Oxidation Of Cu Research Articles

Interactive impacts of organic-inorganic modifiers on surface characteristics of Cu+-doped activated carbon for stable CO-adsorptive separation from CO2

Conventional Cu+-doped activated carbon (C) materials are problematic in carbon monoxide (CO)-selective adsorption from carbon dioxide (CO2) due to their CO2-friendly surface basicity and microporosity. In this study, boehmite (AlOOH) film modified-carbon composite (AlC) was hydrothermally synthesized to dope with 30 wt% Cu+ ions by the impregnation-calcination method. The functional hydroxyl groups of Boehmite behaved as metallic anchoring sites for better Cu+ ion dispersion, enhancing the CO adsorption uptake to 38.84 cm3/g at 25 °C and ∼ 100 kPa in isotherm analysis. Additionally, the improved Lewis acidity of AlC surface interface together with pore widening impact reduced the CO2 uptake to 14 cm3/g, around half that of Cu+-doped activated carbon, by undergoing Lewis acid-acid repelling interaction between boehmite film and CO2. However, to address rapid oxidation of Cu+ ions in the hygroscopic AlC structure, iron (II) chloride (FeCl2) surface modification on the Cu+-doped AlC composite created a Fe3+-Cu+ bimetallic interface with high Cu+ immobilization, enriching the CO adsorption stability to 92 % even after 30 day-air exposure. Noticeably, pre-complexation of FeCl2 with thiourea (NH2CSNH2) before its dispersion over the doped Cu+ ions led to distinct Cu+ stabilization mechanisms without bimetallic redox interaction. This involves developing auto-redoxable iron (II) sulfides as barrier coatings for Cu+ species against oxidation and raising the Cu2+ reducibility via cyanide-ligands of thiourea. These combined preservation effects for Cu+ ions ensured CO adsorption stability of 91 %, underlining higher CO adsorption uptake (39.38 cm3/g) and CO/CO2 selectivity (67.49 at 0.2 kPa and 3.09 at ∼ 100 kPa) than modification effects of boehmite and FeCl2.

A potential strategy for eco-friendly and efficient copper recovery: Ferricyanide-enhanced glycine leaching of copper

E-waste contains significant amounts of metal elements, particularly copper. Efficient and eco-friendly recovery of copper is essential for both the resourceful utilization of e-waste and the mitigation of environmental pollution. Glycine leaching is a green method for copper recovery, but the use of conventional oxidants suffers from slow reaction kinetics and low leaching yields. Herein, by introducing ferricyanide ([Fe(CN)6]3−) as an oxidant in the glycine leaching of copper, the efficient dissolution of copper was realized. Electrochemical measurements and various physical characterizations demonstrate that the [Fe(CN)6]3− oxidant effectively increases the initial potential of the solution by forming a [Fe(CN)6]3−/ [Fe(CN)6]4− redox couple. This promotes the rapid oxidation of Cu to Cu2+, facilitates the formation of soluble copper complexes with gly−, and prevents the development of an oxidized passivation layer on the copper surface, resulting in efficient copper dissolution. Compared to 0.15 M H2O2, the addition of 0.01 M [Fe(CN)6]3− increased the initial potential of the solution from 192.33 mV to 489.30 mV and raised the dissolved copper concentration from 225.60 ppm to 330.40 ppm after 24 h. The “potential enhancement” effect of ferricyanide in this work provides an effective strategy for efficient copper recovery.

Epitaxial growth and characterization of copper gallate (CuGa2O4) thin films by pulsed laser deposition

