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“Solar energy to fuels If a leaf can do it we can do it". Lee Kuan Yew NTU Lecture 10 th November 2008 James Barber Imperial College London

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Page 1: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

“Solar energy to fuelsIf a leaf can do it we can do it".

Lee Kuan Yew NTU Lecture10th November 2008

James BarberImperial College London

Page 2: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Mean Global Energy Consumption Rate

4.52

2.7 2.96

0.286

1.21

0.2860.828

0

1

2

3

4

5

TW

Oil Coal Biomass NuclearGas Hydro Renew

Total: 14TW U.S.: 3.3TW

Over 85% from fossil fuel

Page 3: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Map of the world based on population

From M. Newman

Page 4: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Map of the world based on energy consumption

From M. Newman

Page 5: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction
Page 6: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

“2H2” + CO2 (CH2O)Fuel

(Organic molecules)

But why not do what the leaf does?

Page 7: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

But needs H2 -Where does it come from?

Page 8: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

2H2O O2+ “2H2”

Solar Energy

From Water

Page 9: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

2H2O O2+ “2H2”

Solar Energy

“2H2” + CO2 (CH2O)Organic

molecules

Two basic reactions of photosynthesis

Page 10: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Macroscopic Reaction Vessel

2H2O O2 + 4H+ + 4eSunlight

Organic moleculeof life

+CO2

Page 11: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction
Page 12: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

1000 millions years to producefossil fuels and used in ~ 1000 years

0rOne year of fossil fuel consumption =one million years of photosynthesis

5 Billion Year Clock

Page 13: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Global Photosynthesis “The Engine of Life”

Page 14: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

2H2O 4H+ + 4e CH2OOrganicmolecules

CO2

CO2

O2

O2

Solar Energy(100,000 TW)

photosynthesis

respiration biomassfood

fossil fuelscombustion

light reactions dark reactions

Biology adopted the perfect solution to the energy problem

EnergyDecreased entropy

& heat 200 TW

0.2% efficiency

“Cyclic”

Page 15: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

2H2O O2+ “2H2”

Solar EnergyLight reactions

“2H2” + CO2 (CH2O)Organic

molecules

Dark reactions

Two basic reactions of photosynthesis

Page 16: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction
Page 17: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Thylakoid membranes(Light reactions)

Stroma(Dark reactions)

Page 18: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Photosynthetic efficiency

Lucky to get 2% dry matter and 0.5% starch/sugarwith inputs

Page 19: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction
Page 20: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Brazil (sugar)Bioenergy 30% of

total energy

~50% of cars sold in 2005were “Flex-Fuel” vehicles

able to use ethanol andpetrol

USA (corn) 6 million carsable to use E85

But only~2% of fuel

Page 21: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction
Page 22: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Miscanthus

5 tons of bioethanol/acre to be competitive at present(i.e. 5:1 conversion)

Page 23: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

~ 30% of the US energy requirements

2005 USDA/DOE Report

Currently ~ 3%

Page 24: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

But need solar energy conversion at 10% or better

The big loss factor

Page 25: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

2H2O 4H+ + 4e Organicmolecules

CO2

CO2

O2

O2

Solar Energy

photosynthesis

respirationbiomass

food fossil fuelscombustion

light reactions dark reactions

Hydrogen

Hydrogenase

For high efficiency of energy conversion use the front end of photosynthesis“Light Reactions”

Page 26: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Solar Land Area Requirementsat 10% efficiency

6 Boxes at 3.3 TW Each

Page 27: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Ni-Fe typehydrogenase

Fe-S typehydrogenase

Page 28: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Hydrogenase

H2O Organic substrates

Hydrogen

(CH20)n

e/H+O2

green algaChlamydomonas

Page 29: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

2H2O 2H2

O2

O2

Solar Energy (100,000TW)

EnergyTotal global (14TW)

Liquid fuel

One hour of solar =annual global energy consumption

H2/O2/H2O cycle driven by solar energy

The Perfect Solution“Cyclic”

+CO2

The Artificial Leaf

Page 30: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

2H2O O2+ “2H2”

Solar EnergyLight reactions

The Water Splitting Reaction

Page 31: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

5 Billion Year Clock

Big Bang ofEvolution

H2O splitting

Oxygenic atmosphere&

Ozone layer

Page 32: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Photosystem II (PSII) is the enzymefound in plants, algae and cyanobacteria

which uses solar energy to split water into molecular

oxygen and reducing equivalents

Page 33: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

0

-1

+1

P680+

P680*Pheo-

PQA

PQB

RedoxscaleeV

P680+ is highly oxidisingEm ~ 1.3eV at pH 7

Tyrz (YZ)

H2O

Red.

