Journal Pre-proof

Copper oxide nanofibers obtained by solution blow spinning as catalysts for oxygen
evolution reaction

Alison P. Dantas, Rafael A. Raimundo, Pedro F.C. Neto, Caio M.S. Lopes, Jakeline
R.D. Santos, Francisco J.A. Loureiro, Thiago O. Pereira, Marco A. Morales, Eliton S.
Medeiros, Daniel A. Macedo
PII: S0272-8842(24)00226-8
DOI: https://doi.org/10.1016/j.ceramint.2024.01.213
Reference: CERI 39536

To appear in: Ceramics International

Received Date: 25 August 2023

Revised Date: 25 December 2023
Accepted Date: 15 January 2024

Please cite this article as: A.P. Dantas, R.A. Raimundo, P.F.C. Neto, C.M.S. Lopes, J.R.D. Santos,
F.J.A. Loureiro, T.O. Pereira, M.A. Morales, E.S. Medeiros, D.A. Macedo, Copper oxide nanofibers
obtained by solution blow spinning as catalysts for oxygen evolution reaction, Ceramics International
(2024), doi: https://doi.org/10.1016/j.ceramint.2024.01.213.

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 Copper oxide nanofibers obtained by solution blow spinning as catalysts
for oxygen evolution reaction

Alison P. Dantasa, Rafael A. Raimundob,*, Pedro F. C. Netoa,c, Caio M. S. Lopesa,c, Jakeline

R. D. Santosd, Francisco J. A. Loureiroe,f, Thiago O. Pereiraa,c, Marco A. Moralesb, Eliton
S. Medeirosa,c,**, Daniel A. Macedoa,***

a
Department of Materials Science and Engineering, UFPB, 58051-900, João Pessoa, Brazil
b
Department of Physics, Federal University of Rio Grande do Norte, UFRN, 59078-970, Natal, Brazil
c
Materials and Biosystems Laboratory (LAMAB), DEMAT, UFPB, 58051-900, João Pessoa, Brazil
d
Department of Materials Science and Engineering, UFRN, 59078-970, Natal, Brazil

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TEMA - Centre for Mechanical Technology and Automation, Department of Mechanical Engineering,
University of Aveiro, 3810-193 Aveiro, Portugal.
f
LASI – Intelligent Systems Associate Laboratory, Guimarães, Portugal

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Graphical Abstract
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Corresponding authors:
* rar@academico.ufpb.br; rafael.fisica.ufrn@gmail.com (Rafael A. Raimundo)
**esm@academico.ufpb.br (Eliton S. Medeiros)
***daniel.macedo@academico.ufpb.br (Daniel A. Macedo)
Abstract
In this work, we report copper oxide nanofibers (CuO – N) synthesized by Solution
Blow Spinning (SBS) for oxygen evolution reaction (OER), and their comparison with a
control sample based on a commercial powder (CuO – C). Both materials were characterized
by various techniques, including X-ray diffraction (XRD), magnetometry, scanning electron
microscopy (SEM), and spectroscopy (Fourier transform infrared (FT-IR), Raman and X-
ray photoelectron (XPS)) to confirm the purity, and microstructural and surface chemical
properties. Subsequently, the performance of copper oxide catalysts in a 1.0 M KOH solution
was investigated. Copper oxide with nanofiber morphology (CuO – N) exhibited a small
overpotential of 385 mV @ 10 mA cm−2 and a Tafel coefficient of only 76 mV dec−1, i.e.,
fast kinetics for water splitting, a result that is modulated by oxygen vacancies (O2/O1 =
0.83). The oxygen vacancies are due to the presence of Cu1+ in the lattice. The analyses of

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the magnetization measurements at 5 K suggest a larger amount of Cu1+ in sample CuO – N.

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Therefore, this work sheds light on how to design low-cost nanofibrous catalysts based on
abundant transition metals in the earth’s crust by SBS, an economical and scalable technique,

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which is promising for energy applications.
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Keywords: Copper oxide; Solution Blow Spinning; Nanofibers; Commercial powder;
Oxygen evolution reaction; Water splitting.
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1. Introduction
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Over the past decades, there has been an increasing interest for materials in the
nanometric scale [1]. Amongst these materials are nanofibers from natural polymers, such
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as cellulose, chitosan, collagen, or synthetic ones, such as poly(lactic-co-glycolic acid)

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(PLG/PLGA), polycaprolactone (PCL), poly(lactic acid) (PLA), and polyvinylpyrrolidone

(PVP) [2,3]. Nanofibers have interesting properties such as small diameters, controllable
pore structure, high surface area, good permeability, excellent chemical, physical and
mechanical properties, as well as a high surface-to-volume ratio [2–4]. Electrospinning [5],
wet spinning [6], plasma-induced synthesis [7], template synthesis [8], direct-drawing [9],
self-assembly [10], melt blowing [11], centrifugal spinning [12] and solution blow-spinning
(SBS) [13] are the most used techniques for nanofiber production. These processes are of
great importance since fiber shape, surface texture, and diameter vary according to the used
technique [3].
Solution blow spinning (SBS) was initially developed to produce micro and
nanofibers from polymer solutions at high production rates [14], using a simple and low-
cost apparatus when compared to other techniques [14,15]. It consists of a concentric nozzle
apparatus, needle, injection pump, and a pressurized gas source. When a polymer solution is
ejected through the inner nozzle, the pressurized gas stream ejected from the outer nozzle
drags and shears this solution to form a cone, similar to Taylor’s cone in electrospinning,
from which micro and nanofibers are jettisoned across the working distance, towards the
collector. Meanwhile, the solvent evaporates so that the stretched solution jets give rise to
fibers that are gathered on the collector’s surface to form spun nonwoven mats or cotton-
wool-like 3D structures[16–18].
Solution blow spun nanofibers have high porosity and specific surface area [19].
Fiber morphology and diameter can be controlled by various parameters, such as solution
concentration and flow (ejection) rate, viscosity and surface tension of the spinning solution,

