1

Solar Production of Fuels and Chemicals;
is there a cost-effective path forward?
1
• Big Picture
Outline
Big Picture
• Solar Energy Conversion: What Works, What Doesn’t , and Why
• Strategies and Tactics: Potentially Cost-Effective Artificial
Photosynthetic Processes
• Improved Light Absorbers and Electrocatalysts
2
p g y
• Beyond Water Splitting
2
R di ti F Th l R ti H B Radiation From Thermonuclear Reactions Has Been
And Always Will Be The Most Important Source
Of Energy For The Earth and Human Beings
Societal prosperity through the 19
th
century was powered
by renewable biomass.
3
5
4
Mtoe/year
2011
7 billion
~ 17 TW
Prosperity + Population  Demand
1912
2 billion people
~ 1 TW
• Societal prosperity through the 19
th
century was powered by renewable biomass.
• Global prosperity in the 20
th
Century was possible due to the availability of large quantities
of inexpensive fossil hydrocarbon resources.
• Global prosperity in the 22
nd
century will depend on availability of enormous quantities of
sustainable energy resources (32+TW) and/or significant unprecedented population control.
• The 21
st
Century Better Figure Out How to Get Us There.
Low cost, solar derived, hydrocarbon
fuels have provided unprecedented
opportunities for global egalitarian
prosperity.
8
5
$ 63,000,000,000,000
~ $120/GJ
512,000,000,000 GigaJoules
9
Yes, there is a limit on how much we can spend
Society can not spend (for long) more on energy
than the value created
Conservation of Money
World GDP 2010 ~ $63 Trillion/y
(US/Ger/China/India 14/3.6/6/1.5)
World Energy Use ~ 16 TW
World Gross Domestic Product (GDP)
World Energy Use 16 TW
(US/Ger/China/India 3.5/0.6/3.5/0.9)
Absolute Spending Limit (GDP/Energy Use)
U.S.  $120/GJ Germany $190/GJ
China $50/GJ India $50/GJ
6
Fraction of U.S. GDP
t
Max Total Spending on Energy ~ 10-15% of GDP
< $5 -15/GJ: the lower the better.
spent on energy
11
Raising the price of energy means
the money must come from somewhere else.
Decreased Prosperity.
During times of relative economic stability and increasing
world prosperity food and fuel are inexpensive
< 10-15% GDP
Food ~ $5 - 15/GJ and Fuel ~ $2 - 15/GJ
Corn $2.00 /bushel $7.90 /GJ
Rice  $2.00 /cwt $4.40 /GJ
Wheat $4 50 /bushel $16 46 /GJ
Oil $85.00 /barrel $13.94 /GJ
Coal $50.00 /ton $1.70 /GJ
Natural 
Gas $4.00 /MMBTU $3 70 /GJ
Wheat  $4.50 /bushel $16.46 /GJ
Gas $4.00 /MMBTU $3.70 /GJ
Gasoline $2.50 /Gallon $20.00 /GJ
Electricity $0.05 /kW‐hr $14.00 /GJ
7
Bad Things Happen When
Food and/or fuel > $15/GJ
2008
Oil @ $150/bbl ~ $24/GJ
Wheat @$16/b shel $56/GJ Wheat @ $16/bushel ~ $56/GJ
Electricity @ $0.15/kW-hr = $30/GJ
Cause or Effect ?
Here we go again?
14
8
Where do most people (including scientists) think the money
will come from for new sources of sustainable energy?
15
Sustainable = Environmental and Economical
(non-toxic, renewable) (< $5 - 15/GJ)
n
1
Annual Net Revenue($)
Total Capital($)
(1 discount rate)
n
n
year=
<
+
¿
Production Cost
n Product Price
1
n
1
Total Capital($) 1
Product Price(1- )
System Output(GJ/y) (1 discount rate)
1
~ 8 - 3 for DR~ 10 - 30%, n~10 years
(1 discount rate)
Total Capit
n
year
n
year
=
=
<
+
+
¿
¿
Production Cost
Product Price
al($)
~ 15($/GJ) (1- ) * 5 ~ 60($ / / )
System Output(GJ/y)
y GJ y <
16
Energy Production Cost