High-quality crystalline copper gallate (CuGa2O4) thin films were grown on c-plane sapphire substrates using the pulsed laser deposition (PLD) technique by optimizing the growth parameters (i.e., temperature, oxygen chamber pressure, and laser energy density). The obtained XRD patterns validated that the preferred orientation of the crystalline CuGa2O4 thin film is along the [111] direction, and the crystallinity of the films improved with increasing substrate temperature while maintaining a constant O2 pressure, as assessed by measuring the full width at half maximum (FWHM) of the prominent (222) plane. Reducing the oxygen pressure leads to the emergence of β-Ga2O3 peaks rather than the CuGa2O4 peaks due to the incomplete oxidation of copper (Cu). Subsequent XRD phi (φ) scans revealed a sixfold rotational symmetry of CuGa2O4 and a 30° epitaxial relationship between the film and the sapphire substrate. X-ray photoelectron spectroscopy (XPS) spectra confirmed the presence of Cu1+, Cu2+, and Ga3+ oxidation states in the films. Increasing laser energy density resulted in the complete oxidation of Cu and an increase in the film thickness from 51.8 nm to 183.4 nm. The direct bandgap of CuGa2O4 films was determined to be approximately 4.50 eV by analyzing the UV–Vis absorbance spectra using the Tauc equation. The refractive index was found to be approximately 2.05 ± 0.01 based on the spectroscopic ellipsometry data. While the impact of increasing laser energy density was negligible on the parameters such as crystal structure, rotational symmetry, oxidation states of gallium (Ga), oxygen (O), bandgap, and refractive index of CuGa2O4 thin film, notable alterations in the oxidation state of Cu and film thickness were observed. The surface roughness (Rrms) measured from AFM images showed a strong correlation with the values derived from ellipsometry analysis.

Ligand-free Ni-Cu bimetallic nanocatalyst: Laser synthesis, characterization and its high performance for borohydride assisted catalytic reduction of 4-nitrophenol

In the present work, nickel and copper bimetallic nanoparticles with three different concentration ratios of 70:30, 50:50, and 30:70 were synthesized by laser ablation of Ni and Cu in deionized water. The suitability of Ni-Cu bimetallics as nanocatalysts was investigated in the catalytic reduction of pollutant 4-nitrophenol. The nanocatalysts were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible (UV–Vis) spectroscopy. The morphology using SEM and TEM indicated that Cu had an elongated or flake-like structure, whereas Ni had a quasi-spherical structure. XPS investigation has been performed to study the elemental composition and chemical states near-surface regions of the generated Ni-Cu bimetallic nanoparticles. XRD and XPS confirm high oxidation of Cu to CuO with approximately no residual Cu metal. However, the XRD patterns did not show complete Ni oxidation to NiO, confirming the presence of a Ni dopant part in the Ni-Cu samples. The behavior of the photoelectron peaks in the XPS spectra suggested that the Ni-Cu nanocomposites exhibited surface charge transfer. Pulsed laser ablation developed ligand-free Ni-Cu nanoparticles, which affected the structure and catalytic properties. The nanocatalyst for 50:50 of Ni and Cu had the highest rate constant, corresponding to the shortest time required to achieve 100 % conversion/reduction of the pollutant dye. The apparent synergistic effect between Ni and Cu is clearly dictated by the amount of Cu embedded in the nanocomposites, with this becoming a key factor in lowering the band gap energy values. Overall, the surface charge transfer rate can enhance the catalytic performance by tuning the Ni and Cu concentrations.

Kinetics of regeneration of oxidative Cu(II) and Fe(III) species in aerated acid chloride leaching solutions at 75 °C

In the leaching of copper sulfide ores or refractory gold ores in chloride solutions, the regeneration of oxidative agents such as Cu (II) and Fe (III) is a key aspect for a sustainable process over time. This regeneration is carried out from the oxidation of Cu (I) and Fe (II) with O2, which helps to maintain a conveniently high oxidative potential in solution and a high leaching efficiency. In this context, Cu (I) and Fe (II) oxidation are affected by the accumulation of Cu or Fe species resulting from sulfide dissolution during the process. Therefore, a good understanding of the interaction mechanism of O2 with Cu (I), Cu (II), Fe (II), and Fe (III) species is necessary to describe the oxidation kinetics in this complex environment. The present work reports a study of the Cu (I) and Fe (II) oxidation at 75 °C in solutions containing 4.0 M NaCl and 0.1 M HCl. The solutions used in the experiments contained different initial concentrations of Cu (I), Cu (II), Fe (II), and Fe (III) with values in the range of 0.0001 – 0.1 M. Experiments were conducted in a thermostatized reactor containing 0.5 L solution agitated with a magnetic stirrer at 450 rpm, while oxygenated by air bubbling at 3.5 L/min. The evolution of the concentration of Cu (I), Cu (II), Fe (II), and Fe (III) during oxidation was determined by an electrochemical method, which was mainly based on Eh measurements of solution over time. A reaction mechanism was proposed for the oxidation of Cu (I) and Fe (II) with O2 in the presence of Cu and Fe species, which described very well the results obtained in the oxidation experiments under various conditions. Based on the proposed mechanism, a kinetic model was developed that could predict the concentration of Fe (II), Fe (III), Cu (I), Cu (II), O2, HO2–, H2O2, OH– and H+ in acid aerated chloride solutions satisfactorily. These proved to be a valuable tool to approach the modeling of chloride-leaching reactors.

