Supporting Information

Self-assembled Molecular Hybrids of CoS-DNA for

Enhanced Water Oxidation with Low Cobalt Content
Kannimuthu Karthick1,2, Sengeni Anantharaj1,2, Pitchiah E. Karthik3,
Balasubramanian Subramanian1,2, and Subrata Kundu1,2,4*

1
Academy of Scientific and Innovative Research (AcSIR), CSIR-Central Electrochemical
Research Institute (CSIR-CECRI) Campus, New Delhi, India

2
Electrochemical Materials Science (ECMS) Division, CSIR-Central Electrochemical
Research Institute (CECRI), Karaikudi-630006, Tamil Nadu, India

3
Department of Chemistry, Indian Institute of Science Education and Research (IISER) –
Mohali, Punjab, India

4
Department of Materials Science and Mechanical Engineering, Texas A&M University,
College Station, Texas, TX-77843, USA

* To whom correspondence should be addressed, E-mail: skundu@cecri.res.in;

subrata_kundu2004@yahoo.co.in, Phone/Fax: (+ 91) 4565-241487.

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Reagents and Instruments
Double-stranded DNA from Herring Testes with a base pair of around 50 k, Cobalt
acetate (Co(Ac)2), Sodium sulphide (Na2S) were purchased from Sigma-Aldrich. Potassium
hydroxide (KOH) was purchased from Alfa-Aesar and used as received. The electrochemical
analyzer CHI-6084c, Hg/HgO reference electrode, Pt counter electrode and CC working
electrode purchased from Alfa- Aesar. DI water is used in the entire synthetic process. The as
prepared CoS-DNA molecular hybrids characterized with HR-TEM, (TecnaiTM G2 TF20)
working at an accelerating voltage of 200 kV. The Energy Dispersive X-ray Spectroscopy
(EDS) analysis was done with the FE-SEM instrument (Oxford) with a separate EDS detector
connected to that instrument. The XRD analysis was done with a scanning rate of 5° min-1 in
the 2θ range 10-90° using a Bruker X-ray powder diffractometer (XRD) with Cu Kα radiation
(λ = 0.154 nm). X-ray photoelectron spectroscopic (XPS) analysis was performed using a
Theta Probe AR-XPS system (Thermo Fisher Scientific, UK). Electrochemical analyzer
CHI6084c version 12.13 was used for the entire OER and related studies. Hg/HgO reference
electrode was used along with a Pt-foil counter electrode where our prepared CoS-DNA
molecular hybrids modified CC cloth substrate electrode was used as working electrode.

Sample Preparation for Various Characterizations

As prepared CoS-DNA molecular hybrids were directly taken for XRD and XPS
analyses before cycling. TEM samples were prepared by dispersing required quantity in 1 mL
of Milli Q water followed by drop casting on carbon coated copper TEM grid and dried at RT
for slow evaporation of water before analyses in dark and vacuum. For OER studies, about
68.5 µL of the each solution was directly casted on the acid treated CC electrodes and dried
at ambient conditions for 12 h. For comparison purpose, another working electrode of
RuO2/CC was fabricated following the earlier reports where the loading of RuO2 was 20
times higher (0.2 mgcm-2) than that of the CoS loading.

Determination of Surface concentration from the redox features of CV:

Calculated area associated with the reduction of Co3+ to Co2+ = 0.002157 VA

Hence, the associated charge is = 0.002157 VA / 0.3 Vs-1

= 0.00719 As

= 0.00719 C

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Now, the number of electron transferred is = 0.00719 C / 1.602 ×10-19 C

= 4.488 ×1016

Since, the reduction of Co3+ to Co2+ is a single electron transfer reaction, the number
electron calculated above is exactly the same as the number of surface active sites.

Hence.

The surface concentration of Co that participated in OER is = 4.488 ×1016

Determination of Turnover Frequency (TOF) from OER Current Density

TOF in our study was calculated assuming that the surface active Co atoms that had
undergone the redox reaction just before onset of OER only participated in OER
electrocatalysis. The corresponding expression is,

TOF= j × NA / F × n × Г

Where,

j = current density

NA= Avogadro number

F = Faraday constant

n = Number of electrons

Г = Surface concentration

We have taken the OER current densities of 10 mAcm-2 and 50 mAcm-2 observed at
1.59 V and 1.68 V vs. to calculate TOF

Hence we have,

TOF1.59 V = [(10× 10-3) (6.023× 1023)] / [(96485) (4) (4.488 × 1016)]

TOF1.59 V = 0.3477 s-1

TOF1.68 V = [(50× 10-3) (6.023× 1023)] / [(96485) (4) (4.488 × 1016)]

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 TOF1.68 V = 1.738 s-1

Since CoS-DNA (0.06) and CoS-DNA (0.084) have the same metal content, we did not
calculate the corresponding TOF values as it will be closer to the calculated ones above.

