Cu-O Bond Research Articles

Switching CO2 Electroreduction toward Ethanol by Delocalization State-Tuned Bond Cleavage.

The electrochemical CO2 reduction reaction by copper-based catalysts features a promising approach to generate value-added multicarbon (C2+) products. However, due to the unfavored formation of oxygenate intermediates on the catalyst surface, the selectivity of C2+ alcohols like ethanol remains unsatisfactory compared to that of ethylene. The bifurcation point (i.e., the CH2═CHO* intermediate adsorbed on Cu via a Cu-O-C linkage) is critical to the C2+ product selectivity, whereas the subsequent cleavage of the Cu-O or the O-C bond determines the ethanol or ethylene pathway. Inspired by the hard-soft acid-base theory, in this work, we demonstrate an electron delocalization tuning strategy of the Cu catalyst by a nitrene surface functionalization approach, which allows weakening and cleaving of the Cu-O bond of the adsorbed CH2═CHO*, as well as accelerating hydrogenation of the C═C bond along the ethanol pathway. As a result, the nitrene-functionalized Cu catalyst exhibited a much-enhanced ethanol Faradaic efficiency of 45% with a peak partial current density of 406 mA·cm-2, substantially exceeding that of unmodified Cu or amide-functionalized Cu. When assembled in a membrane electrode assembly electrolyzer, the catalyst presented a stable CO2-to-ethanol conversion for >300 h at an industrial current density of 400 mA·cm-2.

Cu-O-Si-C interface-induced high-adhesion and anticorrosion of the DLC coatings on inner wall of copper tube prepared by PECVD

Deposition of well-adherent diamond-like‑carbon (DLC) films on copper is relatively difficult due to weak bonds between copper and carbon. The Cu-O-Si-C nanostructure was proposed to improve the adhesion and the corrosion-resistance of multilayer Si-DLC/DLC film on an inner surface of copper tube prepared by PECVD. First, the copper alloy was pretreated by oxygen. Then mixture gas of tetramethylhexylsilane (TMS) and oxygen was used to deposit interlayer, and finally multilayer Si-DLC/DLC film was deposited using the gas C2H2 and argon. Transmission Electron Microscope (TEM) demonstrated that there existed CuSiO3, CuO, SiC, SiO2 nanostructures in the interlayer. And X-ray Photoelectron Spectroscopy (XPS) proved that there were actually CuO, SiC and SiO bonds at the interface. These bonds and compounds enhanced the adhesion between multilayer Si-DLC/DLC film and copper substrate. The polarization potential was significantly improved to −0.07 V, achieved through the process of oxygen pre-implantation and the combined deposition of oxygen and TMS. Furthermore, the adhesion of the film was estimated by the Rockwell test and reached HF1-HF2. The Cu-O-Si-C microstructure plays a crucial role in enhancing the adhesion and corrosion resistance of multilayer Si-DLC/DLC film.

Dendritic copper oxide catalyst engineering weak-polarity Cu-O bond for high-efficiency nitrate electroreduction

Nitrate reduction reaction (NO3RR) is deemed a promising pathway for both ammonia synthesis and water purification. Developing a high-efficiency catalyst with excellent NH3 selectivity and catalytic stability is desirable but remains challenging. In this work, a dendritic copper oxide catalyst (Cu-B2) has been developed to efficiently catalyze NO3RR for ammonia production, the Cu-B2 exhibits excellent catalytic performance, achieving an NH3 Faradaic efficiency as high as 94 % and an NH3 yield of 16.9 mg h−1 cm−2 with a current density of 192.3 mA cm−2 at − 0.6 V (vs. RHE, reversible hydrogen electrode). During NO3RR testing, the Cu-B2 catalysts are reduced in situ to form highly active Cu0/Cu+ sites, while retaining its dendritic morphology. Compared with other catalysts, the Cu-O bond in Cu-B2 catalyst has weaker polarity, resulting in Cu0/Cu+ sites in lower oxidation states. In situ attenuated total reflection surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) studies reveal the Cu-B2 catalyst exhibits a potential-independent capability for *NO3- adsorption and high conversion efficiency of NO2- intermediate into ammonia, DFT calculations reveal that Cu-B2 exhibts higher NO3- adsorption energy and lower NO3- adsorption energy barrier than Cu-B1, thus endowing it with a remarkably improved catalytic activity and durability.

