of graphene-based nanomaterials can be further expanded

by modifying its chemical structure. Herein, I will present two works wherein graphene’s chemical structure has been

modified for different energy applications. The first work demonstrates synthesis of a conducting frame with sp2 and sp3

characteristics via thermal activation3 of a reduced graphene admixed with charcoal. The resulting nanomaterial possessed

exceptional long range-short range ordered morphology, excellent electrical conductivity, high surface area and ultra-

microporous structural properties. Owing to the unique characteristics, this nanomaterial demonstrated 534 F/g specific

capacitance at 0.2 A/g current density in 2 M H2SO4 electrolyte employing two-electrode cell assembly which is the highest

for any aqueous electrolyte systems so far. Furthermore, this nanomaterial delivered 90 Wh/kg energy density with extensive

cyclic stability of 94% for 10,000 cycles. Ultra-microporous frame of carbon nanomaterial had shown high adsorption

potential towards CO2 gas4 and ensured 7.78 mmol/g adsorption intakes at 273 K &1 bar. In the second work, reduced

graphene was modified further with amine and acid groups on the edges of sp2 sheets to bring both acid and base

characteristics. In a recent work, hydroxyl functionalized graphene have been shown as a proton conducting nanomaterial

utilizing hydroxyl groups for conduction.2 However, materials having low activation energy barrier for solid state proton

conduction are required for temperature invariant functioning of fuel cells.5 Notably, amine-acid modified graphene material

achieved very low energy barrier of 0.079 eV (lowest among all carbon nanomaterials) from 0.24 eV (in hydroxyl modifies

graphene2) with a high solid state proton conduction value of 3.29*10-3 S/cm at 95 °C and 95% relative humidity. The

material also provided a high specific capacitance value of 266 F/g at 0.5 A/g in three electrode assembly with 71%

capacitive retention. This material had shown 100 % cyclic stability for 10,000 cycles in aqueous media revealing its

superior supercapacitor property as well.

References

1. Singh, C., Mishra, A. K., & Paul, A., J. Mater. Chem. A 3, 18557-18563 (2015). 2. Singh, C., S, N., Jana, A., Mishra, A. K., & Paul, A., Chem. Commun. 52, 12661-12664 (2016). 3. Singh, C., & Paul, A., ACS Sustainable Chem. Eng. 6, 11367−11379 (2018). 4. Dura, G.; Budarin, V. L.; Castro-Osma J. A.; Shuttleworth, P.S.; Quek, S. C. Z.; Clark, J. H.; North, M.; Angew.

Chem. Int. Ed. 55, 9173 –9177 (2016). 5. Kang, D.W., Lee,K.A., Kang, M., Kim, J. M., Moon, M., Choe, J. H., Kim, H., Kim, W., Kim, J.Y. & Hong, C.

S., J. Mater. Chem. A 8, 1147–1153 (2020).

Role of 'Water-in-Salt' Type Electrolytes in tuning hydrogen

evolution reaction Anku Guha,# Nisheal M. Kaley, Jagannath Mondal, and Tharangattu N. Narayanan*

Tata Institute of Fundamental Research - Hyderabad, Sy. No. 36/P, Gopanapally Village,

Serilingampally Mandal, Hyderabad - 500107, India.

(Email: [email protected] or [email protected]) The role of ‘Water in salt’ type electrolytes has been extensively studied for battery application.

The effect of this kind of electrolyte is very limitedly explored for electrochemical hydrogen

evolution reaction (HER) though effect of supporting electrolyte such as Li+ ions in HER is

well studied in recent past. Most of the studies on the effect of supporting electrolytes is either

lacking of fundamental understandings of HER kinetics or limited to only noble transition

metals. Herein, we have unveiled the role of Li+ based ‘water in salt’ type electrolytes in tuning

the kinetics and thermodynamics of the HER of metals (both noble and non noble) and non

metals (CNTs) irrespective of counter ions (TFSI−, OTf−, Cl−, ClO4− and OH−), pH (0,7 and 13)

of the electrolyte by both experimentally and theoretically. It is observed that the HER activities

of metals such as Pt, Ir, and Pd are suppressed by increasing Li+ concentration whereas that of

Au, Fe, Ni and non metals like CNTs augmented with increasing Li+ concentration. Here the

tunability in the metal-hydrogen (M−H) bonding energy which is the only dictator of HER with

Li+ is experimentally and theoretically established, and the studies show that the tunability in

the HER properties of both noble, non-noble metals and CNTs can be achieved irrespective of

the pH and counter ions by tuning the M−H bond energy using Li+.

