Showing papers on "Copper published in 2022"

Copper-induced cell death

Abstract: Description Excess copper causes mitochondrial protein aggregation and triggers a distinct form of cell death Copper and other trace metals are essential for life. However, it is important that these metals are present at the right amount in cells. Too little metal can impair the function of important metal-binding enzymes, and too much metal can overwhelm a cell, leading to death. In humans, mutations that cause excess copper accumulation are life-threatening, and yet there may exist a window such that more focused increases of intracellular copper can be used to selectively kill cancer cells (1). A better understanding of how copper accumulation causes cellular toxicity is therefore of great interest. On page 1254 of this issue, Tsvetkov et al. (2) reveal that copper toxicity involves the disruption of specific mitochondrial metabolic enzymes, triggering an unusual mechanism of cell death. This mechanism may explain the pathology associated with genetic copper overload disorders and suggest new ways to harness copper toxicity to treat cancer.

Stabilizing Cu²⁺ Ions by Solid Solutions to Promote CO₂ Electroreduction to Methane

Abstract: Copper is the only metal catalyst that can perform the electrocatalytic CO2 reduction reaction (CRR) to produce hydrocarbons and oxygenates. Its surface oxidation state determines the reaction pathway to various products. However, under the cathodic potential of CRR conditions, the chemical composition of most Cu-based catalysts inevitably undergoes electroreduction from Cu2+ to Cu0 or Cu1+ species, which is generally coupled with phase reconstruction and the formation of new active sites. Since the initial Cu2+ active sites are hard to retain, there have been few studies about Cu2+ catalysts for CRR. Herein we propose a solid-solution strategy to stabilize Cu2+ ions by incorporating them into a CeO2 matrix, which works as a self-sacrificing ingredient to protect Cu2+ active species. In situ spectroscopic characterization and density functional theory calculations reveal that compared with the conventionally derived Cu catalysts with Cu0 or Cu1+ active sites, the Cu2+ species in the solid solution (Cu-Ce-Ox) can significantly strengthen adsorption of the *CO intermediate, facilitating its further hydrogenation to produce CH4 instead of dimerization to give C2 products. As a result, different from most of the other Cu-based catalysts, Cu-Ce-Ox delivered a high Faradaic efficiency of 67.8% for CH4 and a low value of 3.6% for C2H4.

Copper-induced tumor cell death mechanisms and antitumor theragnostic applications of copper complexes.

Abstract: Recent studies found that unbalanced copper homeostasis affect tumor growth, causing irreversible damage. Copper can induce multiple forms of cell death, including apoptosis and autophagy, through various mechanisms, including reactive oxygen species accumulation, proteasome inhibition, and antiangiogenesis. Hence, copper in vivo has attracted tremendous attention and is in the research spotlight in the field of tumor treatment. This review first highlights three typical forms of copper's antitumor mechanisms. Then, the development of diverse biomaterials and nanotechnology allowing copper to be fabricated into diverse structures to realize its theragnostic action is discussed. Novel copper complexes and their clinical applications are subsequently described.

Accelerating CO2 Electroreduction to Multicarbon Products via Synergistic Electric-Thermal Field on Copper Nanoneedles.

Abstract: Electrochemical CO2 reduction is a promising way to mitigate CO2 emissions and close the anthropogenic carbon cycle. Among products from CO2RR, multicarbon chemicals, such as ethylene and ethanol with high energy density, are more valuable. However, the selectivity and reaction rate of C2 production are unsatisfactory due to the sluggish thermodynamics and kinetics of C-C coupling. The electric field and thermal field have been studied and utilized to promote catalytic reactions, as they can regulate the thermodynamic and kinetic barriers of reactions. Either raising the potential or heating the electrolyte can enhance C-C coupling, but these come at the cost of increasing side reactions, such as the hydrogen evolution reaction. Here, we present a generic strategy to enhance the local electric field and temperature simultaneously and dramatically improve the electric-thermal synergy desired in electrocatalysis. A conformal coating of ∼5 nm of polytetrafluoroethylene significantly improves the catalytic ability of copper nanoneedles (∼7-fold electric field and ∼40 K temperature enhancement at the tips compared with bare copper nanoneedles experimentally), resulting in an improved C2 Faradaic efficiency of over 86% at a partial current density of more than 250 mA cm-2 and a record-high C2 turnover frequency of 11.5 ± 0.3 s-1 Cu site-1. Combined with its low cost and scalability, the electric-thermal strategy for a state-of-the-art catalyst not only offers new insight into improving activity and selectivity of value-added C2 products as we demonstrated but also inspires advances in efficiency and/or selectivity of other valuable electro-/photocatalysis such as hydrogen evolution, nitrogen reduction, and hydrogen peroxide electrosynthesis.