Effect of Rapid Thermal Annealing on CuO Nanoparticles

Abstract This work is a comparative study of the effect of two different annealing methods on copper oxide (CuO) nanoparticle properties obtained previously by direct precipitation method. The prepared samples were annealed in air at various temperatures (300, 400, 500°C) for 1 hour. Then they were characterized by employing scanning electron microscopy (SEM), X-ray diffraction (XRD), UV-Visible, and Fourier Transform Infrared (FT-IR) spectroscopy. The main results revealed an increase in the grain size in both methods as the annealing temperature increases. It reaches 30.93 nm in RTA and 26.75 nm in STA at 500°C. XRD spectra showed, in the case of RTA at 500 °C, a significant decrease in the intensity corresponding to the (002) and (111) orientations. This result indicated that beyond 400 °C, one hour of RTA is not suitable for enhancing CuO nanoparticle crystallinity compared to STA. The optical analysis demonstrated that the energy of the optical band gap in STA is higher than that in RTA. It reaches 2,88 eV at 500°C using RTA which is close to the gap value of CuO in the range of 1.8–2.8 eV. FT-IR results showed, for both methods, the presence of characteristic peaks of the Cu-O bonds in the monoclinic CuO structure without any trace of Cu2O structure. Nevertheless, samples exposed to RTA for one hour are more susceptible to absorbing species of C=O bond (C=O bond is due to the atmospheric CO2 absorption and the presence of organic impurities from the synthesis process) than those of STA. Hence, RTA at 500 °C is far from producing CuO nanoparticles with preferred characteristics; it needs further research to examine the effect of higher temperature by controlling the annealing time.

Dual mechanisms in hydrogen reduction of copper oxide: surface reaction and subsurface oxygen atom transfer.

The study of the reduction of copper oxide (CuO) by hydrogen (H2) is helpful in elucidating the reduction mechanism of oxygen carriers. In this study, the reduction mechanism of CuO by H2 and the process of oxygen atom transfer were investigated through the density functional theory (DFT) method and thermodynamic calculation. DFT calculation results showed that during the reaction between H2 and the surface of CuO, Cu underwent a Cu2+ → Cu1+ → Cu0 transformation, the Cu-O bond (-IpCOHP = 2.41) of the Cu2O phase was more stable than that (-IpCOHP = 1.94) of the CuO phase, and the reduction of Cu2O by H2 was more difficult than the reduction of CuO. As the surface oxygen vacancy concentration increased, it was more likely that the subsurface O atoms transfer to the surface at zero H2 coverage (no H2 molecule on the surface), allowing the surface to maintain a stable Cu2O phase. However, when the H2 coverage was 0.25 monolayer (ML) (one H2 molecule every four surface Cu atoms), the presence of H atoms on the surface made the upward transfer of O atoms from the subsurface more difficult. The rate of consuming surface O atoms in the reduction reaction was greater than the rate of subsurface O atom transfer induced by the reduction reaction and the surface Cu2O phase could not be maintained stably. Through thermodynamic analysis, at high H2 concentration, the reaction between H2 and CuO was more likely to generate Cu, while at low H2 concentration, it was more likely to generate Cu2O. In summary, the valence state of Cu in the reaction process between CuO and H2 depended on the concentration of H2.

Crystal-to-crystal polymerisation of monosubstituted [PW11O39Cu(H2O)]5- Keggin-type anions.