Energy Product Price
Total Capital($/Watt) 1.8 *(1 - ) <
9
Science and Engineering have provided society with low cost
processes for economically sustainable energy production.
Can we do it both
$0.25 - 1/Watt
$1-3/Watt
Solar Wind Electricity
Can we do it both
Environmentally
And Economically
Sustainably ?
$0.5-1/Watt
2050
~ 30 TW
from where?
Solar Conversion Processes
200 W/m
2
~ 1 mMoles photons/m
2
s
Inputs Outputs
18
Output Value - Input Costs - CapX - OpX > 0
10
How to use solar radiation ?
Inputs Outputs
19
Utilization of electrochemical potential from electronic excitations
• (e-,h+) EMF  Photovoltaics
• (e-,h+) EMF, EChem  Photosynthesis
• (e-,h+) EMF, Thermal Wind, Hydro, Solar-Thermal
Earth as a conversion system
• (e-,h+) EMF, Thermal Wind, Hydro
• (e-,h+) EMF, EChem  Photosynthesis
~ 1% Wind
~ 10% Hydro
120 000 TW
Bi Oth
20
120,000 TW
Biomass, Other
11
Cost-Effective Solar Energy Conversion: Wind and Hydro-Power
21
Why Solar-to-Chemical Photosynthesis Works
200 W/m
2
200 W/m
2
c=0.1%
0.2 J/s-m
2
Rice ~ $10-20/GJ Corn ~ $10-20/GJ
22
0.0063 GJ/y-m
2
~ $ 0.1/m
2
year Revenue
Because, it costs farmers less than $0.1/m
2
-year to grow biomass,
AND – only because they don’t need to produce very much of it.
~ 200 Watts/person
Rice $10-20/GJ Corn $10-20/GJ
12
Why Solar-to-Electricity Does Not Work
200 W/m
2
200 W/m
2
c ~ 10%
20 J/s-m
2
Electricity Value ~ $15/GJ
23
0.63 GJ/y-m
2
~ $ 10/y-m
2
Revenue
A modern cell system installed @ $5/W
peak
Capital Cost ~ $500/m
2
Why $500/m
2
It’s a wild world out there  $$$
13
price ($)
per m
2
(not for land)
To be cost effective on capital alone, a solar converter
must cost less than ~ $40/m
2
for c~10% and less than ~ $400/m
2
@ c=100%
(not for land)
paint (3 mils) 0.6
plastic (6 mils PE) 1.1
plywood 6.5
astro-turf 8.2
sod lawn 8.6
vinyl flooring 10.8
1" concrete 13.5
tar roof 43 0
+ lots of
land
tar roof 43.0
roof tile 64.6
Asphalt road 172.2
Si Solar Cell($5/W) 500.0
Home Construction 1500.0
Only VERY Inexpensive Systems
land
26
14
2009
27
Google: Grid Parity?
28 https://docs.google.com/present/view?id=dfhw7d9z_0gtk9bsgc&pli=1
15
29
30
16
Wealthy nations (with low GDP growth) “tolerate” economically
unsustainable renewables such as solar cells because
they are balanced by relatively low cost fossil/nuclear/wind
China ~ 3.5 TW
U.S. ~ 3.5 TW
Germany~ 0.6 TW
31
Chemical sciences and engineering must create options
for massive quantities of sustainable sources
of energy that are affordable by all people
Cost reductions over the last decade
l l d f i i
32
are largely due to use of increasing
numbers of low wage workers not
improved technology. The majority
of the costs are paid from taxpayer
subsidies.
17
33
~1780
~1880 Adams&Day, Fritts
Se Solar Cells (c~1-2% efficiency)
More than
100 years of
Development
No Significant
Cost-Effective
Applications
18
C*(e-,h+)
e-
h+
A
D
e-
h+
A
-
What about Solar-to-Chemical ?
¸ chemical potential
CC
D
+
2e
-
+ 2H
+
+xCO
2
C
x
H
2
O
z
H
2
O + 2h
+
½ O
2
+ 2H
+
Reducing
Potential
35
Growth Driven By Unsustainable Economics
36
19
Growth Driven By Unsustainable Economics
Biodiesel
37
Can Man Beat Nature ? “Artificial” Photosynthesis
G. Ciamician, Science 1912
20
Solar Energy, Volume 2, Issue 2, April
1958
Semiconductor Photoelectrodes

