The role of metal oxides in promoting a copper catalyst for methanol synthesis

The coverage of oxygen formed on the surface of catalysts during methanol synthesis from CO₂ has been measured for copper-based catalysts including various metal oxides using a method called reactive frontal chromatography (RFC). An excellent correlation between the specific activity for methanol synthesis and the oxygen coverage () was obtained, where the activity increased linearly with oxygen coverage at<0.16 and then decreased at>0.18. The results strongly indicate that the support effect or addition of metal oxides revealed in methanol synthesis over copper catalysts is ascribed to the ratio of Cu⁺ to Cu⁰ on the surface of copper particles.     

Behaviour of poly(ethylene glycol) during electrodeposition of bright copper coatings in sulfuric acid electrolytes

The interaction of poly(ethylene glycol) M _n= 3000 with copper I and II ions in aqueous-acidic media was studied by investigation of the specific electrical conductivity, optical density and the cyclic voltamperometric curves in Cu⁺ and Cu²⁺ solutions. The results suggest the formation of complexes of the {Cu⁺(-EO-)₃(x – 1)H₂O} and {Cu²⁺(-EO-)₄.(y – 1)(H₂O)₂} types. In the case when {–CH₂CH₂-O-} _n and Cl^– are simultaneously present in the copper electrolyte, the possibility of simultaneous complex formation between both copper ions and ethylene oxide units, and copper ions and chloride ions is considered. The strong increase in copper electrodeposition over-potential after the addition of polyethers to the electrolytes containing brighteners is explained by the formation of these complexes.     

Study on the ion-exchange copper-loaded antibacterial glasses

In this paper, copper-loaded antibacterial glasses were prepared by an ion-exchange method with CuSO₄ or CuCl as copper sources. The effects of different molten salts and ion exchange duration on the antibacterial properties of copper-loaded glasses were investigated. The experimental results show that the glasses exchanged with CuSO₄/Na₂SO₄ mixed molten salts have a higher surface copper loading than that with CuCl/KCl mixed molten salts. The sample color results from the reduced Cu⁰. The equilibrium between Cu⁺ and Cu⁰ is related to the Sn²⁺ ions existed in the lower surface of float glass. Finally, the antibacterial function of glass samples was found to be related to the charge transfer between Cu⁺+e^??Cu⁰, and has a proportional correlation with the content of Cu⁺ ions on the glass surface.     

Current-time behaviour for copper electrodeposition. II. Experimental examination of surface diffusion and direct incorporation models at hemispherical sites

The surface diffusion model has been examined by the measurement of current-time transients for copper electrodeposition on to a polycrystalline copper electrode in acidic copper sulphate solution. The results did not satisfy the surface diffusion model criteria. The current-time profiles showed a linear dependence on 1/t ^1/2 except at high overpotentials. This behaviour could be explained by a direct incorporation model at hemispherical sites through a hemispherical diffusion layer. A parameter characterizing this model, the number of sites, was estimated to be of the order of 10⁴ cm^–2.     

Changes of copper location in CuY zeolites induced by preparation methods

The location of transition ions in copper- and copper-zinc-loaded Y type zeolites prepared by different procedures has been studied by temperature-programmed reduction, infrared spectroscopy of CO adsorbed on pretreated samples and X-ray photoelectron spectroscopy. Samples outgassed at 673 K showed Cu⁺ species due likely to reduction of Cu²⁺ ions under vacuum. Over exchanged CuY zeolites copper species in exchange sites were detected, while an impregnated sample exhibited bands of CO adsorbed on both Cu²⁺ and Cu⁺ ions developed at the surface of CuO crystals, and small proportions of Cu⁺ ions located in accessible exchange sites S_II and Sn_II. Similar findings were observed in Zn- and Cu-exchanged zeolites although the relative proportion of Cu in S_I positions was decreased due to competition between Cu²⁺ and Zn²⁺ ions. Samples reduced in hydrogen at 523 K showed the appearance of Cu⁰ species in impregnated samples, whereas Cu⁺ dominated in the exchanged counterparts. Reduction at 598 K led to substantial changes in Cu-exchanged samples in water. The proportion of Cu⁺ species decreased by reduction to Cu⁰ and simultaneously migration to Cu⁺ to S_II sites occurred. While Cu²⁺ or Cu⁺ were found on outgassed samples, only Cu⁰ and intrazeolite Cu⁺ were observed after H₂-reduction at 623 K. Changes in copper exposure as a function of sample pretreatments were also revealed by X-ray photoelectron spectroscopy.     