The reaction between neutral bis(picolinate)copper(II) complexes and copper(II)-monosubstituted Keggin-type phosphotungstate anions formed in situ leads to the formation of the hybrid [C(NH2)3]10[{PW11O39Cu(H2O)}2{Cu(pic)2}]·10H2O compound (1, pic = picolinate) in the presence of structure-directing guanidinium cations. Single-crystal X-ray diffraction studies demonstrate that 1 contains dimeric {PW11O39Cu(H2O)}2{Cu(pic)2} molecular species constituted by two Keggin-type anions linked by one {Cu(pic)2} octahedral complex through axial coordination to their terminal oxygen atoms. The extensive hydrogen-bonding network established by guanidium cations and Keggin clusters plays a key role in retaining the crystallinity of the system throughout dehydration to allow a single-crystal-to-single-crystal (SCSC) transformation into the anhydrous [C(NH2)3]10[{PW11O39Cu}2{Cu(pic)2}] (2a) at 170 °C. Structural modifications involve the re-orientation, shifting in ca. 1.5 Å and condensation of all the {PW11O39Cu} units to result in {PW11O39Cu}n chains in an unprecedented solid-state polymerisation. This phase transition also implies the cleavage of Cu-O bonds induced by the rotation and translation of Keggin-type anions, in such a way that hybrid dimeric units in 1 are dismantled and {Cu(pic)2} complexes become square planar. The irreversibility of the phase transition has been confirmed by combined thermal and diffractometric analyses, which evidence that the anhydrous phase adsorbs only one water molecule per cluster to become the [C(NH2)3]10[{PW11O39Cu}2{Cu(pic)2}]·2H2O (2h) hydrated derivative without any significant alteration in its cell parameters, nor in its crystalline structure. Phase transformations have been monitored by electron paramagnetic resonance spectroscopy.

Green Synthesis of CuO Nanoparticles Using Tragopogon porrifolius and Their Antioxidant and Photocatalytic Applications

Copper oxide nanoparticles (CuO NPs) were produced by green synthesis method which is a cheap, easy and effective method using Tragopogon porrifolius extract. The shape, bond and crystal structure of the nanoparticles were determined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and X-ray diffractometer (XRD) analysis methods. SEM analysis showed that the particles were spherical and EDX analysis showed the elemental composition of Cu and O as Cu 58.17 % and O 32.73 %. Cu-O bond structure was identified in FTIR analysis. In XRD analysis, peaks defining CuO NPs were observed. The antioxidant and photocatalytic activity of the synthesized CuO NPs were investigated. Antioxidant capacities were examined in the range of 50-500 μg/mL. The free radical scavenging activity of the nanoparticles was determined as 70.75 % at a concentration of 500 μg/mL. In photocatalytic studies, Reactive Red 120 (RR 120) dye degradation was investigated. The degradation time was calculated as 76 % in 30 min.

Crystal structure, lattice energy and microwave dielectric properties of melilite-type Ba1-xSrxCu2Ge2O7 ceramics

The Ba1-xSrxCu2Ge2O7 was successfully obtained through the solid-state reaction method, with single-phase BaCu2Ge2O7 formed at 850 °C. Scanning electron microscopy analysis revealed the excellent chemical compatibility of Ba1-xSrxCu2Ge2O7 with silver. The properties of Ba1-xSrxCu2Ge2O7 ceramics were explained using the P-V-L theory. The εr-corr decreased with the polarization rate (Σχu*Nbu) and ion polarization of the unit cell. The Q×f increased with the chemical bond strength and lattice energy (Ucal), particularly the lattice energy of the Ge-O bond (U(Ge-O)). The τf exhibited an opposite trend to the Q×f value and was influenced by the U(Cu-O) and susceptibility of the Cu-O bond (χ(Cu-O)). Sintering at 875 °C for 3 h yielded optimal microwave dielectric performance for Ba1-xSrxCu2Ge2O7 ceramics, with observed values of εr = 9.26 ± 0.14, Q×f = 85,660 ± 4200 GHz, and τf = −15.6 ± 1.1 ppm/°C at x = 0.10. These promising microwave dielectric properties make Ba1-xSrxCu2Ge2O7 a potential candidate for LTCC material applications.

