1. Course on Carbon dioxide to Chemicals and Fuels
PRESENTATION - FIVE
24TH February 2014
On Line Course of NCCR
(Total Number of Projections for this Lecture is 20)
NCCR on Line L3

2. PHOTOELECTROREDUCTION OF CO2
Appealing Approach!
An important energy input contribution from light might be expected, thus diminishing electricity consumption
Principle
An Example
J.P. Collin & J.P. Sauvage, Coord. Chem. Rev. 93 (1989) 245

3. A study on photo-electro-reduction of CO2
Possible Mechanistic Route
By insitu-IR
Photovoltomogram, λ= 560 nm (0.5 mW \cm2)
J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249

4. Study on photo-electro-reduction of CO2
J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249
Metal islet catalysts deposited on a p-CdTe electrode in DMF-0.1 M TEAP/5% H20
Product analysis results for CO2 reduction on phthalocyanine/p-CdTe
MPc catalysts adsorbed on a p-CdTe electrode
in DMF-0.1 M TEAP/5% H20

5. Study on Photo-electro-reduction of CO2
Current-potential curves for trinuclear carbonyl catalysts
adsorbed on a p-CdTe electrode in DMF-0.1 M TEAP/5% H20.
Product analysis results for CO2 reduction on carbonyl/p-CdTc
Iron carbonyl is the best among the three carbonyls studied
J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249

6. Study on photo-electro-reduction of CO2
Current-potential curves for crown ether catalysts added to the electrolyte for a p-CdTe electrode in DMF-0.1 M TEAP/S% H20
Product analysis results
J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249

7. Catalytic shift (ΔE) For metal-phthalocyanine catalysts on p-CdTe
as a function of M-O bond energy
Catalytic shift (ΔE) times the CO faradaic efficiency for metal catalysts on p-CdTe as a function of M-O bond energy
J, O‘M. Bockris & J. C. Wass
Mater Chem Phys, 22 (1989) 249
ΔE values for CO production are linear

8. For trinuclear carbonyl catalysts on p-CdTe
Catalytic shift (ΔE)
J, O‘M. Bockris & J. C. Wass, Mater Chem Phys, 22 (1989) 249
For trinuclear carbonyl catalysts on p-CdTe
as a function of M-C bond energy

9. CARBON MANAGEMENT
Fertilization of open waters to increase primary production &
hence to absorb more carbon in fixed form
Disposal of captured carbon dioxide directly into oceanic waters
Injection of captured CO2 into sub-seabed geological formations

10. Barriers to wider implementation
CO2 sequestration
Barriers to wider implementation
High cost of capturing, processing, & transporting anthropogenic CO2
Incomplete understanding of reservoir processes
Underdeveloped monitoring & verification technologies
Unclear emissions trading regulations
Potential conflicts of interest between sequestration & EOR or natural gas recovery

11. CO2 Sequestration The technology is in its infancy and unproven
Public Perception
The technology is in its infancy and unproven
The technology is too costly
Not enough is known about the long-term storage of CO2
The capture and storage of CO2 are seen as being energy intensive
The option presents an enormous engineering and infrastructure challenge
It is not a long-term solution
Barriers can only be overcome by research and design
& effective demonstration of the technology

12. Perceptions: Large-Scale CO2 Utilization & Sequestration
Two big challenges
Reducing costs
Developing storage Reservoirs
Utilization scores on these two challenges but opportunities are limited
Utilization will play a major role in initial sequestration
Utilization will play a minor role for long term large scale sequestration

13. UTILIZATION Opportunities Help economics Estimates storage issues
Why large scale use of CO2 such a challenge?
Market sizes
Transportation costs
Product life times
Energy considerations

14. TRANSPORTATION COSTS Many production sources
CO2 expensive to transport well in small quantities.
Use sources of opportunities (process by products natural wells)
Example –US 1997 capacity for liquid CO2
9.7 million metric tons
93 plants
Largest 900 metric tons/day
Average 300 metric tons /day

15. WHAT HAS BEEN COVERED SO FAR
The electronic structure of Carbon dioxide

16. CHEMICAL REDUCTION OF CARBONDIOXIDE
ADDING HYDROGEN AND ELIMINATING WATER
M. A. Scibioh & B. Viswanathan,Proc. Indn. Natl. Acad. Sci., 70 A (3),

17. Electrochemical Reduction of CO2
The possible electrochemical Reactions and the corresponding potentials
E Delta G0 (Kcal/mol)
H2O to H2(g)+ 0.5O2(g)
CO2 + H2 to HCOOH
CO2 + H2O to HCOOH + 0.5O
CO2 + H2 to CO + H2O
CO2 to CO + 0.5O
CO2 + 3H2 to CH3OH + H2O `
CO2 + 4H2 to CH3OH + 2 H2O
CO2 + 2 H2O to CH3OH + 1.5O
CO2 + 2 H2O to CH4 + 2 O

18. Table : Sector-wise contribution of CO2 emissions
Sector Percent Contribution
Land use and forestry
Industry
Residential and commercial
Buildings
Transportation
Power
waste and waste water

19. Scheme.1.Chemical Transformations of CO2

20. Barriers for Further Progress
(1) the magnitude of environmental consequences,
(2) the economic costs of these consequences,
(3) options available that could help avoid or diminish the damage to our environment and the economy
(4) the environmental and economic consequences for each of these options
(5) an estimate of cost for developing the technology to implement these options
and (6) a complete energy balance which accounts for energy demanding steps and their costs.

21. Suggested Some References
1. A Beher, Carbon Dioxide Activation by Metal Complexes VCH, Weinheim (1988)
2. Catalytic Activation of Carbon Dioxide (ACS Symp Ser) (1988) 363
3. M. Aulice Scibioh and V.R. Vijayaraghavan, J. Sci. Indus. Res., 1998, 57,
4. M. Aulice Scibioh and B. Viswanathan, Proc. Indn. Natl. Acad.Sci., 70 A (3), 2004,
5. M. Aulice Scibioh and B. Viswanathan, Editor. Satoshi Kaneco, Japan, Photo/ Electrochemistry and Photobiology for Environment,Energy and Fuel, 2002, 1- 46, ISBN:
6. F. Bertilsson and H. T. Karlsson, Energy Convers. Mgmt Vol. 37,No. 12, pp , 1996
7. I. Omae, Catalysis Today 115 (2006) 3352
8. M. Gattrell, N. Gupta and A. Co, J. Electroanal Chem, 594, (2006),1-19.
9. Enzymatic and Model Carboxylation and Reduction Reaction for Carbon Dixoide Utilization (NATO ASF Ser C 314 (1990)
10. Electrochemical and Electrocatalytic Reaction of Carbon Dioxide (Eds B P Sullivan, K Krist and H E Guard) Elsevier Amsterdam (1993)
11. M M Halmann Chemical Fixation of Carbon Dixoide CRC Boca Raton (1993) D Walther Coord Chem Rev 79 (1987) 135.
12. P. G. Jessop, F. Jo, C-C Tai, Coordination Chemistry Reviews 248 (2004)

22. THE TOPIC THAT FOLLOWS IS DRY REFORMING OF CARBON DIOXIDE

23. Topics in Reforming of Carbon dioxide (1) what is this reaction and why this reaction? (2)what are the concurrent possible reactions? (3) The basic thermodynamics of the reaction (4) Catalyst systems that have been studied. (5) The rationale for the selection of catalysts