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 ID: 1037924
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1. Artificial photosynthesis for solar fuelsStenbjörn StyringUppsala university
2. Swedish Consortium for Artificial Photosynthesis1994- Sw. Energy agency, Knut and Alice Wallenberg Foundation; EU; VR
3. 0102030The global conceptNuclear Biomass Hydro others.....TW4080%Fossil2011; ca 17 TW yearsGlobal energy use
4. Energy supply 2008, Sweden:33 32 12 23 % of totalLocal vs. global conceptFossilNuclearBiomassHydro
5. Energy supply 2008, Sweden:33 32 12 23 % of totalLocal vs. global conceptFossilNuclearEnergy supply 2008; Germany82 11 7 % of totalFossilBiomassHydro
6. TW20500102030The global concept402011: 17 TW80%FossilFossil
7. TW20500102030The global conceptNote! This comes from people that don´t use energytoday. They can not solve this by saving energy!!!402011: 17 TW80%FossilFossil
8. 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; silicon solar 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
9. TW1020Everything is not electricity2011; ca 17 TW yearsFossil80%Total production
10. TW102080%Electricity 17%FossilEverything is not electricityTotal productionFinal consumtion
11. TW102080%Electricity 17%The rest, 83% is used as fuel for many thingsFossilEverything is not electricityTotal productionFinal consumtion
12. Electricity is an energy carrier. It is used to carry a minor part of the energy in the world.Critical insights
13. 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
14. Renewable technologies Biomass derivedTechnologically mature with markets hydroelectric; geothermal;in at least some countries woody biomass; onshore wind landfill gas; bioethanol; silicon solar 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 stage Many give electricity. All fuel technologies are based on biomass
15. 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 biomassCritical insights
16. !! !! Converted solar energy; Oil,biomass….Electricity Solar cells ! ? Solar fuelfor storage Heat;Low tempHigh tempSolar Energy, Options12
17. The energy system – local versus global aspects; the place for solar energy; need for fuelVarious concepts for solar fuelsOur science in the Swedish Consortium for Artificial Photosynthesis
18. Solar fuel; hydrogen or carbon basedSolar energy and waterSustainable methods to make solar fuels/hydrogen
19. Solar fuel; hydrogen or carbon basedIndirectDirect methodsSolar energy and waterSustainable methods to make solar fuels/hydrogen
20. PhotovoltaicsSolar fuel; hydrogen or carbon basedIndirectElectrolysis→H2Solar energy and waterSustainable methods to make solar fuels/hydrogen
21. PhotovoltaicsSolar fuel; hydrogen or carbon basedIndirectElectrolysis→H2Leads to discussions about the hydrogen societySolar energy and waterSustainable methods to make solar fuels/hydrogen
22. PhotovoltaicsSolar fuel; hydrogen or carbon basedIndirectElectrolysis→H2C-based fuelFrom H2 and CO2Solar energy and waterSustainable methods to make solar fuels/hydrogen
23. Solar fuel; hydrogen or carbon basedBiomassConversionPyrol.,ferm., chop wood etcIndirectSolar energy and waterSustainable methods to make solar fuels/hydrogen
24. PhotosynthesisSolar fuel; hydrogen or carbon basedIndirectBiomassConversionSolar energy and waterSustainable methods to make solar fuels/hydrogen
25. Photovoltaics PhotosynthesisSolar fuel; hydrogen or carbon basedIndirectElectrolysis→H2BiomassConversionPyrolysis, ferment., etcC-based fuelFrom H2 and CO2Solar energy and waterSustainable methods to make solar fuels/hydrogen
