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Global Supplies for Chemical Feedstocks in the 21st Century Tuesday, June 18, 2013, 7:00 p.m. EDT (-4 GMT)
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Upcoming ACS Webinars™ www.acswebinars.org Thursday, June 13, 2013
Barrels of Chemistry: Decoding How Oak Affects Wine Flavor Dr. Susan Ebeler, Professor of Enology, University of California, Davis Dr. Sara Risch, Director of R&D, Popz Europe
Thursday, June 20, 2013
2013 Chemical Entrepreneurship Series: Building a Successful Social Enterprise Dr. Teresa Smith, Founder, Dreams for Change Dr. Stephen Conroy, Professor of Economics, University of San Diego
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ACS WEBINARS™ March 28, 2013 Innovations in Green Chemistry: Organics from CO2 , Sunlight and Water
Dr. Joseph Fortunak Howard University
Dr. Andrew Bocarsly Princeton University
Download the presentation ONE WEEK after webinar: http://acswebinars.org/organics-from-carbon-dioxide Co-Produced with the ACS Green Chemistry Institute
Organics from CO2 , Sunlight and Water Innovations in Green Chemistry
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Prof. Arrhenius in 1896 On the Influence of Carbonic Acid in the Air upon the Temperature of the Ground Svante Arrhenius Philosophical Magazine and Journal of Science Series 5, Volume 41, April 1896, pages 237-276.
This photocopy was prepared by Robert A. Rohde for Global Warming Art (http://www.globalwarmingart.com/) from original printed material that is now in the public domain. Arrhenius’s paper is the first to quantify the contribution of carbon dioxide to the greenhouse effect (Sections I-IV) and to speculate about whether variations in the atmospheric concentration of carbon dioxide have contributed to long-term variations in climate (Section V). Throughout this paper, Arrhenius refers to carbon dioxide as “carbonic acid” in accordance with the convention at the time he was writing. Contrary to some misunderstandings, Arrhenius does not explicitly suggest in this paper that the burning of fossil fuels will cause global warming, though it is clear that he is aware that fossil fuels are a potentially significant source of carbon dioxide (page 270), and he does explicitly suggest this outcome in later work.
A Story of Three Princeton Undergrads (The Tupperware ® Problem) • Student A: Prof. Coates at Cornell has developed very interesting chemistry for reacting CO2 with nature products found in lemon to make a polymer with excellent properties as a plastic. So we can make Tupperware from it! • Student B: CO2 can be reduced to elemental carbon (carbon black) and this is needed for making tires. • Student C: We can do your chemistry Professor Bocarsly, and convert CO2 into methanol, which is a fuel.
What is your answer to this problem A, B or C?
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Before we consider your answers we need one more piece of information:
A GigaWatt Coal Fired Power Plants …
Generate 1,000 lbs. of CO2 per SECOND!
On hearing this Student A responded, “ No one can use that much Tupperware!” Schematic diagram of possible CCS systems
Sequestration
SRCCS Figure TS-1
Fuels
93%
CO2 Mitigation
7% Polymers, Solid-State Products
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How About Electrochemical Conversion? Turn CO2 into something you can sell as a fuel!
Counting the Cost If 1 Mole of CO2 is converted: CO2 reduction kinetics 3.0eV photon
0.57 Moles CO2 ≥170kJ/mole (1.4V) (0.4V)
H2O O2 kinetics CH3OH + 3/2O2
1.6eV
According to the US DOE a gas fired power plant generates 1135 pounds of CO2/MWH 2.82 Moles CO2 –1.00 Moles Consumed 1.82 Moles Net Formed!
2.25 Moles CO2 6e-/6H+ 690kJ/mole (1.2V•6e-) CO2 + 2H2O
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The Catalyst: Pyridinium
N
+
H
The Catalyst: Aromatic Amines
Start
Reduction add CO2
methanol
10mM pyr,
under Ar
and pyr.