Ammonia-induced corrosion and modification of chrysocolla surface for enhanced adsorption of sulfide species

The copper content of chrysocolla is an oxidized ore, which has high industrial value in terms of development and utilization. Flotation is generally used to recover such minerals. However, few studies have been conducted on the mechanism of ammonium enhanced flotation in the flotation process of chrysotile asbestos at the atomic level, including the enhanced sulfidation process in solution and mineral surface. This study demonstrated that the presence of NH3 only enhances the reaction between Na2S⋅9H2O and Cu ions. The formation of copper-ammonia complexes facilitated the sulfide reaction and led to the generation of more Cu-S species, which can adsorb onto the chrysocolla surface. The NH3 destroys the hydration film of the Cu6[Si6O18]6H2O (1 1 0) surface, creating favorable conditions for sulfidation. The CuS formed in catalytic sulfidation has higher stability compared with CuS formed through direct sulfidation. The NH3 molecule corrosion of the Cu6[Si6O18]6H2O (1 1 0) surface was advantageous in terms of energy, and the formation of Cu(NH3)42+ was − 539.32 kJ·mol−1. After the Cu atom ultimately lost 0.37 e electrons, the Cu-O bond broke, and Cu(NH3)42+ relaxed towards the vacuum layer, which formed a defect at the Cu6[Si6O18]6H2O (1 1 0) surface. The catalytic sulfidation path in the solution was Cu(NH3)4(OH)2 + HS− + 17 H2O + Na+ → CuS + 4NH3 + OH− + 17 H2O + Na+. The total energy of the reaction was − 0.88 kJ·mol−1, which indicated that the catalytic sulfidation reaction could spontaneously occur. The CuS generated by catalytic sulfidation was stably adsorbed to the Cu6[Si6O18]6H2O surface of defects through the formation of stable chemical bond between Cu and O. The obtained results revealed the complex interaction between ammonium and minerals, which paves the way for its efficient sulfide flotation.

Stabilizing lattice oxygen redox in layered sodium transition metal oxide through spin singlet state

Reversible lattice oxygen redox reactions offer the potential to enhance energy density and lower battery cathode costs. However, their widespread adoption faces obstacles like substantial voltage hysteresis and poor stability. The current research addresses these challenges by achieving a non-hysteresis, long-term stable oxygen redox reaction in the P3-type Na2/3Cu1/3Mn2/3O2. Here we show this is accomplished by forming spin singlet states during charge and discharge. Detailed analysis, including in-situ X-ray diffraction, shows highly reversible structural changes during cycling. In addition, local CuO6 Jahn-Teller distortions persist throughout, with dynamic Cu-O bond length variations. In-situ hard X-ray absorption and ex-situ soft X-ray absorption study, along with density function theory calculations, reveal two distinct charge compensation mechanisms at approximately 3.66 V and 3.99 V plateaus. Notably, we observe a Zhang-Rice-like singlet state during 3.99 V charging, offering an alternative charge compensation mechanism to stabilize the active oxygen redox reaction.

Constructing Active Cu2+-O-Fe3+ Sites at the CuO-Fe3O4 Interface to Promote Activation of Surface Lattice Oxygen.