26. Solar fuel; hydrogen or carbon basedElectricityElectrolysisIndirectSolar cells in Sala/HebyTwo systems -solar cells and electrolyserSolar energy and waterSustainable methods to make solar fuels/hydrogen
27. Solar fuel; hydrogen or carbon basedIndirectBiomass,Trees; Waste; GrassesConversionSeveral systems must be integratedSolar energy and waterSustainable methods to make solar fuels/hydrogen
28. Solar fuel; hydrogen or carbon basedElectricityElectrolysisIndirectSolar cells in Sala/HebyBiomass,Waste; Trees; GrassesConversionGeneral - Extra systems cost Losses in extra step(s)Solar energy and waterSustainable methods to make solar fuels/hydrogen
29. Solar fuel; hydrogen or carbon basedDirect methodsSolar energy and water
30. Thermochemical cycles (CSP for H2)Solar fuel; hydrogen or carbon basedDirect methodsSolar energy and water
31. Artificial Photosynthesis in materials and nanosystemsArtificial Photosynthesis in molecular systemsSolar fuel; hydrogen or carbon basedDirect methodsThermochemical cycles (CSP for H2)Solar energy and water
32. e-e-D2 H2O O2 + 4 H+A2 H24 H+ H+ H+ e-e-PJoining in cellsP
33. Artificial Photosynthesis in materials and nanosystemsArtificial Photosynthesis in molecular systemsSolar fuel; hydrogen or carbon basedDirect methodsThermochemical cycles (CSP for H2)System costs might become lower in a direct processSolar energy
34. Solar fuel; hydrogen or carbon basedSemi-directSolar energyPhotosynthesis(compartmentalized)Light reactionsNADPH & ATPDark reactionsH2, alcohols etcPhotobiological processes – not harvesting the organismExcreted
35. H2 forming heterocystVegetative cellsGreen algae –ChlamydomonasCan make hydrogen under special conditionsCyanobacterium – NostocPhotobiological hydrogen and fuel production using living organisms.
36. Solar fuel; hydrogen or carbon basedSomething in betweenMixing biological and non-biological partsSolar energyPSIIPSIH2sesRuPtHybridesEnzyme & metal catalystsTiO2etc
37. Artificial Photosynthesis in materials and nanosystemsThermochemical cycles (CSP for H2)PhotovoltaicsArtificial Photosynthesis in molecular systems PhotosynthesisSolar fuel; hydrogen or carbon basedIndirectDirect methodsSemi-directSolar energy and waterLight reactionsNADPH & ATPDark reactionsH2, alcohols etcElectrolysis→H2BiomassConversionPyrolysis, ferment., etcC-based fuelFrom H2 and CO2Photosynthesis(compartmentalized)
38. The energy system – local versus global aspects; the place for solar energy; need for fuelVarious concepts for solar fuels A little on our science in the Swedish Consortium for Artificial Photosynthesis
39. H2PWe follow two branches to Solar hydrogen, common link biochemistry, biophysicsH2O
40. H2PPhotobiological hydrogen production in photosynthetic microorganismsH2ODesign of organismsSynthetic biology, genomics, metabolomics
41. H2OH2PDesign and synthesisSpectroscopyArtificial photosynthesis, synthetic light driven catalytic chemistryMnMnRuFeFeCo
42. Artificial photosynthesis: Target – fuel from solar energy and water!Visionary – but how?
43. Artificial photosynthesis - manmade: Visionary – but how?Idea for a short cut: Mimic (copy) principles in natural enzymesMethodBiomimetic chemistry
44. MnPO2O2O2O2? Secret of lifeElement: MnAtomic weight: 55MnMnMnFour manganese atoms are the secret behind the splitting of waterO2O2O2WaterPhotosystem II – the wunderkind in nature!
