First Principles-based Atomistic Modeling
in Hydrogen Fuel Cell Technologies:
Promises and Challenges
SUMBER :
OLEH Center for Nano- and Molecular
Science and Technology
HUSNI HUSIN Texas Materials Institute
Institute of Theoretical Chemistry
TEKNIK KIMIA
GREEN POWER: Hydrogen Fuel Cells
HYDROGEN + FUEL CELLS
Combines hydrogen and oxygen to produce electricity, heat, and water.
Address the two most important energy challenges:
▪ reducing carbon dioxide emissions;
▪ lowering dependence on non-renewable fossil fuels.
Rosy Outlook:
Angstrom ✓ Electric and hybrid vehicles,
Connecticut
✓ Potable electronic devices,
✓ Base load power plants,
✓ Emergency power systems,
✓ ……
Toshiba
Boeing
Fukuoka Eco-Sailboat
Hydrogen Town
Hydrogen
Fuel Cells
HYDROGEN FUEL INITIATIVE – yr 2003
"Tonight I am proposing $1.2 billion (for 5 years) in
research funding so that America can lead the world in
developing clean, hydrogen-powered automobiles."
January 28, 2003
State of the Union Address
The initiative’s goal is to develop the technologies
by 2015 that will enable U.S. industry to make
hydrogen-powered cars available to consumers by
2020.
Korea: The government only started funding
hydrogen-related R&D in 1998, but is emerging as
a major player. A new program was launched in
2004 with a budget of $586 million through to
2011.
Technical Challenges:
… that needs to be addressed through R&D to pave the way for commercialization
of fuel cell and hydrogen infrastructure technologies
Hydrogen Production and Delivery
Hydrogen Storage
Fuel Cell Cost and Durability
Recent Progress in R & D:
Hydrogen program led by the Department of Energy (DOE) has made
important progress in R & D:
▪ reduce the cost of producing hydrogen from natural gas;
▪ develop a sophisticated model to identify and optimize major elements of a
projected hydrogen delivery infrastructure;
▪ increase by 50% the storage capacity of hydrogen;
▪ reduce the cost and improve the durability of fuel cells.
MORE DIFFICULT CHALLEGES lie ahead:
• find a technology that can store enough hydrogen on board a vehicle to
achieve a 300-mile driving range;
• reduce the cost of delivering hydrogen to consumers;
• further reduce the cost and improve the durability of fuel cells.
Fuel Cells: Fundamental Issues
Reliable; Low-cost; High-performance
▪ High Temperature (> 100oC) Membranes
FC stack ▪ Water Management
▪ Stack Cooling
▪ High System Complexity
▪ Uneven Reactant Distribution
▪ ….
ELECTRIC CIRCUIT
(40%-60% Efficiency)
Catalyst Research
Fuel H2 O2 from Air
H2 → 2H+ + 2e– Platinum (Pt)
2H+ + 2e– + ½O2 → H2O catalysts
Heat (85 oC)
▪ Increasing catalytic activity, particularly
Used Fuel for the oxygen reduction reaction (ORR)
Recirculates H2O(g), Air
Flow Field Plate
▪ Reducing CO poisoning
Anode Cathode ▪ Developing cheaper, more abundant
Catalyst alternatives to Pt.
Proton Exchange Membrane (PEM)
Catalyst Design: Magic or Science ..??!
Alchemy
2007 Nobel Prize
In Chemistry
Gerhard Ertl
“Chemist Wins Nobel For Catalyst Studies” Max Planck Society
Non-Platinum Catalysts for PEM Fuel Cells
Develop low-Pt or Pt-free metal catalysts, with similar (or better) activity and
performance durability to the currently used Pt-based catalysts …
Pt monolayer supported on
Pt-M alloys (M=Ni,
less expensive metals
Co, Fe, Ti, V,…)
Core-Shell Nanoparticles
Novel Pt-free Catalysts
▪Binary/ternary combinations of Pd, Au, Ag, Co …
▪…
Our current research is focused on gold-based bimetallic alloys,
such as gold-palladium group metals.
Why Gold-based Nanocatalysts ?
Gold nanoparticles exhibit extraordinarily high activity for various catalytic
oxidation processes at or below room temperature, while its bulk counter part
has long been known to be chemically inert.
Advantages of gold-based alloy nanocatalysts include:
▪ much less sensitive to CO poisoning than Pt
▪ less expensive than Pt
▪ bifunctional catalytic activity ---- can be used for both anode and cathode reactions
in fuel cells
Kyle Hwang
Metal Alloy Nanoparticles for Catalysis
Metal nanoparticles are ideal catalysts, exhibiting high activity and
moreover their catalytic function can be controlled by tailoring their
PtCo/C
size and shape.