Steel-copper functionally graded material produced by twin-wire and arc additive manufacturing (T-WAAM)

Abstract: In this work, a functionally graded material (FGM) part was fabricated by depositing a Cu-based alloy on top of a high strength low alloy (HSLA) steel by twin-wire and arc additive manufacturing (T-WAAM). Copper and steel parts are of interest in many industries since they can combine high thermal/electrical conductivity, wear resistance with excellent mechanical properties. However, mixing copper with steel is difficult due to mismatches in the coefficient of thermal expansion, in the melting temperature, and crystal structure. Moreover, the existence of a miscibility gap during solidification, when the melt is undercooled, causes serious phase separation and segregation during solidification which greatly affects the mechanical properties. Copper and steel control samples and the functionally graded material specimen were fabricated and investigated using optical microscopy, scanning electron microscopy, and high energy synchrotron X-ray diffraction. Retained δ-ferrite was found in a Cu matrix at the interface region due to regions with mixed composition. A smooth gradient of hardness and electric conductivity along the FGM sample height was obtained. An ultimate tensile strength of 690 MPa and an elongation at fracture of 16.6% were measured in the FGM part.

Copper-catalyzed radical relay in C(sp3)-H functionalization.

Abstract: Radical-involved transition metal (TM) catalysis has greatly enabled new reactivities in recent decades. Copper-catalyzed radical relay offers enormous potential in C(sp3)-H functionalization which combines the unique regioselectivity of hydrogen atom transfer (HAT) and the versatility of copper-catalyzed cross-coupling. More importantly, significant progress has been achieved in asymmetric C-H functionalization through judicious ligand design. This tutorial review will highlight the recent advances in this rapidly growing area, and we hope this survey will inspire future strategic developments for selective C(sp3)-H functionalization.

Steering the structure and selectivity of CO2 electroreduction catalysts by potential pulses

Abstract: Abstract Convoluted selectivity trends and a missing link between reaction product distribution and catalyst properties hinder practical applications of the electrochemical CO 2 reduction reaction (CO 2 RR) for multicarbon product generation. Here we employ operando X-ray absorption and X-ray diffraction methods with subsecond time resolution to unveil the surprising complexity of catalysts exposed to dynamic reaction conditions. We show that by using a pulsed reaction protocol consisting of alternating working and oxidizing potential periods that dynamically perturb catalysts derived from Cu 2 O nanocubes, one can decouple the effect of the ensemble of coexisting copper species on the product distribution. In particular, an optimized dynamic balance between oxidized and reduced copper surface species achieved within a narrow range of cathodic and anodic pulse durations resulted in a twofold increase in ethanol production compared with static CO 2 RR conditions. This work thus prepares the ground for steering catalyst selectivity through dynamically controlled structural and chemical transformations.

A Site Distance Effect Induced by Reactant Molecule Matchup in Single-Atom Catalysts for Fenton-like Reactions.

Abstract: Understanding the site interaction nature of single-atom catalysts (SACs), especially densely populated SACs, is vital for their application to various catalytic reactions. Herein, we report a site distance effect, which emphasizes how well the distance of the adjacent copper atoms (denoted as dCu1-Cu1) matches with the reactant peroxydisulfate (PDS) molecular size determines the Fenton-like reaction reactivity on the carbon-supported SACs. The optimized dCu1-Cu1 in the range of 5-6 Å that matches the molecular size of PDS endows a nearly two times higher turnover frequency than that of dCu1-Cu1 beyond this range, accordingly achieving the record-breaking kinetics for emerging organic contaminant oxidation. Further studies suggest that this site distance effect originates from the alteration of PDS adsorption to a dual-site structure on Cu1-Cu1 sites when dCu1-Cu1 falls in 5-6 Å, significantly enhancing the interfacial charge transfer and consequently resulting in the most efficient catalyst for PDS activation so far.

Exploration of Twin-Modified Grain Boundary Engineering in Metallic Copper Predominated Electromagnetic Wave Absorber.

