EDITORIAL
Essay
−2
The Comprehensive Understanding of 10 mA cm geo as an
Evaluation Parameter for Electrochemical Water Splitting
Chao Wei and Zhichuan J. Xu*
Comparing the overpotential required to reach the current density of
−2 −2
10 mA cm geo (per geometric area of an electrode) (η@10 mA cm geo
ular method of ranking electrocatalysts for water-splitting reactions, i.e., the
hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER).
However, such methodology is, in essence, not reasonable for studying the
intrinsic chemistry difference of electrocatalysts. To have a rational under-
standing of η@ 10 mA cm geo −2 , here, its historical origin and its limitations
on reflecting the intrinsic electrocatalytic activity are discussed. The η@
−2 is a valid practical parameter to assess water-splitting devices,
10 mA cm geo
but it cannot determine whether a particular electrocatalyst is intrinsically
active or not.
1. Introduction
Storing electrical energy generated by sustainable resources
such as solar and wind is a critical component in a sustain-
able energy infrastructure.[1] To address this issue, water elec-
trolysis is a simple technique to store the energy in the form
of hydrogen gas.[1,2] Water electrolysis consists of two half-cell
reactions: the hydrogen evolution reaction (HER) at the cathode
that produces hydrogen gas, and the oxygen evolution reaction
(OER) at the anode that generates oxygen gas.[1,3] The overall
energy efficiency of water electrolysis is collectively dominated
by the catalyst for each half-cell reaction, which has been moti-
vating great efforts of inventing highly active HER and OER
electrocatalysts. The key to the successful identification of the
optimal catalyst is to establish a valid metric for quantitatively
Dr. C. Wei, Prof. Z. J. Xu
School of Materials Science and Engineering
Nanyang Technological University
50 Nanyang Avenue, Singapore 639798, Singapore
E-mail: xuzc@ntu.edu.sg
Dr. C. Wei, Prof. Z. J. Xu
The Cambridge Centre for Advanced Research and Education in Singapore
1 CREATE Way, Singapore 138602, Singapore
Dr. C. Wei, Prof. Z. J. Xu
Solar Fuels Laboratory
Nanyang Technological University
50 Nanyang Avenue, Singapore 639798, Singapore
Prof. Z. J. Xu
Energy Research Institute @ Nanyang Technological University
50 Nanyang Avenue, Singapore 639798, Singapore
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smtd.201800168.
DOI: 10.1002/smtd.201800168
Small Methods 2018, 1800168 1800168  (1 of 3)
www.small-methods.com
evaluating the activity of a particular cata-
lyst. One of the prevailing activity metrics
) is a pop- used to describe the HER and OER rates
is the overpotential to reach 10 mA cm −geo 2
(η@ 10 mA cm −geo 2 [1]
), which is the cur-
rent density normalized to the geometric
area of electrode (abbreviated as geo). The
η@ 10 mA cm −geo2
quantifies the electro-
chemical performance at a device level,
but it is not a valid metric to reflect the
intrinsic activity of a given electrocata-
lyst. However, the widespread confusion
has been brought by the numerous pub-
lications that erroneously rely on the
η@ 10 mA cm −geo2
metric for intrinsic
activity analysis, and therefore a rational
understanding of η@10 mA cm −geo 2
is needed. Here, we aim
to discuss the rationales underlying η@10 mA cm −geo 2
, and
more importantly, its limitations on describing the intrinsic
activity. We briefly introduce the historical background of η@
10 mA cm −geo2
for benchmarking the device performance, and
rationalize that η@10 mA cm −geo 2
does not relate to the intrinsic
activity of a particular catalyst.