E
RED
Photocathode
p type SC
hv
+
+ +
RED
OX
p-type SC
Photoanode

+
hv
− −
RED
OX
E
n-type SC
21
Suspended PV “platelets”   1981
Hydrogen
Platelets
N-type semiconductor
p-type
semiconductor
Ohmic
contact
Platelet
100 + Years of
Photoelectrocatalysis (PEC)
Science has provided efficient systems
but not cost-effective energy production
TiO
2
PEC
42
PEC Air
“Purifier”
2
Mosquito Trap
22
Going Forward: Strategies and Tactics
How to do the right thing and get others to pay for it.
Options:
1) Scare them into it.
2) Keep making promises that are impossible
to keep.
3) Create options that, if tough problems are
creatively solved, might ultimately prove
economically sustainable.
43
Is there a cost-effective solar
PEC Process that can
make use of the material system?
Find and understand an
efficient PEC material system
23
Conceptual Engineering Process Models
Photoelectrodes = PV ($$) + electrolyzer($$)
Un-biased
Photoelectrode(s)
Chemically biased
Photoelectrode(s)
Electrically biased
Photoelectrode(s)
Bottom Up vs Top Down
do not underestimate the engineering 
Design a conceptual cost-effective
Solar Chemical Process
Can a material system be
found that meets the
minimum requirements ?
24
Artificial Photosynthesis
47
c ~ 10%
c ~ 0.1 %
c ~ 0.1 %
Conceptual Engineering Process Models
Photoelectrodes = PV ($$) + electrolyzer($$)
Un-biased
Photoelectrode(s)
Chemically biased
Photoelectrode(s)
Electrically biased
Photoelectrode(s)
A
-
D A + D
A
-
D
Split Z-Scheme
Slurry Photoreactor
Single Tank
Slurry Photoreactor
25
Today, there is only one known system for solar fuels 
(hydrogen) which might make economic sense.
ASSUMES that a stable, c=10% slurry material exists
Only slurry-based
James B, Baum G, Perez J, B.K. Technoeconomic Analysis of Photoelectrochemical
(PEC) Hydrogen Production. Analysis 22201, (2009).
y y
systems might meet basic
economic targets. $6/GJ
hv
Can we do better than Nature?
What structures should we make and calculate
D
-
D
A
A
-
e
-

e
-

50
26
Hybrid PEC “Nanoreactors”
Low cost inorganic semiconductor based heterostructures
Our Strategy
Theory
New/improved low cost semiconductors
Understanding of excitation/separation/
de-relocalization of charge size shape composition
h
+
e
-
hv
A
-
A
D
-
D
de-relocalization of charge size, shape, composition
Interface charge transfer. Recombination
Electrocatalysis
D
Synthesis/Experiment
New/improved low cost, high-quality semiconductors
Heterostructures
Diffusion barrier/encapsulation
AA
-
Zn
2+
Zn
o
-0.76
-0.26 V
3+
V
2+
Approach
hv
Maximize Stored SolarChemical Potential
D
-
D
A
A
-
2I
-1
I
2
0.54
D
-
D
(C
n
H
m
)OH (C
n
H
m
)O 0.6
2H
+
H
2
0.00
AgCl Cl
-
+Ag
o
0.34
0.22
Cu
2+
Cu
o
CO
2
CH
4
0.17
1) Identify cost effective optimal solar absorbing
semiconductor E
gap
~ 1eV systems with IQE >90%.
h
+
e
-
H
2
O2H
+
+1/2O
2
1.23
2Br
-1
Br
2
1.07
Fe
2+
Fe
3+
0.77
2Cl
-1
Cl
2
1.36
g p
2) Select and match best practical redox systems that
could provide stored energy AG ~ 0.9*E
gap
3) Maximize selective kinetics (minimize back reaction)
4) Determine means for stabilizing the material in the
redox system
27
HighThroughput
Methodology
Al2O3
3000 Å
Al2O3
1500 Å
V
800 Å
V
1600 Å
SnO2
4800 Å
4000 Å
1000 Å
La2O3
4000 Å
1000 Å
Y2O3
4000 Å
1000 Å
MgO
4000 Å
1000 Å
SrCO3
Sampl e: 826962
Theor y Gui ded
0 Å
5
3
0
Å
0 Å
2
6

0 Å
2
4
0
Å
0 Å
2
5
0Å Eu2O3 Tb4O7 Tm2O3 CeO2
Science 279, 837-839 (1998)
y
Li br ar y Desi gn:
Diversit y in Composit ion
Diversit y in Synt hesis
Rapi d Synt hesi s and Pr ocessi ng:
Elect rochemical Deposit ion
PVD, I nk Jet , Solgel,
Parallel vs Rapid Serial
Small vs Large Element Size
Hi gh-Thr oughput Scr eeni ng:
Opt ical, Chemo-opt ical
Phot oelect rochemical
GC-MS
Start with a known reasonable host Try to make it better
Make efficient material
more stable
Bak et. al., Int. J. Hydrogen Energy,
vol 27 (2002) 991-1022
Zn
n
X
m
O
40
45

W
n
X
m
O
p
H2O/H2
O2/H2O
1.23 eV
Cu2O TiO2 Electrolyte
Eabs
(eV)
- 4
- 5
- 6
- 7
- 8
- 3
ENHE
(eV)
0
+
1
+
2
+
3
- 1
- 2
2.0 eV
3.0 eV
0.30
Cu
2
O/XO
n
0 20 40 60 80 100
0
1
2
3
4
15
20
25
30
35
40