Abstract: High density and skin effect restrict the research progress of metal predominated electromagnetic wave absorbing (EMA) materials. Although some works try to solve it, they do not focus on the metal itself and do not involve the optimization of the active site of the inherent defects of the metal. In this work, the modulation of morphology, composition, interface, defects, and conductivity is achieved by adjusting the ratio of copper salt to reducing agent chitosan. Uniquely, the appearance of twin boundaries (TBs) accelerates the ability of the homogeneous interfaces to transfer charges, resists the oxidation of metal Cu0 , keeps the high electric conductivity of Cu0 nanoparticles, and enhances the conduction loss, which provides a boost for electromagnetic wave dissipation. As a result, the metal Cu0 predominated absorber (Cu-NC (N-doped carbon)-10,) exhibits an ultra-width effective absorption band of 8.28 GHz (9.72-18.00 GHz) at a thickness of 2.47 mm and the minimum reflection loss (RL) value of -63.8 dB with a thickness of 2.01 mm. In short, this work explores the EM regulation mechanism of TBs compared with grain boundaries (GBs), which provides a new insight for the rational design of metal predominated EMA materials.

The role of Cu1–O3 species in single-atom Cu/ZrO2 catalyst for CO2 hydrogenation

Abstract: Copper-based catalysts for the hydrogenation of CO2 to methanol have attracted much interest. The complex nature of these catalysts, however, renders the elucidation of their structure–activity properties difficult. Here we report a copper-based catalyst with isolated active copper sites for the hydrogenation of CO2 to methanol. It is revealed that the single-atom Cu–Zr catalyst with Cu1–O3 units contributes solely to methanol synthesis around 180 °C, while the presence of small copper clusters or nanoparticles with Cu–Cu structural patterns are responsible for forming the CO by-product. Furthermore, the gradual migration of Cu1–O3 units with a quasiplanar structure to the catalyst surface is observed during the catalytic process and accelerates CO2 hydrogenation. The highly active, isolated copper sites and the distinguishable structural pattern identified here extend the horizon of single-atom catalysts for applications in thermal catalytic CO2 hydrogenation and could guide the further design of high-performance copper-based catalysts to meet industrial demand. Copper-based catalysts are traditionally very effective for the hydrogenation of CO2 to methanol, although control over the active site has remained elusive. Here, the authors design a Cu1/ZrO2 single-atom catalyst featuring a Cu1–O3 site responsible for a remarkable performance at 180 °C.

Regulating surface oxygen species on copper (I) oxides via plasma treatment for effective reduction of nitrate to ammonia

Abstract: Electrochemical nitrate reduction (NO3-RR) to synthesize ammonia is considered to be a promising strategy to enable artificial nitrogen cycle. Great efforts have been devoted to improving the efficiency and selectivity of the electrocatalysts for NO3-RR. Herein, we demonstrate that tuning the oxygen chemical environment via Ar plasma treatment is an effective approach to improve the NO3-RR activity of Cu2O. Combining synchrotron-based X-ray absorption spectroscopy and other advanced spectroscopy techniques, we find that plasma treatment can effectively promote the formation of oxygen vacancies and hydroxyl groups on Cu2O surface. In-situ diffuse-reflectance infrared Fourier transform spectroscopy and density functional theory calculation further reveal that oxygen vacancies and hydroxyl groups facilitate the adsorption of nitrate and proton transfer on the Cu2O surface, thus leading to improved ammonia selectivity. Our results clarify the critical role of surface oxygen species for NO3-RR and can guide the design of other electrocatalysts via surface engineering.

Adsorption of copper and nickel by using sawdust chitosan nanocomposite beads – A kinetic and thermodynamic study

Abstract: The adsorption behavior of biomaterial activated Sawdust-Chitosan nanocomposite beads (SDNCB) powder was investigated along with synthesis and experimental techniques approaches to study the removal efficiency of some heavy metal ions including Ni (II) and Cu (II) ions from aqueous solutions by assessing the surface-modified activated carbon by the cost-effective non-conventional method. Structural analysis of the entitled compound was evaluated by the PXRD techniques and its surface morphology was inferred by the following techniques: TEM, EDAX. The behavior of the functional group presents in the compound was discussed using the FTIR technique. Such parameters like dosage, pH, time, temperature, and initial concentration of copper and nickel were associated with this to examine the effect of adsorption of heavy elements that exist in the portable solution. Further, the cellulose and chitosan beads complex material have an appropriate surface area, it demonstrated metal ions removal efficiency was more appreciable due to the action of activated carbon, where this showed fast rate sorption kinetics due to strong involvement of Cu+ & Ni+ towards cellulose and chitosan's functional groups in the bio composite. The isotherm model so-called Langmuir, Freundlich, and Temkin model was utilized to plot the experimental adsorption dataset to infer the maximum adsorption capacity. Based on this model, the adsorption properties of the beads treated compound was determined by plotting the graphs in which sorption intensity (n) which implies expected sorption, and the correlation value are 1.989, 0.998, and 0,981 respectively.

