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Copper peroxide
Copper peroxide
Copper peroxide
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Copper(II) peroxide
Names
IUPAC name
Copper(II) peroxide
Identifiers
3D model (JSmol)
ChemSpider
  • InChI=1S/Cu.O2/c;1-2/q+2;-2
    Key: CNBDXDKFMUKCIQ-UHFFFAOYSA-N
  • [Cu+2].[O-][O-]
Properties
CuO2
Molar mass 95.945 g/mol
Appearance Dark olive-green solid
Related compounds
Related compounds
 Copper(IV) oxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Copper peroxide is a hypothetical inorganic compound with the chemical formula CuO2. The 1:2 ratio of copper and oxygen would be consistent with copper in its common +2 oxidation state and a peroxide group. Although samples of this composition have not been isolated, CuO2 has attracted interest from computational perspective. One highly cited analysis concludes that gaseous CuO2 is a superoxide, with copper in a +1 oxidation state: Cu+O−2.[1]

History

[edit]

Species claimed to be "copper peroxide" have been claimed, e.g., by the reaction of cold solutions of Schweizer's reagent—a source of copper(II)—and hydrogen peroxide.[2] The Schweizer's reagent used must not contain excess ammonia.[2]

It was once claimed to result from the very slow reaction of finely divided cupric oxide with cold hydrogen peroxide.[3]

Several molecular copper peroxide complexes have been reported, but these species always feature supporting organic ligands.[4]

References

[edit]
Revisions and contributorsEdit on WikipediaRead on Wikipedia

Copper peroxide

View on Grokipedia
from Grokipedia
Copper peroxide is a hypothetical inorganic compound with the chemical formula CuO₂, consisting of copper in the +2 oxidation state coordinated to a peroxide dianion (O₂²⁻). It is highly unstable and has not been isolated as a stable bulk solid, readily decomposing under acidic conditions or upon heating to release copper(II) ions, hydrogen peroxide, or oxygen gas. Due to its instability, copper peroxide is challenging to isolate and store, often existing as an intermediate in reactions involving copper(II) compounds and oxidants. It is typically prepared by coordinating hydrogen peroxide (H₂O₂) with Cu²⁺ ions in the presence of hydroxide ions, such as through the reaction of copper(II) hydroxide with H₂O₂. Advancements reported in 2019 include its synthesis as stable nanodots or nanoparticles via coordination-driven methods, enabling controlled decomposition in targeted environments. These nanomaterials exhibit pH-responsive behavior, remaining intact in neutral conditions but dissociating in acidic media to generate reactive species. Copper peroxide has garnered attention for its role in and , particularly in chemodynamic (CDT) for , where it self-supplies H₂O₂ in the acidic to fuel the Fenton reaction, producing cytotoxic hydroxyl radicals (•OH) that induce cell death. Additionally, CuO₂-based nanocomposites demonstrate potent antibacterial activity against pathogens like and Staphylococcus aureus by generating upon pH-triggered decomposition, with applications in wound dressings and coatings. Its electronic properties, including a HOMO-LUMO gap of approximately 1.6–1.8 eV in cluster forms, also suggest potential in superconducting materials and electrocatalysis.