Electrochemical Corrosion Behavior and the Related Mechanism of Ti3SiC2/Cu Composites in a Strong Acid Environment.

The electrochemical corrosion behaviors of Ti3SiC2/Cu composites in harsh media including dilute HNO3 and concentrated H2SO4 were studied in detail and the related corrosion mechanisms were explored. Under open-circuit potential, the corrosion resistance of Ti3SiC2/Cu in dilute HNO3 was worse than that in concentrated H2SO4. In dilute HNO3, Ti3SiC2/Cu exhibited a typical passivation character with a narrow passivation interval. During the corrosion process, the dissolution of Cu-Si compounds resulted in the destruction of the passivation layer on the surface. Additionally, with the increasing of the potentials, the oxidation of Cu and Si atoms led to the generation of the oxide film again on the surface. In concentrated H2SO4, the Ti3SiC2/Cu composite was covered by a double-layered passivation layer, which was composed of an internal layer of TiO2 and an external layer of Cu2O and SiO2. This was because Cu diffused into the surface and was oxidized into Cu2O, which formed a denser oxidized film with SiO2. In addition, it was found that Ti3SiC2/Cu has better corrosion resistance in concentrated H2SO4.

Promoted stability of Cu/ZnO/Al2O3 catalysts formethanol production from CO2 hydrogenation by La modification

Deactivation of Cu/ZnO/Al2O3 catalysts in CO2 hydrogenation to methanol reaction is one of the main reasons limiting their application. We synthesized a series of La modified Cu/ZnO/Al2O3 catalysts by adding different contents of La to improve the stability. In the 100 h short-term stability test at 200 °C under 3 MPa with a GHSV of 12000 mL/(g·h), the unmodified Cu/ZnO/Al2O3 catalysts degraded obviously over 100 h. In sharp contrast, the stability was significantly promoted by the addition of La. The best activity was achieved with 5% La added samples (4% CO2 conversion and 85% methanol selectivity),which also showed impressive stability over 1000 h except about 17% deactivation during the initial 190−220 h. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results revealed that the addition of 5% La improved the dispersion of Cu and Zn, inhibited the sintering of Cu, stabilized the Cu0/+ species and retarded oxidation of Cu in catalysts, which attributed to the high stability of the catalysts.

Near-infrared-II photocharging nanozyme for enhanced tumor immunotherapy

In tumor therapy, copper (Cu)-based nanozymes with peroxidase-like activity play a crucial role in converting hydrogen peroxide into hydroxyl radicals (OH). This process induces immunogenic cell death, which in turn activates the body’s immune response, enhancing the efficacy of tumor immunotherapy. Nonetheless, the efficiency of this reaction is curtailed due to the oxidation of Cu(I) to Cu(II), leading to the self-depletion of the nanozyme’s activity and an insufficient yield of OH for effective immunotherapeutic activation. To surmount this challenge, our research introduces a photocharging self-doped semiconductor nanozyme, copper sulfide (Cu9S8). The photocharging effect enables the nanozyme to convert internal Cu(II) back to Cu(I) through charge transfer induced by near-infrared (NIR)-II photothermal energy, thereby effectively maintaining the enzyme-like activity of the nanozyme. Additionally, Cu9S8 is enhanced with a calcium sulfide (CaS) coating. This coating reacts in the acidic microenvironment of tumors to generate hydrogen sulfide (H2S) gas, which in turn suppresses the catalase activity inherent in tumor cells, ensuring a plentiful supply of H2O2 for the nanozyme’s operation. This dual strategy of amplifying enzyme-like activity and substrate availability culminates in the generation of ample OH within tumor cells, leading to significant immunogenic cell death and thereby realizing potent immunotherapy.