Impedance investigation of the mechanism of copper electrodeposition from acidic perchlorate electrolyte

The mechanism of the copper electrodeposition from acidic perchlorate electrolyte has been investigated with polarization and impedance methods. The impedance of the copper electrode in copper perchlorate electrolytes has been measured as a function of frequency for different Edc overpotential values and different copper(II) ion concentrations. The relations between the shape of a complex plane impedance display and the copper electrode potential values as well as the concentration of CuII ion were analysed in terms of the electrode reaction mechanism. It is shown, that the presence of the intermediate cuprous ion and its sinusoidal change of transport rate is one of the main factors determining the depressed shape of the impedance arc. The quantitative relation between the faradaic impedance and the rates of electrode reaction rates was established. The impedance arc was simulated with a set of parameters involving: rate constants, Tafel slopes, diffusion coefficient of cuprous ion and double layer capacitance. The rate constants were calculated with respect to ECu2 + Cu00 as: k10 = 6.50 × 10−5 cm s−1, k20 = 0.139 cm s−1, k−20 = 1.88 × 10−7 mol cm−2 s−1.     

Electrochemical behaviour of copper in trimethyl-n-hexylammonium bis((trifluoromethyl)sulfonyl)amide, an ammonium imide-type room temperature molten salt

The redox behaviour of copper species in an ammonium imide room temperature molten salt was examined to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis((trifluoromethyl)sulfonyl)amide (TMHA-Tf₂N), having an electrochemical window of 5.6 V (50 °C), and the corresponding copper(II); salt were used to prepare the solution. In TMHA-Tf₂N media the monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species as: Cu²⁺ + Cu 2Cu⁺. Cathodic electrodeposition of copper metal and its anodic dissolution were, thus one-electron reactions and their current efficiencies were almost 100%.     

Dehydrogenation of cyclohexanol on Cu–ZnO/SiO2 catalysts: The role of copper species

For the dehydrogenation of cyclohexanol a series of Cu–ZnO/SiO₂ catalysts with various Cu to ZnO molar ratios was prepared using the impregnation method, with the loading of copper fixed at 9.5 at.%. The catalysts were characterized by XPS, H₂–N₂O titration, BET, H₂-TPR, NH₃-TPD and XRD techniques. The results indicate that the addition of ZnO can improve the dispersion of copper species on reduced Cu–ZnO/SiO₂ (CZS) catalysts. Cu⁰ and Cu⁺ species were found on the reduced CZS catalysts surface, and the amount of Cu⁺ increased with the content of ZnO increasing. The addition of ZnO increased the acidity of the CZS catalysts. However, only Cu⁰ species can be found on the reduced Cu/SiO₂ (CS) catalyst surface. According to the reaction results, we found that the selectivity to phenol was related to the amount of Cu⁺ species, the Cu⁺ species should be the active sites for the production of phenol, the Cu⁰ is responsible for cyclohexanol dehydrogenation to cyclohexanone.     

Evidence and analysis of parallel growth mechanisms in Cu2O films prepared by Cu anodization

We have studied the preparation of Cu₂O films by copper anodization in a 0.1 M NaOH electrolyte. We identified the potential range at which Cu⁺ dissolution takes place then we prepared films with different times of exposure to this potential. The morphology, crystalline structure, band gap, Urbach energy and thickness of the films were studied. Films prepared with the electrode unexposed to the dissolution potential have a pyramidal growth typical of potential driven processes, while samples prepared at increasing exposure times to dissolution potential present continuous nucleation, growth and grain coalescence. We observed a discrepancy in the respective film thicknesses calculated by coulometry, atomic force microscopy and optical reflectance. We propose that anodic Cu₂O film formation involves three parallel mechanisms (i) Cu₂O nucleation at the surface, (ii) Cu⁺ dissolution followed by heterogeneous nucleation and (iii) Cu⁺ and OH⁻ diffusion through the forming oxide and subsequent reaction in the solid state.     

