Download - Peidong Yang at BASF Science Symposium 2015
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Peidong Yang Department of Chemistry
University of California, Berkeley Materials Science Division
Lawrence Berkeley National Lab
Artificial Photosynthesis: Challenges & Strategies
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It is about environment
• Total worldwide power consumption was ~15 terawatts with 80 to 90 percent derived from the combustion of fossil fuels.
•Currently low percentage of renewable energy in world-wide energy portfolio
• Pollution, Global warming, CO2 emission, Health
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US: cut carbon emissions 26-28% on 2005 levels by 2025. China: make “best efforts” to peak emissions before 2030; increase the share of
non-fossil fuels energy consumption to around 20% by 2030.
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• Solar Cell: Solar energy to electricity, requires energy storage solution.
• Artificial Photosynthesis: Solar energy directly to chemical energy, solving the energy conversion and storage problems in one integrated system.
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Harvesting Solar Energy: Solar to fuel
Carbon-Neutral Solution
Artificial Photosynthesis
Hydrogen Methanol, Ethanol
Gasoline CO2, H2O
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Solar Fuels Generation Reactions Reaction
ΔGo (kJ mol-1)
n
ΔEo (eV)
____________________________________________________________________________
H2O → H2 + ½ O2 237 2 1.23
CO2 + H2O → HCOOH + ½ O2 270 2 1.40
CO2 + H2O → HCHO + O2 519 4 1.34
CO2 + 2H2O → CH3OH + 3/2 O2 702 6 1.21
CO2 + 2H2O → CH4 + 2O2 818 8 1.06
Require the invention of new photoactive materials that accomplish the combined tasks of light harvesting, charge separation, and compartmentalized chemical transformation.
Solar-to-Fuel Conversion efficiency Cost-effective Earth-Abundant elements Less energy-intensive processes
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Solar Water Splitting with single bandgap light absorber
Fujishima & Honda, Nature 238, 37 - 38 (07 July 1972).
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Photosynthesis
Light Capture
Light Capture
Oxidation Catalysis
Reduction Catalysis
Nature’s Functional Solar-Fuel Generation System
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Arthur J. Nozik, Photochemical Diodes, Applied Physics Letters 30, 567-569 (1977). C. Liu, N. P. Dasgupta, P. Yang, Chem. Mater., 26, 415 (2014)
Photochemical diodes: Dual absorber Concept
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Two light absorbers vs. One
e-/s.nm2
1200
900
600
300
• Earth-abundant, Low-cost • Photoelectrochemically stable • Small-bandgap • Suitable CBM & VBM
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The Matching Problem
~10-20 mA/cm2
~600-1200 e/s.nm2 Cathode-anode current matching Catalyst TOF -Photocurrent matching
C. Liu, N. P. Dasgupta, P. Yang, Chem. Mater., 26, 415 (2014)
Single optical path
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e-/s.nm2
1200
900
600
300
Planar Electrodes
Nanowire Arrays (D=500nm, L=25 µm)
e-/s.nm2
12
9
6
3
High surface area semiconductor nanowire arrays with large carrier mobility as photoelectrodes
Nanowire arrays enable the stacking of catalysts in third dimension, effectively relax the stringent needs for
catalysts with high TOF, also lower the overpotential.
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-0.6 -0.3 0.0 0.3 0.6 0.9-350
-300
-250
-200
-150
-100
-50
0
Dark 75mW/cm2
Curr
ent (
pA)
Bias vs NHE (V)
Boron doped (~1018) Length=8.5μm ,Diameter=650nm
VLS Single Nanowire Photocathode
Y. Su, J. Tang, Unpublished Results
Current Density ~6-12 electron.s-1.nm-2
sampling entire nanowire surface.
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Final Products: Hydrogen Methanol …
The Helios Design (~2003) “Semiconductor nanowire array: potential substrates for
photocatalysis and photovoltaics”, Y. Wu, H. Yan, P. Yang, Topics in Catalysis, 19, 197, 2002.
