, Echihi S, Tabyaoui M, Qafsaoui W (2019) Inhibitive effect of 1,3,4-thiadiazole-2,5-dithiol on copper corrosion in chloride media. with the reproduced material. a: Nyquist representation., Article  4b indicates that Cu and O atoms are the main elements of EDX analysis which confirms that the developed layer is principally composed of copper oxides. The authors indicated that ORR is mainly controlled by the number of available free copper sites where O2 molecules can be adsorbed, and showed that the adsorption of large amount of sulfate anions on copper inhibited ORR rate by blocking the active sites for oxygen molecules co-adsorption [32, 34]. 9a. Correspondence to 3a) is uniform and is characterized by the presence of scratches caused while pre-polishing the electrode. Electrochim Acta 24:131–138. Vazquez et al. Biosens Bioelectron 24:2825–2829. The previous studies on copper suggested a four-electron pathway mechanism involving the effect of the metal oxidation state on the reaction kinetics [20, 23,24,25, 27, 32,33,34]. The inner barrier layer being Cu2O and the aqueous outer layer being a CuO–Cu(OH)2 complex. It is interesting to mention that no trace of oxide was detected after just one hour of immersion in the solution containing 10–2 M PDTC (Fig. This confirms the EDX analysis where Cu and O atoms were the main elements detected (Fig. Electrochim Acta 54:3972–3978., Schiffrin DJ, Pletcher D (1983) The Electrochemistry of oxygen, specialist periodical reports:electrochemistry., Liao QQ, Yue ZW, Yang D, Wang ZH, Li ZH, Ge HH, Li YJ (2011) Self-assembled monolayer of ammonium pyrrolidine dithiocarbamate on copper detected using electrochemical methods, surface enhanced Raman scattering and quantum chemistry calculations. (6), and then, the kinetic current does yield almost constant values. After pre-treatments, copper surface was characterized by SEM images coupled with EDX analysis and XRD. To discuss and analyze the fitted parameters, the values of Rd were considered., Huang VM-W, Vivier V, Orazem ME, Pébère N, Tribollet B (2007b) The apparent constant-phase-element behavior of an ideally polarized blocking electrode. Corros Sci 106:96–107. ORR proceeding via reactions (2) and (3) is considered a serial mechanism, while the reduction following reactions (1) and (2–3) is called parallel mechanism [22]. Indeed, Fig. 6a, ORR process displays four distinct behaviors. Yonghong Lu et al. [27] findings are in accordance with the findings presented herein indicating that the presence of a duplex copper layer had an inhibitive effect on the electrochemical reduction on copper. c Variation of kinetic current ik as a function of potential., Fateh A, Aliofkhazraei M, Rezvanian AR (2017) Review of corrosive environments for copper and its corrosion inhibitors. The regulation of catalytic activity in the oxygen reduction reaction (ORR) is significant to the development of metal–air batteries and other oxygen involving energy conversion devices. Benzbiria, N., Zertoubi, M. & Azzi, M. Oxygen reduction reaction kinetics on pure copper in neutral sodium sulfate solution. The fitting and analysis of the results were performed by using EC-Lab., Stephens IEL, Bondarenko AS, Grønbjerg U, Rossmeisl J, Chorkendorff I (2012) Understanding the electrocatalysis of oxygen reduction on platinum and its alloys. We have used energy-dispersive X-ray analyzer (EDX, Bruker) with accelerating voltage of 20 kV in order to investigate the elements composing the species accumulated on copper surface. Accordingly, earlier studies claimed that ORR rate is slower on oxidized surfaces than on bare electrodes [21, 27, 29,30,31]. 13b and c) clearly shows the presence of a capacitive loop at high frequencies above several kHz. The influence of adsorbed anions existing in the solution was also reported [23, 25, 27, 32, 34]. As the surface condition of copper plays a major role in the kinetics of ORR, it is necessary to initially assess and characterize the different surface conditions, namely pre-reduced, passivated and covered with PDTC molecule. In the case of copper covered with PDTC, it is interesting to note that the overall current density decreases considerably in absolute value by a factor of 5 (0.17 mA cm−2 at  − 1 V/ECS for a rotation rate of 1000 rpm) if compared to both pre-reduced and passivated copper surfaces. In fact, PDTC behaves in an irreversible way since once it reacts with the surface, the inhibition remains despite removal of the activity of the inhibiting species by placing the copper electrodes back in the inhibitor free 10–2 M Na2SO4 solution. Oxygen reduction reaction kinetics on pure copper in neutral sodium sulfate solution, $${\text{O}}_{2} + 2{\text{H}}_{2} {\text{O}} + 4e^{ - } \to 4{\text{OH}}^{ - }$$, $${\text{O}}_{2} + {\text{H}}_{2} {\text{O}} + 2e^{ - } \to {\text{HO}}_{2}^{ - } + {\text{OH}}^{ - }$$, $${\text{HO}}_{2}^{ - } + {\text{H}}_{2} {\text{O}} + 2e^{ - } \to 3{\text{OH}}^{ - }$$, \({\text{Cu}}\left( {\text{I}} \right)_{ads}^{*}\), \(\left( {{\text{HO}}x} \right)_{ads}^{*}\), $$\frac{1}{i} = \frac{1}{{i_{d} }} + \frac{1}{{i_{k} }} = \frac{1}{{B\omega^{{\tfrac{1}{2}}} }} + \frac{1}{{nkFC_{ox} }}$$, $${\text{B}} = 0.62nFC_{ox} D_{ox}^{{\tfrac{2}{3}}} \upsilon^{{\tfrac{ - 1}{6}}}$$, $$i_{k} = - kC_{ox} \left( \infty \right)\exp \left( { - b_{c} V} \right)$$, $$Z_{CPE} = \frac{1}{{Q(j\omega )^{\alpha } }}$$, $$C_{dl} = (Q_{dl} R_{ct}^{{1 - \alpha_{dl} }} )^{{\frac{1}{{\alpha_{dl} }}}}$$, $$C_{f} = (Q_{f} R_{f}^{{1 - \alpha_{f} }} )^{{\frac{1}{{\alpha_{f} }}}}$$, $$Z_{diff} = R_{d} \frac{{th\left( {\sqrt {\tau_{d} j\omega } } \right)}}{{\sqrt {\tau_{d} j\omega } }}$$, $${\text{Cu}}_{{2}} {\text{O }} + {\text{O}}_{{2}} + {\text{H}}_{{2}} {\text{O}} \to {\text{2CuO}} + {\text{H}}_{{2}} {\text{O}}_{{2}}$$, $${\text{Cu}}_{{2}} {\text{O}} + {\text{H}}_{{2}} {\text{O}}_{{2}} + {\text{H}}_{{2}} {\text{O}} \to {\text{2CuO}} + {\text{H}}_{{2}} {\text{O}}$$, $${\text{4CuO}} + {\text{2H}}_{{2}} {\text{O}} + {\text{4e}}^{ - } \to {\text{2Cu}}_{{2}} {\text{O}} + {\text{4OH}}^{ - }$$, $$\frac{1}{i} = \frac{1}{{i_{d} }} + \frac{1}{{i_{k} }} + \frac{1}{{i_{el} }}$$,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,