Determination of Faradaic Efficiency (FE)

Faradaic Efficiency determination has now been accepted as important activity

parameter which has to be determined to ensure that the supplied energy is efficiently used
for water oxidation than other side reactions. Following is the formula used for the
calculation of FE.

Faradaic Efficiency = jR × nD/jD × nR × NCL

where, jR and jD are the ring and disk current densities at a particular potential, nD and nR are
the number of electrons transferred at disk and ring. NCL is the collection efficiency of the
RRD electrode used here.

FE = 15.6 × 4 / 46.7 × 4 × 0.37

= 0.9028 × 100

= 90.28%

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 Table S1: Details on the concentration of reagents, time and the visual observations of the
total synthesis procedure

Concentration Concentration Concentration Total volume Total reaction Final color of

Set. No of DNA (M) of Co(Ac)2 of Na2S (M) of the solution time the solution
(M)

1 0.036 3 × 10-3 1 × 10-2 100 30 Black

2 0.06 3 × 10-3 1 × 10-2 100 30 Black

3 0.084 3 × 10-3 1 × 10-2 100 30 Black

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Scheme S1: The snapshots of the synthesis carried with and without DNA.

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 50
CoS@DNA
40

30
Intensity (a.u)

20

10

-10

-20

-30
10 20 30 40 50 60 70 80 90

2 Theta (deg.)

Figure S1: XRD pattern of the CoS-DNA molecular hybrids.

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Figure S2: EDS spectrum of the CoS-DNA molecular hybrids.

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Figure S3: (a) HAADF STEM Micrograph of CoS-DNA(0.084). (b-f) color maps of O K, S
K, Co K, P K and N K shells in the chosen area of the same.

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 5
1.2x10
Survey scan of CoSx - DNA hybrids

1.0x10
5 Na 1s

4
8.0x10
Co 2p
4 O KLL O 1s
cps

6.0x10
N 1s
4
4.0x10 C 1s
C KVV
4 S 2p
2.0x10

0.0
1200 1000 800 600 400 200 0

Binding Energy (eV)

Figure S4: XPS survey spectrum of the CoS-DNA molecular hybrids.

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 CoS-DNA(0.036)/CC
0.030 CoS-DNA(0.06)/CC
CoS-DNA(0.084)/CC

0.024
-2

-2
0.013 µFcm
∆j (ja-jc) / mAcm

0.018

-2
0.012 0.009 µFcm

0.006 -2
0.005 µFcm

20 40 60 80 100 120 140 160 180 200 220

-1
ν / mVs

Figure S5: Plot of the difference in double layer charging current vs. scan rates.

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 (a)
0.006 CV of CoS-DNA showing the redox features

0.004 2+ 3+
Co Co

0.002
-2
j / Acm

0.000

-0.002

-0.004
2+ 3+
Co Co
-0.006
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
E / V vs. Hg/HgO
(b)
3+ 2+
0.006 Reduction area of Co to Co chosen
for determining surface active sites

0.004

0.002
-2
j / Acm

0.000

-0.002
area = 0.002157 VA

-0.004
2+ 3+
Co Co
-0.006
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
E / V vs. Hg/HgO

Figure S6: (a-b) CV of CoS-DNA(0.036)/CC showing the area of redox features considered
for the calculation of number of surface active sites.

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 0.10 LSV of CoS-DNA(0.036) coated on disk
Relative ORR current from

0.08

0.06 -2
46.7 mAcm
-2

0.04
j / Acm

0.02

0.00

-0.02 -2
15.6 mAcm

-0.04
1.2 1.3 1.4 1.5 1.6 1.7 1.8
E / V vs. RHE

Figure S7: The RRDE polarization and the corresponding ORR response obtained with CoS-
DNA (0.036) hybrids for faradaic efficiency calculation.

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