Overview

Definition and nomenclature

Copper peroxide is an inorganic compound nominally represented by the formula CuO₂, consisting of copper in the +2 oxidation state bonded to a peroxide ligand (O₂²⁻). It is commonly referred to as copper(II) peroxide to explicitly indicate the oxidation state of copper. This nomenclature distinguishes it from copper oxides, such as copper(I) oxide (Cu₂O) and copper(II) oxide (CuO), in which oxygen exists as discrete oxide ions (O²⁻) rather than as a peroxide unit, and from potential copper superoxides involving the superoxide anion (O₂⁻). The oxidation state in copper peroxide is formally Cu²⁺ with O₂²⁻, though spectroscopic analyses of related copper-oxygen species sometimes suggest an alternative Cu⁺ O₂⁻ superoxide description depending on coordination and bonding. Actual isolated species referred to as copper peroxides include basic copper peroxide, with the approximate formula CuO·H₂O₂ (or CuO₂·H₂O), which is an adduct of copper(II) hydroxide and hydrogen peroxide rather than a stoichiometric peroxide and thus misnamed as a pure peroxide compound. Another related species is Cu₂O₂, known as dicopper peroxide or copper(I) peroxide, featuring two Cu⁺ ions with a peroxide ligand, but it is often misnamed due to structural ambiguities and instability leading to oxide-like behavior. Pure copper peroxide (CuO₂) remains a hypothetical compound, as it has not been isolated in a stable, pure crystalline form owing to its thermodynamic instability and propensity to decompose into copper(II) oxide (CuO) and molecular oxygen (O₂). Although recent advances have enabled the synthesis of CuO₂ in nanoscale forms, such as nanodots for specific applications, these are stabilized by their size and environment rather than representing bulk material, underscoring the challenges in achieving a persistent solid phase. Computational studies on the gaseous CuO₂ support its peroxide-like character, predicting a bent or side-on geometry where the peroxo (O₂²⁻) unit binds to Cu(II). These calculations indicate a peroxo coordination mode, though the overall structure is energetically unfavorable relative to products. Such modeling highlights the kinetic barriers that prevent isolation under standard conditions. Related to the ideal CuO₂, basic copper peroxide is the most commonly referenced analog, with an approximate formula of CuO·H₂O₂ (or CuO₂·H₂O). This compound forms as a yellow-brown upon reaction of copper(II) salts with under cold, neutral conditions, but it exhibits limited stability, decomposing more rapidly when moist and slowly in dry form to release H₂O₂ or evolve O₂. Anhydrous Cu₂O₂, envisioned as a peroxide-bridged dimer with a rhomboidal Cu₂O₂ core, has been computationally and in transient species but lacks isolation as a discrete bulk compound; instead, it manifests in stabilized molecular complexes. These complexes, such as [Cu(η²-O₂)] with supporting ligands like β-diketiminates or hydrotris(pyrazolyl)borates, demonstrate enhanced stability through coordination, allowing reversible O₂ binding and spectroscopic of the peroxo moiety.
CompoundFormulaColorStability
Pure copper peroxideCuO₂N/A (hypothetical)Thermodynamically unstable; decomposes to CuO + ½O₂
Basic copper peroxideCuO·H₂O₂Yellow-brown, amorphousModerately unstable; dry form decomposes slowly, moist form faster
copper peroxideCu₂O₂N/A (dimeric core)Unstable in isolation; stable in ligand-supported molecular complexes

Chemical and physical properties

Molecular structure

The anhydrous , CuO₂, is considered hypothetical, with no isolated bulk samples reported. (DFT) calculations on the monomeric form identify key , including a bent CuOO structure as the for the neutral and a linear OCuO configuration for the anion. In the bent CuOO , the coordinates end-on to the dioxygen unit, with a Cu-O of approximately 1.85 and an O-O of 1.342 , consistent with (O₂⁻) rather than (O₂²⁻) character. The linear OCuO , while higher in energy for the neutral , features more covalent bonding between and oxygen atoms, though its O-O separation remains indicative of assignment in most computational models. Distinction between superoxide and peroxide ligation in copper-dioxygen complexes relies on the O-O bond length, with values exceeding 1.49 signifying a (bond order 1) and those around 1.2–1.3 indicating (bond order 1.5); in copper peroxo complexes, observed O-O lengths typically fall in the 1.35–1.45 range, reflecting partial multiple bonding. For the bent peroxo coordination mode, the O-O unit binds side-on to copper, potentially adopting a bent with Cu-O-O angles near 70–90°, whereas end-on ligation favors more linear arrangements. In contrast, the known basic copper peroxide, formulated as CuO·H₂O₂ or equivalently Cu₂O₂·H₂O, is an , as evidenced by X-ray diffraction patterns lacking sharp peaks indicative of crystallinity. of this compound reveals the characteristic O-O stretching frequency for peroxo groups at 800–900 cm⁻¹, supporting the presence of intact O₂²⁻ moieties coordinated to . The bonding in these species involves dative interaction from the peroxide ligand's oxygen lone pairs to the Cu²⁺ center, forming a σ-donor complex with possible π-backbonding contributions. Due to the d⁹ electronic configuration of Cu(II), Jahn-Teller distortion manifests in the , often resulting in elongated axial Cu-O bonds in pseudo-octahedral or square-planar environments involving peroxo ligation. Schematic representations depict the hypothetical CuO₂ monomer as a bent Cu-OO unit with the dioxygen tilted relative to the Cu-O axis, while the basic peroxide adopts a polymeric network where Cu²⁺ ions are bridged by bidentate peroxo (O₂²⁻) and hydroxo (OH⁻) groups, forming extended chains or layers without discrete molecular units. Recent syntheses of CuO₂ nanodots via coordination-driven methods show a structure where H₂O₂ coordinates to Cu²⁺ in the presence of hydroxide, exhibiting peroxide character confirmed by pH-responsive decomposition.