Activating surface lattice oxygen (Olatt) through the modulation of metal-oxygen bond strength has proven to be an effective route for facilitating the catalytic degradation of volatile organic compounds (VOCs). Although this strategy has been implemented via the construction of the TM1-O-TM2 (TM represents a transition metal) structure in various reactions, the underlying principle requires exploration when using different TMs. Herein, the Cu2+-O-Fe3+ structure was created by developing CuO-Fe3O4 composites with enhanced interfacial effect, which exhibited superior catalytic activity to their counterparts, with T90 (the temperature of toluene conversion reaching 90%) decreasing by approximately 50 °C. Structural analyses and theoretical calculations demonstrated that the active Cu2+-O-Fe3+ sites at the CuO-Fe3O4 interface improved low-temperature reducibility and oxygen species activity. Particularly, X-ray absorption fine structure spectroscopy revealed the contraction and expansion of Cu-O and Fe-O bonds, respectively, which were responsible for the activation of the surface Olatt. A mechanistic study revealed that toluene can be oxidized by rapid dehydrogenation of methyl assisted by the highly active surface Olatt and subsequently undergo ring-opening and deep mineralization into CO2 following the Mars-van Krevelen mechanism. This study provided a novel strategy to explore interface-enhanced TM catalysts for efficient surface Olatt activation and VOCs abatement.

Enhanced cuprate superconductivity from elongated to compressed coordination

In 1986 Professor Müller and Bednorz discovered the historic superconductor of LaBaCuO (La214) that opens the prelude of unprecedented era for high Tc superconductivity research worldwide. The Jahn Teller effects combining with strong interlayer Coulomb interactions lead to the elongated copper oxygen coordination in La214, giving rise to the orbital order scenario that the Cu3dx2-y2 locates near Fermi surface while the 3dz2 is far below without contributions to the conductivity, hence single band model is favorite. We recently discovered a new type of cuprate superconductor Ba2CuO4-y (Ba214) synthesized at extreme high oxygen pressure that shares a similar crystal structure to the classical La214 but with notably a very rare compressive type octahedron. The compressed octahedron coordination results from the longer in plane CuO bond length than that for apical oxygen bond. The compressed octahedron will lead to a reversed orbital order, i.e. the 3dz2 will be lifted above 3dx2-y2,which is generally considered unfavorable to superconductivity based on the current theories of high Tc cuprates. Ba214 however exhibits bulk superconducting transition with Tc above 70 K at ambient pressure, a surprisingly 80 % enhancement from that for isostructural La214. Here we briefly introduce the unique structure features as well research progress for Ba214, indicating the paradigm shifts roles of 3dz2 orbital in (I) enhancing cuprate superconductivity, (II) favoring multiband scenario; (III) enabling the s wave pairing mechanism.

Negative magnetoresistance effect in Ba-doped layered double perovskite La2CuSnO6

The layered double perovskite La2-xBaxCuSnO6 (0.05 ≤ x ≤ 0.20) ceramics were synthesized successfully by solid-state reaction, and the crystal structure, transport and magnetic properties are investigated. It is found that the temperature-dependent resistivity ρ(T) shows a semiconductor behavior, which is related to magnetic ordering in two-dimensional CuO2 layers, and the MR effect exists in La2-xBaxCuSnO6. With decreasing the temperature, the MR effect changes from positive to negative, giving a positive maximum at Tmax (≈ TC) and showing a large negative MR effect at around 40 K with a value of about 20–30% under field H = ± 50 kOe. It is suggested that the negative MR effect in Ba-doped La2CuSnO6 is attributed to the field-induced suppression of in-plane spin-disorder scattering in CuO2 layers. A small amount of Ba doping can adjust the competition and synergy of the AFM and FM interactions through changing the tilt and distortion of CuO6 octahedrons, the in-plane Cu-O bond lengths, and the content of Jahn-Teller exciton Cu2+ ions, besides the stabilization of the La2CuSnO6 structure. The competition and synergy of the AFM and FM interactions CuO2 layers dominate the transport and magnetic properties of Ba-doped La2CuSnO6.