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spinning pressure as well as ambient temperature and relative humidity [20]. These fibers
have been used in various applications ranging from batteries, fuel cells, supercapacitors,

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solar cells, hydrogen storage and generation, and piezoelectric systems to biosensors,
regenerative medicine, and oxygen reduction (ORR) and evolution reactions (OER) [21–
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30].
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The oxygen evolution reaction (OER) is one of the half-reactions of water splitting,
a sustainable process for producing hydrogen and oxygen gases. The other half-reaction is
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called the Hydrogen Evolution Reaction (HER). Both occur at the anode and cathode,
respectively [31]. General water splitting (Eq. (1)) is a non-spontaneous process under
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atmospheric conditions. It occurs when a specific voltage is applied to the electrochemical

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cell consisting of the two electrodes (anode and cathode) immersed in an aqueous electrolyte,
where the pH can range from neutral, to alkaline (Eqs. (2-3) or acid (Eqs. (4-5)) [32].
H2O → H2 + ½ O2 E° = 1.23 V (Eq. 1)
2OH– → H2O + ½ O2 + 2e– E° = −0.40 V (Anode) (Eq. 2)
2H2O + 2e– → H2 + 2OH− E° = 0.83 V (Cathode) (Eq. 3)
H2O → 2H+ + ½ O2 + 2e– E° = −1.23 V (Anode) (Eq. 4)
2H+ + 2e– → H2 E° = 0.00 V (Cathode) (Eq. 5)
However, the kinetic reaction that takes place at the anode (Eqs.(2,4)) (OER) is slow,
due to the multi-step nature of the reaction that involves several charge transfer processes,
decreasing its efficiency [32–34]. The use of electrocatalysts is necessary to improve the
faradaic efficiency, since the biggest challenge is the development of catalytically active
electrodes from low-cost and abundant elements such as transition metals once noble metals
based on ruthenium, iridium, and platinum are considered the most used electrocatalysts for
OER, despite their scarcity and high cost [34–37].
SBS can be used to obtain various types of metal oxide nanofibers [13,31], such as
copper oxide (CuO), with electronic configuration of Cu+2 [38]. Copper oxide has drawn
much attention from researchers due to properties such as high solar absorption, degree of
stability, exceptional electrical, thermal conductivity, high theoretical capacity, non-toxic,
environmentally friendly, low thermal emission, highly abundant, inexpensive, and with
good electrical and electrocatalytic properties. In addition, it CuO a p-type semiconductor
with a narrow band gap (Eg = 1.2 - 2.1 eV) [39–44]. Bulk CuO crystallizes in the monoclinic
structure. It is well established that a transition from a paramagnetic to incommensurate

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antiferromagnetic (AF) state occurs near TN  230 K, followed by a first-order transition to
commensurate AF state near 213 K, with the moments aligned along the monoclinic b axis

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[45,46]. It is known that Cu1+ ion is a 3d10 system, therefore it has no unpaired spin electrons,
and therefore, Cu1+ is diamagnetic. On the other hand, Cu2+ is 3d9 and has a single unpaired
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spin electron, hence, it has an effective moment of 𝜇 = √3 𝜇𝐵 , where B is Bohr magneton.
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In an earlier work, CuO nanorods showed an anomalous ferromagnetic behavior at low

temperatures, and it was discussed in terms of uncompensated Cu2+ moments at the surface
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of the nanorods [47]. Magnetization studies performed on CuO nanoparticles, produced by

sol–gel route, revealed weak ferromagnetic signals in 6.6 nm CuO, which were suggested to
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be originated from the uncompensated surface Cu2+ spins [48]. Several studies have already
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reported the use of metal oxide-based nanofibers for the water oxidation reaction produced
by solution blow spinning, including those developed by our research group [49–51], as well
as by electrospinning [52–54].
Within this context, CuO nanofibers were prepared by SBS, which was observed that
there is no report on these nanofibers found in the literature. Therefore, this work is the first
report on the synthesis of CuO nanofibers (denominated CuO – N) while also comparing
with a control sample of CuO commercial (denominated CuO – C), in relation to their
structural, vibrational, morphological, magnetic and electrochemical properties (application
as catalyst for OER in alkaline medium).
2. Experimental

2.1. Materials and reagents

Copper nitrate (Cu(NO3)2.2.5H2O, Sigma-Aldrich, 98 %), commercial copper oxide

(CuO, Vetec, 99 %, average particle size 15.7 μm (Fig. S1)) poly(vinyl pyrrolidone) (PVP-
K90, 1300.000 g/mol, exode scientific), Nafion® solution 5 wt.% (Aldrich), ethanol (99%,
Vetec), N-dimethylformamide (DMF, 99%, Vetec), glacial acetic acid (GAC, 99%, Vetec),
potassium hydroxide (KOH, >85%, Nuclear) and Nickel foam (Ni 99.8%, porosity > 95%,
QiJing Ltd., China) were used as starting materials.

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Fig S1.