References:

1. Suo, L.; Borodin, O.; Gao, T.; Olguin, M.; Ho, J.; Fan, X.; Luo, C.; Wang, C.; Xu, K. Science. 2015, 350 (6263), 938–943.

2. Guha, A.; Narayanaru, S.; Narayanan, T. N. ACS Appl. Energy Mater. 2018, 1, 7116–7122.

3. Guha, A.; Kaley, N. M.; Mondal, J.; Narayanan, T. N. J. Mater. Chem. A 2020, DOI : 10.1039/c9ta12926j.

4. Borodin, O.; Self, J.; Persson, K. A.; Wang, C.; Xu, K. Uncharted Waters: Super-Concentrated Electrolytes. Joule 2020, 4 (1), 69–100.

5. Guha, A. and Narayanan T. N. J. Phys. energy. Submitted.

Magnetic tuning of electrocatalytic interface for sustained kinetic enhancement of

hydrogen evolution Jayeeta Saha, Ranadeb Ball, Chandramouli Subramaniam*

Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai, Maharashtra 400076,

INDIA

Email: [email protected]

Hydrogen is considered as cleanest and high specific energy density fuel source. Thus, the purpose is to produce maximum hydrogen gas by providing catalysts with lowest applied energy (overpotential, η). In direction, other than tuning the catalyst for the better electrocatalysis by reduce the η, another approach is to provide the energy in another form, like magnetic field. Here, we establish the involvement of mesoporous nanocarbon florets (NCF) based spinel Co3O4 nanocubes catalyst to increase the double layer charge transfer (400%) and decrease the charge transfer resistance (65%) in presence of magnetic field. Thus, the catalytic efficiency enhances (decrease of η by 20% and increase of j by 650%) by compacting the diffusion layer of electrode-electrolyte interface and enhancing the mass transport due to magnetization of magnetic catalyst. Along with this, the unique morphology of NCF helps to sustain the magnetization after removal of the magnet. The enhancement of size of the NCF due to the presence of surface magnetic catalyst assists to enhance the electrochemically active surface are by 12%, which reflects in the improved catalytic efficiency. By doing the energy balance calculation it is observed that the total energy saved by using a 300 mT magnet is 19% of its regular usage. References

1. A. Sundaresan, R. Bhargavi, N. Rangarajan, U. Siddesh, C. N. R. Rao, Phys. Rev. B -

Condens. Matter Mater. Phys. 2006, 74,161306. 2. W. Mtangi, F. Tassinari, K. Vankayala, A. Vargas Jentzsch, B. Adelizzi, A. R. A.

Palmans, C. Fontanesi, E. W. Meijer, R. Naaman, J. Am. Chem. Soc. 2017, 139, 2794. 3. F. A. Garcés-pineda, M. Blasco-ahicart, D. Nieto-castro, N. López, J. R. Galán-

mascarós, Nat. Energy 2019, 4, 519. 4. J. Saha, R. Ball, A. Sah, V. Kalyani, C. Subramaniam, Nanoscale 2019, 11, 13532. 5. J. Saha, S. Verma, R. Ball, C. Subramaniam, R. Murugavel, Small 2019, 1903334.


Kinetic Study of the photocharged Co-Bi modified BiVO4 for PEC water

oxidation

Sriram Kumar and Ashis Kumar Satpati*

Analytical Chemistry Division, Bhabha Atomic Research Centre Trombay, Mumbai-400085, India

Homi Bhabha National Institute, Anushaktinagar, Mumbai-400094, India

Corresponding Author email: [email protected]

Abstract

BiVO4 is the promising anode material for the solar harvesting due to its bandgap (~2.4 eV),

band alignment with the water oxidation band and high Solar to hydrogen efficiency (~9%)

[1].However, fast charge recombination, short hole diffusion and sluggish surface catalysis are

the main challenge of the commercial application. In this study we have incorporated the oxygen

evolution catalyst (OEC) Co-Bi to BiVO4 to enhance the surface OER kinetics [2, 3].