2. The Historical Origin of η@ 10 mA cm geo
−2
The HER and OER catalyst metric of η@10 mA cm −geo 2
concep-
tually originates from artificial photosynthesis. The figure of
merit for quantifying the performance of artificial photosyn-
thesis systems is the solar-to-fuel (STF) conversion efficiency,
which is expressed as the ratio between the total energy stored
in fuels and the total energy input from sunlight irradiation.[4]
The reproducible STF conversion efficiencies currently obtained
from photocatalysis are ≈1% at most, but must be increased up
to 10%, because the STF conversion efficiency determines the
hydrogen cost in solar water-splitting systems.[5] It has been
estimated that to realize the ultimate goal of industrializing
solar hydrogen production, the STF conversion efficiency for a
one-step photoexcitation system must reach ≈10% to enable the
hydrogen production to be cost-competitive with conventional
industrial processes, such as methane steam reforming.[5] Cov-
ering 1% of the earth’s surface with 10%-STF-efficient solar
water-splitting cells is sufficient to satisfy the predicted global
energy needs in the year 2050.[4] Hence, as our target and
benchmarking performance, 10% STF conversion efficiency is a
parameter of great practical importance to solar-to-fuel studies;
and also this is the historical origin of η@ 10 mA cm −geo 2
. The
current density expected in solar water-splitting cells, which
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possess an STF conversion efficiency of 10% under 1 sun illu-
mination is ≈10 mA cm −geo2 [6–8]
. The derivation of 10 mA cm −geo
2
from 10% STF conversion efficiency is demonstrated as fol-
lows. The standard terrestrial solar spectrum is defined as
AM1.5G, which yields a total energy of 100 mW cm −geo 2
(namely
[4]
the energy input under 1 sun illumination). Considering a
redox potential of 1.23 V for water splitting, a 100% STF con-
version efficiency gives a current density of ( 100 mW cm −geo
2
)/
−2 −2 [6]
(1.23 V) = ( 100 mA V cm geo )/(1.23 V) = 83 mA cm geo . Thus
the STF conversion efficiency of 10% generates 8.3 mA cm −geo 2
, dependence of η@10 mA cm −geo
which is approximately taken as 10 mA cm −geo 2
for bench-
marking solar-to-fuel device performance.[8] As mentioned in
the introduction, either the HER or the OER is tightly relevant
to artificial photosynthesis, because electrochemical water split-
ting converts the electrical energy generated by sunlight to
chemical energy stored in H2 and O2. Due to this connection,
η@10 mA cm −geo 2
is brought from artificial photosynthesis to
benchmark the performance of electrochemical water-splitting
devices, and also erroneously used for screening the intrinsic
activity of HER and OER electrocatalysts.
3. η@10 mA cm geo
−2
 ≠ Intrinsic Catalytic Activity
As discussed above, η@10 mA cm −geo 2
serves as a performance
metric that is of great practical importance to solar-to-fuel
devices. However, η@10 mA cm −geo 2
is not considered as a
reasonable activity metric of reflecting the intrinsic electro-
catalytic activity, because of the following problems. First, η@
10 mA cm −geo
2
is predominantly governed by the loading mass
of catalysts. As schematically shown in Figure 1a, assuming
that we load more catalysts on the current collector (such as
glassy carbon), which has a fixed geometric area, the resulting
number of active sites is increased; and thus, we certainly
will just need a smaller overpotential to reach any given cur-
rent density normalized to the geometric area of electrode,
including 10 mA cm −geo 2
. This is a universal law that has been
widely proved. For example, our data suggests that, with more
IrO2 nanoparticles (NPs) loaded on glassy-carbon rotating disk
electrode (RDE), the OER polarization curve shifts toward
the negative direction (Figure 1b, inset), and the OER η@
10 mA cm −geo 2
decreases drastically (Figure 1b). This is con-
sistent with a benchmark study where the catalyst-loading
2
is demonstrated by OER meas-
urement for commercial IrO2 particles (Premetek) with various
loading masses (Figure 1c).[9] The same trend is also reported at
La0.7Ba0.15Sr0.15Co0.8Fe0.2O3−δ-50 nm perovskite, where a higher
loading mass gives an earlier onset of OER in terms of cur-
rent density normalized to geometric area of electrode;[10] and
a series of perovskite catalysts.[11] Second, η@ 10 mA cm −geo 2
is