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2.2. Fabrication of CuO nanofibers by Solution Blow Spinning (SBS)
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First, the precursor solution was prepared with 3.2029 g of PVP-K90 dissolved in 20
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mL of ethanol, 20 mL of DMF, and 500 µL of acetic acid under stirring. Then 1.5127g of
copper nitrate was added to the solution using a 1:1 molar ratio of PVP and nitrate. After
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adding all the reagents, the resulting solution was left to stir for 24 h. The CuO nanofibers
(CuO – N) were then produced using the following parameters: injection rate of 4 mL h-1,
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working distance of 50 cm, and pressure of 0.41 MPa. The collected material was then left
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at 60°C for 24 h to completely remove the solvent and then calcined in a muffle furnace
using two heating ramps: (1) 200°C at 5°C min-1 for 2 h, followed by (2) 700°C at 2 °C min-
1
for 2 h, generating the final CuO nanofibers (CuO – N) product. All steps of obtaining
copper oxide with nanofiber morphology (CuO – N), and the microstructural, surface
chemical, and electrochemical characterizations of both samples are shown in Fig. 1.

Fig 1.
2.3. Structural, chemical, and morphological and magnetic characterization

The structure of copper oxide (CuO – N and CuO – C) was characterized by X-ray
diffraction (Shimadzu XRD-7000 diffractometer) equipped with Cu-Kα radiation (λ =
1.5418 Å). The diffraction patterns were obtained in the angular range of 20-90°, with a step
size of 0.02° and an acquisition time of 1 s per step. Rietveld refinement was applied to the
diffraction patterns using the Total Pattern Analysis Solution (TOPAS, software version 4.2)
[55]. The morphological characterization was performed by scanning electron microscopy
(SEM, TESCAN, model VEGA4 LMS, UFPB) equipped with model EDS Essence, 30 mm2
(WD=5.77 and 6.08 mm, voltage of 15 kV). Raman spectroscopy measurements were
performed at room temperature using a 532 nm laser as the excitation source. The Raman
spectrometer is LabRAM-HR Evolution-HORIBA. The laser power was maintained at 1
mW with an acquisition time of 10 s for accumulation. Fourier transform infrared
spectroscopy (FTIR) (Shimadzu IRPrestige21 spectrophotometer) measurements were
obtained in the 400 e 4000 cm-1 range, using pressed KBr pellets containing 1 wt.% sample.

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The ultraviolet-visible spectra (UV-Vis) were obtained in a spectrophotometer from
Shimadzu in the UV-2600i. The chemical surface analysis for the samples was performed by

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X-ray photoelectron spectroscopy (XPS) using a conventional XPS spectrometer
(ScientaOmicron ESCA+) with a high-performance hemispheric analyzer (EAC2000) with
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monochromatic Al Kα (h ν = 1486.6 eV) radiation as the excitation source. The operating
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pressure in the ultra-high vacuum chamber (UHV) during the analysis was around 10−9 Pa.
The XPS high-resolution spectra were recorded at constant pass energy of 20 eV with a 0.05
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eV per step for the high-resolution spectra. A charge neutralizer (CN10) was used to exclude
the surface charging effects. PeakFit version 4.1 fitting software was used for deconvoluting
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the spectra, obtaining the height, area, and position of the analyzed peaks. The magnetic
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measurements were done in physical properties measurements system (PPMS) equipped

with a vibrating sample magnetometer (VSM) from Quantum Design, model Dynacool.

2.4. Electrode preparation and electrochemical characterization

The electrochemical measurements of the copper oxides (CuO – N and CuO – C)

were carried out using Metrohm Autolab equipment (PGSTAT204-FRA32 M) in the
formation of three electrodes plus an electrolyte alkaline solution of KOH (1 M, pH = 13.6)
at 25 °C. In this case, platinum and Ag/AgCl were used as the counter and reference
electrodes, respectively. The working electrodes were prepared by depositing the catalytic
ink (5 mg of CuO nanofiber or commercial, 500 µL of isopropanol mixed with 50 µL of 5%
Nafion and sonicated for 16 minutes) on a substrate (nickel foam, with an area of 1 cm × 1
cm). The paint was then deposited on the previously cleaned Ni foam and dried at room
temperature. All the potential values (iR corrected) were converted to the reversible
hydrogen electrode (RHE) using the Nernst equation: (ERHE = EAg/AgCl + 0.059×pH +
0.1976), while the overpotential values (η) were calculated using the equation: (η = ERHE -
1.23 V). Linear sweep voltammetry (LSV) was performed at 5 mV s-1. The cyclic
voltammograms were obtained at different scan rates in a potential range (5 mV s-1 to 200
mV s-1). The specific capacitance can be converted into the electrochemical active surface
area (ECSA) using the specific capacitance value (CS, 0.040 mF cm-2) by the following
equation of ECSA = CDL/CS. Electrochemical impedance spectroscopy (EIS) was carried out
using the frequency range (0.1 Hz to 10 kHz) under DC potentials (1.3, 1.6, and 1.64 V vs.

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RHE).

