INREP Electrochemistry Summer School

- Electrocatalysis -

Lior Elbaz
Chemistry Department, Bar-Ilan University

September, 2014
Unauthorized use or publication is prohibited
Outline

1) What is Electrocatalysis?

2) Example: electrocatalysis of oxygen reduction

3) Analysis of electrocatalytic reactions

4) Volcano plots

5) The Mechanism of electrocatalysis

6) Consideration in choosing an electrocatalys

What is a catalyst?

1: a substance that enables a chemical reaction to proceed at a

usually faster rate or under different conditions (as at lower temp.)
than otherwise possible.

2: an agent that provokes or speeds significant change or action

Five Broad classes of catalysis research
What is an Electrocatalyst?

“Electrocatalysis may be defined as the relative ability of different

substances, when used as electrode surfaces under the same
conditions, to accelerate a given electrochemical process.”

“Electrocatalysts are a specific form of catalysts that function

at electrode surfaces or may be the electrode surface itself. An
electrocatalyst can be heterogeneous such as a platinum surface
or nanoparticles, or homogeneous like a coordination complex
or enzyme. The electrocatalyst assists in transferring electrons
between the electrode and reactants, and/or facilitates an
intermediate chemical transformation described by an overall half-
reaction.”
Electrocatalysis comes in different forms
Three key energy conversion reactions in need of improved electrocatalysts
Standard equilibrium potentials - Thermodynamics
 H2/O2 Polymer Electrolyte Fuel Cell (PEMFC)

e-

e-

Anode Cathode

Cathode
Membrane
Anode
+ - 0 + - 0
H2 H2  2H + 2e E =0.00V O2 +H2O4H + 4e  2H2O E =1.23V O2

H+

Cell :
2H2 + O2  2H2O E0=1.23V
Reaction kinetics involving H2O-H2-O2
Oxygen reduction reaction (ORR)

Without Electrocatalyst

With Electrocatalyst

A. Schneider et al. Phys. Chem. Chem. Phys., 2008, 10, 1931

Electrocatalysis of oxygen reduction reaction (ORR)

I. Stephens et al. Energy Environ. Sci., 2012, 5, 6744

Three primary figures of merit for catalysts
The butler-Volmer Equation

It is desirable to have the ORR occurring at potentials as close as possible to the

reversible electrode potential (thermodynamic electrode potential) with a satisfactory
reaction rate.

Ic - Oxygen reduction reaction current density

ioO2 - Exchange current density
naO - Number of electrons transferred in the rate determining step
aO - Transfer coefficient
hc - Overpotential of ORR
F - Faraday constant
R - Gas constant
T - Temperature in Kelvin.

To obtain high current at low overpotential, the exchange current density ioO2 should
be large, and/or should be small.
Four primary figures of merit for electrocatalyst activity

• Exchange current density, i0 (mA/cm2)

• Tafel slope, b (mV/decade)
• Current density at given overpotential,
iE (mA/cm2)
• Overpotential needed to reach a given
current density, hi (mV)
Tafel Slope

If the overpotential is large, the B-V equation can be reduced to:

RRDE
Data analysis

K+D

K
Three ways to report current densities

• Per geometric area (cm2geo)

• Per surface area (cm2real)
• Per electrochemically active surface area (cm2ECSA)
• Closest to a true turnover frequency (TOF)

P. Reinlander et al., ECS transactions, 2012 (2), 2163-2174

How to choose an electrocatalyst: volcano plots

-4

-5 Pt
Pd

-6
log10i at 800 mV vs. NHE

Kīlauea, Hawaii
Ir,Rh
-7 Ru

-8 Os

-9

-10
Au

-11
0.2 0.4 0.6 0.8 1.0 1.2 1.4
Relative Gads (V)
Villiarrica, Chile
 Volcano plots
Paul Sabatier (1911): An optimal catalyst will bind reaction intermediates moderately on its
surface; not too strongly nor too weakly.

Roger Parsons (1957): The first ‘qualitative ‘ volcano in electrocatalysis, indicating the best
HER catalysts should exhibit GH~0 eV.
Measured Catalytic Activity

Calculated by DFT
J. Greeley et al., Nature Materials 2006 (5), 909-917
 Development of catalysts for ORR in fuel cells: Pt NanoRafts
0.0 100
900 rpm, 5 mV/s
-0.5 O2 Sat. 0.1 M HClO4
80
-1.0

EASA (% of initial)
-1.5 60
j (mA/cm )
2

-2.0
40
-2.5

-3.0
20

-3.5 Pt Nanorfts
5%wt Pt/XC-72 Nano-raft Pt on XC72
-4.0 0
0.2 0.4 0.6 0.8 1.0 1.2 0 1000 2000 3000 4000 5000

E(V) vs. RHE Number of Cycles

0
(c) Mo2C 5% Pt imb
Mo2C 20% Pt dep
Mo2C
-200

-400

(b)
) -600
Pt
im (A g-1

-800

-1000
(a)

-1200

-1400
0.8 0.9 1.0 1.1
10 20 30 40 50 60 70 80 90

2 (degrees)
E(V) vs. RHE
Electrocatalysts types

1) Metallic

2) Metal Complexes

3) Metal-free
Electrocatalysis – Mechanisms: Metallic surfaces

Just as with heterogeneous catalysis, in the case of metallic surfaces the mechanism involves
three parts:

1) Adsorption on the surface

2) Bond weakening
3) Reaction
Electrocatalysis – Mechanisms: Metal Complexes
Electrocatalysis – Mechanisms: Enzymatic
Electrocatalysis – Mechanisms: Non-metallic
Electrocatalyst Durability: Metallic

J. Meier et al., Beilstein J. Nanotechnol. 2014, 5, 44–67.

Electrocatalyst Durability: Metal Complexes

Low pH can be detrimental to the stability of transition metal complexes!!!

Electrocatalyst Selectivity

> >
Electrocatalyst Activity – Metal Complexes

Rajesh and Zelenay, Nature 443 (2006), 63-66 Wu, More, Johnston, Zelenay, Science 332 (2011), 443-447
Electrocatalyst Activity

Gasteiger and Markovic, Science 324 (2009), 48-49

Electrocatalyst Activity – Metal Complexes

J.Y. Cheon et al., Nature 2013 (3) 2715

 Development of catalysts for fuel cells: Non-Precious group metal catalysts

Objective: design and synthesis transition

metal complexes as catalysts for ORR in
fuel cells that will exceed the US
department of energy targets in durability
and activity

Achievements: very active and cheap

transition metal complexes for ORR using
various techniques: (1) pyrolysis (2)
metallo-organic synthesis of bio-inspired
transition-metal complexes. The Non-
precious group metal (NPGM) catalysts
show very high activity even compared to
the state-of-the-art NPGMs.