Solar Fuels I

Kristin Persson
3106 Etcheverry
LBNL 33-143D
384 HMMB
kristinpersson@berkeley.edu

What are solar fuels

Substances that store the suns energy as useful chemical energy allowing
for reasonable rate conversion into other forms of energy

Common forms: H2, ethanol,

methane, ammonia

Earliest form of energy source except food :

combustible biomass

Solar Fuels
http://www.chalmers.se/ap/EN/research/chemical-physics/

Solar fuels are substances that store solar energy in

the form of usable chemical energy.
Candidates should:
Possess adequate energy density

Exhibit flexible conversion to heat, electrical or mechanical

energy

Capable of being produced, transported and stored

efficiently

Be environmentally friendly enabling sustainable

incorporation of conversion products into global circulation
in biosphere

C. Graves et al. / Renewable and Sustainable Energy Reviews 15 (2011) 1

http://www.ccisolar.caltech.edu/

1800 H2 electrolysis;
Nicholson and Carlisle

First combustion engine used H2

1807 de Rivaz engine featured spark ignition

and H2 as fuel

The compressed hydrogen gas fuel was stored

in a balloon connected by a pipe to the cylinder
Oxygen was supplied from the air by a separate
air inlet
Manually operated valves allowed introduction
of the gas and air at the correct point in the cycle

Solar Fuels
Process that converts sunlight, water and/or CO2 into some version of carbohydrates and oxygen

biomass

Water and CO2

splitting

biofuel

Convert into fuels

Direct combustion

Photolysis
Electrolysis
Thermolysis

Exotic
hybrids

Integrating
bacteria

Biomass and solar fuel

Pellets big in US and Europe

There is uncertainty to what degree making heat or electricity by burning wood

pellets contributes to global climate change, as well as how the impact on climate
compares to the impact of using competing sources of heat. Factors in the
uncertainty include the wood source, carbon dioxide emissions from production
and transport as well as from final combustion etc.

Efficiency of biomass
For actual sunlight, where only 45% of the light is
in the photosynthetically active wavelength range,
the theoretical maximum efficiency of solar
energy conversion is approximately 11%
Plants do not absorb all incoming sunlight (due to
reflection, respiration requirements of
photosynthesis and the need for optimal solar
radiation levels)
Hence, not all harvested energy is converted into
biomass, which results in a MAXIMUM overall
photosynthetic efficiency of 3 to 6% of total solar
radiation.

Biomass potential
In reality, its worse: solar to biomass conversion
(total cycle) is inefficient (0.3%)

Land with crop production potential, 1990:

25 Tera m2
Cultivated Land, 1990: 9 Tera m2
Additional land needed to support 9 billion
people in 2050: 4 Tera m2
Remaining land available for biomass energy:
13 Tera m2
At 8.5-15 oven dry tons/hectare/year:
energy potential is 7-12 TW
Possible/likely this is water resource limited
25% of U.S. corn in 2007 provided 2% of transportation fuel

Biomass conversion to liquid fuel

The reason for the current focus on using biomass for liquid
fuels rather than for direct combustion is that coal is abundant
and inexpensive, it is less expensive to transport (per joule)
and it burns with higher energy efficiency and less ash than
biomass.

Estimated ~3x1021 J of chemical energy stored in

usable photosynthetic biomass per year.

Even with enhanced conversion efficiencies for biofuel production and large-scale
use of biomass waste, clearing sludge, animal wastes, and wood it will be hard to
provide ALL the required amounts of renewable chemical energy necessary to fuel
an industrializing world economy and to cover the needs of todays world
population and that of the future.

http://solarwindgreenenergy.blogspot.com/2011/10/biofuel-facts.html

Fraction that can be used in a sustainable way depends on:

Emissions, economics and efficiencies of conversion of biomass into usable gas
and liquids
Social issues - about one-sixth of humans are undernourished (competition
between food and biofuel)
30%40% of net produced biomass already used as food, feed, fiber, and fuel,
which corresponds to ~ 10-18% of the actual worlds primary energy supply.

