photocatalytic reduction of carbon dioxide
TRANSCRIPT
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Area of Interest:
Designing efficient materials for
photocatalytic conversion of CO2
HARIPRASAD NARAYANAN
NATIONAL CENTRE FOR CATALYSIS RESEARCH
INDIAN INSTITUTE OF TECHNOLOGY, MADRAS
Photocatalytic Reduction of Carbon Dioxide
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Photocatalytic Reduction of Carbon Dioxide
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©2016 JCAPhttp://solarfuelshub.org/why-solar-fuels
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©2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv.Mater., 2015, 27, 1957–1963.
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Gaseous phase reduction
Liquid phase reduction or carbonate pathway
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Environmental Chemistry by Colin Baird , ©2012 W.H Freemanhttps://en.wikipedia.org/wiki/Carbon_dioxide
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NCurr. Opin. Biotechnol. 2010 Jun;21(3):298-310, © 2010 Elsevier
©2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
©2013 BASF
Adv.Mater., 2015, 27, 1957–1963.
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LEnergy Environ. Sci., 2016,9, 2177-2196 ©2016 The Royal Society of Chemistry
Environmental Chemistry by Colin Baird , ©2012 W.H Freeman
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Anal. Methods, 2013,5, 1086-1097
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Reaction pH 0 pH7 pH14
E0 (V vs NHE)
+0.169 -0.24 -0.65
+0.030 -0.39 -0.79
-0.071 -0.55 -0.89
-0.103 -0.51 -0.93
-0.199 -0.58 -1.02
-0.425 -0.888 -1.29
-0.103 -0.52 -0.93
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If the first electron transfer to the CO2 reduction
needs such a high overpotential up to -1.9 V vs NHE
at pH 0, then how would be the reduction reaction
taking place in the semiconductors with a reduction
potential far less than required?
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Energy Environ. Sci., 2016,9, 2177-2196 ©2016 The Royal Society of Chemistry
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Carbon Dioxide and Organometalics, Xiao-Bing Lu©2016 Springer
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Carbon Dioxide Radical Anion I
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Reaction Mechanisms in Carbon Dioxide Conversion ,Aresta, Michele, Dibenedetto, Angela,
Quaranta, Eugenio ©2016 Springer
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Catalyst modifications like doping, metal
deposition, use of sacrificial reagents etc. does
not change the position of conduction band
towards more negative. Then, how these
modifications give rises to more products yield
(marginal yield only) compared to the bare
photocatalytic material?
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Advances in CO2 conversion and utilization, Yun Hang Hu, 2010
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Sacrificial Reagents
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Reactive Oxygen Species
Photocatalysis and Water Purification by Pierre Pichat©2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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The new cobalt catalyst also splits water into hydrogen
and oxygen without creating the kind of reactive oxygen
molecules that can damage DNA or other processes
essential to continuing life. "I don't know why yet," Nocera
says. "That will be fun to figure out."
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Fate of insitu reduction products
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J. Phys. Chem. Lett., 2013, 4 (20), pp 3479–3483
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Reaction Pathways
Angew. Chem. Int. Ed. 2013, 52, 7372 – 7408©2013 WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim
Novel Materials for Carbon
Dioxide Mitigation
Technology, 1st Edition
©2013 Elsevier
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CARBON DIOXIDE REDUCTION OR ACTIVATION ?
Do we need to be concerned on the
activation of carbon dioxide?
or
Its subsequent reaction with hydrogen for
the formation of value added chemicals?
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