Alternative Materials to Replace Platinum in

Catalytic and Electrocatalytic Applications

Jingguang Chen
Department of Chemical Engineering
University of Delaware
Newark, DE 19711
jgchen@udel.edu

Outline of Presentation

Brief overview of Pt utilization in catalysis and

electrocatalysis

Example in electrocatalysis: reducing Pt loading for H2

production from water electrolysis

Example in catalysis: replacing Pt in conversion of

biomass-derived oxygenates

Abundance of Elements of Catalytic Interests

Pt-group metals (Pt, Ir, Pd, Rh, Ru) are expensive and limited in supply

Needs of Pt in Catalysis and Electrocatalysis

-

Demand in Heterogeneous Catalysis:

Pt catalysts are used in many chemical and refining processes

Demand in Emerging Clean Energy Technologies:

Pt electrocatalysts are required in low-temperature fuel cells,
electrolyzers, and photoelectrochemical cells in significant amounts

Research Efforts in Solving Pt Challenge:

I. Replace Pt with alternative materials with similar activity and stability
II. Reduce loading of Pt using monolayer catalysts and electrocatalysts

I. Replace Pt with Transition Metal Carbides

IV

VI

Physical properties of carbides:

High hardness, wear resistance
High temperature stability
Excellent electrical conductivity
Chemical properties of carbides:
Similar catalytic activity to
Pt-group metals

Levy & Boudart, Science, 181 (1973) 547

Oyama, Transition Metal Carbides and Nitrides, (1996)
Hwu & Chen, Chemical Reviews 105 (2005) 185
Chen Research Group: Angew. Chem. Int. Ed. 49 (2010) 9859
Thompson Research Group: J. Catalysis, 272 (2010) 235
Davis Research Group: J. Catalysis, 282 (2011) 83

II. Reduce Pt Loading with Monolayer (ML) Pt

Challenge: Identify substrates with Pt-like bulk properties

Esposito & Chen, Energy & Env. Sci. (2011)

Research Approaches
-

Avoid trial-and-error, empirical approach, i.e., randomly picking elements

from the Periodic Table

Use theory and model systems to obtain design principles for identifying
catalysts with little or no Pt, while maintaining Pt-like activity and stability

Single Crystal
Model Surfaces

- UHV studies
- DFT modeling

Bridging
Materials Gap

- Thin films
- Supported catalyst

Bridging
Pressure Gap

- Reactor studies
- Electrochem cells

Example 1: Reducing Pt Loading

Single Crystal
Model Surfaces
- UHV studies
- DFT modeling

Bridging
Materials Gap
- Thin films
- Supported catalyst

Bridging
Pressure Gap
- Reactor studies
- Electrochem cells

Examples of of reducing and replacing Pt :

1. H2 production from water electrolysis with monolayer Pt
2. Conversion of biomass-derived oxygenates with Pt-free catalysts

H2 from Water Electrolysis on ML Pt/WC

Esposito, Hunt & Chen,

Angew. Chem. Int. Ed.
49 (2010) 9859

Motivation for Water Electrolysis

H2 is a mobile energy carrier
H2 has a high gravimetric energy density
No CO2 emission when H2 is made from the electrolysis of
water using renewable energy such as solar

Hydrogen Production from Water Electrolysis

(+)

Oxygen Evolution Reaction (OER)

EoH2O/O2=+1.23 V vs. NHE

Hydrogen Evolution Reaction (HER)

EoH+/H2=0.0 V vs. NHE

Anode
(OER Catalyst)

e-

Power
Input

(-)
e-

H2(g)
O2(g) + 2H+

H2O

Cathode
(HER Catalyst)

Overall Reaction

Schematic electrolysis cell

Challenge: HER requires relatively large Pt particles (~ 5nm)

Questions of Using ML Pt/WC as Electrocatalysts

- What is the descriptor responsible for making Pt the optimal
catalyst for the hydrogen evolution reaction (HER)?
- Does ML Pt/WC meet such descriptor for high HER activity?
- Is ML Pt/WC stable under the relatively harsh HER
conditions?

HER Activity and Hydrogen Binding Energy (HBE)

(Strong)

(Weak)

Classic volcano curve observed for the HER is explained by

SabatiersPrinciple[2]
(Volmer Step)

(Tafel Step)
[1] Data from: Norskov, Bligaard, Logadottir, Kitchin, Chen, Pandelov, Stimming, J.Electrochem. Soc., 152 (2005) J23-26.
[2] P. Sabatier, Catalysis in Organic Chemistry, D. Van Nostrand Company, New York, 1922.