Enhanced photodegradation of CuCo2O4 nanoflower for the dye degradation of Rhodamine B and Methyl Violet

The investigation examined into the effect of different hydrothermal reaction temperatures and durations on the formation of nanoflower-shaped CuCo2O4 nanostructures (CCO NPs). The structural, morphological, functional, optical, and magnetic properties of the synthesized CCO NPs were thoroughly examined. The optimal calcination temperature was determined using Thermogravimetric and Differential Thermal Analysis (TG/DTA), which identified 400 °C as the ideal temperature. Following X-ray Diffraction (XRD) analysis, pure CuCo2O4 samples were formed, with calculated average crystallite sizes of 27 nm for CCO-A, 48 nm for CCO-B, 30 nm for CCO-C, and 31 nm for CCO-D samples. Fourier Transform Infrared (FTIR) analysis provided additional confirmation of pure CuCo2O4 formation, with characteristic bands in the 665–662 cm-1 and 583–567 cm-1 ranges indicating the presence of CuO and CoO bonds. SEM, High-Resolution SEM (HRSEM) and High-Resolution Transmission Electron Microscopy (HRTEM) all supported the observation of a distinct flower-like structural morphology. The optical properties of an optimized sample were revealed by UV–Visible Diffuse Reflectance Spectroscopy (UV-DRS) analysis, which revealed a band gap of 3.3 eV. According to Vibrating Sample Magnetometer (VSM) results, the magnetic behavior of CCO-D nanostructures at room temperature exhibited paramagnetic characteristics. The saturation magnetization (Ms), remanent magnetization (Mr) and coercivity (Hc) values were determined to be 0.26218 emu/g, 2.7214 × 10–3 emu/g and 29.787 Oe, respectively. To evaluate photocatalytic performance, the CCO-D photocatalyst was used to degrade Methyl Violet and Rhodamine B dyes. CCO-D degraded MV dye with greater efficiency (93%) than RhB (85%) when exposed to sunlight. These findings highlight CCO-D's potential as a photocatalyst for the degradation of organic dyes.

Cation Incorporation into Copper Oxide Lattice at Highly Oxidizing Potentials.

Electrolyte cations can have significant effects on the kinetics and selectivity of electrocatalytic reactions. We show an atypical mechanism through which electrolyte cations can impact electrocatalyst performance─direct incorporation of the cation into the oxide electrocatalyst lattice. We investigate the transformations of copper electrodes in alkaline electrochemistry through operando X-ray absorption spectroscopy in KOH and Ba(OH)2 electrolytes. In KOH electrolytes, both the near-edge structure and extended fine-structure agree with previous studies; however, the X-ray absorption spectra vary greatly in Ba(OH)2 electrolytes. Through a combination of electronic structure modeling, near-edge simulation, and postreaction characterization, we propose that Ba2+ cations are directly incorporated into the lattice and form an ordered BaCuO2 phase at potentials more oxidizing than 200 mV vs the normal hydrogen electrode (NHE). BaCuO2 formation is followed by further oxidation to a bulk Cu3+-like BaxCuyOz phase at 900 mV vs NHE. Additionally, during reduction in Ba(OH)2 electrolyte, we find both Cu-O bonds and Cu-Ba scattering persist at potentials as low as -400 mV vs NHE. To our knowledge, this is the first evidence for direct oxidative incorporation of an electrolyte cation into the bulk lattice to form a mixed oxide electrode. The oxidative incorporation of electrolyte cations to form mixed oxides could open a new route for the in situ formation of active and selective oxidation electrocatalysts.

