Innovations in Green Chemistry: Organics from Carbon

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6/6/2013

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Acknowledgement: This presentation was co-produced by the ACS Green Chemistry Institute.

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Next in the Green Chemistry Series: "Integrating Green Chemistry Efficiently in Education" Thursday, September 5, 2013 2pm EST

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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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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 CO2isopropanol

Clean GaAs (111) CO2HCO2H

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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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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

Make a “SHOUT OUT” to your friend, professor, co-worker or mother during an ACS Webinars Broadcast! For More Details:

www.acswebinars.org/shoutout

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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)

Join us and participate virtually in this session at the 17th Annual Green Chemistry & Engineering Conference For more information and free registration please visit

http://gcande.org/hybrid 39

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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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