Biomass Derived Glycerol for Hydrogen Production

- A Sustainable Photocatalytic Method

INVITED SPEAKER
Prof.M.V.Shankar, CChem., FRSC (London)
Dept of Materials Science and Nanotechnology
YOGI VEMANA UNIVERSITY, Vemanapuram
Kadapa – 516 005, Andhra Pradesh
shankarnano@gmail.com

International Conference on
Emerging Trends in Catalysis (ETC-2020)
VIT, Vellore, Tamil Nadu 06-08 January 2020

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I. YVU, Nanocatalysis & Solar Fuels Research Laboratory

II. Role of biomass derivatives in photocatalysis to boost

H2 production & Platform chemicals

III.Nanocomposite photocatalyst for H2 production using

biomass derived glycerol

IV. Conclusions and future perspectives

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 Sir C.V.Raman Science Building
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 Central Research
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 RUSA Sponsored Infrastructure Facilities On-going: 32 nos.
www.yogivemanauniversity.ac.in
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Photocatalytic Materials for H2 Energy and Environment

Nanobiotechnology (with collaborators)

• Photoconversion device for Artificial Retina Applications (France)
• Anti-cancer treatment using nanostructured Materials
• In vivo & in vitro study using nanomaterial for autoimmune diseases
Organic Synthesis / Membrane Separation / Envtl.
• Selective organic synthesis using nanostructure catalysts
• Polymeric nanocomposites for membrane applications
• Defluoridation of drinking water 5
 Photocatalyst Rate of H2 Publication
production
µmol.h-1.g-1
CuO/TiO2 nanotubes 99.823 Chem. Commun. 49 (2013) 9443
Cu2O/TiO2 nanorods 50,339 Sol. Eng. Mat. Sol. Cells 136 (2015) 157
Ag2O/TiO2 nanotubes 55,766 Sol. Eng. Mat. Sol. Cells 154 (2016) 78
Bi2O3/TiO2 nanostructures 22,060 Indus. Eng. Chem. Res.57 (2018) 568
Ni(OH)2/TiO2 nanotubes 45,570 ACS Sus. Chem. Engg. 6 (2018) 3754
Cu-Ag/TiO2 nanotubes 56,600 J. Cat. 350 (2017) 226-239
CdS/ZnS core-shell 68,700 Int. J. Hydrog. Energy 43 (2018) 22315
CdS/NiO core-shell 19,949 Mat. Res. Bull. 101 (2018) 223
CdS/TiO2 core-shell 20,310 Mat. Res. Bull. 103 (2018) 122
Cu2S/TiO2 core-shell 41,600 Appl. Cat. B 254 (2019) 174
MWCNT/nano-TiO2 8,800 Int. J. Hydrog. Energy 43 (2018) 4036
CNT/TiO2 nanohybrid 2,134 Int. J. Hydrog. Energy 40 (2015) 1665

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Publications: SCI Journals/Books/Proceedings
Publications: 101 h-index: 29, Cumulative IF: 315, Citations: 4675+
1) Applied Catalysis B 254 (2019) 174 (I.F.14.229)
2) ACS Sustainable Chemistry & Engineering 6 (2018) 4036 (I.F.6.1)
3) Journal of Colloid and Interface Science 538 (2019) 83 (I.F. 6.361)
4) Materials Research Bulletin 101 (2018) 223 (I.F.2.44)
5) Ind. Eng. Chem. Res., 57 (2018) 568 (I.F.3.1)
6) ChemSusChem 10 (2017) 3588 (I.F.7.43)
7) Journal of Catalysis 350 (2017) 226 (I.F.7.35)
8) Solar Energy Materials and Solar Cells 146 (2016) 63 (I.F.5.33)
9 Nanoscale 7 (2015) 7849 (I.F.7.2).
10) Chemical Communications 49(2013) 9443 (I.F.6.86)
Patent(s) [CSIR-IICT- YVU R&D collaboration]
1) US Patent No. US US9776162 B2, 20171003.
2) India Patent No. 302246, 20181016.
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 Solar Energy for
Fuels & Chemicals

Prof.G.L.Ciamician
Science (1912)

 Selective
 Ambient temp.
 Atm. Pressure
 Lower concen.
 Utilize Sunlight
 Aq.-based solvent
Goal: Sustainable Energy, Environment and Chemicals production

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Photoelectrochemical
Water splitting
into H2 and O2

Fujishima and Honda

Nature (1971)

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 Hydrogen

Current Opinion in Green and Sustainable Chemistry 2019, 15:38–46 10

 Semiconductors with band gap between 2 to 3 eV. TiO2, ZnO etc.

 Conduction Band (CB) potential < 0.1 eV and Valence Band (VB)
potential > +2 eV, these charge carries involves red-ox reactions.

 Plenty of catalytic active sites.