45. TyrZ 161His 190Glu 189Asp 170Gln 165CaWater oxidation - the main playersOHMnMnMnMn
46. NNNNNND A S H O 2 2 O 2 + e - e - 4H + 4H + H 2 2 LinkLinklightRuthenium instead of chlorophyllSupramolecular chemistrychemical LEGORu
47. NNNNNND A S H O 2 2 O 2 + e - e - 4H + 4H + H 2 2 LinkLinklightSupramolecular chemistrychemical LEGOMnMnLinkRuManganese as in Photosystem II
48. MnMnMn2(II/II) BPMP has been connected to Ru and electron acceptorsN N N N N N EtO 2 C NH O N N O N N N N O O O Me Me Me Ru MnMnNNNNNNNNNNC8H17OOOOC8H17OOOOONNNNNNNHOEtO2COOOO3+RuMnMnNDI acceptorMw 2800
49. 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 transferCo-based systems have potential - We seek molecular systems - We seek light driven systems
50. Cobalt as a water oxidation catalystKanan and Nocera, Science 2008, 321, 5892, 1072-1075Yin, Tan, Besson, Geletii, Musaev, Kuznetsov, Luo, Hardcastle and Hill, Science 2010, 328, 342-345
51. 1 O2/CoONOFFON100 % light50 % lightCo(III) oxidePhoto-driven O2 evolution with a new Co-nanoparticle
52. e-Co2 H2O O2 + 4 H+RuDevelopment of a Co-ligand system for use in the split cell.1. Link the Ru-sensitizer with ligandH4M2P (M2P for short)methyldiphosphonic acid
53. e-Co2 H2O O2 + 4 H+Ru1. Synthesized and characterized.Ru(M2P)Development of a Co-ligand system for use in the split cell.1. Link the Ru-sensitizer with ligandH4M2P (M2P for short)methyldiphosphonic acid
54. + Pi buffer+ persulfate+ lightIsolated Ru(M2P)Co65 µg Ru(M2P)Co (ca 40 µM Ru)6 mM S2O82-25 mM Pi (pH 8.4)Development of a Co-ligand system for use in the split cell.Ca 1 turnoverPhotocatalytic oxygen evolution!
55. e-Co2 H2O O2 + 4 H+RuSynthesized and characterized.Yes, it binds Co and the system is photo-catalytic!Ru(M2P)Development of a Co-ligand system for use in the split cell.Link the Ru-sensitizer with ligand2. Can it bind Co and is it active?H4M2P (M2P for short)methyldiphosphonic acid
56. NNNNNND A S H O 2 2 O 2 + e - e - 4H + 4H + H 2 2 LinkLinklightSupramolecular chemistrychemical LEGOMnMnLinkRuCo(III) oxideCobolt
57. NNNNNND A S H O 2 2 O 2 + e - e - 4H + 4H + H 2 2 LinkLinklightSupramolecular chemistrychemical LEGOMnMnLinkRuManganese like Photosystem IICo(III) oxideCobolt
58. Hydrogenases: Enzymesthat can make and handlehydrogen FeFe
59. Many complexes making hydrogen!!seconds 0200400600-12-8-40turnovers510152025Hydrogen formation. Electrochemistry under very acidic conditionsBackground Our complex
60. Aromatic dithiolate ligandsTuning for catalysis at milder potentialsDiiron complexes with aromatic dithiolate ligandsquinoxalinecarborane
61. 123e-e-4H+5½ H2Ascorbic acidRu(bpy)32+Fe2(μ-Cl2-bdt)(CO)6Bimolecular approachSetup:150 W halogen lamp as light source 455 nm long-pass filter + infrared filter light power at sample (=after filtering) ~ 1 W sample degassed and under Ar atmosphere solvent: H2O:Acetonitrile 1:1 orH2O:Dimethylformamide 1:1 typical concentrations:Ascorbic acid: 0.1MSensitizer: 140 μMCatalyst: 14 μMtypical sample volume: 2.6 ml H2 detected by gas chromatographyComponents: Ascorbic acid as proton and electron donor Ruthenium(II)tris-bipyridine as photosensitizer Diiron-(μ-Dichlorobenzene-dithiolate)hexacarbonyl catalyst
62. An interesting development – complexes with only one Fe can also make hydrogen.SSFeIIPh2PPPh2CONOOHydrogen at low overpotential
63. NNNNNND A S H O 2 2 O 2 + e - e - 4H + 4H + H 2 2 LinkLinklightSupramolecular chemistrychemical LEGOMnMnLinkRuCo(III) oxideCoboltFeFeFe
64. We have water oxididation catalyst Co-nanoparticleWe have many hydrogen forming catalysts Fe-complexesWe can drive them with light!Can we combine them?
65. O2 + 4H+e-e-2 H2O4H+e-e-2 H2e-e-TiO2NiOA ”Split-cell” for complete water oxidation/fuel formation with catalysts of earth abundant elements from our laboratory
66. ArtificialSystemsOrganisms in BioreactorsH2 by photosynthesisWater as substrateSoon-will work-explored by many
67. ArtificialSystemsBioreactorsH2 by photosynthesisWater as substrateSoon-will work-explored by manyLong term- big potential- more unproven
68.