Topics

biomass

Water and CO2

splitting

biofuel

Convert into fuels

Direct combustion
Photolysis
Electrolysis
Thermolysis

Lysis (/lass/; Greek lsis, "a loosing" from lein, "to unbind")

Exotic
hybrids

Integrating
bacteria

Many Roads to Hydrogen

Courtesy of Harry Atwater

Solar Fuels Production & Use

http://www.rsc.org/ScienceAndTechnology/Policy/Documents/solar-fuels.asp

Chemical Feedstocks

http://www.rsc.org/ScienceAndTechnology/Policy/Documents/solar-fuels.asp

Common intermediate: syngas

In principle, syngas can
be produced from any
hydrocarbon feedstock,
including: natural gas,
naphtha, residual oil,
petroleum coke, coal,
and biomass.
Syngas is a crucial
intermediate resource for
production of hydrogen,
ammonia, methanol, and
synthetic hydrocarbon
fuels. Syngas is also an
intermediate in producing
synthetic petroleum for
fuel or lubricant via the
FischerTropsch process
and methanol to gasoline
process.

Spath and Dayton NREL report 2003

Syngas is combustible but with less than

half the energy density of natural gas.

Hydrogen flow ; every node needs innovation

http://www.rsc.org/ScienceAndTechnology/Policy/Documents/solar-fuels.asp

Solar Fuel as Energy Storage and Distribution

C. Jooss, H. Tributsch, Solar Fuels (Chap. 47) in

Fundamentals of Materials for Energy and
Environmental Sustainability,D. Ginley and D.
Cahen Eds, Cambridge Univ. Press (2012)

Materials Science and Engineering of Clean Energy [3.70]

Drivers & Disincentives

CO2 capture
Water splitting to generate H2
Use of solar energy
CO2 conversion to CO
H2 + CO conversion to HC feedstocks
HC feedstock conversion to
Fertilizer
Plastics
Pharmaceuticals
Synthetic fuel for transport

What role do the following play & which will likely be most critical ?
Environmental issues
Regulations
Competition
Investment culture
Incentives
Installed infrastructure
Trade regulations
Public opinion
Experience
Taxes
Politics
Inertia
Rate of innovation
International relations
Culture
Specific inventions
Education
Corporate culture

A Race for Efficiency, Low-cost and Durability

Requires sustainable mass production of solar fuels.
The storage of light and electrical energy in molecular chemical bonds easily stored and
transported.
Chemical energy easily converted to other useful forms of energy.

Requires interconversion of simple molecules H2, H2O, CH4 and CO2, a continuing challenge.
Bottleneck: durable and inexpensive catalysts for photo-induced and/or thermally assisted
conversion of various redox pairs with catalyst for O2 reduction the central issue.

http://people.ucalgary.ca/~cberling/research.html

Solar Fuel Characteristics

C. Jooss, H. Tributsch, Solar Fuels (Chap. 47) in Fundamentals of Materials for Energy and
Environmental Sustainability,D. Ginley and D. Cahen Eds, Cambridge Univ. Press (2012)

Hydrogen as Fuel
High energy density/mass (141 MJ/kg vs 45.7 MJ/kg for gasoline):
Good for weight-limited transportation (space).
Abysmal volumetric energy
Low energy density/volume, liquid boils at 20.27 K
Explosive mixture 4-74% vol in air
Clean emissions, only small amount of NOx
70 million metric tons produced per year, nearly all from fossil fuels
By steam reforming of methane or natural gas (700-1100C)

Followed by water gas shift reaction: 130 C

Ammonia

C. Jooss, H. Tributsch, Solar Fuels (Chap. 47) in Fundamentals of Materials for Energy and
Environmental Sustainability,D. Ginley and D. Cahen Eds, Cambridge Univ. Press (2012)

Ammonia as Fuel
NH3 cheaply produced from hydrogen or syngas via Haber Bosch process
N2 + 3 H2 2 NH3 (H = 92.22 kJmol1)
Catalyst: iron promoted with K2O, CaO, SiO2, and Al2O3
N2 (g) N2 (adsorbed)
N2 (adsorbed) 2 N (adsorbed)
H2(g) H2 (adsorbed)
H2 (adsorbed) 2 H (adsorbed)
N (adsorbed) + 3 H(adsorbed) NH3 (adsorbed)
NH3 (adsorbed) NH3 (g)

Can be combusted in benign

manner (but must handle NOx)
Used as fuel in alkaline and solid
oxide fuel cell
Can be stored as liquid (8 kbar/RT)
or in metal ammine complexes but
highly toxic.
Use as hydrogen storage medium.

