Supplementary Information

Optimization of Ascorbic Acid in the Synthesis of Cobalt Oxide for Enhanced

Electrocatalytic Activity Towards Oxygen Evolution Reaction

Maurya Gyanprakash1,2,*, Chandresh Kumar Rastogi1,* Karthik Raitani1, Manu Prakash

Maurya1, Vivek Choudhary2, Romil Chaudhary1, Manjunatha C*3

1Centre for Advanced Studies, Lucknow-226031, India

2Department of Chemical Engineering, Indian Institute of Technology, Kanpur-208016, India

3Department of Chemistry, RV College of Engineering, Bengaluru-560059, Karnataka, India

Corresponding Authors: gyan@cas.res.in chandresh@cas.res.in, and

manjunathac@rvce.edu.in

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Fig. S1 Current density of all sample @0.25V vs Ag/AgCl in 1M NaOH at different scan rates

for (a) Sample S1(b) Sample S2 (c) Sample S3, and (d) Sample S4.

Estimation of ECSA:

Double layer capacitance (Cdl) = ECSA* capacitance per unit surface area on standard

electrode like Au (CAu)

C𝑑𝑙
𝐸𝐶𝑆𝐴 = 𝐶𝐴𝑢

Here 𝐶𝐴𝑢 is taken as 40 µF.

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 Estimation of OER Tafel slope at Co3O4 in alkaline medium

The OER mechanism in the alkaline medium over the metal oxide catalyst is given by1,

S + OH ― S ― OH + e ― (1)

2S ― OH S + S ― O + H2O (2)

S ― O + OH ― S ― OH2 + e ― (3)

2S ― O S + O2 (4)

The Tafel slope for any electrochemical reaction is given by2,

dη R.T
b = d(lnI) = F.α (5)

R.T d(lnI)
α= F . dη
(6)

Here b, I,η, R, T,n, F, and α are the Tafel slope, current density, overpotential, gas constant,

temperature, number of electrons involved in the overall reaction, faraday’s constant, and

transfer coefficient.

The transfer coefficient for an elementary and non-elementary reaction is given by2,

1 𝜂
α=β=2+𝜆 (For elementary electrochemical reaction)

𝑛𝑏
α= 𝜐 + 𝑛𝑟.𝛽 (For non-elementary electrochemical reaction)

Here, 𝜆 is the reorganization energy, 𝑛𝑏 is the number of electrons transferred before the rate-

controlling step, 𝜐 is the number of occurrences of the rate-determining step (RDS) in the

overall reaction, 𝑛𝑟 denotes the number of electrons involved in the RDS. For OER elementary

steps if the step 2 is taken as RDS. Thus, the 𝑛𝑏 = 1, 𝜐 = 1, and 𝑛𝑟 = 0, gives Tafel slope of 59

mV/dec. Sample S2 and S3 showed the Tafel slope of 54.46 and 67.53 mV/dec, which indicates

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for these sample, step 2 is RDS with slight change in transfer coefficient. The transfer

coefficient physically depends on strong and weak adsorption of intermediate, which can alter

the Tafel slope. On the other hand, if the step 1 is taken as RDS, 𝑛𝑏 = 0, 𝜐 = 1, and 𝑛𝑟 = 1, and

𝛽 = 0.5, gives α = 0.5 and Tafel slope is around 118 mV/dec. If the symmetry factor for

reaction step 1 is 0.635, and 0.56 gives the Tafel slope 93.04 and 105.95 mV/dec for sample

S1 and S4. Thus, for sample S2 and S3, step 2 is RDS which gives low Tafel slope results in

higher activity. On contrary, the sample S1 and S4 showed the step 1 as RDS giving the higher

Tafel slope, indicating low activity.

References:

1. Riddiford, A. C., Mechanisms for the evolution and ionization of oxygen at platinum
electrodes. . Electrochimica Acta, 1961 4(2-4), , pp.170-178.
2. Guidelli, R., Compton, R.G., Feliu, J.M., Gileadi, E., Lipkowski, J., Schmickler, W. and Trasatti,
S., , Defining the transfer coefficient in electrochemistry: An assessment (IUPAC Technical Report). .
Pure and Applied Chemistry, 2014 86(2), , pp.245-258.

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