Electroreduction of nitrate ions on Pt(1 1 1) electrodes modified by copper adatoms

Kinetics and mechanism of nitrate ion reduction on Pt(1 1 1) and Cu-modified Pt(1 1 1) electrodes have been studied by means of cyclic voltammetry, potentiostatic current transient technique and in situ FTIRS in solutions of perchloric and sulphuric acids to elucidate the role of the background anion. Modification of platinum surface with copper adatoms or small amount of 3D-Cu crystallites was performed using potential cycling between 0.05 and 0.3 V in solutions with low concentration of copper ions, this allowed us to vary coverage θ_Cu smoothly. Following desorption of copper during the potential sweep from 0.3 to 1.0 V allowed us to estimate actual coverage of Pt surface with Cu adatoms. Another manner of the modification was also applied: copper was electrochemically deposited at several constant potentials in solutions containing 10⁻⁵ or 10⁻⁴ M Cu²⁺ and 5 mM NaNO₃ with registration of current transients of copper deposition and nitrate reduction.It has been found that nitrate reduction at the Pt(1 1 1) surface modified by copper adatoms in sulphuric acid solutions is hindered as compared to pure platinum due to induced sulphate adsorption at E < 0.3 V. Sulphate blocks the adsorption sites on the platinum surface and/or islands of epitaxial Cu(1 × 1) monolayer thus hindering the adsorption of nitrate anions and their reduction. The extent of inhibition weakly depends on the copper adatom coverage. Deposition of a small amount of bulk copper does not affect noticeably the rate of nitrate reduction.Nitrate reduction on copper-modified Pt(1 1 1) electrodes in perchloric acid solutions occurs much faster as compared to pure platinum. The steady-state currents are higher by 4 and 2 orders of magnitude at the potentials of 0.12 and 0.3 V, respectively. The catalytic effect of copper adatoms is largely caused by the facilitation of nitrate adsorption on the platinum surface near Cu_ad and/or on the islands of the Cu(1 × 1) monolayer (induced nitrate adsorption).Hydrogen adatoms block the adsorption sites on platinum for NO₃⁻ anion adsorption and inhibit reactions of nitrate reduction even at moderate surface coverage.The products of nitrate reduction in sulphuric and perchloric acids are essentially the same (NO and ammonia) irrespective of the presence or absence of Cu on the platinum surface.     

Hydrogenation of methyl acetate to ethanol by Cu/ZnO catalyst encapsulated in SBA‐15

The hydrogenation of methyl acetate (MA) is one of the important key processes for synthesis of ethanol from syngas. This work reports a highly efficient Cu‐ZnO/SBA‐15 catalyst prepared by facile solid‐state grinding method. Both copper and zinc species were encapsulated in SBA‐15 in high dispersion with the presence of organic template. The mixed homogeneity and interaction between copper and zinc species was enhanced as well with the help of organic template, resulting in the formation of Cu⁺ species in the reduced catalysts. Moreover, TOF_Cu(0) linearly increased with the Cu⁺/Cu⁰ ratio, indicating that a high proportion of Cu⁺/Cu⁰ induced by ZnO should be a key prerequisite to achieve favorable hydrogenation performance. It seems that the Cu⁺ species originated from Cu‐ZnO_x species are more active than that from Cu‐O‐Si species in the activation of MA. These results may provide an inspiration in rational design of Cu‐ZnO‐based catalysts for esters hydrogenation. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2839–2849, 2017     

Investigation of hydrophobic porous electrodes. II. Pseudocapacitance changes during underpotential copper deposition

Differential capacitance measurements in 96%o-phosphoric acid at 160° C have been used to follow the underpotential deposition of copper on supported platinum in a porous electrode. At a potential in the range 0·2–0·3 V versus RHE the capacitance,C, increased as copper deposition proceeded and a plot ofC versust ^1/2 was linear during a substantial part of the deposition process. The slope dC/dt ^1/2 was proportional to the copper concentration in solution, suggesting that the Cu/Cu²⁺ pseudocapacitance reflected the quantity of copper deposited and that copper deposition was diffusion controlled. The effective diffusion coefficient estimated from the results was 10^–7 cm² s^–1 — some 40 times smaller than the copper ion diffusion coefficient measured separately. At potentials of 0·4 V and above, capacitance measurements could not be used to follow copper deposition because the Cu/Cu²⁺ pseudocapacitance decayed with time.     