500 million tons (453 billion kilograms) of nitrogen fertilizer produced per year, mostly in
the form of anhydrous ammonia, ammonium nitrate, and urea. 35% of world natural gas
production is consumed in the Haber process (~12% of the world's annual energy supply)

http://en.wikipedia.org/wiki/Haber_process

Methane

C. Jooss, H. Tributsch, Solar Fuels (Chap. 47) in Fundamentals of Materials for Energy and
Environmental Sustainability,D. Ginley and D. Cahen Eds, Cambridge Univ. Press (2012)

Methane as Fuel
CH4 is a nature gas and provides ~30% of US energy requirements
Greenhouse warming potential = 72 x that of CO2 which makes containment an issue
Produced from syngas, coal gasification, pure CO2 and biomass conversion

Sabatier method : 250-500 C @ 5-10 bar

Up to 95% efficiency achieved

Methane from CO2:

Two-reaction process:
Water gas shift

+
CO methanation

Conversion efficiencies: electrolysis (to get H2) + methanation= 46-86% reduced

by 15% using atmospheric CO2. Alternatively use CO2 dissolved in sea water
containing 140 x that in atmosphere and extract via electrolysis.

Ethanol

C. Jooss, H. Tributsch, Solar Fuels (Chap. 47) in Fundamentals of Materials for Energy and
Environmental Sustainability,D. Ginley and D. Cahen Eds, Cambridge Univ. Press (2012)

Ethanol as Fuel

Ethanol, C2H5OH: volatile, colorless liquid

Combustion: water, CO2, NOx
Biofuel with production increased from 17-74 billion liters between 2000-2009
leading to 5% share of fuel for cars.
Resultant shortages in corn and sugar cane for food purposes.
Water limited
Reductions in greenhouse emissions relative to gasoline ~18-28% but sometimes
increased! Depends on feedstock, transport, and conversion process

Microbial fermentation of sugar/distillation/dehydration

A more sustainable ethanol production via hydrogenation of CO2 e.g. with Rh based catalyst

Methanol

C. Jooss, H. Tributsch, Solar Fuels (Chap. 47) in Fundamentals of Materials for Energy and
Environmental Sustainability,D. Ginley and D. Cahen Eds, Cambridge Univ. Press (2012)

Methanol compared to diesel

Methanol is used directly as a
fuel in race cars and has been
proposed as the energy carrier
of choice in the methanol
economy parallel to the
hydrogen economy
FT produces synthetic crude
that must be refinedit does
not directly produce fuel
The MTG process produces
gasoline directly, no further
refining required.

ExxonMobils Methanol-to-Gasoline (MTG) Technology for Coal-to-Liquids

Project

Solar Fuel Production all uphill

C. Jooss, H. Tributsch, Solar Fuels (Chap. 47) in Fundamentals of Materials for Energy and
Environmental Sustainability,D. Ginley and D. Cahen Eds, Cambridge Univ. Press (2012)

Topics

biomass

Water and CO2

splitting

biofuel

Convert into fuels

Direct combustion
Photolysis
Electrolysis
Thermolysis

Exotic
hybrids

Integrating
bacteria

Thermolysis

Direct Thermolysis

Slightly easier for CO2 than for H2O

Still very challenging, multi-step reaction schemes
Necessity of separating O2/H2 in final product

Thermochemical Cycles

or CO2

or CO

Integrated solar capture and fuel production

Oxygen and fuel produced in separate steps
Challenges due to structural change & volatilization (vapor pressure)
Fuel largely limited to hydrogen
Although a large number of thermochemical cycles have been proposed, only a small number have
been demonstrated experimentally and none are commercialized.