Partially sintered copper‒ceria as excellent catalyst for the high-temperature reverse water gas shift reaction

Abstract: For high-temperature catalytic reaction, it is of significant importance and challenge to construct stable active sites in catalysts. Herein, we report the construction of sufficient and stable copper clusters in the copper‒ceria catalyst with high Cu loading (15 wt.%) for the high-temperature reverse water gas shift (RWGS) reaction. Under very harsh working conditions, the ceria nanorods suffered a partial sintering, on which the 2D and 3D copper clusters were formed. This partially sintered catalyst exhibits unmatched activity and excellent durability at high temperature. The interaction between the copper and ceria ensures the copper clusters stably anchored on the surface of ceria. Abundant in situ generated and consumed surface oxygen vacancies form synergistic effect with adjacent copper clusters to promote the reaction process. This work investigates the structure-function relation of the catalyst with sintered and inhomogeneous structure and explores the potential application of the sintered catalyst in C1 chemistry.

Large-Area Perovskite-Related Copper Halide Film for High-Resolution Flexible X-ray Imaging Scintillation Screens

Abstract: Flexible copper halide films of 400 cm2 area were fabricated with outstanding mechanical stability, excellent film uniformity, nearly 100% photoluminescence quantum yields, and resistance to water and heat. The re-absorption-free X-ray imaging scintillators engineered based on these films exhibit superior scintillation performance with a detection limit as low as 48.6 nGy/s and 17 lp/mm X-ray imaging resolution, representing the highest imaging resolution for powder-based screens.

Electrocatalytic CO2-to-C2+ with Ampere-Level Current on Heteroatom-Engineered Copper via Tuning *CO Intermediate Coverage.

Abstract: An ampere-level current density of CO2 electrolysis is critical to realize the industrial production of multicarbon (C2+) fuels. However, under such a large current density, the poor CO intermediate (*CO) coverage on the catalyst surface induces the competitive hydrogen evolution reaction, which hinders CO2 reduction reaction (CO2RR). Herein, we report reliable ampere-level CO2-to-C2+ electrolysis by heteroatom engineering on Cu catalysts. The Cu-based compounds with heteroatom (N, P, S, O) are electrochemically reduced to heteroatom-derived Cu with significant structural reconstruction under CO2RR conditions. It is found that N-engineered Cu (N-Cu) catalyst exhibits the best CO2-to-C2+ productivity with a remarkable Faradaic efficiency of 73.7% under -1100 mA cm-2 and an energy efficiency of 37.2% under -900 mA cm-2. Particularly, it achieves a C2+ partial current density of -909 mA cm-2 at -1.15 V versus reversible hydrogen electrode, which outperforms most reported Cu-based catalysts. In situ spectroscopy indicates that heteroatom engineering adjusts *CO adsorption on Cu surface and alters the local H proton consumption in solution. Density functional theory studies confirm that the high adsorption strength of *CO on N-Cu results from the depressed HER and promoted *CO adsorption on both bridge and atop sites of Cu, which greatly reduces the energy barrier for C-C coupling.

An Enzyme‐Engineered Nonporous Copper(I) Coordination Polymer Nanoplatform for Cuproptosis‐Based Synergistic Cancer Therapy

Abstract: Cuproptosis, a newly identified form of regulated cell death that is copper‐dependent, offers great opportunities for exploring the use of copper‐based nanomaterials inducing cuproptosis for cancer treatment. Here, a glucose oxidase (GOx)‐engineered nonporous copper(I) 1,2,4‐triazolate ([Cu(tz)]) coordination polymer (CP) nanoplatform, denoted as GOx@[Cu(tz)], for starvation‐augmented cuproptosis and photodynamic synergistic therapy is developed. Importantly, the catalytic activity of GOx is shielded in the nonporous scaffold but can be “turned on” for efficient glucose depletion only upon glutathione (GSH) stimulation in cancer cells, thereby proceeding cancer starvation therapy. The depletion of glucose and GSH sensitizes cancer cells to the GOx@[Cu(tz)]‐mediated cuproptosis, producing aggregation of lipoylated mitochondrial proteins, the target of copper‐induced toxicity. The increased intracellular hydrogen peroxide (H2O2) levels, due to the oxidation of glucose, activates the type I photodynamic therapy (PDT) efficacy of GOx@[Cu(tz)]. The in vivo experimental results indicate that GOx@[Cu(tz)] produces negligible systemic toxicity and inhibits tumor growth by 92.4% in athymic mice bearing 5637 bladder tumors. This is thought to be the first report of a cupreous nanomaterial capable of inducing cuproptosis and cuproptosis‐based synergistic therapy in bladder cancer, which should invigorate studies pursuing rational design of efficacious cancer therapy strategies based on cuproptosis.

