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Dynamic electrodeposition of structured copper catalyst for effective formaldehyde electrooxidation reaction

Authors:
Abdenour Serradj
Abdenour Serradj
Abdenour Serradj
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Charif Dehchar at University of Skikda
Charif Dehchar
Djamel Selloum at University Ferhat Abbas of Setif
Djamel Selloum
S. Tingry at Université de Montpellier
S. Tingry
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Abstract and Figures

This work reports the preparation of high-performance electrocatalytic electrodes based on structured copper deposits. The metal catalysts are synthesized by potentiostatic electrodeposition on a stainless steel substrate under hydrogen co-generation. This deposition technique generates evolving gases that lead to the formation of copper deposits in the form of dendrites, revealed by scanning electron microscopy. These catalysts exhibit high electrocatalytic activity for formaldehyde electrooxidation reaction (FOR) in alkaline media, showing a peak overpotential of − 0.6 V (peak current of 2.3 mA cm⁻²) in 0.1 M KOH + 2.0 M HCHO. The results show that the electroactivity of the catalysts depends on the value of the electrodeposition overpotential, with the best performance observed at − 0.8 V. Besides, the anodic peak of the catalyst based on dendrite microstructures for formaldehyde oxidation is 2.3 times higher than that of smooth copper obtained without hydrogen co-generation and exhibit good durability results.
a Cyclic voltammogram of SS substrate in a solution of 0.15 M CuSO4  + 0.5 M H2 SO4 at a scan rate of 10 mV s⁻¹ (inset is the CV curve obtained in a solution of 0.5 M H2 SO4). b Linear sweep voltammetry curves of Cu deposition from three different copper solutions containing 0.1, 0.15, and 0.3 M CuSO 4 in 0.5 M H2 SO4. c Chronoamperometric curve characteristic of copper deposition on SS substrate at different overpotentials: − 0.5, − 0.6, − 0.7, and − 0.8 V. Deposition duration = 60 s
a Cyclic voltammogram of SS substrate in a solution of 0.15 M CuSO4  + 0.5 M H2 SO4 at a scan rate of 10 mV s⁻¹ (inset is the CV curve obtained in a solution of 0.5 M H2 SO4). b Linear sweep voltammetry curves of Cu deposition from three different copper solutions containing 0.1, 0.15, and 0.3 M CuSO 4 in 0.5 M H2 SO4. c Chronoamperometric curve characteristic of copper deposition on SS substrate at different overpotentials: − 0.5, − 0.6, − 0.7, and − 0.8 V. Deposition duration = 60 s
… 
SEM micrographs of copper electrodeposits grown on SS substrate under potentiostatic conditions at different overpotentials: a − 0.5, b − 0.6, c − 0.7, and d − 0.8 V. e EDX spectrum of a sample of the electrodeposited Cu film (overpotential =  − 0.8 V). f XRD patterns of copper electrodeposits obtained at different overpotentials
SEM micrographs of copper electrodeposits grown on SS substrate under potentiostatic conditions at different overpotentials: a − 0.5, b − 0.6, c − 0.7, and d − 0.8 V. e EDX spectrum of a sample of the electrodeposited Cu film (overpotential =  − 0.8 V). f XRD patterns of copper electrodeposits obtained at different overpotentials
… 
a Cyclic voltammograms of Cu/SS and pristine SS in 0.1 M KOH + 0.3 M HCHO at a scan rate of 10 mV s⁻¹. b CV curves of Cu/SS in 0.1 M KOH in the absence and presence of HCHO (0.3 M). Scan rate = 10 mV s⁻¹. c CVs of Cu/SS (overpotential =  − 0.8 V) in 0.1 M KOH with different concentrations of HCHO (scan rate = 10 mV s⁻¹). d Response for the oxidation of HCHO on Cu/SS catalysts prepared at different overpotentials (scan rate = 20 mV s⁻¹). e Current–time transients for HCHO oxidation on the Cu/SS catalysts at applied potential of − 0.5 V vs. SCE. Electrolyte: 0.1 M KOH + 1 M HCHO. f The ECSA of Cu/SS catalysts prepared at different overpotentials. g CVs of Cu/SS (overpotential =  − 0.8 V) in 0.1 M KOH + 0.3 M HCHO at different scan rates. h The plot of log(jp) vs. log(v)
a Cyclic voltammograms of Cu/SS and pristine SS in 0.1 M KOH + 0.3 M HCHO at a scan rate of 10 mV s⁻¹. b CV curves of Cu/SS in 0.1 M KOH in the absence and presence of HCHO (0.3 M). Scan rate = 10 mV s⁻¹. c CVs of Cu/SS (overpotential =  − 0.8 V) in 0.1 M KOH with different concentrations of HCHO (scan rate = 10 mV s⁻¹). d Response for the oxidation of HCHO on Cu/SS catalysts prepared at different overpotentials (scan rate = 20 mV s⁻¹). e Current–time transients for HCHO oxidation on the Cu/SS catalysts at applied potential of − 0.5 V vs. SCE. Electrolyte: 0.1 M KOH + 1 M HCHO. f The ECSA of Cu/SS catalysts prepared at different overpotentials. g CVs of Cu/SS (overpotential =  − 0.8 V) in 0.1 M KOH + 0.3 M HCHO at different scan rates. h The plot of log(jp) vs. log(v)