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3.1. X-Ray Diffraction (XRD)
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The refined X-ray diffraction (XRD) patterns of CuO – N and CuO – C are shown in
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Fig. 2a. As noted, all peaks are characteristic of the copper oxide phase (CuO) (Fig. 2b), with
a structure of the type CuO(mS8), from the crystal system monoclinic, and with lattice
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parameters a = 4.690(1) Å, b = 3.420(1) Å and c = 5.131(1) Å (ICSD n° 87125, space group

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C12/c1 (15)) [56]. Furthermore, characteristic peaks of any other copper oxide phase (e.g.,
Cu2O) were not observed, and CuO – N and CuO – C are both crystalline.
The X-ray diffraction pattern of CuO – N confirmed the successful synthesis of
copper oxide nanofibers by solution blow spinning. Table S1 summarizes all data obtained
from Rietveld refinement, including lattice parameters (Å) and refinement indices (Rwp, Rexp,
χ2). The lattice parameters obtained are in accordance with those reported in the ICSD card
file n° 87125. The maximum values for Rwp and Rexp are 7.49 % and 4.66 % (see Table S1).
The good quality of the Rietveld refinements is proved by the low values of the χ2 index (see
Table S1).
Fig 2.
Table S1
3.2. Scanning electron microscopy (SEM)

The morphological characteristics of copper oxides (CuO – N and CuO – C) were

inspected by scanning electron microscopy (SEM) analysis coupled with energy dispersive
spectrometry (EDS). The SEM images are shown in Fig. 3. Figs. 3a-c show branched CuO
nanofibers (which interconnect in a 3D lattice) that are constituted by the joining of small
grains (particles), which are obtained after calcination of the green fiber in an atmosphere
rich in oxygen. Unlike the report by Silva et al. [49,57], the copper oxide nanofibers (CuO
– N) obtained here have a rough surface and irregular geometry (non-cylindrical).
Furthermore, the diameter of most nanofibers is less than 1 µm, and the length is up to a few

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micrometers (see Figs. 3a-b). SEM images of commercial copper oxide powder (CuO – C)
in Figs. 3d-f show that this oxide is formed by spherical agglomerates of heterogeneous

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nature in size, reaching values in the micrometric scale. EDS mapping was used to examine
the distribution of copper and oxygen elements in the oxides (CuO – N and CuO – C). As
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can be seen in Fig. 3, the elements copper and oxygen, which are shown in green and pink,
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respectively, are uniformly distributed in the nanofibers and in the micrometric particles of
CuO. Therefore, our results confirm that the SBS technique allows the synthesis of
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nanofibrous materials with a homogeneous distribution of chemical elements, as well as, this
type of morphology should facilitate the contact of the active material with the electrolyte,
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leading to a fast charge transfer and better electrochemistry performance for oxygen
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evolution reaction (OER) [49,58], as will be seen later.

Fig 3.

3.3. Fourier transform infrared (FTIR), Raman, and Ultraviolet-visible (UV-vis)

spectroscopies

Copper oxides (CuO – N and CuO – C) were analyzed by FT-IR in the range of 400
and 4000 cm−1, and the results are shown in Fig. 4a. Bands below wavenumber 1000 cm-1
are assigned to Cu-O stretching modes [59–61]. The band located at 1384 cm-1 is due to the
C-C vibrational mode [51], while the band at 1035 cm-1 is characteristic of C-O stretching
vibrations [62]. Absorption bands above wave number 1600 cm-1 are related to O-H
stretching and bending vibrations [63]. Raman spectroscopy was used to observe the active
modes of vibration and attest to the purity of copper oxides. Raman spectra were collected
from 150 to 900 cm-1, as shown in Fig. 4b. Three vibration modes were detected at positions
294, 343, and 639 cm-1 and are characteristic of Ag, Bg(1), and Bg(2) phonons [64],
respectively. Moreover, according to Funda Aksoy Akgul et al. [65], the modes are related to
first-order scattering. Band structures and the associated gap for copper oxides were
evaluated using the Tauc plot (Egap) plots shown in Figs. 4c-d. The optical gap values of CuO
– N and CuO – C were determined to be 2.4 and 3.36 eV, respectively. The FT-IR, Raman,
and Egap data reported in this work agree with those reported in the literature [59,66,67].

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Fig 4.

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3.4. X-ray photoelectron spectroscopy (XPS)
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To understand the surface chemical composition of both samples, X-ray
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Photoelectron Spectroscopy (XPS) was conducted. Fig. 5 depicts the high-resolution spectra
obtained for the Cu 2p (Figs. 5a-b) and the O 1s (Figs. 5c-d) regions.
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The high-resolution spectra obtained for Cu 2p3/2 core level were deconvoluted into
four main peaks (Figs. 5a-b) for each sample. The peaks at 932.530 eV or 932.775 eV for
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the commercial (CuO – C) and the nanofibers (CuO – N) powders, respectively, can be
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ascribed to the Cu+1 oxidation state. The peaks at 933.615 eV or 933.920 eV for the
commercial (CuO – C) and the nanofibers (CuO – N), respectively, can be ascribed to the
Cu+2 oxidation state of CuO [68,69]. The Cu1+/Cu2+ ratio was determined to be 0.43 and 0.24
for CuO – N and CuO – C, respectively. Conversely, the peaks at 935.350 eV or 935.240 eV,
respectively, for each sample, may have resulted from the formation of Cu(OH)2 species
[69]. In addition, at higher binding energies, two additional peaks were further deconvoluted,
corresponding to the corresponding shake-up satellite features [69].
In the high-resolution spectrum obtained for the O 1s region of both CuO – N and
CuO – C samples (respectively, Figs. 5c-d), three main peaks were determined at 529.799
eV or 529.611 eV (O1), 531.440 eV or 531.177 eV (O2), and 532.856 eV or 531.927 eV (O3),
respectively, for the nanofibers and the commercial powders. These peaks have been
typically described to be related to surface lattice oxygen (Olat, O2−), adsorbed oxygen
species (Oads, O2−, O22−, and O−), and adsorbed water species (OH2O), respectively, O1, O2,
and O3 [70–72]. The O2/O1 ratio was determined by integrating the corresponding areas from
each peak [73] to yield a value of 0.83 and 0.36, respectively for CuO – N and CuO – C.
These results suggest a much higher oxygen-ion vacancy concentration at the surface of the
nanofibers, thus, corroborating the increased OER performance of this sample [70–72]. In
this regard, it is known that the charge carriers in oxide semiconductors can be related to the
oxygen vacancy concentration [73,74]. The oxygen (O2) is lost from the oxide surface
sublattice, creating a doubly charged oxygen vacancy VO•• and two electron carriers,
according to the Eq. (6):
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OxO = O2 (g) + VO•• + 2e−

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(Eq. 6)

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Fig. 5.