High‐temperature oxidation of Cu–Al–Ni–Mn shape‐memory alloy

AbstractThe isothermal oxidation behavior of the Cu‐11.35Al‐3.2Ni‐3.5Mn (wt.%) shape‐memory alloy (SMA) in the temperature range of 500–900°C in oxygen was studied using the thermogravimetric (TG) method. TG curve showed that the alloy has parabolic isothermal oxidation characteristics. The effect of oxidation on the surface morphology and chemical composition of the Cu–Al–Ni–Mn alloy was determined by scanning electron microscopy, energy‐dispersive spectroscopy, and X‐ray photoelectron spectroscopy (XPS) analyses. The oxidation rate of SMA increases up to 700°C, remains stable at 800°C, and increases again up to 900°C. The XPS analysis identified that the corrosion products mainly contained MnO2, MnO/Mn2O3, and Al2O3.

Direct Work Function Measurement Using in-situ Ambient Pressure X-ray Photoemission Spectroscopy and Its Application on Copper Oxidation Process.

The work function (WF) measurement plays a critical role in engineering energy materials and energy devices. However, the ultra-high vacuum (UHV) environments of photoemission method limit the practical application for absolute work function measurements of materials, especially under complex working conditions. To understand the energy level of materials under complex chemical environments, the in-situ measurements of work function is necessary in complex metal/semiconductor system for various application. In this paper, we describe the utilization of ambient pressure X-ray photoemission spectroscopy (APXPS) with utilization of low photon energy X-ray for absolute WF measurements at BL02B of the Shanghai Synchrotron Radiation Facility. We herein present the WF measurement during oxygen adsorption on Pt(111) and oxidation of Cu(111) in ambient oxygen environment as demonstration of the APXPS capability for WF measurement. After oxygen chemisorption on Pt and formation of Cu2O, the WF will increase. This is due to charge transfer from metal to chemisorbed oxygen atoms. After the formation of bulk Cu2O and CuO, the WF value almost remain at ~5.5 eV. We believe the direct measurement of absolute work function via APXPS could help bridge the gap between the physical properties and the surface chemical species for metal/semiconductor materials.

High-Speed Thermo-Compression Sinter-Bonding Properties in Air of a Paste Containing Dendritic Cu Particles Having Oxalate Skins

To enhance the sinter-bonding speed of Cu dendrite particle-based paste, the particles were surface-treated with oxalic acid solution. This treatment transitioned the particle surface from an oxide layer to a CuC 2 O 4 phase, which suppressed the oxidation of Cu until thermal decomposition between 284-315 °C generating Cu nanoparticles. Using the surface-treated Cu dendrite particle-based paste, sinter bonding at 320 °C under 5 MPa pressure in air provided a sufficient shear strength of 23.4 MPa in just 60 s, reaching the maximum of 28.7 MPa after 180 s. The in situ generated Cu nanoparticles from the thermal decomposition of CuC<sub>2</sub>O<sub>4</sub> directly contributed to the very rapid sintering-bonding behavior at 320 °C. However, the bondings at 300 °C and 350 °C showed poorer bonding characteristics than that of before treatment, indicating that the surface treatment strategy for forming CuC<sub>2</sub>O4 skins is effectively implemented by appropriately setting the following sinter-bonding temperature.

Electrochemical redox of arsenic (III) and Cu (II) mixtures with ultraflat Au(111) thin films in water

The ability to detect trace concentrations of arsenite, As (III), in real water solutions is impacted by co-contamination of other metals and co-occurring ions. The presence of copper (II) ions are the most likely co-contaminant in natural waters to interfere with electrochemical As (III) detection, due to the close oxidation potentials of Cu (II) and As (III). The use of well-oriented ultraflat Au(111) thin film electrodes provided increased peak separation and sensitivity for electrochemical deposition and oxidation of Cu (II) and As (III) in 0.5 M sulfuric acid compared to an Au wire electrode. However, mixtures of Cu (II) and As (III) altered the oxidation peak positions during both cyclic voltammetry (CV) and linear stripping voltammetry (LSV) analysis. Calibration curves using the standard additions method in trace concentrations were conducted for Cu, As, and Cu & As solutions. Sweeping the potential at 10 mV s−1 during CV in Cu & As mixtures resulted in a sequential deposition condition where a layer of Cu inhibited co-deposition of As to the electrode. In contrast, the rapid potential stepping of LSV to a potential where Cu and As reduction simultaneously occurs produced a peak profile different from Cu or As alone. A larger oxidation peak during LSV was also observed when both Cu and As were present. X-ray photoelectron spectroscopy indicates a Cu-As alloy is formed on the surface after LSV deposition.SYNOPSIS: Analysis of Cu (II), As (III) and Cu (II) & As (III) mixtures suggests that a Cu3As intermetallic phase is formed during LSV which impacts trace As detection even in trace Cu conditions. This has important implications for the ability to determine As concentrations near the MCL of 10 µg L−1 in natural water systems which may contain Cu (II) and other co-contaminants.