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Overview of Mechanism
HCOOH
2HCOH
Formic Acid (HCOOH)
Formaldehyde (HCOH)
CO2
CO2
2
2 N H
+
.
2
2
N
N
H
H
+
MeOH + HCOOH
.
2
2
N
N
H
H
+
. N H
p-GaP MeOH Evolving Cell CO2 + 6e- + 6H+ CH3OH + H2O pH 5.2, 10mM pyridine
465nm
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The Liquid Light Process Highlights
Renewable Energy Source ee-
Water
2H2O 4H+ + 4e- + O2
e-
xH+
CO2 + + xe product
* Abundant cathode materials Chemicals & Fuels
Product Extraction
* Efficient and selective catalysts * Low cell voltages (energy efficient) * Stability
Waste CO2 CO2 Generating Source
Formic Acid System Scale-Up
Currently producing target chemicals at grams/day with product concentration streams > 3% and CD > 100 mA/cm2 and 1000 hr stability testing, now scaling up to kg/day over the next year.
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A Three Cell Stack for Formate Production
Solar Fuel is Here! Solar Panel Provided By and
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Which of these C1 compounds has the best production cost to market price ratio when made electrochemically from CO2? 1. 2. 3. 4.
Carbon Monoxide Formic acid Formaldehyde Methanol
P-GaAs: The Surface Counts Dark
Light+catalyst
Photocatalytic CO2 reduction
GaAs (111) + Pt particles CO2isopropanol
Clean GaAs (111) CO2HCO2H
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Product Branching Pt/GaAs(111)
Faradaic Efficiency, % Catalyst
Light source
Formic acid
Acetic acid
Pyridinium
HgXe
14
10
13C
Acetone 2-Propanol n-Butanol 7
50
~20
Labeled Products by Mass Spec
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Acknowledgement
Research Funding
Advancing CO2 Chemistry
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6/6/2013
ACS WEBINARS™ March 28, 2013 Innovations in Green Chemistry: Organics from CO2 , Sunlight and Water
Dr. Joseph Fortunak Howard University
Dr. Andrew Bocarsly Princeton University
Download the presentation ONE WEEK after webinar: http://acswebinars.org/organics-from-carbon-dioxide Co-Produced with the ACS Green Chemistry Institute
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Acknowledgement: This presentation was co-produced by the ACS Green Chemistry Institute.
For more information please visit http://bit.ly/AcsGCI 35
Next in the Green Chemistry Series: "Integrating Green Chemistry Efficiently in Education" Thursday, September 5, 2013 2pm EST
http://bit.ly/13nBSc6
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Upcoming ACS Webinars™ www.acswebinars.org Thursday, June 13, 2013
Barrels of Chemistry: Decoding How Oak Affects Wine Flavor Dr. Susan Ebeler, Professor of Enology, University of California, Davis Dr. Sara Risch, Director of R&D, Popz Europe
Thursday, June 20, 2013
2013 Chemical Entrepreneurship Series: Building a Successful Social Enterprise Dr. Teresa Smith, Founder, Dreams for Change Dr. Stephen Conroy, Professor of Economics, University of San Diego
Contact ACS Webinars™ at
[email protected]
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Global Supplies for Chemical Feedstocks in the 21st Century Tuesday, June 18, 2013, 7:00 p.m. EDT (-4 GMT)
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Upcoming ACS Webinars™ www.acswebinars.org Thursday, June 13, 2013
Barrels of Chemistry: Decoding How Oak Affects Wine Flavor Dr. Susan Ebeler, Professor of Enology, University of California, Davis Dr. Sara Risch, Director of R&D, Popz Europe
Thursday, June 20, 2013
2013 Chemical Entrepreneurship Series: Building a Successful Social Enterprise Dr. Teresa Smith, Founder, Dreams for Change Dr. Stephen Conroy, Professor of Economics, University of San Diego
Contact ACS Webinars™ at
[email protected]
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