Oxid.

Electron transfer in Photosystem II

H+

Page 34: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Water splitting reactionis a four photon process

2H2O + 2PQ O2 + 2PQH2Light (4hv)

PSII

Page 35: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

+

+

+

2

S-state cycle – Kok & Joliot

dark stable state

Page 36: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Oxygen emission induced by flashesJoliot & Kok ~1969

Page 37: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Photosystem II (PSII)

Water splitting rapid turnover of D1“a repair process”

Page 38: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

From Black Boxto

Atomic Resolution

SPEM

EC X-ray

PSII

1994

1995

1998

2001

2004

Plant PSII

Cyanobacterial PSII

Page 39: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Mn4CaO4

Photosystem Two: The water splitting enzyme

2H2O O2 + 4e + 4H+4hv

Ferreira et al Science 2004

Page 40: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Active Branch Protective Branch

Page 41: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Lumenal view of PSII monomer within the dimer

Page 42: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Oxygen Evolving CentreAnomalous diffraction for Mn (1.89A) and Ca

(2.25A)

bicarbonate?

Ferreira et al Science 303(2004)1831-1838

Page 43: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Water Splitting-Oxygen Evolving Catalytic Site

A344

Page 44: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction
Page 45: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Cubane-like Mn3CaO4 cluster linked to a 4th Mn by a mono-μ-oxo bond

6 + 1 Amino acid ligands5 + 1 D1 protein1 CP43

Page 46: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Diagrammatic representationof the water splitting

centre

Page 47: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

CaO

O O

MnIV MnIV

O

MnIVMnV

O

OHighly electrophilic oxo (or oxyl radical)

S4

Nucleophilic attackH H Cl

Page 48: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

a) hv

b) e-

c) e-

C60-Por-Bi-PhOH

Biomimetic Systems

Tom Moore andcolleagues

ASU

Page 49: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

From Natural

A Q Q B

P 680

O

Mn

Mn

Tyr

Acceptor

N

EtO 2 C

NH

O

NN ON N

N NO OO

Me Me

Me

MnMn

Ru

NN

N

NN

to

Photosynthesis

Artificial

Hammerstrom & StyringU. of Uppsala

Page 50: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Fe

O

BOH

Design of an artificial water splitting system

H

MnIVMnIVMnIVMnV

O

OCa

O

OO

Cl

O

Daniel NoceraMIT

Page 51: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

2H2O 2H2

O2

O2

Solar Energy

EnergyTotal global

Carbon basedfuels

The Artificial Leaf

+CO2

Page 52: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

RuBisCO +H2O

Calvin Cycle

Page 53: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Crystal structure of RuBisCo isolated from spinach

Page 54: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Leonardo’s Dream

Page 55: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

2H2O 2H2

O2

O2

Solar Energy (100,000TW)

EnergyTotal global (14TW)

“If a leaf can do it we can do it”

“Its only chemistry”

One hour of solar =annual global energy consumption

EnergyTotal global

(14TW)

Solar Energy (100,000TW)O2

O2

2H2O 2H2

The ArtificialLeaf

+CO2Liquid fuel

Our Dream

Page 56: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction
Page 57: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

Jules Verne’s Dream (1875)

“I believe that water will one day be used as a fuel, because the hydrogen and oxygen which constitute it, used separately or together, will furnish an inexhaustible source of heat and light. I therefore believe that, when coal deposites are oxidised, we will heat ourselves by means of water. Water is the fuel of the future”

Page 58: “Solar energy to fuels If a leaf can do it we can do it. · “Solar energy to fuels. If a leaf can do it we can do it". ... 5 Billion Year Clock. ... Water splitting reaction

“If the leaf can do it, wecan do it”

I say -


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