P
h
o
t
o
c
u
r
r
e
n
t
(
µ
A
/
c
m
2
)
[Mo]
1V bias
zero bias
J. Combi. Chem. 4(6), 573-578, 2002
4 6 8 10 12
0.10
0.15
0.20
0.25
P
h
o
t
o
c
u
r
r
e
n
t

(
m
A
/
c
m
2
)
pH
J. Comb. Chem., 7, 264-271, (2005)
28
Doped: ZnO
The “Science” of Synthesis
55
J. Comb. Chem., 7, 264-271, (2005)
WO
3
4
15
20
25
30
35
40
45


r
e
n
t
(
µ
A
/
c
m
2
)
1V bias
W
n
X
m
O
p
MoO
3

MoO
3
W
0 2
Mo
0 8
O
3
56
0 20 40 60 80 100
0
1
2
3
4
P
h
o
t
o
c
u
r
r
[Mo]
zero bias
J. Combi. Chem. 4(6), 573-578, 2002
500 550 600 650 700 750 800 850 900 950 1000 1050 1100
W
0.2
Mo
0.8
O
3
W
0.3
Mo
0.7
O
3
W
0.5
Mo
0.5
O
3
W
0.7
Mo
0.3
O
3
W
0.8
Mo
0.2
O
3
WO
3

I
n
te
n
s
ity

(
a
.
u
.
)
Raman Shift (cm
-1
)
20 22 24 26 28 30
0.2 0.8 3
W
0.5
Mo
0.5
O
3
W
0.8
Mo
0.2
O
3
WO
3
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
2 u
29
In spite of decades of research, there is no evidence that
wide gap oxides (TiO
2
, WO
3
, ZnO, …) can be modified to serve
as efficient solar absorbing hosts.  Fe ? Cu ?
Fe
2
O
3
 n-Type Indirect Bandgap 2 - 2.2 eV
 40% solar spectrum absorbed
 Globally scalable
 Abundant, inexpensive
 Non-toxic
 Photo-stable against corrosion
 Mott Insulator (Poor carrier transport )
 Anisotropic conductivity
 Low electrocatalytic activity
Theory Guided Experimentation
Undoped Fe
3+
Fe
2
O
3
Pt
4+
doped
Cr
+3
doped Al
+3
doped
LDA+U
58
Flat Conduction band  large effective mass, poor conductivity.
1) Majority Carrier Donor Concentration (traditional doping)
2) Create Impurity bands which have smaller mass
3) Break C-T Mott Insulator, spin forbidden electron transport
LDA+U
U=5.7 eV
12 Fe +18 O
30
Characterization of substituted Fe
2
O
3
B
g
=2.1 eV
J. Phys Chem C. 20(12),3803, (2008)
Chem. Mater., 20, 3803–3805, (2008)
Energy Env. Sci. 4,1020, (2011)
1%Ti
•Optical properties show little change with dopants
• Higher valence dopants (n-dope) “helps”
• Isovalant substitutions with large cation size differences (strain) “helps”
Del af ossi t es (CuMX
2
)
CuCrO
Cu
+
C
3+
Theoretical bandgap
Direct: 3.0 eV
Indirect: 2.1 eV
Experimental bandgap: 1.3 eV
CuCrO
2
Cr
3+
In general, poor efficiency.
31
Phosphides
(start with an efficient material and make it more stable)
• Easy to make ( from libraries of oxides)
• M
x
O
y
+H
3
PO
4
;  H
2
at 900 C
• .
• Easy to break
• Zn
3
P
2
+ 6H
2
O → 2PH
3
+ 3Zn(OH)
2
Strategy -> keep
h f
H
+
Na
6
[H
x
M
y
O
z
] + NH
4
HPO
4
MPO
x
+ NH
4
OH +NaOH +H
2
O
 H
2
at 900 C
FeP InP Zn
3
P
2
Ni
x
P
y
WP MoP
them safe
Sulfides  (SnS)
Electrodeposited Film              powder
32
Identification of efficient, stable, cost effective solar
absorbing materials remains
the #1 challenge for solar energy PEC
Work to date with all oxides has been discouraging.
- Although their visible band absorption can be improved, not by nearly Although their visible band absorption can be improved, not by nearly
enough. The common wide gap oxide semiconductors (TiO
2
, ZnO, WO
3
)
will not work as absorbers for solar fuel applications.
- Iron oxides are intrinsically poor candidates for solar PEC applications
TiO
2
63
and in spite of attempts to improve their properties they remain far too
inefficient by 10-100x.
Sulfides and Phosphides Deserve More Attention
Don’t forget Si !
Silicon
Fe
2
O
3
Last oxide hope Cu
x
O
Theory Guided Identification of Active, Stable,  
and Selective Electrocatalysts
h
+
e
-
hv
D
D
-
2H
+
H
22
“In situ membrane”
33
65
Pt-Au Alloy Nanoparticles for ORR
Slope ~ n
e
66
34
Co/Au
Fe/Ni
Bimetallic OER Electrocataysts
Co Au
Pt/Au
67
Electrochem.Com. 11 (2009) 1150–1153
Pt/Au
Choice of the electrocatalyst assumes you know the reaction you want.
2H
+
H
2 AA
-
What is the best form of the chemical potential product?
H
2
fast, separable, easily reacted (H
2
+ CO
2
CH
4
)
1) High efficiency, cost-effective absorbers, E
gap
~ 1eV.
2) Identify stable redox chemistry that can be integrated into a major
chemical cycle.
10
12
14
16
18
Zero Bias
NaOH
Glycerol
Erythritol
Xylitol