Such tunability may allow design and synthesis of next generation 50 nm
catalysts with:
from G.G. Scherer
1. Higher activity → Less catalytic usage
2. Higher selectivity → Little or no byproducts and waste
3. Longer lifetime → Reduced catalyst cost
low metal coordination e- diffusion layer e-
metal-support interaction H2O
single crystal
metal-metal
surfaces
interaction H2
supported H+ O2
single metal
nanoparticles
(Pd, Pt, Au, ..) bimetallic
Anode Cathode
nanoparticles
(Pd-Au, Pt-Au, ..) electrolyte catalyst
membrane
Nanocatalysts: Fundamental Issues
❑ Catalytic properties are governed by
from Krumeich, ETH
– particle size and shape
– particle surface composition and structure
– particle-support interfacial interactions
❑ Weak particle-support Interactions
– shape change
– sintering
– loss of their unique properties
❑ Therefore it is necessary to better understand:
– synthesis, structure and thermal stability of supported
metal nanoparticles
– surface structure and chemistry of support materials
– dependence on catalytic activity on particle structure,
metal-metal interactions in metal particles, and metal-
support interfacial interactions
from Goodman, TAMU
“ Better understanding the fundamentals is key to developing more effective nanocatalysts”
Rational Design and Development of Novel Bimetallic Electrocatalysts for
Fuel Cell Applications through First Principles-based Atomistic Modeling
Develop a quantitative understanding of the nature and reactivity of
Au-based bimetallic nanocatalysts, with particular focus on the
effects of catalyst support materials and process conditions on:
Nucleation, Growth and Structure
Surface Composition and Configuration
Catalytic Activity and Poisoning
Rational Design and Synthesis
AuPd/C
Gold-Palladium Nanocatalysts
Bimetallic palladium-gold (Pd-Au) alloys
have been found to significantly increase
What alloying effects
catalytic efficiency, compared to the
….. ???
monometallic Pd and Au counterparts, in
various reactions including:
▪ Direct synthesis of H2O2 from H2 and O2
▪ Oxidation of carbon monoxide
▪ Production of vinyl acetate monomers
▪ …..
H2 O2
Pd-Au catalysts have also recently received much
OH+OH
attention for hydrogen fuel cell applications,
O+OH
because they are much less sensitive to CO H2O2
poisoning than pure Pt or even Pt-Ru.
Direct H2O2 Synthesis: Role of Pd Ensembles
Pd monomer
0.53
1.55 Pd-Au Pt-Au
Pd monomers surrounded by less
active Au atoms that suppress O-O
Pure Pd bond scission are primarily
0.24
responsible for the significantly
enhanced selectivity towards H2O2
formation on PdAu alloys.
0.89
Ham, Hwang et al.,
0.51 J. Phys. Chem. C, in press (2009)
in eV
Gold Nanoparticles on TiO2(110)
… unusual catalytic activity for CO oxidation even below room temperature …
Haruta, catalytic today (1997)
O=O O=O
Tsurf < 300 K
single crystalline TiO2 supported Au
Au surfaces nanoparticles
… shows strong size-dependent
low metal coordination catalytic activity.
particle-support interaction
... ???
CO oxidation
Activity Goodman et al.
Science (1998)
Mean particle diameter, nm
Gold Nanoparticles on TiO2: Surface Chemistry
O2 adsorption & diffusion Au particle growth & structure
o
1.48 A
CO oxidation
▪ Gold particle – low coordination
▪ Au-TiO2 interface
Supported Au Clusters
( Role of the cluster-support interface)
O2 dissociation …
0.4 eV
1.4 eV
Supported Au Clusters
( Role of the cluster-support interface)
… no sizable barrier, in good agreement with
CO oxidation experimental observations*
*Haruta, Gold Bul. 37, 27 (2004)
+ CO(ad)
2.0 eV
Haruta (2004)
Promise of Atomistic Modeling
Science 227, 917 (1985)
First principles-based atomistic modeling can
complement experimental observations and
also provide many valuable hints on how to
control the structure and function of supported
metal nanocatalysts, while current
experimental techniques are often limited to
providing complementary real space
information.
This further offers an invaluable guide to the
rational design and synthesis of bimetallic
nanoparticle-based materials for various
catalytic applications
Supercapacitor energy storage Si/Ge nanowire: batteries, thermoelectrics
SiO2
Si
Au Si
Synthesis Structure Properties
…. ???
Nanocrystal memory
Computational Nanoengineering Lab
UT – Austin (since Fall 2001) Au
Si
SiO2
TiO2(110)
Metal nanocatalysts
Semiconductor processing
First Principles-based Atomistic Modeling
❑ …. allows us to explore complex chemical and physical phenomena
occurring at nanomaterials and nanosystems at the atomic scale. So it
has emerged as an increasingly important area of research in
nanoscale science and engineering.
❑ Progress from the computation approach contributes greatly to
realizing experimental control of materials properties in the
nanoscale regime.
Exponential Growth in Computation
In past 35+ years, computational power (driven by Moore’s Law) has increased
by over 6+ orders of magnitude.
ENIAC (1947-1955)
Supercomputer
Computational modeling now ‘auto-catalyses’ its own progress exponentially!!!
Acknowledgements
Current & Former Group Members:
▪ Fourteen (14) PhD Students
▪ Three (3) Post Doctoral Associates
▪ Four (4) Visiting Professors
Sponsors (Current & Past):
▪ National Science Foundation (NIRT, CAREER, SGER, CBET)
▪ Department of Energy (SISGR)
▪ Robert A. Welch Foundation (2002-present)
▪ Semiconductor Research Corporation (CSR, BEP, FE)
▪ International SEMATECH (AMRC)
▪ Korea Institute of Science and Technology
▪ Tokyo Electron, Inc.
▪ Applied Materials, Inc.
▪ SKC, KCC, Intel, University of Texas at Austin
▪ Texas Advanced Computing Center
