Post on 25-Feb-2016
description
Artificial photosynthesis for solar fuels
Stenbjörn Styring
Uppsala university
Swedish Consortium for Artificial Photosynthesis
1994-
Sw. Energy agency, Knut and Alice Wallenberg Foundation; EU; VR
0 10 20 30
The global concept
Nuclear Biomass Hydro others.....
TW40
80%
Fossil 2011; ca 17 TW years
Global energy use
Energy supply 2008, Sweden:
33 32 12 23 % of total
Local vs. global concept
Fossil NuclearBiomassHydro
Energy supply 2008, Sweden:
33 32 12 23 % of total
Local vs. global concept
Fossil Nuclear
Energy supply 2008; Germany
82 11 7 % of total
Fossil
BiomassHydro
TW
2050
0 10 20 30
The global concept
40
2011: 17 TW
80%
Fossil
Fossil
TW
2050
0 10 20 30
The global concept
Note! This comes from people that don´t use energytoday. They can not solve this by saving energy!!!
40
2011: 17 TW
80%
Fossil
Fossil
Renewable technologies (Sims et al, IPCC 2007) ElectricityTechnologically mature with markets hydroelectric; geothermal;in at least some countries woody biomass; onshore wind
landfill gas; bioethanol; siliconsolar cells.....
Technologically mature with small, new solid waste energy in towns;markets in few countries biodiesel; offshore wind; heat
concentrating solar dishes...
Under technological development thin film PV; tidal change; wavedemonstration plants, upcoming biomass gasification; pyro-
lysis; bioethanol from ligno-cellulose; thermal towers.......
Many give electricity
TW10 20
Everything is not electricity
2011; ca 17 TW yearsFossil
80%
Total production
TW10 20
80%
Electricity 17%
Fossil
Everything is not electricity
Total production
Final consumtion
TW10 20
80%
Electricity 17%The rest, 83% is used as fuel for many things
Fossil
Everything is not electricity
Total production
Final consumtion
1. Electricity is an energy carrier. It is used to carry a minor part of the energy in the world.
Critical insights
1. Electricity is an energy carrier. It is used to carry a minor part of the energy in the world.
2. Biomass is limited on a global scale. Although important in many regions, there is not enough to replace fossile fuels.
Critical insights
Renewable technologies Biomass derivedTechnologically mature with markets hydroelectric; geothermal;in at least some countries woody biomass; onshore wind
landfill gas; bioethanol; siliconsolar cells.....
Technologically mature with small, new solid waste energy in towns;markets in few countries biodiesel; offshore wind; heat
concentrating solar dishes...
Under technological development thin film PV; tidal change; wavedemonstration plants, upcoming biomass gasification; pyro-
lysis; bioethanol from ligno-cellulose; thermal towers.......
Research stageMany give electricity. All fuel technologies are based on biomass
1. Electricity is an energy carrier. It is used to carry a minor part of the energy in the world.
2. Biomass is limited on a global scale. Although important in many regions, there is not enough to replace fossile fuels.
3. Need for fuels from other renewable resources than biomass
Critical insights
!!
!!
Converted solar energy; Oil,biomass….
Electricity Solar cells ! ?
Solar fuelfor storage
Heat;Low tempHigh temp
Solar Energy, Options
12
The energy system – local versus global aspects; the place for solar energy; need for fuel
Various concepts for solar fuels
Our science in the Swedish Consortium for Artificial Photosynthesis
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Sola
r en
ergy
and
wat
erSustainable methods to make solar fuels/hydrogen
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Indirect
Direct methods
Sola
r en
ergy
and
wat
erSustainable methods to make solar fuels/hydrogen
Photovoltaics
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Indirect
Electrolysis→H2
Sola
r en
ergy
and
wat
erSustainable methods to make solar fuels/hydrogen
Photovoltaics
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Indirect
Electrolysis→H2
Leads to discussions about the hydrogen society
Sola
r en
ergy
and
wat
erSustainable methods to make solar fuels/hydrogen
Photovoltaics
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Indirect
Electrolysis→H2C-based fuelFrom H2 and CO2
Sola
r en
ergy
and
wat
erSustainable methods to make solar fuels/hydrogen
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Biomass ConversionPyrol.,ferm., chop wood etc
Indirect
Sola
r en
ergy
and
wat
erSustainable methods to make solar fuels/hydrogen
Photosynthesis
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Indirect
Biomass Conversion
Sola
r en
ergy
and
wat
erSustainable methods to make solar fuels/hydrogen
Photovoltaics
Photosynthesis
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Indirect
Electrolysis→H2
Biomass ConversionPyrolysis, ferment., etc
C-based fuelFrom H2 and CO2
Sola
r en
ergy
and
wat
erSustainable methods to make solar fuels/hydrogen