Single optical path
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• Nanowire arrays as photoelectrodes • Nanowire arrays for solar cell (DSC). • The nanowire array concept also inspired many of recent solar
fuel generator designs. Law, M., Greene, L. et al. Nature Mater. 4, 455 (2005). M. Law et al. J. Phys. Chem. B, 110, 22652 (2006).
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Artificial Photosynthesis: Materials Challenges
Photoanode materials critical part of
the solar Fuels Technology.
Catalysts with higher TOF, and Lower overpotential.
Photocathode materials for Water & CO2 reduction.
Ion-conductive membrane gas impermeable, mechanically stable,
optically transparent .
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Photocathode for Water Reduction: Silicon Nanowire Array
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Si wire array as photocathode
High surface area photocathode, can be decorated with Pt or MoS2, CoSx nanoclusters.
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ALD of Catalytic Pt Clusters on Silicon Nanowire Photocathodes
• Atomic layer deposition (ALD) of Pt allows for quantitative control of Pt loading in the sub-monolayer regime, with a conformal surface coating
• 1 cycle of Pt provides nanoparticles with diameters < 1 nm, with a surface mass loading of ~13 ng/cm2
• HER activity can be controlled by varying the ALD cycle number, demonstrating the lower limits of Pt loading on high surface area electrodes.
N. P. Dasgupta et al., J. Am. Chem. Soc. 135, 12932 (2013)
18
16
14
12
10
8
6
4
2
0
%
of T
otal
4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 Diameter (nm)
1x 3x 10x
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Photocathode: Silicon nanowire array
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JSun et al, J. Am. Chem. Soc. 133, 19306, 2011 C. Liu, J. Sun, J. Tang, P. Yang, Nano. Lett, 12, 5407, 2012.
GaP Nanowire Photocathode for water & CO2 reduction
• Surfactant-free solution process • Low temperature • Large scale production • Tunable doping (e.g. Zn precursor) • Applicable to InP, InGaP alloys
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Colloidal Processable GaP Nanowire Photocathode
large scale production
Processable J. Sun et al, J. Am. Chem. Soc. 133, 19306, 2011
C. Liu, J. Sun, J. Tang, P. Yang, Nano. Lett, 12, 5407, 2012.
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Si, 1.1eV, 39 mA/cm2
InP, 1.34eV, 31 mA/cm2
WO3, 2.7eV, 3.3 mA/cm2 BiVO4, 2.4eV, 6.3 mA/cm2
GaP, 2.3eV, 7.4 mA/cm2 Fe2O3, 2.2eV, 8.9 mA/cm2
Rutile, 3.0eV, 1.4 mA/cm2
Anatase, 3.2eV, 0.8 mA/cm2
ZnO, 3.4eV, 0.5 mA/cm2
UV region: GaAs, 1.43eV, 28 mA/cm2
WSe2, 1.2eV, 35 mA/cm2
WS2, 1.51eV, 25 mA/cm2
400 nm 750 nm
Cu2O, 2.1eV, 10.7 mA/cm2
Also: Cu2S 1.2eV; CdTe 1.5eV; GeS 1.7eV; Zn3P2 1.7 eV; CdS 2.4eV CIGS & CZTS: 1.0~1.7 eV;
CdSe, 1.7eV, 20 mA/cm2
x-axis: energy of photon (eV) y-axis: current density (mA/cm2) Based on 100mW/cm2 AM1.5G solar spectrum
1 mA/cm2
62 electron per nm2 per sec
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Macroscopic: linked-electrode configuration ~0.35 mA/cm2 under one-sun illumination (AM 1.5G). Overall efficiency: 0.21%. Faradic efficiency: 91%.