Physical characteristics

Copper peroxide materials, particularly in their basic or hydrated forms such as CuO·H₂O₂ or CuO₂·H₂O, typically appear as a or precipitate. No confirmed color is reported for the hypothetical form, CuO₂. This coloration in basic forms arises from the electronic structure involving copper-oxygen bonding, as detailed in molecular analyses. The of CuO₂ is 95.55 g/mol, while the monohydrate CuO₂·H₂O has a of 113.57 g/mol. These compounds exhibit an estimated of approximately 3.5 g/cm³, though precise measurements are limited due to instability. Copper peroxide is insoluble in but decomposes upon contact with acids, releasing . For the basic hydrated forms, decomposition begins at lower temperatures, often around 50–100°C. Early literature suggests the hypothetical CuO₂ may decompose at 110–120°C to yield CuO and O₂, though no distinct is observed owing to prior decomposition; no confirmed experimental data exists for the form. CuO₂ nanodots, synthesized as of , appear as stable dispersions in neutral conditions but decompose in acidic media.

Stability and reactivity

Basic copper peroxide is unstable, particularly in its pure form, undergoing decomposition at , though dry forms decompose slowly while moist forms decompose more rapidly, highlighting the influence of hydration on stability. The hypothetical CuO₂ is predicted to decompose spontaneously via the reaction 2CuO₂ → 2CuO + O₂, releasing oxygen gas. As an oxidant, copper peroxide facilitates the decomposition of , especially in alkaline media, where copper compounds exhibit catalytic activity through cycling. It also engages in Fenton-like reactions with H₂O₂, wherein Cu²⁺ is reduced to Cu⁺ according to the equation Cu²⁺ + H₂O₂ → Cu⁺ + O₂⁻ + 2H⁺, enabling the subsequent generation of hydroxyl radicals (OH•) that drive oxidative processes. Stability is notably pH-dependent, with the compound proving more stable in neutral conditions (e.g., minimal Cu²⁺ release at 7.4) compared to acidic environments, where accelerates to yield Cu²⁺ and H₂O₂. CuO₂ nanodots remain intact in neutral but dissociate in acidic media to generate reactive species, as reported in 2019 studies. Sensitivity to light and heat further promotes , as these factors trigger peroxide bond cleavage typical of such compounds. From , the oxygen release during poses risks, including potential behavior in confined spaces due to rapid gas evolution and buildup.

Synthesis and preparation

Historical synthesis methods

Early preparations of copper peroxide involved treating copper(II) compounds with solutions at low temperatures near 0°C, producing a brown precipitate approximating CuO₂·H₂O. The product required quick removal of excess and washing with alcohol and ether to isolate the solid, which was crystalline on a microscopic scale. One early claim from described a reaction of finely divided cupric oxide with cold yielding a product attributed to CuO₂. However, such historical syntheses often resulted in impure mixtures containing oxides and hydroxides, with rapid decomposition under thermal or hydrolytic conditions, and lacked modern analytical confirmation like until the mid-20th century.

Modern synthesis techniques

Modern synthesis techniques for copper peroxide have advanced significantly since 2019, leveraging to produce stable nanoscale forms through controlled reactions that address the compound's inherent tendencies. A seminal approach involves the of copper peroxide nanodots via the reaction of CuCl₂ with H₂O₂ in the presence of stabilizers such as (PVP) and NaOH under elevated temperature and pressure conditions. This method coordinates ligands to Cu²⁺ ions, yielding amorphous CuO₂ nanoparticles, as determined by (TEM). (XRD) analysis confirms the amorphous nature without crystalline peaks typical of copper oxides, ensuring high purity of the phase. Encapsulation strategies further improve the stability of synthesized copper peroxide by confining it within protective matrices. Copper peroxide nanodots are loaded into metal-organic frameworks (MOFs), such as ZIF-8, through coordination during framework assembly, resulting in composites where the peroxide retains its amorphous while gaining resistance to ambient , as shown by prolonged stability in aqueous environments via spectroscopic characterization. Polymer encapsulation, using materials like or , involves dispersing or impregnating nanodots into the polymer network, providing pH-responsive barriers that prevent premature H₂O₂ release and maintain purity over extended storage, with confirming intact morphology post-encapsulation.