General considerations
Reactor design and
operation, a point
of diminishing
returns exists with
respect to T high ,
above which
thermal radiation
losses dominate

Highest possible efficiency = 1 Tlow/Thigh

Adv. Energy Mater. 2014, 4, 1300469

1773 K (1500 C) is a
realistic upper limit

Thermodynamic Analysis
MOxMOx-1+ 0.5O2
MOx1+ H2OMOx+ H2 or MOx1 + CO2MOx + CO

Greduction(Tr)= HMOx1 HMOx-TTr(SMOx1 +0.5 SO2 SMOx) 0

Ggas splitting(Tgs)= HMOx HMOx-1HH2O-TTgs(SMOx+SH2-SMOx1 SH2O) 0
or
Ggas splitting(Tgs)= HMOx HMOx-1 HCO2-TTgs(SMOx+SCO-SMOx1 SCO2) 0
Assume that we can ignore the difference in entropy between
the two solid states ; common practice

Thermo contd

Meredig and Wolverton 2009

Set Hred = HMOx1 HMOx

Greduction(Tr)= Hred 0.5TTrSO2 0

(1)

Ggas splitting(Tgs)= -Hred HH2O-TTgs(SH2SH2O) 0

(2)

or
Ggas splitting(Tgs)= -Hred HCO2-TTgs(SCOSCO2) 0 (3)

No practical reaction below 1350 K

Setting equations to zero gives the necessary condition for favorable reactions
Adding (1) + (2) or (3) eliminates the only solid materials dependent quantity Hred

Thus the only quantity that really matters is the one we neglected the difference in solid state entropy !

All thermo with no solid state

materials input
No practical reaction below
1800 K ; exp finds 1350 K
Lowering pressure for
reduction cycle can help gas
release
Materials may be highly
volatile or suffer irreversible
degradation at very high TR
temperatures 2000 K and
kinetic processes will be
very slow at very low GS
temperatures < 1000 K

Meredig and Wolverton 2009

Entropic Considerations

Bringing entropy back into the

picture we find that

Sred = SMOx1 SMOx 0

makes the reactions more favorable
at lower temperatures

Meredig and Wolverton 2009

However, for most simple oxides, Sred is negative.

Which binary oxides have favorable

entropy change ?
Meredig and Wolverton 2009

According to
computational
considerations; no
binary oxide falls in the
optimal gap. A few of
the better candidates
are already considered:
Fe-O, ZnO and CeO2

Considered Systems
Systems with large oxygen cycling under largely homomorphic constraints
Other considerations: reaction thermodynamics, radiation losses and emissivity, vaporization
losses and corrosion, reaction kinetics, microstructural stability, phase stability and/or
formation of multiple phases, and interactions with support materials influence the choice of
materials:

metal-substituted ferrites (magnetite and spinel) and ceria

1/MFexO4 1/ [MFexO4] + 1/2O2 (M = Fe, Co, Ni, or Zn)
1/[MFexO4] + CO2 1/ MFexO4 + CO
1/CeO2 1/CeO2+1/2 O2
1/CeO2+CO2 1/ CeO2 + CO

Ceria cycle

Ceria thermodynamics and phase diagram well-known

High melting temperature 2500 C, non-volatile

HT Homomorphism important
HT structure is
the same for
large change in
oxygen content

Kinetics ; morphology
Oxygen diffusion
even at high
temperatures
needs to be
facilitated by
high surface
areas and foamlike morphology
Ceria is better
than most : D ~
10-5 -10-4 cm2/s
600 C

Ferrites

Magnetite (Fe3O4), this reduction can proceed as far as an overall composition of Fe3O3.1
before a phase boundary is reached where metallic Fe forms

Compared to ceria, ferrites have a much greater reduction capacity at a given temperature

However, very deep reductions cannot be achieved using Fe3O4 without heating in excess of
the melting point of the reduction product FeO, which presents serious challenges for practical
implementation.

This problem can be addressed by substituting up to 50% of the Fe(II) cations in the
octahedral sites with a different divalent metal, which lowers the temperature required to
reduce the material and simultaneously raises the melting point. Metal-substituted ferrites
include MnFe2O4 , CoFe2O4 , NiFe2O4 , and ZnFe 2 O 4 ,

Efficiency

Despite interesting materials idea

Todays reactors have abysmal performance; 0.5-2.5 %
Losses by parasitic reactions, O non-reactivity, gas
separation, T radiation