Band gap:
Si: 1.1 eV
Theoretical efficiency: 0.86% (one-sun illumination)
TiO2 (Rutile): 3.0 eV
Si NW
TiO2 NW
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A Fully Integrated Nanosystem
Factors considered:
Sluggish O2 evolution process on TiO2
Inadequate light-absorption of TiO2 Fast charge transport of Si
Length-scale of depletion layer thickness of individual components
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Artificial Photosynthetic Nanosystem
C. Liu et al, Unpublished 2012
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IrOx clusters on TiO2 nanowires
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Artificial Photosynthetic Nanosystem
C. Liu et al, Unpublished 2012
Artificial Photosynthetic Nanosystem
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C. Liu et al, Nano Lett 2013
Artificial Photosynthetic Nanosystem
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Current Matching between Electrodes
M. G. Walter, Chem. Rev., 2010, 110, 6446
Photoanode represents one of the biggest bottlenecks for artificial photosynthesis. We need discovery of
photo-oxidatively stable anodes with high photovoltage and high photocurrent.
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Overall water-splitting efficiency
n+p-Si
p-InP
n-BiVO4 *
n-TiO2
1 2 3
4
1 2 3 4
Max. efficiency 0.7% 1.1% 1.5% 3.0%
* T. W. Kim, K. Choi, Science, 2014, 343, 990-994
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Key Interfaces in Solar-to-Fuel Conversion
Inorganic-molecule
Semiconductor-semiconductor
Semiconductor-catalyst
Oxygen evolution reaction (OER) & ohmic contact
e H2O
O2
Hydrogen evolution reaction (HER)
h
h
e
H2O
H2
h
e
Si Pt ?
h IrOx
? H2O
O2
e
h
Si
TiO2 ?
System Components Interfaces
1 μm
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Nanowire-Bacteria Bio-hybrids Feeding microbes with electrons for CO2 reduction
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A Materials Biology Approach to CO2 Reduction
C. Liu, J. Tang, H. M. Chen, B. Liu, P. Yang, Nano Lett., 2013, 13, 2989
Artificial photosynthesis from hybrid materials/biological CO2 catalysts
Acetogensis, Harold L. Drake, Chapman & Hall, 1994 D. R. Lovley, et. al., mBio, 2010, 1, e00103-10
Light-Harvesting Materials Biological CO2 Catalysts
pH = 0
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Bacteria attached on nanowires with high selectivity.
Patterned SiNWs array - VLS growth - Diameter: 300-400nm - Length: 3-6um - Passivation: SiO2 Bacteria: MR-1 Shewanella oneidensis
H. Jeong, Nano Lett, 2013
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New Oxide-Coated Si Nanowire Arrays are Biocompatible
Chong Liu, 2014
Living bacteria can adhere and grow on nanowire arrays in pH 7 water
5 µm
1 µm
1 µm
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Nanowires Can Protect Bacteria from Oxygen
Nanowire electrode allows operation of strict anaerobes in headspace of atmospheric O2 (20%) while not affecting mass transport of CO2
Some ORR catalyst is required to efficiently remove O2 in nanowire cathode
Chong Liu 2014
Sporomusa ovata
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Unassisted Solar CO2 Reduction by Hybrid Catalyst
Light source: 100mW/cm2 AM 1.5G, 300W Xenon lamp
2 CO2 + 2 H2O CH3CO2H + O2 hν
Integrated nanowire/bacterial catalyst can drive pure solar CO2 fixation
E0 = 1.09 V
Efficiency = 0.38%
Chong Liu, Eva Nichols, Joe Gallagher 2014
Sporomusa ovata
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P. Yang, M. Chang, C. Chang, 2014
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Towards systems materials engineering
Dual light absorber Configuration -Integrated photoanode/cathode, mimicking photosynthesis in Nature.
Efficiency ~0.5% for fully integrated system has been demonstrated.
Photocathode materials: ~700mV; ~30 mA/cm2
Photoanode materials : ~1V; >10 mA/cm2
Catalysts on high surface area, high charge mobility semiconductor support with higher TOF, and Lower overpotential:
> 10 electrons/s.nm2
< 100 meV? for water reduction, oxidation & CO2 reduction
P. Yang, J. Tarascon, Nature Mater., 11, 560, 2012.
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Chen et al. Science, 343, 1339,2014
Bimetallic Catalysts: synergistic geometric and electronic effects for CO2 reduction
D. Kim et al. Nature Comm, 5, 4948, 2014
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Chemical Fuels; Drug Intermediates; Biopolymers….