Creating Coordinatively Unsaturated Metal Sites in Metal-

Organic-Frameworks as Efficient Electrocatalysts for the

Oxygen Evolution Reaction: Insights into the Active Centers

Li Tao,a,1 Chun-Yu Lin,b,1 Shuo Dou,a Shi Feng,a Dawei Chen,a Dongdong Liu,a Jia
Huo,a Zhenhai Xia,b* and Shuangyin Wanga*
a
State Key Laboratory of Chem/Bio-Sensing and Chemometrics, Provincial Hunan Key Laboratory for
Graphene Materials and Devices, College of Chemistry and Chemical Engineering, Hunan University,
Changsha, 410082, P. R.China;

b
Department of Materials Science and Engineering, Department of Chemistry, University of North
Texas, Denton, Texas 76203, USA.

1
These authors contributed equally to this work.

*E-mail for S.W.: [email protected]; and Z.X.: [email protected]

Experimental Section

ZIF-67 synthesized as our previous work.[1] Namely, 1.642 g 2-methylimidazole (2-

MI) and 1.455 g cobalt nitrate hexahydrate dissolved in 80 mL methanol respectively.
Then, the dimethyl imidazole solution was slowly added in cobalt nitrate solution and
stirring for 30 s. After that, the solution kept at room temperature for 24 h without
stirring. The precipitate of the solution was washed with CH3OH for several times and
dried in 60 ℃. The CUMSs-ZIF-67 synthesized by N2 DBD plasma irradiation. Then
put the ZIF-67 in DBD plasma reactor and treated under nitrogen atmosphere. The
reactor input voltage and current are 100 V and 3.0 A respectively.

Characterazition
X-ray powder diffraction (XRD) carried out on a Siemens D500 diffractometer
with a Cu Kα source (1.54056 Å). Diffraction data collected for 2θ angles from 10° to
90° at a scan rate of 8° / min. The morphology and microstructure of the graphene
were investigated by scanning electron microscope (SEM, Hitachi, S-4800) and
Transmission electron microscopy (TEM, 200 kV JEOL 2011). Atomic resolution
analytical microscope (ARM) investigations performed using a 200 kV JEOL 2011
instrument. X-ray photoelectron spectroscopy (XPS) measurements and analysis
recorded on a Thermo Fisher-VG Scientific (ESCALAB 250Xi) photoelectron
spectrometer. The Brunauer-Emmmett-Teller (BET) specific surface area
characterizations were carried out by a nitrogen adsorption-desorption method (ASAP,
2020HD88).
Electrochemical measurement
Electrochemical measurements of graphene for OER were conducted at room
temperature on a standard three-electrode cell on CHI760E (CH Instrument, USA)
electrochemical workstation, and a rotating ring disk electrode apparatus (Pine,
AFMSRCE 3493, USA) with 1600 rpm, the 1 M KOH solution was used as the
electrolyte. A glassy carbon electrode (5 mm in diameter) used as the working
electrode; a large surface area Platinum mesh (1 cm × 1 cm) and saturated calomel
electrode (SCE) were used as the counter and reference electrode, respectively. 4 mg
of catalyst was dispersed in 2 ml ethanol and ultrasonicated for 1 h, then, 100 µl of 5
wt% Nafion solution (5 wt%, Sigma Aldrich, USA) was added into the slurry
followed by ultrasonication for anther 1h. After that, the working electrode coated
with 10 µL of the above catalyst ink, and dried naturally. All potentials were been
converted to the reversible hydrogen electrode (RHE) to unequivocally compensate
for the pH changes.

Density Functional Calculations

In alkaline environment, OER could occur over ZIF-67 in the following four
electron reaction pathways,

(S1)

(S2)

(S3)

(S4)

where (*) refers to active site on the surface of ZIF-67, the subscripts (g) and (l) stand
for gas and liquid phases, respectively, and O*, OOH*, and OH* refer to adsorbed
intermediates. The thermodynamic reaction can be correctly calculated by using the
density functional theory (DFT) involving the SHE model developed by Nørskov [2][3].
For a catalyst structure, the absorption energies of intermediate species are calculated
as follows,
∆EO* = E (O*) - E (*) - (EH2O-EH2) (S5)
∆EOH* = E (OH*) - E (*) - (EH2O-0.5EH2) (S6)
∆EOOH* = E (OOH*) - E (*) - (2EH2O-1.5EH2) (S7)
where E (*) means the ground state energy of cleanly unabsorbed surface, E (O*), E
(OH*), E (OOH*) refer to the ground state energy of surface absorbed with O*, OH*,
and OOH*, respectively, and EH2O, EH2 are water and hydrogen molecule in gas phase,
respectively[3]. Also, we considered the zero-point energy (ZPE) and entropy in
following equation,

