ChE 635A Introduction to Electrochemical Engineering

Quiz-2 (30 minutes); Total points: 30; Closed notes and open minds; July 3rd, 2022

1. (8 pts) The following plot shows the efficiencies of some energy conversion devices (fuel
cell(s) and Carnot engine(s)). Please note that the efficiency is > 1 in some temperature
regimes. (Note: In the following graph, temperature refers to temperature of heat source
in a Carnot engine, and the operating temperature of a fuel cell)

A
1 B
Efficiency

Temperature

1.1) Can you guess which curves are for fuel cell(s) and which are for Carnot engine(s) (3).
1.2) For the fuel cell(s) and Carnot engine(s), give the thermodynamic expression for
efficiencies used to plot the above curves (3).
1.3) Using thermodynamic reasons, rationalize why the curves change the way they do with
temperature (2).
2) (22 pts)
2.1) (1 pt) Which concept/principle has helped rationalize electrocatalysis by different
electrocatalysts? For e.g. rationalize why Pt and Pd and their alloys are the best catalysts for
Oxygen reduction reaction (ORR).

Despite thousands of manuscripts and considerable effort in this, the reduction in the
overpotential (OP) has not been significant (see figure below):
This question will address this issue.

2.2) (2 pt) What are the two possible electrochemical reactions for Oxygen reduction?

2.3) (2 pt) Can you anticipate what are the possible intermediates for ORR to H2O?

2.4) (2 pt) During ORR, can there be elementary steps that do not depend on the electrochemical
potential? Be specific/precise and support an answer via a specific example.

2.5) (1 pt) What does “computational hydrogen electrode” (CHE) refer to and state it’s physical
principles?

2.6) (1 pt) What aspects of electrocatalysis that are not typically captured by CHE?

2.7) (1 pt) How does CHE help in computing the potential energy surface (PES) relevant to
ORR?

2.8) (2 pts) Based on PES, can you rationalize the OP of a typical electrocalysts?

2.9) (2 pts) Sketch the PES of a “perfect” ORR electrocatalyst?

2.10) (3 pts) Computations suggest that the binding energy of 3 chemical species/intermediates
are strongly correlated and change monotonically for different metals. What do you think are the
3 relevant chemical species/intermediates?

2.11) (3 pts) It has been suggested that the above-mentioned correlation in 2.10 is the reason why
much research has not resulted in dramatic decrease in OP. Can you rationalize using relevant
PES why this is so?

2.12) (2 pts) Can you anticipate how we can break the correlations between the binding energy
of different intermediates so that binding energy of different intermediates may change non-
monotonically for different metals? State some specific material scenario to implement your
suggestions?