Study of Crystal Structure and Magnetics Properties in the Normal State of Electron-Doped Eu<sub>2-</sub><i><sub>x</sub></i>Ce<i><sub>x</sub></i>Cu<sub>0.97</sub>Zn<sub>0.03</sub>O<sub>4+</sub><i><sub>α-δ</sub></i> in Overdoped Regime

The normal state of high-Tc superconducting cuprates is crucial to understanding of the mechanism in superconductivity. There are two main ways to remove superconductivity so that the sample is in a normal state, that is by applying a large magnetic field or adding impurities such as Zn to the sample. To investigate the crystal structure and magnetic properties in the normal state of electron-doped high-Tc cuprates in overdoped regime, Eu2-xCexCu0.97Zn0.03O4+α-δ (ECCZO) with x = 0.16, 0.17, 0.18, and 0.19 has been synthesized by the solid-state reaction method. The crystal structure and magnetic properties of the samples were characterized by XRD and SQUID measurements. The results of XRD measurements shows all samples have T’-structure and the values of lattice parameters a, CuO bond length, and crystallite size increased with increasing x. On other hand, the value of lattice parameters c decreased with increasing x, causing the expansion of the tetragonal unit cell in the horizontal direction. From susceptibility measurements, in the normal state with 3% of Zn impurity all samples have the paramagnetic behaviour. The magnetic parameters of these samples analysed by the Curie law. With increasing of Ce concentration, the C and the are increased. The increase in the magnetic parameters since the increasing in magnetic ordering.

Rational Design of Cu-Doped Tetrahedron of Spinel Oxide for High-Performance Nitric Oxide Electrochemical Sensor

The real-time detection of nitric oxide (NO) in living cells is essential to reveal its physiological processes. However, the popular electrochemical detection strategy is limited to the utilization of noble metals. The development of new detection candidates without noble metal species still maintaining excellent catalytic performance has become a big challenge. Herein, we propose a spinel oxide doped with heteroatom-Cu-doped Co3O4 (Cu-Co3O4) for the sensitive and selective detection of NO release from the living cells. The material is strategically designed with Cu occupying the tetrahedral (Td) center of Co3O4 through the formation of a Cu-O bond. The introduced Cu regulates the local coordination environment and optimizes the electronic structure of Co3O4, hybridizing with the N 2p orbital to enhance charge transfer. The CuTd site can well inhibit the current response to nitrite (NO2-), resulting in a high improvement in the electrochemical oxidation of NO. The selectivity of Cu-Co3O4 can be markedly improved by the pore size of the molecular sieve and the negative charge on the surface. The rapid transmission of electrons is due to the fact that Cu-Co3O4 can be uniformly and densely in situ grown on Ti foil. The rationally designed Cu-Co3O4 sensor displays excellent catalytic activity toward NO oxidation with a low limit of detection of 2.0 nM (S/N = 3) and high sensitivity of 1.9 μA nM-1 cm-2 in cell culture medium. The Cu-Co3O4 sensor also shows good biocompatibility to monitor the real-time NO release from living cells (human umbilical vein endothelial cells: HUVECs; macrophage: RAW 264.7 cells). It was found that a remarkable response to NO was obtained in different living cells when stimulated by l-arginine (l-Arg). Moreover, the developed biosensor could be used for real-time monitoring of NO released from macrophages polarized to a M1/M2 phenotype. This cheap and convenient doping strategy shows universality and can be used for sensor design of other Cu-doped transition metal materials. The Cu-Co3O4 sensor presents an excellent example through the design of proper materials to implement unique sensing requirements and sheds light on the promising strategy for electrochemical sensor fabrication.

Low-energy gap emerging from confined nematic states in extremely underdoped cuprate superconductors

The pairing mechanism of high-temperature superconductivity in cuprates is regarded as one of the most challenging issues in condensed matter physics. The core issue concerns how the Cooper pairs are formed. Here we report spin-resolved tunneling measurements on extremely underdoped Bi2Sr2−xLaxCuO6+δ. Our data reveal that, when holes are doped into the system, the antiferromagnetic order is destroyed, while at the same time an increasing density of states (DOS) peaked at around 200 meV appears within the charge transfer gap. Meanwhile, an electronic structure with 4a0 × 4a0 basic plaquettes emerges inhomogeneously, with an area fraction that grows with hole doping. In each plaquette, there are some unidirectional bars (along the Cu-O bond) which are most pronounced at energies near peaks in the DOS around at 25 meV, with an intensity that is especially pronounced at oxygen sites. We argue that the atomically resolved low-energy DOS and related gap are closely associated with some kinds of density waves, possibly reflecting modulations of the electron density, or a pair-density wave, i.e. a modulation of the local pairing. Our work sheds new light on the doping induced electronic evolution from the “parent” insulator of the cuprate superconductors.