Enhancement of pool boiling heat transfer by laser texture-deposition on copper surface

To improve the durability of pool boiling, laser texture-deposition technology was introduced to produce massive area of micro/nano structures on copper surface without any chemical treatment. The XPS analysis and the SEM images revealed that the two-tier micro/nano structure was formed on the micron protrusions, where villous cluster nano SiO2 layer was deposited on copper oxide nanoburrs. Subcooled pool boiling experiments indicated that villous cluster nano SiO2 structure delayed the oxidation of Cu, and thus enhanced the durability (capillary wicking/superhydrophilicity). Furthermore, the CHF and HTC of the laser texture-deposition surface reached 2805.8 kW/m2 and 111.8 kW/(m2·K). The CHF and HTC are 2.8 times and 2.1 times that of the original copper surface, respectively. Laser texture-deposition technology proves to be a promising green processing technology for the heat transfer of pool boiling.

A novel organic acids-targeted colorimetric sensor array for the rapid discrimination of origins of Baijiu with three main aroma types

Given the severe problem of Baijiu authenticity, it is essential to discriminate Baijiu from different origins quickly and effectively. As organic acids (OAs) are the most dominant taste-imparting substances in Baijiu, we proposed a simple, fast, and effective OAs-targeted colorimetric sensor array based on the colorimetric reaction of 4-aminophenol (AP)/4-amino-3-chlorophenol (ACP) under oxidation of Cu(NO3)2 for the rapid discrimination of origins of Baijiu with three main aroma types. Hydrogen ions ionized from OAs induced the protonation of the amino group, which blocked the colorimetric reaction, and the different levels of OAs in Baijiu enabled the array to discriminate different origins of Baijiu. The array was implemented to analyze 10 simple OAs and 16 mixed OAs and further for the discrimination of 42 Baijius with an accuracy of 98%. This method provided an efficient research strategy for a basis for rapid quality analysis of Baijiu.

Electrocatalytically enhanced Cu(II)/peroxymonosulfate (PMS) oxidation: Focus on electrically-induced sustained Cu(II)/Cu(I)/Cu(III) cycling and suppression of singlet oxygen (1O2) production

Numerous azo dyes are discharged into industrial wastewater annually, posing significant threats to ecology and human health. In this study, an applied electric field was implemented in a trace copper-activated peroxymonosulfate system (EC/Cu(II)/PMS), achieving high removal efficiency (95.40 %) of Congo red (CR). The electron-donating effect of the cathode greatly enhanced the redox cycling of Cu(II)/Cu(I). Almost complete activation of PMS occurred during the entire reaction with an electrical consumption of merely 0.85 kWh/m3. Using electron paramagnetic resonance (EPR), quenching experiments, and chemical probes, the reactive substance that dominate CR removal, including Cu(III), sulfate radical (SO4•−), hydroxyl radical (HO∙), and singlet oxygen (1O2), were investigated. Cu(III) was identified as the main reactive substance, contributing over 90 %, and was primarily formed through double electron transfer of Cu(I). HO∙ can emerge as a secondary oxide of Cu(III). SO4•− originated mainly from the electroactivation of PMS. It was noted that 1O2 can be physically quenched by water, and thus 1O2 was considered as a side reaction product of PMS. Applying an electric field lowered the overall production of 1O2 and markedly mitigated the inefficient consumption of PMS. Moreover, the degradation pathways proposed for CR, based on mass spectrometry analysis, were in agreement with the predictions made by density functional theory (DFT). The toxicological characteristics of both CR and its intermediates were comprehensively analyzed as well. The study presents a straightforward and efficient strategy for PMS activation with versatile application potential for dye wastewater treatment.