… 
a Evolution of the peak current density (jp) of HCHO oxidation on Cu/SS (overpotential =  − 0.8 V) as a function of the number of cyclic voltammetries. b Current density-time evolution of the response of the Cu/SS electrode in potentiostatic mode. Applied potential =  − 0.5 V vs. SCE. Electrolyte: 0.1 M KOH + 1 M HCHO
a Evolution of the peak current density (jp) of HCHO oxidation on Cu/SS (overpotential =  − 0.8 V) as a function of the number of cyclic voltammetries. b Current density-time evolution of the response of the Cu/SS electrode in potentiostatic mode. Applied potential =  − 0.5 V vs. SCE. Electrolyte: 0.1 M KOH + 1 M HCHO
… 
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Ionics
https://doi.org/10.1007/s11581-025-06276-3
RESEARCH
Dynamic electrodeposition ofstructured copper catalyst foreffective
formaldehyde electrooxidation reaction
AbdenourSerradj1,2· CharifDehchar2,3· DjamelSelloum2,3· SophieTingry4· AhmedZouaoui2
Received: 6 November 2024 / Revised: 15 January 2025 / Accepted: 27 March 2025
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2025
Abstract
This work reports the preparation of high-performance electrocatalytic electrodes based on structured copper deposits. The
metal catalysts are synthesized by potentiostatic electrodeposition on a stainless steel substrate under hydrogen co-generation.
This deposition technique generates evolving gases that lead to the formation of copper deposits in the form of dendrites,
revealed by scanning electron microscopy. These catalysts exhibit high electrocatalytic activity for formaldehyde electrooxi-
dation reaction (FOR) in alkaline media, showing a peak overpotential of − 0.6 V (peak current of 2.3 mA cm−2) in 0.1 M
KOH + 2.0 M HCHO. The results show that the electroactivity of the catalysts depends on the value of the electrodeposition
overpotential, with the best performance observed at − 0.8 V. Besides, the anodic peak of the catalyst based on dendrite
microstructures for formaldehyde oxidation is 2.3 times higher than that of smooth copper obtained without hydrogen co-
generation and exhibit good durability results.
Keywords Copper· Electrocatalyst· Formaldehyde· Fuel cell· Hydrogen evolution
Introduction
Formaldehyde (HCHO) oxidation reaction (FOR) is an
important process due to HCHO’s contribution as a potential
fuel in fuel cells [1, 2], as a promising carrier for hydrogen
storage with a hydrogen capacity of 6.7 wt.% [3], and as a
fuel coupled to water reduction under alkaline conditions
for dual H2 production at the anode and cathode with lower
energy input [4]. Besides, HCHO is one of the major con-
tributors to indoor air pollution, and the FOR is one of the
most practical methods of removing it [5].
To catalyze formaldehyde oxidation, a range of catalytic
materials have been investigated, especially based on car-
bon, as supporting material, mixed with metal nanoparticles
(e.g., Pt, Au, Ag, and Pd) [6, 7]. This configuration results
in active catalysts, benefiting from the synergistic effect
of a high electroactive surface area achieved through the
dispersion of metal nanoparticles and the low-temperature
electrocatalytic properties of noble metals with high elec-
tronic conductivity. However, these catalysts are expensive
and highly sensitive to poisoning by co-products such as
adsorbed carbon monoxide (COads) formed in the HCHO
oxidation process, leading to their deactivation [8, 9]. Conse-
quently, developing alternative cost-effective catalysts with
high tolerance to COads remains a significant challenge.
To address these challenges, researchers have focused
their efforts on exploring low-cost metals such as Fe, Ni,
Co, and Cu, with appropriate electrocatalytic properties.
Many methods have been developed to synthesize catalysts
based on these metals, including melt spinning [10], accu-
mulation-polarization [11], immersion [12], electrodeposi-
tion [13, 14], and electroless plating [15], aiming to increase
their active surface areas and charge transfer kinetics, as
these factors are essential for improving performance and
efficiency. Among them, electrodeposition is the most effec-
tive method for producing structured layers of almost any
* Charif Dehchar
dcharif@hotmail.fr
1 Department ofProcess Engineering, Faculty ofTechnology,
University ofKasdi Merbah, Ouargla, Algeria
2 Laboratoire Croissance Et Caractérisation de Nouveaux
Semi-Conducteurs, Université Ferhat Abbas, Sétif 1, Sétif,
Algeria
3 Department ofChemistry, Faculty ofSciences, University
ofFerhat Abbas, Setif 1, Setif19137, Algeria
4 Institut Européen des Membranes, IEM, Université
Montpellier, ENSCM, CNRS, UMR 5635,
Montpellier34090, France
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