A metal-supported single-atom catalytic site enables carbon dioxide hydrogenation

Abstract: Abstract Nitrogen-doped graphene-supported single atoms convert CO 2 to CO, but fail to provide further hydrogenation to methane – a finding attributable to the weak adsorption of CO intermediates. To regulate the adsorption energy, here we investigate the metal-supported single atoms to enable CO 2 hydrogenation. We find a copper-supported iron-single-atom catalyst producing a high-rate methane. Density functional theory calculations and in-situ Raman spectroscopy show that the iron atoms attract surrounding intermediates and carry out hydrogenation to generate methane. The catalyst is realized by assembling iron phthalocyanine on the copper surface, followed by in-situ formation of single iron atoms during electrocatalysis, identified using operando X-ray absorption spectroscopy. The copper-supported iron-single-atom catalyst exhibits a CO 2 -to-methane Faradaic efficiency of 64% and a partial current density of 128 mA cm −2 , while the nitrogen-doped graphene-supported one produces only CO. The activity is 32 times higher than a pristine copper under the same conditions of electrolyte and bias.

Partially sintered copper‒ceria as excellent catalyst for the high-temperature reverse water gas shift reaction

Abstract: For high-temperature catalytic reaction, it is of significant importance and challenge to construct stable active sites in catalysts. Herein, we report the construction of sufficient and stable copper clusters in the copper‒ceria catalyst with high Cu loading (15 wt.%) for the high-temperature reverse water gas shift (RWGS) reaction. Under very harsh working conditions, the ceria nanorods suffered a partial sintering, on which the 2D and 3D copper clusters were formed. This partially sintered catalyst exhibits unmatched activity and excellent durability at high temperature. The interaction between the copper and ceria ensures the copper clusters stably anchored on the surface of ceria. Abundant in situ generated and consumed surface oxygen vacancies form synergistic effect with adjacent copper clusters to promote the reaction process. This work investigates the structure-function relation of the catalyst with sintered and inhomogeneous structure and explores the potential application of the sintered catalyst in C1 chemistry.

Confined Growth of Silver–Copper Janus Nanostructures with {100} Facets for Highly Selective Tandem Electrocatalytic Carbon Dioxide Reduction

Abstract: Electrocatalytic carbon dioxide reduction reaction (CO2RR) holds significant potential to promote carbon neutrality. However, the selectivity toward multicarbon products in CO2RR is still too low to meet practical applications. Here the authors report the delicate synthesis of three kinds of Ag–Cu Janus nanostructures with {100} facets (JNS‐100) for highly selective tandem electrocatalytic reduction of CO2 to multicarbon products. By controlling the surfactant and reduction kinetics of Cu precursor, the confined growth of Cu with {100} facets on one of the six equal faces of Ag nanocubes is realized. Compared with Cu nanocubes, Ag65–Cu35 JNS‐100 demonstrates much superior selectivity for both ethylene and multicarbon products in CO2RR at less negative potentials. Density functional theory calculations reveal that the compensating electronic structure and carbon monoxide spillover in Ag65–Cu35 JNS‐100 contribute to the enhanced CO2RR performance. This study provides an effective strategy to design advanced tandem catalysts toward the extensive application of CO2RR.

A metal-supported single-atom catalytic site enables carbon dioxide hydrogenation

Abstract: Abstract Nitrogen-doped graphene-supported single atoms convert CO 2 to CO, but fail to provide further hydrogenation to methane – a finding attributable to the weak adsorption of CO intermediates. To regulate the adsorption energy, here we investigate the metal-supported single atoms to enable CO 2 hydrogenation. We find a copper-supported iron-single-atom catalyst producing a high-rate methane. Density functional theory calculations and in-situ Raman spectroscopy show that the iron atoms attract surrounding intermediates and carry out hydrogenation to generate methane. The catalyst is realized by assembling iron phthalocyanine on the copper surface, followed by in-situ formation of single iron atoms during electrocatalysis, identified using operando X-ray absorption spectroscopy. The copper-supported iron-single-atom catalyst exhibits a CO 2 -to-methane Faradaic efficiency of 64% and a partial current density of 128 mA cm −2 , while the nitrogen-doped graphene-supported one produces only CO. The activity is 32 times higher than a pristine copper under the same conditions of electrolyte and bias.