∆Gads = +∆ ZPE-T ∆S (S8)

where ∆Gads is the free energy of adsorption, refers to binding energy

determined by DFT, T is the temperature, and is the entropy capacity. The ZPE,

which is vibrational frequencies, were calculated with adsorbed species such as

O*,OH*, and OOH* to obtain ZPE of free energy expression.[4]
For each elementary step, free energy is represented by the expression,
∆G = ∆E + ∆ZPE-T∆S + ∆GU + ∆GpH (S9)
where ∆G is determined by initial state and final states, and ∆E is the reaction energy
between the absorbed energy on the surface molecular of the reactants and products.
∆GU= -eU, where e is the charge transfer, U means the potential at the electrode, ∆G pH
is the value of correct of the H+ free energy by this following equation.
∆GpH = -kBTln[H+] (S10)
For the OER reactions, Nørskov et al [3] developed a method to determine the overpotentials,

(S11)

V (S12)

where, , , , are the free energy of Reactions (S1)-(S4),

respectively. The rate-limiting step of the elementary reactions of OER is the step
with maximum reaction free energy.
A series of models are developed to simulate OER on ZIF67 and CUMSs-ZIF-
67 with various number of nitrogen ligands (ZIF-xN, x= 1 - 4). Density functional
theory (DFT) with Hubbard (DFT + U) [5]were carried out using soft projector-
augmented wave (PAW) pseudopotentials[6,7] and the Perdew-Burke-Ernzenhof [7]
(PBE) exchange correlation functional, as implemented in the VASP code [8,9]. The k-
point setting of Brillioun zone was obtained by 3 x 3 x 1 grid generating meshes with
their origin point at the gamma point. The plane wave kinetic energy has a high cut of
energy of 450 eV throughout the computations and a vacuum spacing of at least 20 Å
in z direction. Moreover, the all spin-polarized calculations were converges to 0.01 eV
Å-1 for all surfaces and the geometries.
 Figure S1. SEM images of ZIF-67 (a) and CUMSs-ZIF-67 (b).

Figure S2. TGA curves of the ZIF-67 and CUMSs-ZIF-67 catalysts recorded in air at
5 K min-1.
 Figure S3. The CO adsorption FT-IR spectra of ZIF-67 and CUMSs-ZIF-67.

Figure S4. Co 2p (a), N 1s (b), C 1s (c) and O 1S (d) spectra of ZIF-67 and CUMSs-
ZIF-67.
 Figure S5. The CVs of ZIF-67 and CMUSs-ZIF-67 electrocatalyst in 1 M KOH
aqueous solution at a scan rate of 2 mV s-1.

Figure S6. ESCA tests of CUMSs- ZIF-67 and ZIF-67 towards OER in 0.5 M
KBi. a) CV curves of ZIF-67 and b) CUMSs- ZIF-67 with different scanning rates
from 10 to 80 mV s-1; c) Charging current plotted against scanning rates at 1.25 V vs.
RHE.

Figure S7. (a) LSV polarization curves of the ZIF-67 and CUMSs-ZIF-67
electrocatalysts in O2 saturated 1 M KOH aqueous solution; (b)LSV polarization
curves of the CUMSs-ZIF-67, RuO2 and annealed ZIF-67 electrocatalysts in O2
saturated 1 M KOH aqueous solution; (c)The corresponding Tafel plots from the LSV
curves; (d)EIS of ZIF-67 and CUMSs-ZIF-67 electrocatalyst recorded at a constant
potential of 1.53 V vs. RHE; (e) Ring current of CUMSs-ZIF-67 electrocatalyst on an
RRDE (1600 rpm) with a ring potential of 1.5 V in O2-saturated 1 M KOH aqueous
solution; (f)Ring current of CUMSs-ZIF-67 electrocatalyst on an RRDE (1600 rpm)
with a ring potential of 0.40 V in N2-saturated 1 M KOH aqueous solution.

Figure S8. LSV polarization curves of ZIF­67 and CUMSs­ZIF­67 normalized by

the BET surface area.

Figure S9. PXRD patterns of CUMSs-ZIF-67 and Ligand-repaired CUMSs-ZIF-67.

Figure S10. LSV polarization curves of the ZIF-67 and CUMSs-ZIF-67 with different
treat time in O2 saturated 1 M KOH aqueous solution.

Figure S11. SEM images of ZIF-67 treated by DBD plasma for 11 min.
 Figure S12. The stability testing of CUMSs-ZIF-67 for 2000 cycles in 1 M KOH.