SEM Electron-Beam-Induced Ultrathin Carbon Deposition Layer on Cu Substrate: Improved Dry Oxidation Protection Performance than CVD Single Layer Graphene.

An amorphous carbon deposition layer (CDL) with nanoscale thickness induced by scanning electron microscope (SEM) electron beam is studied as a carbon-based protective layer on copper (Cu). CDL is prepared by inducing the deposition of pollutants or hydrocarbons in the cavity of SEM through electron beam irradiation (EBI). Wrinkles and cracks will not form and the interfacial spacing of CDL/Cu is smaller than Graphene/Cu (Gr/Cu). The thickness and coverage of the interfacial oxide layer of CDL/Cu are all smaller than that of the Gr/Cu after the same oxidation conditions. Characterization of Raman mapping also demonstrates that CDL shows better oxidation inhibition effects than graphene. The structure of CDL is determined to be C = C and C = O, CH3- and C-O can be loaded vertically on CDL. Density functional theory (DFT) is employed for demonstrating the smaller interfacial gap of CDL/Cu, less wrinkles and cracks and larger adsorbing energy of water/oxygen compared with Gr/Cu. Molecular dynamic (MD) simulation also indicates that the diffusion of water or oxygen into CDL/Cu is more difficult and the oxidation of Cu covered by CDL is well suppressed. This work provides a new approach for the study of carbon-based antioxidant materials on Cu.

Facile and novel method for the recovery of gold from a calcined concentrate via copper–ammonia -thiourea system and activated carbon

Cyanidation, as the primary method for gold extraction, poses significant risks to the environment and animals. Therefore, an eco-friendly, sustainable, and effective leaching approach has been devised for extracting gold from a gold concentrate after calcination, utilizing copper(II)-ammonia and thiourea. This research focuses primarily on optimizing leaching conditions, gold recovery from leach solution, and cyclic utilization of the leaching solution. Furthermore, we investigated the potential mechanisms behind the leaching and recovery processes using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and thermodynamic analysis. The leaching process exhibits a spontaneous reaction, and the mechanism for alkaline thiourea leaching of gold is as follows: (a) reduction of Cu(NH3)42+ to Cu(TU)4+, (b) oxidation of Au(0) to Au(TU)2+ and (c) oxidation of Cu(TU)4+ back to Cu(NH3)42+, in the presence of oxygen, regenerating the catalyst. Under optimal leaching conditions, the proposed method achieves a gold extraction efficiency of approximately 86.6%, approaching that of cyanidation. The barren leach solution can be reused for subsequent leaching experiments, with consistent gold extraction efficiency and thiourea consumption. Therefore, this method presents a promising alternative to gold leaching via cyanidation.

The Influence of the Interfacial pH on the Electrochemical CO2 Reduction Towards Formate on Cu Electrodes

The electrochemical reduction of CO2 (CO2RR) using renewable electricity is considered a promising way to replace fossil fuels as feedstock. In aqueous media, the activity and selectivity for the CO2RR is strongly influenced by electrolyte composition at the solid-electrolyte interface. Due to competing H+ reduction, the interfacial pH is strongly affected by the applied potential which in turn determines the balance between CO2, HCO3 -, and CO3 2-. The Bicarbonate equilibrium and cation-hydroxide interactions are directly connected to the CO2RR and HER rate.[1]To learn more about the impact of the electrolyte composition within the double layer on the CO2RR mechanism we deploy time-resolved (sub-second) FT-IR reflection-absorption spectro-electrochemistry at grazing angle using polarized light. This allows us to differentiate conversions at the electrode-electrolyte interface (i.e. CO2RR) from the diffuse double layer (i.e. pH effects). Herein, we elucidate the electrochemical CO2RR towards formate on polycrystalline Cu in aqueous bicarbonate electrolyte. We compare the rate of CH formation to the interfacial pH changes determined by the ratio between the intensity of the CO2, HCO3 -, and CO3 2- bands. We discuss how potential steps and sweeps relate to interfacial pH and CO2RR.By applying a ‘pre’potential more positive from the open circuit potential (OCP: ca. +0.5 V vs. RHE) before stepping to -0.9 V vs. RHE, the interfacial pH decreases due to the oxidation of Cu. As a result, the rate of C-H formation is initially hindered for several seconds before setting off. Likewise, an applied ‘pre’potential more negative from the OCP results into poor C-H formation kinetics.Reference:[1] Liu, X.; Monteiro, M.C.O.; Koper, M. T. M. Phys. Chem. Chem. Phys. 2023, advance article. Figure 1