Copper Complex Catalyzed Two-Electron and Proton Shuttle Mechanism of O-O Bond Formation from DFT-Based Metadynamics Simulations.

We performed first-principles metadynamics simulations to explore the mechanistic pathway of oxygen-oxygen bond formation catalyzed by cis-bis(hydroxo) and cis-(hydroxo)oxo copper complexes. The ligands of considered complexes involve modified bipyridine ligands with oxo and hydroxo groups on 6, 6' positions. The study focuses on the kinetics and thermodynamics of the oxygen-oxygen bond formation. The individual migration of the proton to the hydroxyl group and hydroxide to the oxo and hydroxo moieties of the complexes was examined. The proton transfer requires more kinetic barrier than the hydroxide migration. The nature of the electronic density was analyzed with the help of spin population analysis. The molecular orbitals and natural orbital analysis were carried out to examine the nature of the orbitals involved in the oxygen-oxygen bond formation. The σ*(dx2-y2-px) molecular orbital of the Cu-O or Cu-OH bond overlaps with the pz orbital of the hydroxide ion in forming the oxygen-oxygen bond. The two-electron two-centered (2e--2C) bond is observed in the oxygen-oxygen bond formation. In the oxidation process, these ligands stabilize the electron density from the water or hydroxide ion. These redox-active ligands also help stabilize the formed hydrogen peroxide or peroxide complexes.

Application of physical vapor deposition technology for practical utilization of nano-size copper oxide for lead uptake from solution: kinetics, equilibrium, and recycling studies

For the first time, copper oxide-coated glass beads (CuO-GBs) were fabricated using physical vapor deposition (PVD) technology for sequestrating Pb2+ ions from solution is addressed. Compared to other coating procedures, PVD offered high-stability uniform CuO nano-layers attached with 3.0-mm glass beads. Heating of copper oxide-coated glass beads after deposition was rather necessary to achieve the best stability of the nano-adsorbent. Detection of nano-size copper oxide on the beads was made by FTIR (intense peak at 655cm-1 for CuO bond stretching) and XRF (Cu peak at 8.0keV). Scanning electron micrographs taken at high magnification power indicated the presence of CuO in nano-range deposited over glass beads. The maximum deposited amount of CuO on the beads was 1.1% and accomplished at the following operational conditions: internal pressure 10-5mmHg, Ar flow rate 8.0mL/min, voltage 84V, pre-sputtering time 20s, total sputtering time 10.0min, and post-heating temperature 150°C for 3h. A univariate analysis indicated that the optimum Pb2+ uptake by CuO-GBs from solution was achieved at pH 7.0-8.0, 7 beads/50mL, 120-min contact time, and 15-mg/L initial concentration. Kinetic data for Pb2+ uptake was best presented by a pseudo-second-order model with a relative prediction error of 3.2 and 5.1% for GBs and CuO-GBs, respectively. On the other hand, Pb2+ equilibrium isotherms at 25°C were fairly presented by the Langmuir model, and the predicted saturation values were 5.48 and 15.69mg/g for GBs and CuO-GBs, respectively. CuO and CuO-GBs had similar Pb2+ saturation values (~ 16mg/g), although the latter demonstrated 4 times faster kinetic, thanks to fixation CuO on glass beads. Moreover, the chemical stability of copper oxide-coated glass beads was tested under different conditions. Recycling of copper oxide-coated glass beads was also investigated, and 90% of the surface was recovered using 0.01-M HNO3.