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Electricity Electrolysis
Indirect
Solar cells in Sala/Heby
Two systems -solar cells and electrolyser
Sola
r en
ergy
and
wat
erSustainable methods to make solar fuels/hydrogen
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Indirect
Biomass,Trees; Waste;
GrassesConversion
Several systems must be integrated
Sola
r en
ergy
and
wat
erSustainable methods to make solar fuels/hydrogen
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Electricity Electrolysis
Indirect
Solar cells in Sala/Heby
Biomass,Waste; Trees;
GrassesConversion
General - Extra systems costLosses in extra step(s)
Sola
r en
ergy
and
wat
erSustainable methods to make solar fuels/hydrogen
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Direct methodsSo
lar
ener
gy a
nd w
ater
Thermochemical cycles (CSP for H2)
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Direct methodsSo
lar
ener
gy a
nd w
ater
Artificial Photosynthesis in materials and nanosystems
Artificial Photosynthesis in molecular systems
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Direct methodsThermochemical cycles (CSP for H2)
Sola
r en
ergy
and
wat
er
e-e-D2 H2O
O2 + 4 H+ A 2 H2
4 H+
H+ H+
e- e-
P
Joining in cells
P
Artificial Photosynthesis in materials and nanosystems
Artificial Photosynthesis in molecular systems
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Direct methodsThermochemical cycles (CSP for H2)
System costs might become lower in a direct process
Sola
r en
ergy
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Semi-direct
Sola
r en
ergy
Photosynthesis(compartmentalized)
Light reactionsNADPH & ATP
Dark reactionsH2, alcohols etc
Photobiological processes – not harvesting the organism
Excreted
H2 forming heterocyst
Vegetative cells Green algae –Chlamydomonas
Can make hydrogen under special
conditionsCyanobacterium – Nostoc
Photobiological hydrogen and fuel production using living organisms.
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Something in between
Mixing biological and non-biological parts
Sola
r en
ergy
PSIIPSI
H2ses Ru
Pt
HybridesEnzyme & metal catalysts
TiO2etc
Artificial Photosynthesis in materials and nanosystems
Thermochemical cycles (CSP for H2)
Photovoltaics
Artificial Photosynthesis in molecular systems
Photosynthesis
Sola
r fu
el; h
ydro
gen
or c
arbo
n ba
sed
Indirect
Direct methods
Semi-direct
Sola
r en
ergy
and
wat
er
Light reactionsNADPH & ATP
Dark reactionsH2, alcohols etc
Electrolysis→H2
Biomass ConversionPyrolysis, ferment., etc
C-based fuelFrom H2 and CO2
Photosynthesis(compartmentalized)
The energy system – local versus global aspects; the place for solar energy; need for fuel
Various concepts for solar fuels
A little on our science in the Swedish Consortium for Artificial Photosynthesis
H2
P
We follow two branches to Solar hydrogen, common link biochemistry, biophysics
H2O
H2
P
Photobiological hydrogen production in photosynthetic microorganisms
H2O
Design of organismsSynthetic biology, genomics,
metabolomics
H2O H2
P
Design and synthesisSpectroscopy
Artificial photosynthesis, synthetic light driven catalytic chemistry
MnMn
Ru
Fe
Fe
Co
Artificial photosynthesis: Target – fuel from solar energy and water!
Visionary – but how?
Artificial photosynthesis - manmade: Visionary – but how?
Idea for a short cut: Mimic (copy) principles in natural enzymes
MethodBiomimetic chemistry
Mn
PO2
O2O2
O2
? Secret of life
Element: MnAtomic weight: 55
MnMn
Mn
Four manganese atoms are the secret behind the splitting of water
O2O2
O2
Water
Photosystem II – the wunderkind in nature!
TyrZ 161 His 190
Glu 189
Asp 170
Gln 165
Ca
Water oxidation - the main players
OH
MnMnMn Mn
N
NN
N
NN
D A S H O 2 2
O 2 + e - e - 4H +
4H +
H 2 2 LinkLink
light
Ruthenium instead of chlorophyll
Supramolecular chemistrychemical LEGO
Ru
N
NN
N
NN
D A S H O 2 2
O 2 + e - e - 4H +
4H +
H 2 2 LinkLink
light
Supramolecular chemistrychemical LEGO
MnMn
Link Ru
Manganese as in Photosystem II
O
N NO NN
NN O OO
Mn Mn
Mn2(II/II) BPMP has been connected to Ru and electron acceptors
N N
N
N
N
N
EtO 2 C
NH
O
N N O N N
N N O O O
Me Me
Me
Ru
MnMn
NN
N
N
NN
NN
NNC8H17
O
O
O
O
C8H17
O
O
O
O
O NN
N N
NN
NHO
EtO2C
O OO O
3+
Ru
Mn Mn
NDI acceptor
Mw 2800
We seek catalysts based on abundant metals,
Mn-based systems have potential- The Mn4 cluster works in Photosystem II- It is the most efficient and stable part of PSII electron transfer
Co-based systems have potential- We seek molecular systems- We seek light driven systems
Cobalt as a water oxidation catalyst
Kanan and Nocera, Science 2008, 321, 5892, 1072-1075
Yin, Tan, Besson, Geletii, Musaev, Kuznetsov, Luo, Hardcastle and Hill, Science 2010, 328, 342-345
1 O2/CoON
OFF
ON
100 % light
50 % light
Co(III) oxide
PO-O
-O
PO- O
-O
Photo-driven O2 evolution with a new Co-nanoparticle
e-Co2 H2O
O2 + 4 H+ Ru
Development of a Co-ligand system for use in the split cell.