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3.5. Magnetic Properties
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The samples were examined by the magnetometry technique in order to study the
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actual magnetic moments of samples. In the present work, for both samples, we noticed a
ferromagnetic behavior in the M-H measurements at 5 K. The M-H measurements for CuO
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– N and CuO – C samples are shown in Fig. 6a. The sample CuO – C shows an M-H curve
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which is a composition of a ferromagnetic hysteresis superposed with a linear curve. The

linear behavior is of the type H, where  is the susceptibility of the AF phase. The sample
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CuO – N exhibits a ferromagnetic signal superposed with a linear diamagnetic signal. The
diamagnetic signal evidences the presence of Cu1+ ions in the CuO lattice. If we subtract a
straight line in both M-H curves we obtain, in an approximate manner, the hysteresis curves
due to the ferromagnetic phases (see Fig. 6b). According to our XPS study, both samples
have Cu2+ and Cu1+ ions (see Fig. 5). It is clear that the saturation magnetization (Ms) of
sample CuO – C (0.02 emu g-1) is the largest when compared with sample CuO – N (0.003
emu g-1). The sample CuO – C has a smaller crystallite size than the CuO – N, hence, it
should have a larger amount of uncompensated surface Cu2+ moments. The presence of
surface uncompensated moments has been discussed in several works [47]. However, since
the magnetization of the sample CuO – N is diamagnetic, thus, this sample has a larger
amount of Cu1+ compared with sample CuO – C. Of course, the presence of Cu1+, within the
crystallite, will also uncompensate neighbors Cu2+ moments. Therefore, the sample CuO –
C has a higher Ms value because its larger amount of surface uncompensated Cu2+ moments.
On the other hand, the diamagnetic behavior of sample CuO – N and its lower Ms (0.003
emu g-1) are because of the larger amount of Cu1+ ions which bear no magnetic moment. The
coercivity field (Hc) of samples CuO – N and CuO – C were 6 kOe and 430 Oe, respectively.
It is clear that the Cu1+ ions may be distributed throughout the crystallite volume, and it will
create uncompensated Cu2+ magnetic moments within the crystallites. These moments
interact with each other through dipolar interaction and it may favor the increase of the
coercivity field in the sample CuO – N. Since the crystallites tend to reach the charge
neutrality, the sample with a higher content of Cu1+, i.e. CuO – N, should have oxygen
vacancies in order to compensate the reduced amount of cationic charge.

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Fig. 6.

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3.6. Electrodes kinetics for Oxygen evolution reaction (OER) and Electrochemical
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impedance spectroscopy (EIS) measurements
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The electrocatalytic activity of the copper oxide electrodes was investigated by several
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electrochemical characterization techniques (linear scanning voltammetry (LSV), cyclic

voltammetry (CV), and electrochemical impedance spectroscopy (EIS)). Fig. 7a shows
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anodic polarization curves of CuO – N, CuO – C, and Ni foam, which show overpotentials
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of 385, 412, and 515 mV vs. RHE, respectively, to provide a current density J = 10 mA cm-
2
. The CuO – N electrode presents better catalytic performance for oxygen evolution and,
consequently, better performance over the entire analyzed current density range (see Fig.
7b). In fact, the available literature has already shown that nanofibers perform better than
synthesized or commercially obtained particles/nanoparticles, for example, Silva et al. [49],
who reported that the morphology impacts the performance of the electrocatalyst. They
observed that for nanostructured electrodes based on nickel oxide, nanofibers had a catalytic
capacity superior to that of the nanoparticles, where a difference of 133 mV vs. RHE was
observed between the nanofibers and nanoparticles, as well as the amount of O2 moles
evolved during the reaction is 122 higher for the nanofibers. Furthermore, the overpotential
obtained at 10 mA cm-2 for CuO – N is lower than that of commercial IrO2 (400 mV vs.
RHE) [75] under the same conditions. The CuO – N overpotential result is lower than that
of copper-based materials, namely: (i) CuO nanosheets prepared by a simple molten salt
method (η = 420 mV @ 10 mA cm-2) [76] and (ii ) CuO nanoplates synthesized by an easy
precipitation process (η = 492 mV @ 10 mA cm-2) [77]. In general, the results observed in
this research for copper oxide nanofibers (CuO – N) agree with the best electrocatalysts
based on copper oxide reported in the literature (Table S2).
Additional information on the kinetics of copper oxide catalysts was obtained through
the Tafel slope plots (ƞ = a + b log j0), where: ƞ is the overpotential, j0 is the current density,
a is the intercept relative to the exchange current density j0 and b represents the Tafel slope
[78]. CuO – N shows a minimal Tafel slope (76 mV dec-1) when compared to CuO – C (87
mV dec-1) and Ni foam (157 mV dec-1) (see Fig. 7c). According to Kaiwan et al. [79] and Yu