Photoelectrochemical (PEC) efficiency is improved by the photocharging of the BiVO4 and Co-

Bi modified BiVO4. The details kinetics study and electronic properties of the photoanodes are

investigated due in the course of the study. BiVO4 (BV) was coated on the FTO using spin

coating technique and the Co-Bi/BiVO4 heterojunction were synthesized by the photo-assisted

electrochemical deposition of the Co-Bi.

Figure 1. (A) SEM image of BV, (B) XRD patterns of the BV and Co-Bi modified BV and (C)

effect of photocharging on chopped light voltammetry of BV.

SEM images of BV shows the uniform coating of BV on FTO with granular shape. XRD spectra

confirm the synthesis of BV (JCPDS: 014-0688) with growth along the (121) direction. The

significant improvements in photocurrents are obtained from 0.96 mAcm-2 to 1.95 mAcm-2, with

103 % improvements upon Co-Bi incorporation. The photocurrents of the photoanodes were

(A) (B) (C)

enhanced by ~ 35% after photocharging treatment. The significant improvements in the

photocurrent are due to the improvements in the bulk and surface properties as investigated by

the electrochemical impedance spectroscopy and Mott-Schottky analysis. Further, electrode-

electrolyte interface kinetics has been investigated using the scanning electrochemical

microscopy (SEC) technique. The interfacial hole transfer rate constant of BV is 8.510-3 cm s-1

and is improved by ~28% upon Co-Bi modification. The hole transfer rate constant is further

improved by ~18% upon the photocharging.

References

1. F.F. Abdi, N. Firet, R. van de Krol, ChemCatChem, 5 (2013) 490-496.

2. C. Ding, J. Shi, D. Wang, Z. Wang, N. Wang, G. Liu, F. Xiong, C. Li, Physical Chemistry

Chemical Physics, 15 (2013) 4589-4595.

3. D. Xue, M. Kan, X. Qian, Y. Zhao,ACS Sustainable Chemistry & Engineering, 6 (2018)

16228-16234.

Sustainable synthesis of nanomaterial: Application for one pot multicomponent reactions Gunjan Purohit and Diwan S Rawat*

Block A, Department of Chemistry, University of Delhi, Delhi 110007, India


Nanocatalysis is a promising area that has attracted the attention of chemist over the years.1 A functionalized material with

nano- or submicro-dimension demonstrates significant and dramatic catalytic activity in comparison to their bulk counter

parts, due to the increased surface area and multiple catalytic centers and in turns fulfils the mandate of green chemistry.2,3

Increasing aspects of catalytic potential of nanocatalyst in the synthesis of heterocycles, we recently reported hierarchically

porous sheet-like copper aluminum mixed oxide (CuAl-MO) nanocatalyzed synthesis of substituted

pyrrolidines/piperidines.4 In another study we, displayed the catalytic potential of amine functionalized silica coated

magnetically recoverable palladium nanoparticles i.e. Pd@Co/C-SiO2-NH2 for the hydrogenation of nitro-

arenes/alkenes/alkynes.5 We also developed powdered wurzite phased copper indium sulphite nanocomposites i.e PW-

CIS500 for the sustainable synthesis of substituted imidazopyridines.6 In continuation to these exciting results, we designed

a unique copper/palladium based nanomaterial for various organic transformation reactions such as hydrogenations,

cycloisomerization reactions etc. providing better and greener results. Many important heterocycles are synthesized by

making use of this methodology e.g. benzofuran, substituted piperidines/pyrrolidines, imidazopyridines etc. The present

methodology has several advantages over the reported methods such as selectivity in product formation, high yields in short

reaction time, and follows green principles.

References 1. Polshettiwar, V., Luque, R., Fihri, A., Zhu, H., Bouhrara, M. & Basset, J, M. Chem Rev. 111, 3036 – 3075 (2011).