Active species of copper chromite catalyst in C–O hydrogenolysis of 5-methylfurfuryl alcohol

The active sites of copper chromite catalyst, CuCr₂O₄·CuO, were investigated for the condensed-phase hydrogenolysis of 5-methylfurfuryl alcohol to 2,5-dimethylfuran at 220 °C. The bulk and surface features of the catalyst were characterized by XRD, H₂-TPR, N₂ adsorption, CO chemisorption, N₂O titration, NH₃-TPD, XPS, and AES. Maxima of both of the potential active species, Cu⁰ and Cu⁺, occurred after reduction in H₂ at 300 °C compared to 240 and 360 °C. These Cu⁰ and Cu⁺ maxima also coincided with the highest specific rate of reaction based on the surface area of the reduced catalyst. The trends of Cu⁰ and Cu⁺ observed by N₂O titration and CO chemisorption were also observed qualitatively by AES. Correlations between activity and the possible active species suggested that Cu⁰ was primarily responsible for the activity of the catalysts.     

Enhanced high rate properties of ordered porous Cu2O film as anode for lithium ion batteries

Highly ordered porous Cu₂O film is electrodeposited on copper foil through a self-assembled polystyrene sphere template. Compared with the dense Cu₂O film and the octahedral Cu₂O powder, the ordered porous Cu₂O film exhibits an improved electrochemical cycling stability. The capacity of the porous Cu₂O film can maintain 336 mAh g⁻¹ and 213 mAh g⁻¹ after 50 cycles at the rate of 0.1 C and 5 C, respectively. The reversible capacity holds 63.4% as the discharge-charge rate even increases by 50 times. The enhanced high rate properties of the ordered porous film should be attributed to the sufficient contact surface of Cu₂O/electrolyte and the short diffusion length of Li⁺. Moreover, the direct contact between Cu₂O and current collector and the decreasing inactive interfaces of Cu₂O/polymer binder are also suggested as being responsible for the enhanced high rate property.     

Effect of boric oxide doping on the stability and activity of a Cu–SiO2 catalyst for vapor-phase hydrogenation of dimethyl oxalate to ethylene glycol

Stable and efficient B–Cu–SiO₂ catalysts for the hydrogenation of dimethyl oxalate (DMO) to ethylene glycol were prepared through urea-assisted gelation followed by postimpregnation with boric acid. Auger electron spectroscopy and CO adsorption by in situ Fourier transform infrared spectroscopy revealed that the Cu⁺ species on the catalyst surface increased together with an increase in the amount of boric oxide dopant. X-ray diffraction and N₂O chemisorption indicated that a suitable amount of boric oxide doping tended to improve copper dispersion and retard the growth of copper particles during DMO hydrogenation. Catalytic stability was greatly enhanced in the B–Cu–SiO₂ catalyst with an optimized Cu/B atomic ratio of 6.6, because of the formation and preservation of appropriate distributions of Cu⁺ and Cu⁰ species on the catalyst surfaces. The effect of boric oxide was attributed to its relatively high affinity for electrons, which tended to lower the reducibility of the Cu⁺ species.     

Unusual Elastic and Mechanical Behaviors of Copper Phosphate Glasses with Different Copper Valence States

Elastic and mechanical properties such as Young's modulus E, Poisson's ratio ν, Debye temperature θ_D, Vickers hardness H_v, fracture toughness K_c, and fracture surface energies γ_f of yCuO_x·(100−y)P₂O₅ glasses (y= 45, 50, 55) with different copper valence states, i.e., R(Cu⁺) = Cu⁺/(Cu⁺+ Cu²⁺), at room temperature (humidity 64%) have been examined. The following features have been found: (1) the glass transition temperature (218–434°C), H_v (2.7–4.4 GPa), E (50.6–78.2 GPa), and θ_D (358–434 K) decrease largely with increasing R(Cu⁺); (2) the mean atomic volume, K_c (0.56–1.14 MPa·m^1/2), and γ_f (1.9–11.2 J·m⁻²) tend to increase with increasing R(Cu⁺); (3) 50CuO_x·50P₂O₅ glasses with R(Cu⁺) = 0.42 and 0.55 have a high resistance against crack formation in Vickers indentation tests and no crack is observed in the 45CuO_x·55P₂O₅ glass with R(Cu⁺) = 0.57 under an applied load of about 98 N. The results demonstrate that elastic and mechanical properties of yCuO_x·(100−y)P₂O₅ glasses depend strongly on the copper valence state and the CuO_x/P₂O₅ ratio. The unusal mechanical and elastic properties of copper phosphate glasses are well explained qualitatively by considering unique oxygen coordination and bonding states of Cu⁺ ions, i.e., lower coordination number and more covalent bonding compared with Cu²⁺ ions.     