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ding et al. [80], Tafel slope ranging from 40 to 120 mV dec−1 indicates that the adsorption
of intermediate species (OH−) and *-O− production are the rate-determining steps based on

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the reaction model proposed by Krasil’shchikov for alkaline solutions [81].
The kinetics of copper oxide electrodes was studied by conducting cyclic voltammetry
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(CV) experiments to determine the electrical double layer capacitance (CDL) and the
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electrochemical active surface area (ECSA). Cyclic voltammograms were recorded in a non-
faradaic region of fixed potential (1.19–1.25 V vs. RHE), with different sweep rates (10, 20,
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30, 40, 50, 100, and 200 mV s-1, see Fig. S2). CDL was calculated using the linear relationship
between the anode current density (Jia) and the sweep rate (ʋ), according to the equation Jia
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= ʋ x CDL [82]. It can be easily observed that the CDL of CuO – N is higher than that of CuO
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– C (see Fig. 7d). More specifically, the CDL for CuO – N and CuO – C were calculated to
be 4.74 mF and 4.54 mF, respectively (Fig. 7d). The higher CDL value of the CuO – N
electrocatalyst implies higher ECSA. The electrochemical active surface area (ECSA) was
estimated using the equation (ECSA = CDL/CS), where CS is the specific capacitance. For
copper-based electrodes in an alkaline solution, a typical value of CS = 0.040 mF cm-2 was
used [83]. The ECSA (Fig. 8a) calculated for the CuO – N and CuO – C electrodes were
118.5 cm2 and 113.5 cm2, respectively. Therefore, the CuO – N electrode has a greater
electrochemically active surface area, that is, more active and exposed sites, confirming its
superior electrocatalytic activity for OER, and this is due to its nanofibers characteristic
previously confirmed by SEM images (Figs. 3a-c). A study at high current densities was also
conducted to determine the specific activity (SA, mA cm−2), an important parameter to
understand the reaction kinetics. SA was calculated using the equation SA = J/ECSA, where
J is the current density (450 mA cm-2 at ƞ = 450 mV vs. RHE). According to Fig. 8b, the
specific activity (normalized by ECSA) was determined as 3.79 mA cm−2 and 1.03 mA cm−2,
respectively, for CuO – N and CuO – C. The CuO – N electrode demonstrated superior
catalytic performance through all electrochemical tests performed and standardized (LSV,
TAFEL, CDL, ECSA, and SA), proving that the nanofiber-like structure is beneficial, as well
as modulating the electrocatalytic performance. The superior performance of the CuO – N
catalyst is attributed to the high number of oxygen vacancies (O2/O1 = 0.83, see Fig. 5) that
comes from the approach of the solution blow spinning synthesis method, which has the
capacity to develop electrocatalysts with high efficiency for oxygen evolution reaction. The
durability of the electrodes was evaluated by chronopotentiometry (CP) for 24 h at 10 mA

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cm-2. Fig. S3 shows the behavior of the electrodes. In both electrodes (CuO – N and CuO –
C), there is a small variation in the overpotential value, particularly in the range of 0 to 6 h,

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due to the blocking of the active sites by the oxygen formed during the reaction or the
adsorption of non-reactive species. Despite that, these electrodes exhibit excellent stability
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with negligible changes after long-term testing.
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Fig. 7.
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Table S2
Fig. S2.
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Fig. 8.
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Fig. S3.

The impedance spectra measured at 1.3 V, 1.6 V, and 1.64 V vs. RHE are shown in
Figs. 9a-b for the CuO – N and the CuO – C samples, respectively. All impedance spectra
depict an offset along the real Z′ axis at the highest frequencies, followed by the appearance
of either a large tail (1.3 V vs. RHE), with a relaxation frequency (frelax) of around 10-3 Hz,
or one well-defined semicircle at frequencies in the range of 1 Hz to 10 Hz (1.6 V and 1.64
V vs. RHE), Table S3. Observation of the impedance spectra shows that the shapes and
magnitudes of the impedance alter dramatically with the increasing of the applied difference
of potential. Therefore, a simple Voight equivalent circuit model (EQM) (Fig. 9e) was
selected to model the data, consisting of a resistor (R) in series with two R||CPE elements
(CPE is a constant phase element). The fitting parameters extracted for each sample are listed
in Table S3.
The offset resistance (Rs) represents the ohmic resistance, which contains the
electrolyte contribution, showing effective constant values of ~1  in all tested conditions
(Table S3). The impedance spectra for the CuO – C electrode show the highest charge-
transfer resistance (Rc.t.) between both samples, highlighting the benefit of the CuO – N for
OER (Table S3). Moreover, the corresponding double-layer capacitance (CDL), proportional
to the electrochemical surface area, is also higher for the CuO – C samples. Further analysis
of these results reveals a decrease in CDL with increased applied dc bias. Such a behavior has
been usually reported to be possibly due to a momentaneous adhesion of gas bubbles on the

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electrocatalyst’s surface, resulting in a decrease in the electroactive surface area available
for OER [84–86].