2. Anastas, P. T. & Allen, D. T. ACS Sustain. Chem. Eng. 4, 5820 (2016).

3. Polshettiwar, V. & Varma, R. S. Green Chem. 12, 743 – 754 (2010).

4. Purohit, G., & Rawat, D. S. ACS Sustain. Chem. Eng. 5, 19235 – 19245 (2019).

5. Purohit, G., Rawat, D. S. & Reiser, O. ChemCatChem. 12, 569 – 575 (2020).

6. Purohit, G., Kharakwal, A. & Rawat, D. S. ACS Sustain. Chem. Eng. 8, 5544 – 5557 (2020).

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Abstract

An electrochemical energy-storage cell, also known as a battery, is one of the best electrical

energy-storage devices available. There are types of technologies that come under this

category. Since its initiation, the lithium-ion battery has been used as a commercially viable

rechargeable battery. However, as the demand for energy-intensive applications grows in the

market, there is a requirement for an alternative energy-storage battery technology that can act

a good substitute for Li-ion batteries. The sodium-sulfur (Na-S) battery is a well-known large-

scale electrochemical storage option. The disadvantage of this particular battery technology is

its high operating temperature. Room-temperature sodium-sulfur (RT Na-S) batteries could

overcome these issues, but they have issues of their own. The rapid capacity decay is caused

by the “polysulfide shuttle” and by the low utilization of the active material that results from

the insulating nature of sulfur and the final discharge product. Moreover, the practical

performance remains far from theoretical mainly due to sluggish reaction kinetics, severe

volume change in sulfur during cycling, and low electronic conductivity of the active material,

which limits both their energy and rate characteristics. The practical room temperature sodium-

sulfur (RT-NaS) battery technology has a significant potential that can be exploited, and many

researchers like us are continually working to resolve the issues. So here, we conclude that by

the use of an optimized cathode scaffold which can suppress the polysulfide dissolution and

enhance the cell kinetics can make the RT-NaS battery practical. Further, in-detail studies are

necessary. Nevertheless, we believe that this work may somehow help in finding the new

directions to achieve high capacity and cyclability of RT-NaS battery.

Key Words: Room-temperature Sodium-sulfur batteries; Polysulfide, polysulfide shuttle,

sluggish reaction kinetics, volume change, cathode scaffold.

Room Temperature Sodium-Sulfur BatteriesAjit Kumar and Sagar Mitra,

Indian Institute of Technology (IIT) Bombay, MumbaiEmail: [email protected]

Poly(ionic liquid)–zinc polyoxometalate composite as a cathode for high-performance lithium–sulfur batteries

Mukesh Kumar,1 Debaprasad Mandal* and Tharamani C. Nagaiah*

Department of chemistry, IIT Ropar Rupnagar Punjab-140001, India Email: [email protected] Advance energy storage Li-S batteries are considered to be most promising next generation battery technology beyond

currently market dominating Li-ion batteries due to its high theoretical capacity (1675 mAh g-1), natural abundance and low

cost to support ever increasing energy demand.1 However practical implementation of Li-S batteries impeded by several

technical challenges such as insulating nature of active sulfur, large volume expansion and inherent polysulfide shuttling

results in a low columbic efficiency and fast capacity degradation.2 To tackle these issues here, we reported sandwich

polyoxometalate [WZn3(H2O)2(ZnW9O34)2]12(ZnPOM) over poly(1-vinyl-3(2-(2-methoxyethoxy)ethyl)imidazolium)

cation(PVIMo) matrix as a cathode catalyst for a high-capacity Li-S battery. The cationic polymer PVIMo held the

negatively charged polysulfide ions at the cathode and ZnPOM facilitated the reversible redox conversion of polysulfides

to sulfur and vice versa due to multi electron redox property and high structural stability.3 The synergistic effect between

PVIMo and ZnPOM resulted in outstanding initial discharge capacity of 1450 mA h g-1 at 0.5 C with high capacity retention