Applications

Biomedical and nanomedical uses

Copper peroxide (CuO₂) has emerged as a promising material in , particularly through its forms, which leverage its to generate (H₂O₂) for (ROS)-mediated therapies. This self-supplying mechanism enhances the efficacy of treatments in biological environments where exogenous H₂O₂ is limited. In cancer therapy, CuO₂ nanodots enable chemodynamic therapy (CDT) by decomposing to release H₂O₂, which undergoes Fenton-like reactions to produce hydroxyl radicals (•OH) that induce and in tumor cells. A 2019 study demonstrated that these small nanodots effectively self-supplied H₂O₂ in the , achieving significant cell death in cells via •OH generation without external H₂O₂ addition. This approach exploits the acidic tumor environment to accelerate CuO₂ , minimizing reliance on endogenous H₂O₂ levels that are often insufficient in solid tumors. For , sprayed CuO₂ nanodots promote accelerated closure of diabetic ulcers by combining antibacterial effects with ROS modulation to reduce and enhance tissue regeneration. In a 2021 investigation, these nanodots, applied topically to multidrug-resistant bacteria-infected diabetic wounds in mouse models, showed significant eradication of and reduced healing time compared to controls, attributed to Cu²⁺-induced bacterial membrane disruption and controlled ROS signaling for proliferation. The spray formulation ensures uniform distribution and , avoiding deep tissue penetration that could exacerbate diabetic complications. CuO₂-based also enhance by inducing cuproptosis—a copper-dependent pathway—and to boost antitumor immune responses through lactate modulation in the . A 2025 study on nanospiky CuO₂ structures showed that these particles depleted intracellular lactate, alleviating and promoting maturation, which led to increased ⁺ T-cell infiltration and tumor regression in tumor-bearing mice when combined with checkpoint inhibitors. This dual induction of programmed cell deaths releases damage-associated molecular patterns, further amplifying adaptive immunity. In systems, CuO₂ co-loaded with into silica nanoparticles blocks drug efflux pumps, thereby potentiating efficacy. A 2024 report described CuO₂/@SiO₂ nanoparticles that downregulated multidrug resistance protein 2 (MRP2) via hypoxia-inducible factor-1 inactivation, reducing efflux in resistant cancer cells and achieving synergistic tumor inhibition with higher intracellular drug accumulation compared to free . The silica matrix provides pH-responsive release, ensuring co-delivery at the tumor site. Despite these benefits, CuO₂ nanoparticles pose toxicity risks primarily from Cu²⁺ release, which can induce and off-target damage to healthy tissues such as the liver and kidneys. However, targeted delivery strategies, including surface modifications with or ligands like , confine ion release to the , significantly reducing systemic exposure and mitigating these effects in preclinical models.

Catalytic and industrial applications

Copper peroxide, often formed as an intermediate in Cu(II)-H₂O₂ systems, serves as an effective for the decomposition of in alkaline media, accelerating the breakdown to water and oxygen. This process involves the formation of transient copper-peroxide complexes that facilitate the cycling between Cu(II) and Cu(I), enhancing the rate of O₂ generation. In industrial contexts, such catalysis is applied in to produce oxygen for and oxidative degradation of organic pollutants, improving quality without additional energy inputs. In environmental remediation, copper peroxide participates in Fenton-like processes, where the Cu²⁺/H₂O₂ system generates hydroxyl radicals (•OH) for the oxidation of recalcitrant contaminants such as dyes and . These reactions leverage the peroxide's ability to mediate , enabling efficient mineralization under mild conditions, with copper's abundance and low toxicity making it preferable to iron-based systems in certain aqueous matrices. Typical efficiency in these applications shows turnover numbers ranging from 10 to 100 per , depending on and ligand coordination. Historically, early 20th-century efforts explored for industrial oxygenation and bleaching processes, such as in pulp treatment with H₂O₂, but its inherent instability restricted widespread adoption. ions derived from peroxide complexes accelerated H₂O₂ decomposition to generate active oxygen species for whitening, though uncontrolled reactivity often led to reduced selectivity and process inefficiencies. Emerging applications include electrochemical sensors for H₂O₂ detection, where peroxide-modified electrodes enable sensitive amperometric responses through catalytic reduction or oxidation pathways. For instance, bimetallic Ag/Cu nanoparticles incorporating peroxide-like species on substrates achieve linear detection ranges up to 10 mM with limits of detection around 5 μM, suitable for monitoring in industrial effluents.