Understanding the Corrosion of Copper in Nitric Acid By Tuning the Solution Chemistry

The used fuel container (UFC) is a key engineered barrier to permanently contain and isolate used nuclear fuels underground in deep geological repositories (DGR) to be implemented in Canada, Sweden and Finland.1,2 Copper is used for corrosion protection in the current design of the UFC. Within a DGR, radiolysis of humid air will result in the formation of nitric acid.3 Recent studies showed that copper corrodes faster in nitric acid when oxygen is present, which will be the case for a short period after the UFC’s emplacement.4 When the oxygen becomes depleted in a DGR, the corrosion of copper will be minimal but can be affected by corrosion products such as Cu+, Cu2+, NO2 - and NO. Previous results suggest that the presence of copper ions in the solution surrounding the copper can activate nitrate as a cathodic reagent.5 A possible mechanism is that Cu+ reacts with nitrate through its oxidation to Cu2+, which then reacts with metallic copper through its comproportionation reaction, accelerating the corrosion process.5 Yet, a precise mechanistic understanding of the role of Cu+, such as the degree to which oxidation of Cu+ occurs in solution, or if Cu+ simply acts as a catalyst for nitrate reduction or decomposition, is missing. As a result, an improved understanding of the influence of solution parameters on the corrosion mechanisms of copper in nitric acid is needed, including the presence of oxidants and Cu+-chelating species such as chloride.Herein, the interplay between the dissolved redox couples, Cu+/Cu2+ and NO3 -/NO2 - and Cl- is explored, and their effect on the corrosion of copper is studied by linear sweep voltammetry and polarization resistance and Tafel analysis. The interpretation of linear polarization resistance measurements in the presence of multivalent ions and the role of corrosion products are discussed.1 P. G. Keech, P. Vo, S. Ramamurthy, J. Chen, R. Jacklin and D. W. Shoesmith, Corrosion Engineering, Science and Technology, 49, 2014, 425-430.2 F. King, L. Ahonen, C. Taxen, U. Vuorinen and L. Werme, Copper corrosion under expected conditions in a deep geologic repository (SKB-TR--01-23), 2001. Sweden.3 R. P. Morco, J. M. Joseph, D. S. Hall, C. Medri, D. W. Shoesmith and J. C. Wren, Corrosion Engineering, Science and Technology, 52, 2017, 141-147.4 J. Turnbull, R. Szukalo, M. Behazin, D. Hall, D. Zagidulin, S. Ramamurthy, J. Wren and D. Shoesmith, Corrosion, 74, 2017, 326-336.5 J. Turnbull, R. Szukalo, D. Zagidulin, M. Biesinger and D. W. Shoesmith, Materials and Corrosion, 72, 2021, 348–360.

Formation of a nano-porous structured Cu layer by selective etching of a brass layer and sinter-bonding to achieve direct Cu–Cu bonding

A nano porous structured (NPS) Cu layer was fabricated by a Zn plating-annealing-selective etching process. Furthermore, sinter-bonding was performed by thermocompression after forming the NPS Cu layer instead of the conventional paste sinter-bonding process. The sinter-bonding produced a dense Cu–Cu joint with minimal oxidation by infiltrating the reducing agent into the NPS Cu layer. Sinter-bonding was performed with under a pressure of 5 MPa at 300 °C in air, and excellent bonding strength of 27 MPa was achieved after a bonding time of 1 min. Moreover, the bonding strength increased to 35 MPa by bonding for 1 min while blowing N2. The optimal thickness of the NPS Cu layer for short-duration sinter-bonding was established, and the oxidation of Cu was suppressed by the infiltration of a reducing agent. Consequently, an excellent shear strength was achieved by sinter-bonding using the NPS Cu layer.