innovations in green chemistry: organics from carbon ... · 17th annual green chemistry &...

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Acknowledgement:

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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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Innovations in Green Chemistry:

Organics from CO2 , Sunlight and Water

Download the presentation ONE WEEK after webinar:


ACS WEBINARS™ March 28, 2013

Co-Produced with the ACS Green Chemistry Institute

Dr. Joseph Fortunak

Howard University Dr. Andrew Bocarsly

Princeton University


Innovations in Green Chemistry

6/6/2013

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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?

6/6/2013

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Before we consider your answers we need one more piece of information:

Generate 1,000 lbs. of CO2 per SECOND!

A GigaWatt Coal Fired Power Plants …

On hearing this Student A responded, “ No one can use that much Tupperware!”

Schematic diagram of possible CCS systems

SRCCS Figure TS-1

CO2 Mitigation

Sequestration

Polymers, Solid-State Products

Fuels

7%

93%

6/6/2013

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How About Electrochemical Conversion?

Turn CO2 into something you can sell as a fuel!

Counting the Cost

CO2 + 2H2O

CH3OH + 3/2O2

H2O O2 kinetics

CO2 reduction kinetics According to the US DOE a gas fired power plant generates 1135 pounds of CO2/MWH

2.25 Moles CO2

If 1 Mole of CO2 is converted:

0.57 Moles CO2

2.82 Moles CO2

–1.00 Moles Consumed 1.82 Moles Net Formed!

690kJ/mole (1.2V•6e-)

≥170kJ/mole (1.4V)

(0.4V)

1.6eV

3.0eV photon

6e-/6H+

6/6/2013

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N+

H

The Catalyst: Pyridinium

The Catalyst: Aromatic Amines

Start Reduction add CO2 methanol

10mM pyr, under Ar and pyr.

6/6/2013

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Overview of Mechanism

CO2

Formic Acid

(HCOOH)

HCOOH

Formaldehyde

(HCOH)

CO2 2HCOH

MeOH + HCOOH

N +

H

N

H

. 2 2

N +

H

N

H

. 2 2

N +

H

N

H

. 2 2

p-GaP MeOH Evolving Cell

CO2 + 6e- + 6H+ CH3OH + H2O pH 5.2, 10mM pyridine

465nm

6/6/2013

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The Liquid Light Process

Renewable Energy Source

Waste CO2

CO2 Generating Source

Water

CO2 + xH+ + xe-

product

2H2O 4H+ + 4e- + O2

e- e-

e-

Product Extraction

Chemicals & Fuels

* Abundant cathode materials * Efficient and selective catalysts * Low cell voltages (energy efficient)

* Stability

Highlights

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.

Formic Acid System Scale-Up

6/6/2013

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A Three Cell Stack for Formate Production

Solar Panel Provided By

and

Solar Fuel is Here!

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Which of these C1 compounds has the best production cost to market price ratio when made electrochemically from CO2?

1. Carbon Monoxide

2. Formic acid

3. Formaldehyde

4. Methanol

P-GaAs: The Surface Counts

GaAs (111) + Pt particles

CO2isopropanol

Clean GaAs (111)

CO2HCO2H

Dark

Photocatalytic CO2 reduction

Light+catalyst

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Faradaic Efficiency, %

Catalyst

Light

source

Formic

acid

Acetic

acid

Acetone

2-Propanol

n-Butanol

Pyridinium

HgXe

14

10

7

50

~20

Product Branching

Pt/GaAs(111)

13C Labeled Products by Mass Spec

6/6/2013

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Acknowledgement

Research Funding

Advancing CO2 Chemistry

6/6/2013

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Innovations in Green Chemistry:


Download the presentation ONE WEEK after webinar:


ACS WEBINARS™ March 28, 2013

Co-Produced with the ACS Green Chemistry Institute

Dr. Joseph Fortunak

Howard University Dr. Andrew Bocarsly

Princeton University

34

Make a “SHOUT OUT” to

your friend, professor, co-worker or mother during an ACS Webinars Broadcast!

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6/6/2013

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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

36

6/6/2013

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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

If you enjoyed this ACS Webinar today…

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40

Find the many benefits of ACS membership!

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