based on the current density normalized to the geometric area
of electrode, which neglects that the electrocatalysis reaction
(such as the HER and the OER) is a surface process, where only
the surface atoms participate.[1,12] To reflect the intrinsic elec-
trocatalytic activity, the current density should be normalized to
a quantified parameter about the catalyst surface, such as the
number of active sites,[1,7] or alternatively the surface area of the
catalyst.[1,7]
As evidenced by the above two issues about @ 10 mA cm −geo 2
,
researchers should be cautious about reports that use η@
10 mA cm −geo 2
to compare activities across different catalysts
and those from various reports in the literature. It is highly
possible that the seemingly excellent activity in terms of η@
10 mA cm −geo 2
is not led by the truly active catalyst, but simply
due to the higher catalyst loading. Also, the fundamental inves-
tigations that use η@ 10 mA cm −geo 2
to correlate the activity
with the intrinsic chemistry of electrocatalysts are highly sus-
picious. The correlation might be erroneous, because η@

−2
Figure 1.  a) The schematic illustration of the loading mass effect on η@ 10 mA cmgeo . b) The OER η@ 10 mA cmgeo −2 at IrO NPs (nanoparticles,
2
≈7 nm diameter)[13] as a function of catalyst loading. Material synthesis and drop-cast electrode preparation are included in the Supporting Informa-
tion. The inset shows the corresponding polarization curves normalized to the geometric area of the electrode with iR-correction and background
−2
correction. Data were collected at 10 mV s−1 with a rotation speed of 1600 rpm in O2-saturated 0.1 m KOH. c) The OER η@ 10 mA cmgeo for IrO2
particles (20–30 m2 g−1, Premetek) versus the loading mass. The electrodes are prepared by the conventional drop-casting method with a fixed
Nafion concentration of 40 µL/5 mL. The η@ 10 mA cmgeo −2 is measured by cyclic voltammetry (CV) at a scan rate of 10 mV s−1 and rotation speed of

1600 rpm in O2-saturated 1.0 m NaOH. η@ 10 mA cmgeo −2 is iR-corrected, without background correction. c) Reproduced with permission.[9]
Copyright 2016, Royal Society of Chemistry.

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www.advancedsciencenews.com
10 mA cm −geo 2
does not account for the fact that electrocatalysis
is a surface process. To rationalize the studies on intrinsic
chemistry of materials, especially descriptor studies, we recom-
mend two metrics of intrinsic activity that are commonly used
for such purpose: turnover frequency (TOF)[1,7,14] and specific
activity.[1,7,14,15] The TOF is defined as the number of trans-
ferred electron(s) per active site per second. Unfortunately, it
is difficult to quantify the number of active sites, and therefore
the TOF is often unknown. The specific activity is the current
density per unit surface area of catalyst, which is an approxima-
tion of the TOF, and thus it represents the intrinsic activity.
4. Conclusions and Outlook
We have summarized the historical background of η@
10 mA cm −geo
2
to elucidate why this parameter is practically
important for guiding the design of water-splitting devices, fol-
lowed by a discussion of two issues in using η@ 10 mA cm −geo 2 [3] C. Wei, Z. Feng, G. G. Scherer, J. Barber, Y. Shao-Horn, Z. J. Xu, Adv.
as the evaluation parameter for catalysts. The discussion con-
cludes that η@ 10 mA cm −geo 2
does not reflect the intrinsic
activity of a particular electrocatalyst. With the purpose of stud-
ying the intrinsic chemistry difference of an electrocatalyst, the
activity analysis should refrain from metrics that are based on
the current density per geometric area of electrode, including
η@ 10 mA cm −geo 2
and the geometric current density at a given
potential.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was supported by the Campus for Research Excellence and
Technological Enterprise (CREATE) in Singapore and Singapore Ministry
of Education Tier 2 Grant (MOE2017-T2-1-009). The authors thank the
Small Methods 2018, 1800168 1800168  (3 of 3)
www.small-methods.com
Facility for Analysis, Characterisation, Testing and Simulation (FACTS)
in Nanyang Technological University for materials characterization. The
authors also thank Dr. Yubo Chen for experimental support.
Keywords
−2 , electrochemical water splitting, intrinsic activity
10 mA cmgeo
Received: May 29, 2018
Published online:
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