(97%), high coulombic efficiency (>98%) and a negligible capacity fading rate of 0.02% per cycle with a high areal loading

of 7.68 mg cm-2 and high areal capacity of 11.14 mA h cm-2 (70% sulfur). Quantitative estimation for the loss of sulfur after

of the charge–discharge cycles will be also discussed by EQCM, UV-Vis analysis and potentiometric titration .4

Scheme 1: Schematic representation of the composite interaction with LiPS during the charge–discharge process

References:

1. Y.J. Li, J.M. Fan, M.S. Zheng and Q.F. Dong, Energy & Environmental Science, 2016, 9, 1998-2004. 2. R. Kumar, J. Liu, J.Y. Hwang and Y.-K. Sun, Journal of Materials Chemistry A, 2018, 6, 11582-11605. 3 S. D. Adhikary, A. Tiwari, T. C. Nagaiah and D. Mandal, ACS applied materials & interfaces, 2018, 10, 38872-38879. 4. V. Singh, A. K. Padhan, S. D. Adhikary, A. Tiwari, D. Mandal and T. C. Nagaiah, Journal of materials chemistry A,

2019, 7, 3018-3023.

Towards Efficient Inorganic Catalysis: A Computational Roadmap

Tisita Das1* and Sudip Chakraborty2*

1Condensed Matter Physics, Harish-Chandra Research Institute (HRI), Allahabad 211019, India 2 Discipline of Physics, Indian Institute of Technology (IIT) Indore, Indore 453552, India


ABSTRACT: Hydrogen is inevitable for the quest of sustainable and green environment, while meeting the demand of

increased energy supply in the presently existing fossil fuel economy by maintaining reduced greenhouse effect.

Consequently there has been a worldwide effort to explore potential materials that could serve as suitable, cost competitive

and eco-friendly catalysts to generate hydrogen in an industrial scale. Amongst all the processes of H2 generation,

photocatalytic water splitting in presence of an inorganic catalyst provides the most sustainable route. Since lower

dimensional materials possess more reactive sites as compared to their bulk counterparts, it is expected to realize enhanced

catalytic activity when the material dimension is reduced. Density Functional Theory (DFT) based first-principles approach

serves as an ideal theoretical tool to complement the experimental findings on such electrochemical systems, which

accelerates the development of new inorganic catalysts. The approach is to focus on the free energies of the reaction

intermediates adsorbed on the surface. In this talk, I shall discuss the theoretical approach for enhanced Hydrogen (HER)

and Oxygen Evolution Reaction (OER) on a few specific systems studied recently by our group. The systems include: (a)

an early group-4 planar Transition metal (TM)

dichalcogenide viz. TiS2 monolayer1 - which

acts as bi-functional (HER and OER) catalyst

upon substitutional doping and vacancy creation

on the anionic site as point defect; (b) a novel

planar variety of TM oxides viz. 2D TiO2 HNS2

- with oxygen monovacancy shows promise in

HER while decreasing work function value; (c)

Ag-Ni nanocrystalline hetero-alloy3 which

gives Pt-like HER activity with only ~ 0.13 eV

of DGH value in 5% Ag doping concentration;

and (d) 72 single layered TM trichalcogenides,

where rigorous high throughput computational screening has been performed 4, where FeCS3, FeGeS3, MnSiS3 and NiSiS3

are predicted for optimum HER catalytic activity having DGH in the range < 0.1 eV. I shall end my talk with a brief overview

of our most recently published work on CO2 reduction5 as future outlook, as another way to attain sustainable environment.

References

1. Tisita Das, S. Chakraborty, R. Ahuja and G. P. Das, ChemPhysChem 20, 608-617 (2019).

2. Tisita Das, S. Chakraborty, R. Ahuja and G. P. Das, ACS Appl. Energy Mater. 2, 5074-5082 (2019).

3. R. Majee, A. Kumar, Tisita Das, S. Chakraborty, S. Bhattacharyya, Angewandte Chemie, 59, 2881 (2020).

4. P. Sen, K. Alam, Tisita Das, R. Banerjee, S. Chakraborty, J. Phys. Chem. Letters, 11, 3192 (2020)

5. S Shyamal, S Dutta, Tisita Das, S Sen, S Chakraborty, N Pradhan, J. Phys. Chem. Letters, 11, 3608 (2020)

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