 Non-corrosive under experimental conditions

Challenges:
(i) Efficiency (ii) Stability (iii) Recyclability (iv) Recycle industrial
waste chemicals.
Successful photocatalyst shall comprise properties of both
Semiconductor + heterogeneous catalyst + Type of sacrificial agent
1) Un-productive recombination of photo-excitons within bulk and
catalyst surface (~99%).

2) Absorbs small portion of the irradiated light. Inability to absorb

visible or UV - vis spectrum in solar light.

3) Band potential (CB and VB) alignment in composite material

and availability of fewer active sites on catalytic surface.

4) There is no one standardized reactor set-up/conditions

available to compare the materials performance across the
globe.

5) Solar light intensity varies based on geographical location and

light intensity of lamp decreases with usage.
Lakshmana Reddy et al., Environmental Chemistry Letters. 2018, 16, 765-796
  Crude glycerol (10% w/w)
in bio-diesel processes.

 Continuous supply is available

 Glycerol market by 2020 and

expected to reach
USD 2.52 million.

Composition of crude glycerol:

Methanol, fatty acid, methyl esters, monoglycerides, diglycerides
and unreacted triacyglycerols, trace metals.
Lakshmana Reddy et al., ACS Sustainable Chemistry & Engineering 2018, 16, 765-796
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Synthesis of Ni(OH)2 / TiO2 Nanocomposite

Hydrothermal Method
~ 2 g per batch

Wet-impregnation Method
~ 2 g per batch

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 Characterization – Morphology and size
TNT Ni(OH)2-TNT

TEM and EDX of Ni(OH)2-TiO2

nanotubes composite. 15
Lakshmana Reddy et al., ACS Sustainable Chem. Eng. 2018, 6,3754-3764.
 Characterization – optical property & life-time of
excitons

PL spectra of TNT and

UV-Vis DR spectra of Ni(OH)2/TNT composite
Ni(OH)2/TNT composite

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Photocatalytic reactor for H2 generation

 Quartz reactor – 180 mL

 5 Vol. % Crude-Glycerol
Water mixture
 Expt. Time:10 am to 3 pm
 Catalyst – 5 mg
 Solar Light intensity:
1,00,000 – 1,70,000 Lux
Gas Chromatograph for H2 quantification

 Off-line GC used for gas analysis

 Gas chromatograph equipped

with TCD detector

 Packed column (molecular

sieve-A)

 Nitrogen as carrier gas

 Sample injected 250 L

 Calibrated with std. H2 and

O2 gases

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Photocatalytic H2 fuel / biomass derived glycerol
Crude glycerol
Crude glycerol
NT-3 show 12 folds
higher than TNT

(a)Effect of
Ni loading,
(b)comparison with
pristine catalysts
(c)Stability in
Crude glycerol Pure glycerol crude glycerol and
(d)Activity in pure
Glycerol

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Glycerol vs. Crude glycerol - Cost benefit analysis

Cost of crude glycerol: (Rs. 25/L  $0.37/L)

Cost of pure glycerol : (Rs.1170/L  $18/L)

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Proposed reaction mechanism

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 Conclusions and Future perspectives

 Co-catalytic behaviour of Ni(OH)2 facilitated TiO2

nanotubes for enhanced H2 production.

 Demonstrated utilization of biomass derived crude

glycerol for H2 fuel generation.

 Solar energy conversion efficiency of 1.57 % and cost

of crude glycerol is ~40 folds less and beneficial.

 Work is in progress to examination of intermediates

generated during H2 generation.

 Tune the catalytic properties to achieve improved

efficiency in platform chemicals.

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Acknowledgements

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 Academic / Research Collaborations
Dr.M.Sathish, CSIR-CECRI, Karaikudi, INDIA
 Dr.Venkata Krishnan, IIT-Mandi, India
 Dr.M. Subrahmanyam and Dr.V. Durga Kumari, CSIR-IICT, Hyderabad, India
 Prof.G. Arthanareeswaran, NIT-Tiruchirapalli, INDIA
 Prof. Vishnu Shanker, NIT-Warangal, India
Prof.K.K. Cheralathan, VIT University, Vellore, India
 Prof.S. Balakumar, University of Madras, Chennai, INDIA
 Prof.B. Neppolian, SRM Research Institute, SRM University, INDIA
 Dr.S. Sakthivel, Dr.M. Karthik & Dr.S.Anandan, DST-ARCI, Hyderabad, INDIA
 Dr.P.Prathap, CSIR-NPL, New Delhi, INDIA
 Dr.Vadali V.S.S. Srikanth, Hyderabad Central University, INDIA
 Dr.Valerie Keller, CNRS-European Laboratory for Catalysis, FRANCE
 Dr.C. Madhava Reddy, Dr.L.Dakshayini & Dr.P.Vasu Govardhana Reddy, Yogi
Vemana University, INDIA 24
 Dr.M. Sathish
Sr.Scientist
CSIR-CECRI
Karaikudi

Dr.M. Subramanyam, Dr.V. Durga Kumari, Ex-Emeritus Scientists,

CSIR – Indian Institute of Chemical Technology, Hyderabad

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