History and research

Early claims and investigations

The earliest claims regarding copper peroxide date to the early , when naturalist and illustrator James Sowerby described specimens he termed "peroxide or rather of " (Cuprum hyperoxygenizatum) in his 1808 publication British Mineralogy. Sowerby noted the material's remarkable and hydrated appearance, suggesting it contained excess oxygen beyond simple , though he qualified it as likely a rather than a true due to its instability and decomposition in air. Following Louis Jacques Thénard's 1818 isolation of , chemists began targeted synthesis attempts for metal peroxides, including , by the late 19th century. A notable claim emerged in 1894, when researchers reported the formation of CuO₂ through reactions involving copper salts and alkaline peroxides, though the product was not fully characterized and quickly decomposed, sparking initial skepticism about its purity. These efforts culminated in early 20th-century systematic investigations, particularly by Ludwig Moser in 1907, who tested various oxidizing agents on solutions and found that only neutral 30–50% at near 0°C produced a brown, crystalline precipitate. Moser analyzed the material as approximating CuO₂·H₂O, noting its upon acid addition (regenerating H₂O₂) and slow decomposition in the dry state, but emphasized its instability in alkaline media where it catalyzed peroxide breakdown. Analytical debates persisted through the mid-20th century, fueled by inconsistencies in composition and . Moser's work, revisited in a 1988 NASA technical report, confirmed formation in neutral H₂O₂ but highlighted challenges in obtaining pure samples, with oxygen content varying due to hydration and partial to CuO. Key studies in the by investigators like those examining peroxide complexes in coordination chemistry further probed these issues, reporting evidence of transient Cu-peroxo but rejecting anhydrous CuO₂ as isolable, citing rapid and hydrolytic . Controversies centered on the material's color—ranging from to yellowish in reports—and stability, with conflicting and reactivity data leading to its classification as hypothetical by the , often regarded as a basic copper(II) rather than a stoichiometric .

Recent developments and computational studies

Since the early , computational studies have provided key insights into the electronic structure and stability of copper peroxide species. (DFT) calculations by Gutsev et al. revealed that gaseous CuO₂ adopts a configuration (CuOO), with the superoxo isomer being the and thermodynamically stable in the gas phase, though less favorable for solid-state formation due to its tendency toward dissociation. These models predicted a Cu-O of approximately 200 kJ/mol for the form, highlighting the role of from to the O₂ in stabilizing the complex. This contrasts with earlier unresolved structural debates, confirming the nature through energetic analysis of oxo, peroxo, and superoxo isomers. Advancements in have enabled the synthesis of stable copper , addressing historical challenges in isolating bulk forms. In 2019, researchers reported the aqueous synthesis of copper peroxide (CuO₂) nanodots, approximately 5 nm in size, which decompose in acidic environments to release H₂O₂ while maintaining structural integrity under neutral conditions. These nanodots represent the first Fenton-type metal nanomaterial, offering enhanced stability compared to traditional peroxides. Parallel bioinspired research has drawn on copper-peroxo motifs in enzymes like and , where a 2015 review emphasized their role in O₂ and substrate oxidation, guiding the of synthetic analogs for mimicking enzymatic reactivity. Recent experimental studies have further explored copper peroxide's properties through advanced encapsulation techniques. A 2022 investigation demonstrated the integration of peroxide nanodots into zeolitic imidazolate framework-8 (ZIF-8) metal-organic frameworks (MOFs), enabling H₂O₂ generation and spectroscopic analysis of the peroxo species under controlled conditions. This approach provided direct evidence of the material's decomposition kinetics, with release rates tuned by . A 2023 review highlighted the potential of copper peroxide nanoparticles in modulating tumor microenvironments, noting their ability to disrupt homeostasis and induce selectively in cancer cells. As of 2025, ongoing research has expanded to bimetallic copper peroxide systems for enhanced therapeutic applications. For instance, a 2024 study introduced copper-cerium peroxide nanoparticles as bimetallic peroxide-based nanotherapeutics for immunometabolic modulation in cancer treatment, leveraging synergistic effects for improved reactive oxygen species generation. Similarly, copper-cobalt peroxide nanoparticles were reported in 2024 for pH-activated, self-supplying H₂O₂-mediated cascade reactions in Fenton-like therapy, demonstrating biomimetic enhancements in tumor targeting. Looking ahead, design strategies, such as incorporating sterically hindered or electron-donating groups, show promise for creating stable copper peroxide analogs that persist in solid states or aqueous media. However, questions remain regarding the precise solid-state structure and long-term stability under physiological conditions, warranting further hybrid computational-experimental efforts.

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