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1 We will start momentarily at 2pm ET Download the presentation and slides ONE WEEK after the webinar: Contact ACS Webinars at 1 Have Questions? Use the Questions Box! Or tweet using #acswebinars Download the presentation and slides ONE WEEK after the webinar: Contact ACS Webinars at 2 1

2 Acknowledgement: This presentation was co-produced by the ACS Green Chemistry Institute. For more information please visit 3 Next in the Green Chemistry Series: "Integrating Green Chemistry Efficiently in Education" Thursday, September 5, pm EST 4 2

3 Global Supplies for Chemical Feedstocks in the 21 st Century Tuesday, June 18, 2013, 7:00 p.m. EDT (-4 GMT) Join us and participate virtually in this session at the 17 th Annual Green Chemistry & Engineering Conference For more information and free registration please visit 5 Fan of the Week TM How has ACS Webinars benefited you? making chemistry fun. I have been a chemist for nearly 50 years and have never enjoyed the subject as much as I have with your [ACS] webinars. Dr. Clifford Schoff Consultant for PPG Industries, Inc. Be a featured fan on an upcoming webinar! Write to acswebinars@acs.org 6 3

4 If you enjoy ACS Webinars every Thursday please support the program! ACS Network (search for group acswebinars) Find the many benefits of ACS membership! 7 Make a SHOUT OUT to your friend, professor, co-worker or mother during an ACS Webinars Broadcast! For More Details: 8 4

5 Q: Hungry for a brain snack? A: on TM Feeling short on time? ACS Webinets are 2 minute segments that bring you valuable snippets from some of our most popular full TM length ACS Webinars See all of our ACS Webinets on YouTube at TM 9 Upcoming ACS Webinars 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, 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 acswebinars@acs.org 10 5

6 ACS WEBINARS March 28, 2013 Innovations in Green Chemistry: Organics from CO 2, Sunlight and Water Dr. Joseph Fortunak Howard University Dr. Andrew Bocarsly Princeton University Download the presentation ONE WEEK after webinar: Co-Produced with the ACS Green Chemistry Institute Organics from CO 2, Sunlight and Water Innovations in Green Chemistry 6

7 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 This photocopy was prepared by Robert A. Rohde for Global Warming Art ( 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 CO 2 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: CO 2 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 CO 2 into methanol, which is a fuel. What is your answer to this problem A, B or C? 7

8 Before we consider your answers we need one more piece of information: A GigaWatt Coal Fired Power Plants Generate 1,000 lbs. of CO 2 per SECOND! On hearing this Student A responded, No one can use that much Tupperware! Sequestration Schematic diagram of possible CCS systems Fuels 93% CO 2 Mitigation SRCCS Figure TS-1 7% Polymers, Solid-State Products 8

9 How About Electrochemical Conversion? Turn CO 2 into something you can sell as a fuel! Counting the Cost If 1 Mole of CO 2 is converted: 3.0eV photon CO 2 reduction kinetics 0.57 Moles CO 2 170kJ/mole (1.4V) According to the US DOE a gas fired power plant generates 1135 pounds of CO 2 /MWH (0.4V) H 2 O O 2 kinetics CH 3 OH + 3/2O Moles CO Moles Consumed 1.82 Moles Net Formed! 1.6eV 2.25 Moles CO 2 690kJ/mole 6e - /6H + (1.2V 6e-) CO 2 + 2H 2 O 9

10 The Catalyst: Pyridinium N + H The Catalyst: Aromatic Amines Start Reduction add CO 2 methanol 10mM pyr, under Ar and pyr. 10

11 Overview of Mechanism CO 2 CO 2 Formic Acid (HCOOH) HCOOH Formaldehyde (HCOH) 2HCOH MeOH + HCOOH 2 2 N + H. N H 2 2 N + H. N H 2 2 N + H. N H p-gap MeOH Evolving Cell CO 2 + 6e - + 6H + CH 3 OH + H 2 O ph 5.2, 10mM pyridine 465nm 11

12 The Liquid Light Process Water e - e - e - 2H 2 O 4H + + 4e - + O 2 Renewable Energy Source CO 2 + xh + + xe - product Waste CO 2 Product Extraction Chemicals & Fuels Highlights * Abundant cathode materials * Efficient and selective catalysts * Low cell voltages (energy efficient) * Stability CO 2 Generating Source Formic Acid System Scale-Up Currently producing target chemicals at grams/day with product concentration streams > 3% and CD > 100 ma/cm 2 and 1000 hr stability testing, now scaling up to kg/day over the next year. 12

13 A Three Cell Stack for Formate Production Solar Fuel is Here! Solar Panel Provided By and 13

14 Which of these C 1 compounds has the best production cost to market price ratio when made electrochemically from CO 2? 1. Carbon Monoxide 2. Formic acid 3. Formaldehyde 4. Methanol P-GaAs: The Surface Counts Dark Light+catalyst Photocatalytic CO 2 reduction GaAs (111) + Pt particles CO 2 isopropanol Clean GaAs (111) CO 2 HCO 2 H 14

15 Product Branching Pt/GaAs(111) Faradaic Efficiency, % Catalyst Light source Formic acid Acetic acid Acetone 2-Propanol n-butanol Pyridinium HgXe ~20 13 C Labeled Products by Mass Spec 15

16 Acknowledgement Research Funding Advancing CO 2 Chemistry 16

17 ACS WEBINARS March 28, 2013 Innovations in Green Chemistry: Organics from CO 2, Sunlight and Water Dr. Joseph Fortunak Howard University Dr. Andrew Bocarsly Princeton University Download the presentation ONE WEEK after webinar: Co-Produced with the ACS Green Chemistry Institute Make a SHOUT OUT to your friend, professor, co-worker or mother during an ACS Webinars Broadcast! For More Details:

18 Acknowledgement: This presentation was co-produced by the ACS Green Chemistry Institute. For more information please visit 35 Next in the Green Chemistry Series: "Integrating Green Chemistry Efficiently in Education" Thursday, September 5, pm EST

19 Stay Connected ACS Network (search for group acswebinars) LinkedIn (search group for acswebinars) Contact ACS Webinars at 37 Upcoming ACS Webinars 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, 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 acswebinars@acs.org 38 19

20 Global Supplies for Chemical Feedstocks in the 21 st Century Tuesday, June 18, 2013, 7:00 p.m. EDT (-4 GMT) Join us and participate virtually in this session at the 17 th Annual Green Chemistry & Engineering Conference For more information and free registration please visit 39 If you enjoyed this ACS Webinar today please support the program! ACS Network (search for group acswebinars) Find the many benefits of ACS membership! 40 20

21 ACS Webinars does not endorse any products or services. The views expressed in this presentation are those of the presenter and do not necessarily reflect the views or policies of the American Chemical Society. Contact ACS Webinars at 41 Upcoming ACS Webinars 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, 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 acswebinars@acs.org 42 21

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