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Figs. 9c-d present the Bode plot (phase angle) obtained at different applied dc signals
for the CuO – N and the CuO – C samples, respectively. The results mainly denote a single
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large peak can be observed for all tested conditions that are only fully resolved in the case
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of the measurements performed at 1.6 V and 1.64 V vs. RHE while, in the case of the
measurements acquired at 1.3 V vs. RHE, the relaxation frequency of the peak is shifted
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toward outside of the measured frequency range (Figs. 9c-d, Table S3), concurring with the
previous discussion on the impedance plots.
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Fig. 9.
Table S3

Furthermore, SEM and XRD analyses were performed to observe the microstructure
of the CuO – N and CuO – C electrodes after the chronopotentiometric test for 24 h. SEM
images show that the morphology of nanofibers and particles (commercial powder) of the
copper oxide catalysts are maintained (Figs. S4a-d). The XRD patterns (Fig. S4e) only show
peaks from the copper oxide (electrocatalyst, CuO – ICSD 87125) and nickel (substrate, Ni
– ICSD 64989) phases. SEM and XRD analysis confirm that copper oxide electrocatalysts
exhibit excellent structural robustness.

Fig. S4.
4. Conclusions

A highly active copper oxide (non-noble metal) nanofiber electrocatalyst for oxygen
evolution reaction was produced by solution blow spinning, an easy, scalable, and
economically viable synthesis methodology to prepare nanofibrous electrodes. CuO – N, as
manufactured, showed high efficiency for OER, with an overpotential of only 378 mV @ 10
mA cm-2, a relatively low value when compared to commercial copper oxide (CuO – C, 412
mV @ 10 mA cm-2). Tafel slope, ECSA, SA, and EIS also demonstrate that the CuO – N
electrocatalyst has fast reaction kinetics. The enhanced performance of this sample is mostly
due to oxygen vacancies (O2/O1) which are due to the presence of Cu1+ in the lattice. In fact, at 5 K,

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the ferromagnetic behavior and the saturation magnetization of both samples suggest a larger
concentration of Cu1+ in sample CuO – N. This work presents a viable way to design high-

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performance electrocatalysts with nanofiber morphology, using morphological engineering
to modulate the microstructural, superficial, and electrochemical properties of transition
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metals for water electrolysis.
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Acknowledgments:
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Rafael A. Raimundo, Jakeline R. D. Santos, Eliton S. Medeiros, and Daniel A. Macedo

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acknowledge the national research Council (CNPq, Processes n° 151879/2022-2, n°

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201055/2022-8, n° 306447/2018-5, n° 406973/2022-9 and n° 309430/2019-4). Francisco J.

A. Loureiro is thankful for the Investigator Grant CEECIND/02797/2020. The authors also
acknowledge the projects PTDC/CTM-CTM/2156/2020,
https://doi.org/10.54499/2022.02498.PTDC, UIDB/00481/2020 and UIDP/00481/2020
from FCT, and CENTRO-01-0145-FEDER-022083 from Centro Portugal Regional
Operational Program (Centro2020), under the PORTUGAL 2020 Partnership Agreement,
through the European Regional Development Fund (ERDF).
Author Statement:

Alison P. Dantas: Conceptualization, Validation, Methodology, Software, Investigation,

Writing – original draft, Writing – review & editing. Rafael A. Raimundo: Supervision,
Conceptualization, Validation, Methodology, Software, Investigation, Writing – original
draft, Writing – review & editing. Pedro F. C. Neto: Methodology, Investigation, Writing –
review & editing. Caio M. S. Lopes: Methodology, Investigation, Writing – review &
editing. Jakeline R. D. Santos: Methodology, Investigation, Writing – review & editing.
Francisco J. A. Loureiro: Methodology, Investigation, Writing – review & editing. Thiago
O. Pereira: Methodology, Writing – review & editing. Eliton S. Medeiros: Supervision,

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Conceptualization, Methodology, Investigation, Validation, Writing – review & editing.
Marco A. Morales: Methodology, Investigation, Writing – review & editing. Daniel A.

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Macedo: Supervision, Conceptualization, Methodology, Investigation, Validation, Writing
– review & editing.
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Figures:

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Fig. 1. Schematic illustration of the synthesis of copper oxide nanofibers (CuO - N),
accompanied by the structural, morphological, chemical, and electrochemical
characterization techniques used in this work.
 (a) Experimental
Calculated
Difference
(b)
CuO - ICSD 87125

CuO - C
Intensity (a.u.)

Experimental
Calculated
Difference
CuO - ICSD 87125

CuO - N

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Cu

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O
r
20 30 40 50 60 70 80 90
2q (°)
-p
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Fig. 2. (a) Refined X-ray diffractograms (experimental, calculated and difference) of copper
oxide samples accompanied by ICSD card file n° 87125; (b) Crystalline structure of copper
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oxide simulated in Vesta software.

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(a) (b) (c)

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10 μm 5 μm
2 μm 2 μm 2 μm 2 μm 2 μm

(d) (e) (f)

5 μm 5 μm

10 μm 5 μm

5 μm 5 μm 5 μm

Fig. 3. SEM images of copper oxides with different magnifications and EDS mapping
images of Cu and O. (a-c) nanofibers (CuO – N) and (d-f) commercial (CuO – C).
 CuO - N CuO - N
(a) (b)

294
CuO - C CuO - C

1035

343

630
1638
Intensity (a.u.)