Figure S13. The XRD patterns of CUMSs-ZIF-67 and after 2000 cycles in 1 M KOH
and 0.5 M KBi (The XRD was conducted by drop the samples on Ti foil).
Figure S14. (a) Tope view and (c) side view of ZIF-67-4N, and (b) tope view and (d)
side view of ZIF-67-3N. The colors of blue, pink, deep gold, and silver represented
atoms of Co, H, C, and N, respectively. Boxes are periodic in x, y and z directions.
Figure S15. The associate reaction process of OER in four-electron transfer process.
a) top view and e) side view of the ZIF-67-4N, b) top view and f) side view of the
formation of OH* on Co in ZIF-67-4N, c) top view and g) side view of adsorption of
O on Co in ZIF-67-4N, d) top view and h) side view of the formation of OOH* on Co
in ZIF-67. The colors of red, pink, deep gold, silver and blue represented atoms of O,
H, C, N, and Co, respectively. Boxes are periodic in x, y and z directions.
Figure S16. The associate reaction process of OER in four-electron transfer process.
a) top view and e) side view of the CUMSs-ZIF-67(ZIF67-3N), b) top view and f)
side view of the formation of OH* on Co in CUMSs-ZIF-67(ZIF67-3N), c) top view
and g) side view of adsorption of O on Co in CUMSs-ZIF-67(ZIF67-3N), d) top view
and h) side view of the formation of OOH* on Co in CUMSs-ZIF-67(ZIF67-3N). The
colors of red, pink, deep gold, silver and blue represented atoms of O, H, C, N, and
Co, respectively. Boxes are periodic in x, y and z directions.
Figure S17. Free energy diagrams of ZIF-67-xN (x= 1 - 4) with different number of
nitrogen ligands for OER in acid medium at UNHE = 0.402 V.
Figure S18. Electron charge distribution (ECD) on a) ZIF67-4N, b) ZIF67-3N. The
blue and yellow colors indicate the positive and negative values of electron quantities,
respectively. The isosurface value is set to 0.09. The colors of blue, white and brown
meant atoms of the cobalt, hydrogen and carbon, respectively.

Figure S19. Bader effective charge distribution of (a) ZIF67-4N, and (b) ZIF67-3N.
The colors of green, yellow, blue and red refer to negative, positive, highly negative,
and highly positive charges, respectively.
Figure S20. Charge transfer distribution on ZIF67 with OH adsorption. Top (first
row) and side (second row) views of the electron charge distribution (ECD) on ZIF67
with OH adsorption, from left to right which is (a) (b) (g) (h) ZIF67-4N, (c) (d) (i) (j)
ZIF67-3N, and (e) (f) (k) (l) ZIF67-2N. The blue and yellow colors indicate the
positive and negative values of electron quantities, respectively. The isosurface value
is set to 0.001. Charges are not shown in (b), (d), (f), (h), (j), and (l). The colors of
blue, red, white and brown meant atoms of cobalt, oxygen, hydrogen and carbon,
respectively.
Table S1. The PXRD patterns studies of ZIF-67 and CUMSs-ZIF-67.

ZIF-67 CUMSs-ZIF-67
2-Theta d(Å) FWHM 2-Theta d(Å) FWHM
7.257 12.1705 0.186 7.336 12.0404 0.254
10.282 8.5961 0.167 10.361 8.5308 0.183
12.621 7.0078 0.164 12.699 6.9651 0.192
14.6 6.062 0.166 14.677 6.0303 0.18
16.323 5.4259 0.164 16.418 5.3947 0.177
17.92 4.9459 0.169 17.981 4.9292 0.184
19.38 4.5763 0.153 19.421 4.5667 0.135
22.038 4.0301 0.082 22.077 4.023 0.169
24.38 3.648 0.168 24.46 3.6362 0.149
25.499 3.4904 0.064 25.539 3.4849 0.13
26.559 3.3534 0.164 26.621 3.3457 0.152
28.541 3.1249 0.166 28.619 3.1165 0.081
29.539 3.0215 0.165 29.603 3.0152 0.166
30.462 2.9321 0.126 30.522 2.9264 0.157
31.362 2.8499 0.153 31.475 2.84 0.153
32.261 2.7725 0.16 32.358 2.7644 0.159
33.151 2.7001 0.16 33.166 2.6989 0.085
33.996 2.6349 0.161 33.987 2.6356 0.121

Table S2. The charges and minimum OER overpotentials for various ZIF-67.

Name The number of Charge of Co Charge of N OER

N ligands atom atom
ZIF67-4N 4 0.853 -1.218 0.647
ZIF67-3N 3 0.733 -1.018 0.577
ZIF67-2N 2 0.369 -1.958 1.093
ZIF67-1N 1 0.362 -1.796 1.940

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