DFT Prediction: Similar HBE Values between

Monolayer Pt-WC and Bulk Pt
d-band density of states
Surface
WC(001)
Pt(111)
1 ML Pt-WC(001)

HBE (eV)
-0.99
-0.46
-0.43

DFT-calculated per-atom hydrogen

binding energy (HBE) for WC, Pt, and 1
ML Pt-WC surfaces with a hydrogen
coverage of 1/9 ML.
1 atomic
layer of Pt

Pt

WC

Experimental Verification: HER Activity of Pt/WC

Pt Foil

WC Foil

As Pt coverage nears 1 ML, the

activity of WC electrodes reach
that of Pt foil
Combined DFT and experimental results have identified monolayer Pt on WC
as electrolysis catalyst of similar activity with significant reduction in cost
Esposito, Hunt & Chen, Angew. Chem. Int. Ed. 49 (2010) 9859

Adhesion of ML Pt in the Pt/WC system

Use DFT to compare adhesion of Pt atoms to WC and Pt surfaces:

Binding Energy

Outcome

Pt-(Substrate) < Pt-Pt

Pt

Particles
favored

migration

Pt-(Substrate) > Pt-Pt

ML surface atoms

Pt

ML configuration
favored

Substrate

Binding energy
/ eV

(M-X^) - (M-M) BE
/ eV

Pt(111)

-5.43

0.00

C(0001)

-4.12

1.31

WC(0001)

-6.59

-1.16

W2C(0001)

-6.51

-1.08

ML Pt/WC Shows Excellent HER Stability

XPS Pt 4f spectra and atomic Pt4f/W4f signal ratio

before and after extended stability tests

Physical characterization of ML Pt-WC

surface further confirms that the Pt ML is
stable on WC under HER conditions.

SEM images taken before and after

extended stability tests

From Model Thin Films to Catalytic Particles

Challenge: A synthesis technique to deposit ML Pt on WC particles

Transmission Electron Microscopy of

Atomic Layer Deposition (ALD) of Pt on WC

A thin film of Pt is deposited on WC particles at 50 ALD cycles

HER Activity of ALD Pt/WC Particles

- Similar to thin film results, low loading of Pt (10 ALD cycles) show similar
HER activity as 10 wt% Pt/C catalyst
- Elemental analysis reveals Pt loading of 10 ALD cycle Pt/WC is a factor of
~10 less than 10 wt% Pt/C

Extension to Other ML Metal/Carbide Catalysts

Volcano relationship reveals other potential catalysts: ML Pd/WC and Pd/Mo2C

Extension to Other Electrochemical Devices

WC is electrochemically stable in the pH and potential range for HER

Other applications depend on pH and E range

Weidman, Esposito & Chen, J. Electrochem. Soc. 157 (2010) F179

Example 2: Replacing Pt

Single Crystal
Model Surfaces
- UHV studies
- DFT modeling

Bridging
Materials Gap
- Thin films
- Supported catalyst

Bridging
Pressure Gap
- Reactor studies
- Electrochem cells

Examples of of reducing and replacing Pt :

1. H2 production from water electrolysis with monolayer Pt
2. Conversion of biomass-derived oxygenates with Pt-free catalysts

Pt Catalysts for Biomass-derived Oxygenates

Skoplyak, Barteau & Chen,

ChemSusChem 1 (2008) 524

Replacing Ni/Pt with Ni/WC for Pt-free Catalysts

Ni/WC(0001)

Ni/Pt(111)

Advantages of replacing Ni/Pt wth Ni/WC: lower cost; higher stability

Humbert, Menning & Chen, Journal of Catalysis, 271 (2010) 132

Similar Reaction Pathways on Ni/WC and Ni/Pt

Glycolaldehyde

Ethylene glycol

Acetaldehyde

Acetic Acid

Conversion of Cellulose on Pt-free Catalysts

OH

H2

OH
OH

OH

Hydrogenation

OH

OH

Sorbitol
OH

H2

other
polyols

Hydrogenolysis

OH

Light alkanes
CO2, etc.

Ethylene glycol
OH

OH

HO

O O
HO

Cellulose

OH

OH

OH

H2O

O
n

Hydrolysis

O
HO

OH

HO

CH2OH

OH

Glucose

OH

H2
OH

Hydrogenation

OH

CH2OH

OH

Mannitol

HO

Fructose

OH

OH

OH

isomerization

OH

OH

-H2O

O
O

Dehydration

H2

OH

OH
O

Hydrogenation
HMF

DHM-THF

H+
C-C cleavage+oxdation

Organic acids
(unidentified)

Conversion of cellulose to ethylene glycol on Ni-WC & Ni-W2C:

Ji, Zhang 7 Chen, Catalysis Today, 147 (2009) 77

Cellulose Conversion to Chemicals on Ni-W2C

Results: 100% conversion, 61% EG yield, (6 MPa H2; 518 K; 30 min)

Ji, Zhang, & Chen, Angew. Chem. Int. Ed. 47 (2008) 8510

Conclusions and Challenges

-

Promising results are obtained in reducing Pt loading using

monolayer Pt on carbides for electrocatalysis, achieving
about a factor of ~10 in Pt reduction

Pt-free catalysts are demonstrated for conversion of

biomass-derivatives, using less expensive metal (Ni, Co,
etc.) supported on carbides.

Significant challenges exist for achieving large-scale

applications in catalysis and electrocatalysis:
- synthesis of high surface area carbides (critical for activity)
- deposition of monolayer metal on carbides (critical for saving Pt)
- resistance to carbon deposition (critical for catalysis)
- long-term stability in solution (critical for electrocatalysis)

Acknowledgement

Collaborators: Prof. Barteau (Univ. Delaware); Prof. Willis (Univ. Conn)

Funding: Department of Energy