Artificial Photosynthesis with Biomimetic Nanomaterials: Self-Repairing Solar Cells Jong Hyun Choi School of Mechanical Engineering Birck Nanotechnology Center Bindley Bioscience Center Purdue University jchoi@purdue.edu https://engineering.purdue.edu/~jchoi/
Current Photovoltaic & Photo-electrochemical Technologies Solar radiation: 120,000 TW constantly strikes the surface of the earth Presently, solar energy supplies less than 0.01% of world s energy demand Major challenge in solar energy utilization: Energy harvesting economically competing with cheap fossil fuel Type of Cell Cell Efficiency Current Technology Needs Single-crystalline Si 24 % Multi-crystalline Si 18 % Amorphous Si 13 % Dye-sensitized solar cells 10 12 % Organic solar cells 6 7 % Higher production yields, lowering of cost and energy content Lower manufacturing cost and complexity Lower production costs, increase production volume and stability Improve overall efficiency and lifetime via system regeneration Improve system stability and efficiency significantly Lewis, PNAS (2006) Kamat, JPC (2007) Gratzel, Nature (2001) One of the key drawbacks of Dye-sensitized solar cells: Decrease in the system performance over time due to photo-induced damage of dye
Electrochemical Photovoltaic Cells Electrodes: ITO as WE and Pt as CE Electrolyte solutions Light absorbing dye: Ru compounds, porphyrin derivatives, etc Semiconductor nanomaterials Conducting glass Cathode Dye Gratzel, JPPC PR (2003) E vs. NHE (V) -0.5 0 0.5 1.0 Electron injection Semiconductor S * hv Electrolyte e - e - Red Mediator Ox e - S /S + e -
Electrochemical Photovoltaic Cells Electrodes: ITO as WE and Pt as CE Electrolyte solutions Light absorbing dye: Ru compounds, porphyrin derivatives, etc Semiconductor nanomaterials Currently: Nanostructured materials provide high surface areas for energy conversion Problems: Invariably static structures are unable to cope with degradation of dye molecules over time Solutions: We draw inspiration from natural photosynthesis, where structurally flexible systems self regenerate to improve overall efficiency and lifetime
Self-Repair in Natural Photosynthesis Nature uses rapid and facile mechanisms of self repair that enable energy harvesting under conditions of photo-induced damage or degradation Photo-damaged components (i.e. D 1 protein) in the reaction center are constantly replaced every hour There is no such self generative analog in the synthetic realm! Photosystem II Reaction Centre Barber and Andersson Trends in Biochemical Sciences (1992)
Self-Repair in Plant Photosystem II Decomposition upon photodamage Stroma D 1 protein Thylakoid OEC extrinsic unit Reassembly with new D1 protein This natural self repair process relies on: Molecular recognition and Thermodynamic meta-stability Self assembly processes that can be reversed
Artificial Photosystems We mimic photosynthesis processes by reversibly assembling carbon nanotubes and photosynthetic reaction centers that are capable of self-repair. Photosynthetic proteins that generate electron from solar radiation - extracted from purple bacteria e - Rhodobacter sphaeroids Carbon nanotube as a molecular wire
What is a Carbon Nanotube? Graphene (2D) Semiconductor Semiconductor Semimetal Graphite (3D) Nanotube (1D) Electrons restricted to single dimension Diameter ~1 nm Metal Synthesis Chemical vapor deposition Over metal (Fe, Co, Mo) nanoparticle C 2 H 2 2.5 mm 100 nm C 2 H 2 Length can range from 10 nm to 1 cm Hata, K., Science 306, (2004), 1362
Mimicking Plant Cell Membrane Lipid Nanodisc Nanodisc formation for protein reconstitution System initially stabilized with surfactant: sodium cholate Sligar et al. Nano Lett. (2006) Phospholipids and Membrane scaffold protein (MSP) Nanometer-sized discs Spontaneous self-assembly upon surfactant removal (cholate) 4 nm Platform for suspending membrane proteins (i.e., photosynthetic reaction center or RC) 10 nm
Reversible Self Assembly RC MSP Surfactant removal RC Lipids RC SWNT MSP MSP Cholate Surfactant addition SWNT MSP Lipids RC Lipids Photosynthetic reaction centers (RC) isolated from purple bacterium, Rhodobacter Sphaeroides Nanodiscs reconstitutes RC, while suspending SWNT It could be the basis of light-harvesting devices with infinite lifetime Molecular recognition and thermodynamic meta-stability, just like molecular assembly in plants Ham, Choi et al. Nature Chemistry (2010)
(a) Photoelectrochemical measurement Photocurrent generation Potentiostat Electrochemical Photovoltaic Cell Pt counter electrode Ag/AgCl reference electrode Reference electrode (Ag/AgCl) Counter electrode (Pt) PDMS mold ITO Solution containing RC-based complex Photo-electrochemical cell SWNT working electrode Glass substrate Double redox mediator system: Ubiquinone / ubiquinol Light illumination Ferri- & ferro-cyanide: Fe(CN) 6-3/-4 785 nm laser
Photocurrent Generation via Light Harvesting b 30 25 on off on off on off on off c 1000 800 Current (na) 20 15 10 5 0 Na-cholate addition on Na-cholate removal off Photocurrent (na) 600 400 200-5 0 5 10 15 20 25 30 65 70 75 e Relative photocurrent 1.0 0.8 0.6 0.4 0.2 0.0 0 0 5 10 15 20 25 30 35 Chemically-initiated Time (min) self-regeneration during Complex light concentration harvesting (µm) Regeneration of complex Self-assembled complexes (RC-ND-SWNT) are photoelectrochemically active Disassembled states : no photo-response External efficiency at 785 nm: ~40% Linear dependence of photocurrent generation 0 20 40 60 80 100 120 140 160 Time (hour) Ham, Choi et al. Nature Chemistry (2010)
Acknowledgements Graduate students Undergraduate students Benjamin Baker Tae-Gon Cha Chris Bates Dane Sauffer Hanyu Zhang Janette Salgado Yujun Wu We gratefully acknowledge financial support from Purdue University and NSF Nhigel Hinckson