Electrochemical nucleation and growth of copper on chromium-plated electrodes

Nucleation and growth of copper electrodeposited on chromium plated electrodes in copper sulfate electrolytes were examined, focusing on the influence of prior Cr plating conditions on the nucleation density and growth kinetics of the copper electrodeposits. The Cr-plated electrodes were made by electrodeposition of Cr on copper sheets for 2 to 60 s at 0.1 A cm^–2 in CrO₃ 350 g L^–1 + H₂SO₄ 3.5 g L^–1. Copper was then electrodeposited onto the Cr-plated electrode under potentiostatic conditions. Copper initially nucleated and grew according to a three-dimensional diffusion controlled progressive nucleation process, and later according to an instantaneous nucleation process. The period during which copper nucleation is controlled by the diffusion controlled progressive nucleation process decreases with increasing Cr plating time. The nucleation density of copper was extremely high on the 2 s Cr-plated electrode, producing an extremely fine and uniform electrodeposit. However, on the 4 s Cr-plated electrode, the nucleation density of copper significantly reduced to one hundredth of that on the 2 s Cr-plated electrode, and then decreased slightly with increasing Cr plating time (thickness of Cr layer). These results appear to be associated with the IR drop across the Cr layer, including the surface Cr oxide/hydroxide film (termed the cathode film), which significantly reduces the driving force for the electrodeposition of copper under potentiostatic plating conditions.     

Electrodeposition of copper from spent Li-ion batteries by electrochemical quartz crystal microbalance and impedance spectroscopy techniques

Information about the copper electrodeposition mechanism at different pH values was obtained using an electrochemical quartz crystal microbalance (EQCM) technique, as well as potentiodynamic, potentiostatic, and electrochemical impedance spectroscopy (EIS) techniques. In agreement with the measurements obtained from the EQCM and potentiostatic experiments, an intermediate Cu⁺ species and a CuO layer are formed. Simultaneous mechanism of direct reduction of Cu²⁺ and copper oxide (CuO) reduction at pH 2.0 and 4.5 occur. The EIS experiment shows a diffusion-controlled process by the presence of a Warburg element, a CPE related to the irregular metallic copper electrodeposition, and a resistance of the electrodeposit.     

Evolution in the Oxidation Valences and Sensitization Effect of Copper Through Modifying Glass Structure and Sn2+/Si Codoping

Currently, coupling noble metal species with rare‐earth cations (REI) in amorphous materials has attracted persistent attention, owing to the significant rise in the emission intensity and nonlinear optical response, which allow various potential applications in photoelectric fields. However, the primary investigations are focused on Au‐ and Ag‐doped systems, and there are few systematic reports concerning the interaction between REI and the different oxidation states of copper so far. Herein, we demonstrated the evolution of copper oxidation valences from Cu²⁺ to Cu⁺, and then to Cu⁰ (Cu NPs), and the corresponding effects on Tb³⁺ emissions in borate glasses were systematically investigated by modifying glass structure and Sn²⁺/Si codoping. With increasing the ratio of B₂O₃ to Li₂O, enhancement of reduction efficiency of Cu²⁺ to Cu⁺ was observed. Impressively, the ns²‐type Sn²⁺ emission centers not only generate efficient sensitizers for Tb³⁺ but also lead to efficient reduction in Cu²⁺ to Cu⁺. Based on absorption/transmittance, photoluminescence excitation/emission, and time‐resolved decay spectra, the interplay mechanisms between Tb³⁺ and the different valences of copper were discussed in detail.