Intensity (a.u.)
1384

584
3440

532

294
1638

343
3440

630
584
532
4000 3500 3000 2500 2000 1500 1000 500 150 300 450 600 750 900

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Wavenumber (cm ) Raman Shift (cm )

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(c) CuO - N (d) CuO - C

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(ahv)²
(ahv)²

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2.4 eV 3.36 eV
1.2 1.6 2.0 2.4 2.8 3.2 3.6 4.0 4.4 4.8 1.2 1.6 2.0 2.4 2.8 3.2 3.6 4.0 4.4 4.8

hv (eV) hv (eV)
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Fig. 4. (a-b) FT-IR and Raman spectra; (c-d) Tauc plot for copper oxides nanofibers (CuO –
N) and commercial (CuO – C).
(a) Cu 2p (CuO - N)
(b) Cu 2p (CuO - C)

Cu2+
Intensity (a.u.)

Intensity (a.u.)
Shake-up satellites Shake-up satellites Cu2+

Cu (OH)2 Cu (OH)2
Cu1+ Cu1+

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946 944 942 940 938 936 934 932 930 946 944 942 940 938 936 934 932 930

r
Binding energy (eV) Binding energy (eV)

(c) O 1s (CuO - N)
-p (d) O 1s (CuO - C)
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Intensity (a.u.)

Intensity (a.u.)
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O1
O1

O2 O2
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O3
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O3

535 534 533 532 531 530 529 528 535 534 533 532 531 530 529 528
Binding energy (eV) Binding energy (eV)

Fig. 5. X-ray photoelectron spectroscopy (XPS) spectra obtained in the high-resolution ((a)
and (b)) Cu 2p3/2 and ((c) and (d)) O 1s regions.
(a) 5K (b) 5K
0.15 0.02
As measured As measured
CuO - N CuO - N
0.10 CuO - C CuO - C
Magnetization (emu g-1)

Magnetization (emu g-1)

0.01

0.05

0.00 0.00

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-0.05

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0.04
-0.01

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-0.10 0.00
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-0.15 -0.04
-0.02
-1.5 0.0 1.5
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-8 -6 -4 -2 0 2 4 6 8 -8 -6 -4 -2 0 2 4 6 8

Magnetic Field (x104 Oe) Magnetic Field (x104 Oe)

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Fig. 6. (a) Magnetization versus field measurements recorded at 5 K for samples CuO – N
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and CuO – C (the insert shows the data in a small range of field and magnetization). (b) The
ferromagnetic signal obtained after subtracting a straight line from the as measured data.
 500 900
10 mA cm-2
(a) (b)
50
CuO - N 50 mA cm-2
800
40 CuO - C 100 mA cm-2
400 Ni foam
700 200 mA cm-2
J (mA cm-2)

30
412 mV 300 mA cm-2
385 mV 600 400 mA cm-2
J (mA cm-2)

h (V vs RHE)
300 20 515 mV

10 500

200 0 400
0.0 0.1 0.2 0.3 0.4 0.5 0.6
h (V vs RHE) 300
100
200

0 100

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0
1.0 1.2 1.4 1.6 1.8 2.0 2.2 CuO - N CuO - C

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1.8
E - iR (V vs. RHE) Sample
CuO - N
(c) (d) 1.0

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CuO - C
1.7
-p 0.8
E - iR (V vs. RHE)

re J Ia (mA cm-2)

0.6
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1.6
0.4
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1.5 0.2
CuO - N (76 mV dec-1) CDL = 4.74 mF
CuO - C (87 mV dec-1)
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0.0
Ni foam (157 mV dec-1) CDL = 4.54 mF
1.4
0.1 1 10 100 0 50 100 150 200
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-2 -1
Log [J (mA cm )] Scan rate (mV s )

Fig. 7. (a) LSV, (b) overpotentials at different current densities and (c) Tafel slope for copper
oxides (CuO – N and CuO – C); (d) electrical double layer capacitance (CDL); LSV and Tafel
slope of copper oxides were compared with Ni foam.
 150 5

(a) (b)
120
118.5 113.5 4 3.79

SA (mA cm-2)
90 3
ECSA (cm²)

60 2

1.03
30 1

f
0 0
CuO - N CuO - C CuO - N CuO - C

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Sample Sample

Fig. 8. (a) Electrochemical active surface area (ECSA) and (b) specific activity (SA) for

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copper oxides with nanofibers morphology and commercial.-p
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 18 100

(a) 1.3 V vs. RHE (c) 1.3 V vs. RHE

15 1.6 V vs. RHE 1.6 V vs. RHE
80
1.64 V vs. RHE 1.64 V vs. RHE
12

-Phase (°)
60
-Z'' (Ω)

9 CuO - N CuO - N
40
6

20
3

0 0
0 3 6 9 12 15 18 10-1 100 101 102 103 104

f
Z' (Ω) Log [f (Hz)]

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18 100

(b) 1.3 V vs. RHE

1.6 V vs. RHE
(d) 1.3 V vs. RHE
1.6 V vs. RHE

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15
80
-p
1.64 V vs. RHE 1.64 V vs. RHE
12
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60
-Z'' (Ω)

9 CuO - C CuO - C
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40
6
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20
3
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0 0
0 3 6 9 12 15 18 10-1 100 101 102 103 104
Z' (Ω) Log [f (Hz)]
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(e)

Fig. 9. (a) EIS Nyquist plot obtained at different applied dc signals for the CuO – N; (b) EIS
Nyquist plot obtained at different applied dc signals for the CuO – C; (c) Bode plot (phase
angle) obtained at different applied dc signals for the CuO – N; (d) Bode plot (phase angle)
obtained at different applied dc signals for the CuO – C; (e) Equivalent circuit model (EQM)
used to fit data.
Declaration of interests

☒ The authors declare that they have no known competing financial interests or personal relationships
that could have appeared to influence the work reported in this paper.

☐ The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

Declarations of interest: none

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