1) Researchers at Brookhaven National Laboratory developed a new type of electrocatalyst using core-shell nanoparticles with a palladium or palladium alloy core coated with a single layer of platinum atoms. 2) Testing showed the platinum monolayer core-shell electrocatalysts improved catalytic activity for fuel cells by 5-20 times compared to bulk platinum per weight of platinum used. 3) Collaboration between the Department of Energy, Brookhaven National Laboratory, and industry partners helped optimize synthesis techniques, test fuel cell performance, and demonstrate the potential for scale-up of production.

1. B R O O K H AV E N N AT I O N A L L A B O R ATO RY
Accelerating Innovation
Electrocatalysts forPlan FY Cells
Laboratory Fuel 2010-2019 June
2,
2010
June 2012

2. Technology Description
• Core-shell nanoparticles with a palladium or palladium alloy
core coated by a monolayer of platinum
• All platinum atoms on surface and participate in catalysis
• Lattice contraction improves catalytic activity of platinum
• Reduction of platinum reduces overall precious metal cost
2
BROOKHAVEN NATIONAL LABORATORY

3. Technology Opportunity
• One version of the platinum monolayer core-shell
electrocatalysts is being sold in small quantities by a licensee.
• Manufacturing at commercial scale is accomplished.
• Compositions for other applications must be optimized.
3
BROOKHAVEN NATIONAL LABORATORY

4. Technology Leadership
• Nanoparticles of platinum should work better than bulk
platinum in catalysis because of their higher surface area, but
they don’t.
1.2
P t A u N i5/ C
0.9
@0.9V
-1
jk / A.mg
0.6
P t A u N i5/ C
0.3
P t/ C P t/ C
0.0
Pt m a s s a cti vit y N o ble m e t a l m a s s a cti vit y
• Dr. Adzic’s group was the first to achieve atomically thin layers
of platinum and other platinum group metals on nanoparticles.
4
BROOKHAVEN NATIONAL LABORATORY

5. History: BES-EERE-Industry—Platinum
Monolayer Electrocatalysts
1. Use-inspired BES research on electrochemical interfaces led to the
discovery of a new class of nano-catalysts.
2. The EERE fuel cell program supported the development of the new
catalysts for fuel cell applications.
3. Industrial support via CRADAs demonstrated synthesis scale up and
excellent performance in fuel cell tests.
Ø BES user facilities – the NSLS and Center for
Nanofunctional Materials (CFN) – provided key
characterization capabilities (x-ray absorption
spectroscopy and advanced microscopy).
Ø This work was featured as one of the 10 most impactful
research efforts in the NAS review of the BES Catalysis
Science Program.
5
BROOKHAVEN NATIONAL LABORATORY

6. BES-supported research 1992-present
Fundamental studies of electrocatalysis:
Oxygen reduction reaction (ORR) – mechanism, structure/activity
Insight (2000): Platinum monolayers are promising catalysts
Substrate tunes catalytic activity of Pt overlayer:
-Catalytic activity correlates to O binding energy
-Optimum at intermediate binding: volcano plot
-Stability can also be tuned
Pt monolayer on Pd(111) high ORR activity
Strategy: address critical cost and stability limits of fuel cell ORR catalysts
Pt monolayer
Nanostructured core-shell electrocatalysts
- active monolayer puts all Pt atoms at interface Pd core
- substrate core tunes activity & stability
6
BROOKHAVEN NATIONAL LABORATORY

7. EERE-supported research 2003-present
Pt
1. Several classes: tune properties & reduce cost Pt monolayer on Pd
2. Atomic-level characterization in situ (XAS), ex Pd nanoparticles
situ (STEM), DFT Pt
3. Atomic-level control syntheses fine-tune Pt-core Pt on non-noble metal –
Au
interactions and control morphology noble metal core-shell;
Ni
4. Activity, Stability, and Fuel Cell tests Pt
Pt on nanoparticles with
Pd
Catalytic Activity improved 5x-20x per wt Pt interlayer of Pd
Smooth
Ir, Pd rods
Durability improved: multiple thousand hours in Fe,
Co
LANL tests
Characterization: atomic imaging of one monolayer of
Pt shell on Pd-core nanoparticles using STEM/EELS
at Center for Functional Nanomaterials
7
BROOKHAVEN NATIONAL LABORATORY

8. CRADAs with industry 2005-present
Scale-up, fuel cell testing: Toyota, GM, UTC Fuel Cells, Battelle
1. Demonstrate efficient, reproducible synthesis of
gram quantities of PtML Synthesis: e.g., Demonstrate scale-up to 50
2. Fuel cell tests, performance, stability, potential gram batches of high-activity nanostructured
cycling core-shell electrocatalysts (with Toyota).
Performance: High activity, improved
stability in MEA-level cycling. Scale-up will Understand improved stability: Evidence that Pd
enable full fuel cell stack testing. core acts as ‘sacrificial electrode’ for Pt shell.
Smooth
Pd rods
140
Electrochem. Surface Area (m /g-Pt)
Pt(ML)/Pd/C 0.085 mg-Pt/cm2
120
2
Δ
Δ
Δ 8%
100
Δ
Δ
Δ 23 %
80
Δ 41 %
60 Δ 47 %
40 Δ
Δ
Δ 68 %
Pt/Ketjen
0.3mg-Pt/cm2
20
Pt/C 0.133mg-Pt/cm2
0
0 20,000 40,000 60,000 80,000 100,000 Status: Core-shell nanocatalysts are currently
Potential cycle
promising route to PEM fuel cell commercialization.
8
BROOKHAVEN NATIONAL LABORATORY

9. Applications – Target Customers – Current
Practice
Applica'on
Descrip'on
Target
Customers
Current
Prac'ce
Fuel
Cells
–
Oxygen
Catalyst
manufacturers
Pla<num
on
high
surface
Reduc<on
area
carbon
Fuel
Cells
–
Fuel
Oxida<on
Catalyst
manufacturers
Pla<num
on
high
surface
area
carbon
Hydrolyzers
–
Hydrogen
Catalyst
manufacturers
Pla<num
on
high
surface
Evolu<on
Hydrolyzer
manufacturers
area
carbon
Other
heterogeneous
Catalyst
manufacturers
Pla<num
on
supports
catalysis
Petrochemical
companies
9
BROOKHAVEN NATIONAL LABORATORY

10. Contact Information
• Dr. Radoslav Adzic, +1(631)344-4522, adzic@bnl.gov
Senior Chemist, Chemistry Department
Brookhaven National Laboratory
Bldg. 555 – P.O. Box 5000
Upton, NY 11973
• Dr. Kimberley Elcess, +1(631)344-4151, elcess@bnl.gov
Principal Licensing Specialist
Office of Technology Commercialization and Partnerships
Brookhaven National Laboratory
Bldg. 490C – P.O. Box 5000
Upton, NY 11973
10
BROOKHAVEN NATIONAL LABORATORY