1. Link the Ru-sensitizer with ligand H4M2P (M2P for short)methyldiphosphonic acid
PPOO
HOHO OH
OH
e-Co2 H2O
O2 + 4 H+ Ru
1. Synthesized and characterized.
O
O
HO
HO
OHHO
P
P
RuN
NN
N
N
N
P
P
HO OH
HO
HO
O
O
Ru(M2P)
Development of a Co-ligand system for use in the split cell.
1. Link the Ru-sensitizer with ligand H4M2P (M2P for short)methyldiphosphonic acid
PPOO
HOHO OH
OH
+ Pi buffer+ persulfate+ light
Isolated Ru(M2P)Co 65 µg Ru(M2P)Co (ca 40 µM Ru)6 mM S2O8
2-
25 mM Pi (pH 8.4)
0 100 200 300 4000
10
20
30
40
50
O
2 (nm
ol/m
l)
Time (s)
ON
Development of a Co-ligand system for use in the split cell.
Ca 1 turnoverPhotocatalytic oxygen evolution!
e-Co2 H2O
O2 + 4 H+ Ru
1. Synthesized and characterized.2. Yes, it binds Co and the system
is photo-catalytic!
O
O
HO
HO
OHHO
P
P
RuN
NN
N
N
N
P
P
HO OH
HO
HO
O
O
Ru(M2P)
Development of a Co-ligand system for use in the split cell.
1. Link the Ru-sensitizer with ligand2. Can it bind Co and is it active?
H4M2P (M2P for short)methyldiphosphonic acid
PPOO
HOHO OH
OH
N
NN
N
NN
D A S H O 2 2
O 2 + e - e - 4H +
4H +
H 2 2 LinkLink
light
Supramolecular chemistrychemical LEGO
MnMn
Link RuCo(III) oxide
Cobolt
N
NN
N
NN
D A S H O 2 2
O 2 + e - e - 4H +
4H +
H 2 2 LinkLink
light
Supramolecular chemistrychemical LEGO
MnMn
Link Ru
Manganese like Photosystem II
Co(III) oxide
Cobolt
Hydrogenases: Enzymesthat can make and handlehydrogen S
Fe
S
Fe CN
CONC
OC
S X
NH
OC
Cys
Fe Fe
Many complexes making hydrogen!!
N
S S
Fe Fe
COCO
COOC
OC CO
Br
seconds
0 200 400 600
-12
-8
-4
0
turnovers
5
10
15
20
25
Hydrogen formation. Electrochemistry under very acidic conditions
Background
Our complex
N N Cl Cl
Aromatic dithiolate ligandsTuning for catalysis at milder potentials
Diiron complexes with aromatic dithiolate ligands
quinoxalinecarborane
NN
N
N
N
N
Ru
O O
OHHO
HO
HOFe Fe COOC
S S
OC OCCO CO
Cl Cl
1
2
3
e-
e-
4
H+
5½ H2
Ascorbic acid
Ru(bpy)32+
Fe2(μ-Cl2-bdt)(CO)6
Bimolecular approach
S S
Fe
OC CO
PMe3
RR
1: R = H2: R = Cl
Me3P
An interesting development – complexes with only one Fe can also make hydrogen.
S SFeII
Ph2P PPh2
CO
N
OO
Hydrogen at low overpotential
N
NN
N
NN
D A S H O 2 2
O 2 + e - e - 4H +
4H +
H 2 2 LinkLink
light
Supramolecular chemistrychemical LEGO
MnMn
Link RuCo(III) oxide
CoboltFe
Fe
Fe
We have water oxididation catalyst Co-nanoparticle
We have many hydrogen forming catalysts Fe-complexes
We can drive them with light!
Can we combine them?
O2 + 4H+N
NRu
NN
N
N
2-O3P
2-O3P
e-e-
2 H2O
4H+
S SFep Fed
CO CO
CN
S
OCNC
H
Cys
N[4Fe-4S]
S SH
FeI
OC CO
PMe3Me3P
S S
FeII
PR2 PR2
OC
NR
N
NPh
Ph
O
O
N
N
Ph
O
O
F2B
BF2
CoII
OR2N
NCMeX1 X2 X3
a) b) c)
N
O
O
OAr
OAr
OtBu
tBu
CO2H
ON
O
OOAr
OAr
CO2HN
O
N
O
O O
Oct
Ar =
1
2
e- e-
2 H2
e- e-
TiO2NiO
Co(III) oxide
A ”Split-cell” for complete water oxidation/fuel formation with catalysts of earth abundant elements from our laboratory
ArtificialSystems
Organisms in Bioreactors
H2 by photosynthesisWater as substrate
Soon-will work-explored by many
ArtificialSystemsBioreactors
H2 by photosynthesisWater as substrate
Soon-will work-explored by many
Long term- big potential- more unproven