(
%
)
D
-
D
(C
n
H
m
)OH (C
n
H
m
)O
2 electrodes 1 sun
Ti Doped Fe
2
O
3
H
2
S2H
+
+ S
2HBr 2H
+
+ Br
2
Avoid zero value products
350 400 450 500 550 600
0
2
4
6
8
I
P
C
E
Wavelength (nm)
H
2
O2H
+
+1/2 O
2
2HCl 2H
+
+ Cl
2
Get over water splitting!
35
The formation of adsorbed OOH is limiting
and only at high electrode potential is this
step downhill in free energy. The process
takes place on an oxidized surface.
Oxygen evolution should start at E>1.8 V
69
yg
Functional Nanoparticulate Heterostructures
Fe
2
O
3
@ZrO
2
70
10 nm
36
Hybrid PEC “Nanoreactors”
Low cost inorganic semiconductor based
heterostructures
A
l
2
O
3
A
b
s
o
r
b
e
r
Ag 
(Ohmic Contact)
ħω
h+
e‐
Oxidizing 
reactant
Reduced 
product
Au or Pt 
(Schottky contact)
Reducing 
agent
Oxidized 
product
Mubeen J. Hussaini
Francesca Toma
Martin Moscovits
Galen Stucky
NiO
A
A
b
Electrodeposited Heterojunction in Porous Alumina
CdSe
Au
TiO2
A
l
2
O
3
b
s
o
r
b
e
r
Mubeen J. Hussaini
Francesca Toma
Martin Moscovits
Galen Stucky
37
Large Scale, Cost Effective Processes Are Typically Integrated
Large Scale, Cost Effective Processes Are Typically Integrated
Process Alternative: C
n
H
m
O
z
 H
2
+ CO
2
H
(C
n
H
m
)OH + h
+
(C
n
H
m
)O + H
+
2e
-
+ 2H
+
H
2
H
2
Biomass or
Wastewater
CO
2
X-ols
Catalyst
Regeneration
Reactor Separation
Treatment
Separation
~ 1 kg/person/day organic waste (~ 1 TW )
38
2e
-
+ 2H
+
H
2
2Br
-1
Br
2
Large Scale, Cost Effective Processes Are Typically Integrated
Example Process Alternative: 2HBr  H
2
+ Br
2
Biomass
Regeneration
O
2
+ HBr Br
2
+ H
2
O
Water Air
HBr Br
2
Activation
CH
4
+ Br
2
CH
3
-Br + HBr
Coupling
CH
3
-Br Gasoline + HBr
BioMethane Gasoline
2
39
77
Net Reaction: 8CH
4
+ (16/c) ¸ C
8
H
16
+ 8H
2
(Ideal)
Summary
• Today there are no significant, cost‐effective, manmade solar 
conversion processes because no efficient, stable, scalable, and 
cost‐effective absorbing material system is known.  
• Recent advances in theory, complex surfaces, and synthesis of 
novel materials may have significant impact if directed wisely.  
• Water splitting may or may not ever be cost‐effective, but there 
are potentially many other solar‐to‐chemical conversions that 
might be more cost‐effective and ultimately more useful to 
mankind.  The system matters, many can never work.
• Fundamentally production of chemical fuels from solar energy 
at less than $15/GJ is possible, practically it is very very difficult.
Think outside the box or we will not succeed
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Th k Y Thank You
Collaborators: Alan Kleiman, Yong-Sheng Hu, Peng
Zhang, Nirala Singh, Galen Stucky, Eric McFarland