Copper(I) oxide

Last updated
Copper(I) oxide
CopperIoxide.jpg
Copper(I)-oxide-unit-cell-A-3D-balls.png
Copper(I)-oxide-xtal-3x3x3-3D-bs-17.png
Names
IUPAC name
Copper(I) oxide
Other names
Cuprous oxide
Dicopper oxide
Cuprite
Red copper oxide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.013.883 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 215-270-7
KEGG
PubChem CID
RTECS number
  • GL8050000
UNII
  • InChI=1S/2Cu.O/q2*+1;-2 Yes check.svgY
    Key: KRFJLUBVMFXRPN-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/2Cu.O/rCu2O/c1-3-2
    Key: BERDEBHAJNAUOM-YQWGQOGZAF
  • InChI=1/2Cu.O/q2*+1;-2
    Key: KRFJLUBVMFXRPN-UHFFFAOYAM
  • [Cu]O[Cu]
  • [Cu+].[Cu+].[O-2]
Properties
Cu2O
Molar mass 143.09 g/mol
Appearancebrownish-red solid
Density 6.0 g/cm3
Melting point 1,232 °C (2,250 °F; 1,505 K)
Boiling point 1,800 °C (3,270 °F; 2,070 K)
Insoluble
Solubility in acidSoluble
Band gap 2.137  eV
−20×10−6 cm3/mol
Structure
cubic
Pn3m, #224
a = 4.2696
Thermochemistry
Std molar
entropy
(S298)
93 J·mol−1·K−1
−170 kJ·mol−1
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Danger
H302, H318, H332, H410
P273, P305+P351+P338
NFPA 704 (fire diamond)
NFPA 704.svgHealth 2: Intense or continued but not chronic exposure could cause temporary incapacitation or possible residual injury. E.g. chloroformFlammability 0: Will not burn. E.g. waterInstability 1: Normally stable, but can become unstable at elevated temperatures and pressures. E.g. calciumSpecial hazards (white): no code
2
0
1
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 1 mg/m3 (as Cu) [1]
REL (Recommended)
TWA 1 mg/m3 (as Cu) [1]
IDLH (Immediate danger)
TWA 100 mg/m3 (as Cu) [1]
Safety data sheet (SDS) SIRI.org
Related compounds
Other anions
Copper(I) sulfide
Copper(II) sulfide
Copper(I) selenide
Other cations
Copper(II) oxide
Silver(I) oxide
Nickel(II) oxide
Zinc oxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Copper(I) oxide or cuprous oxide is the inorganic compound with the formula Cu2O. It is one of the principal oxides of copper, the other being copper(II) oxide or cupric oxide (CuO).The compound can appear either yellow or red, depending on the size of the particles. [2] Cuprous oxide is found as the mineral cuprite. It is a component of some antifouling paints, but also has other applications including some that exploit its property as a semiconductor.

Contents

Preparation

Copper(I) oxide may be produced by several methods. [3] Most straightforwardly, it arises via the oxidation of copper metal:

4 Cu + O2 → 2 Cu2O

Additives such as water and acids affect the rate as well as the further oxidation to copper(II) oxides. It is also produced commercially by reduction of copper(II) solutions with sulfur dioxide.

Alternatively, it may be prepared via the reduction of copper (II) acetate with hydrazine: [4]

4 Cu(O2CCH3)2 + N2H4 + 2 H2O→ 2 Cu2O + 8 CH3CO2H + N2

Aqueous cuprous chloride solutions react with base to give the same material. In all cases, the color of the cuprous oxide is highly sensitive to the procedural details. Cu2O degrades to copper(II) oxide in moist air.

Pourbaix diagram for copper in uncomplexed media (anions other than OH not considered). Ion concentration 0.001 mol/kg water. Temperature 25 degC. Cu-pourbaix-diagram.svg
Pourbaix diagram for copper in uncomplexed media (anions other than OH not considered). Ion concentration 0.001 mol/kg water. Temperature 25 °C.

Formation of copper(I) oxide is the basis of the Fehling's test and Benedict's test for reducing sugars. These sugars reduce an alkaline solution of a copper(II) salt, giving a bright red precipitate of Cu2O.

It forms on silver-plated copper parts exposed to moisture when the silver layer is porous or damaged. This kind of corrosion is known as red plague.

Properties

Like all copper(I) compounds, cuprous oxide is diamagnetic. It does not readily hydrate to cuprous hydroxide.

Copper(I) oxide dissolves in concentrated ammonia solution to form the colourless complex [Cu(NH3)2]+, which is easily oxidized in air to the blue [Cu(NH3)4(H2O)2]2+.

Cuprous oxide is attacked by acids. Hydrochloric acid gives the chloride complex CuCl
2
. Sulfuric acid and nitric acid produce copper(II) sulfate and copper(II) nitrate, respectively. [5]

Structure

Large crystal of the mineral form of copper(I) oxide (cuprite). Cuprite-66649.jpg
Large crystal of the mineral form of copper(I) oxide (cuprite).

In terms of their coordination spheres, copper centres are 2-coordinated and the oxides are tetrahedral. The structure thus resembles in some sense the main polymorphs of SiO2, but cuprous oxide's lattices interpenetrate. Cu2O crystallizes in a cubic structure with a lattice constant al = 4.2696 Å. The copper atoms arrange in a fcc sublattice, the oxygen atoms in a bcc sublattice. One sublattice is shifted by a quarter of the body diagonal. The space group is Pn3m, which includes the point group with full octahedral symmetry.

Applications

The dominant use of cuprous oxide is as a component of antifouling paints. [3]

Cuprous oxide is also commonly used as a pigment and a fungicide.

Rectifier diodes based on this material have been used industrially as early as 1924, long before silicon became the standard. Copper(I) oxide is also responsible for the pink color in a positive Benedict's test. In the history of semiconductor physics, Cu2O is one of the most studied materials. Many Semiconductor applications have been demonstrated first in this material:

The lowest excitons in Cu2O are extremely long lived; absorption lineshapes have been demonstrated with neV linewidths, which is the narrowest bulk exciton resonance ever observed. [9] The associated quadrupole polaritons have low group velocity approaching the speed of sound. Thus, light moves almost as slowly as sound in this medium, which results in high polariton densities. Another unusual feature of the ground state excitons is that all primary scattering mechanisms are known quantitatively. [10] Cu2O was the first substance where an entirely parameter-free model of absorption linewidth broadening by temperature could be established, allowing the corresponding absorption coefficient to be deduced. It can be shown using Cu2O that the Kramers–Kronig relations do not apply to polaritons. [11]

In December 2021, Toshiba disclosed a transparent cuprous oxide (Cu2O) thin-film solar cell. The cell achieved an 8.4% energy conversion efficiency, the highest efficiency ever reported for any cell of this type as of 2021. The cells could be used for high-altitude platform station applications and electric vehicles. [12]

Similar compounds

An example of natural copper(I,II) oxide is the mineral paramelaconite, Cu4O3 or CuI
2
CuII
2
O3. [13] [14]

See also

Related Research Articles

<span class="mw-page-title-main">Exciton</span> Quasiparticle which is a bound state of an electron and an electron hole

An electron and an electron hole that are attracted to each other by the Coulomb force can form a bound state called an exciton. It is an electrically neutral quasiparticle that exists mainly in condensed matter, including insulators, semiconductors, some metals, but also in certain atoms, molecules and liquids. The exciton is regarded as an elementary excitation that can transport energy without transporting net electric charge.

<span class="mw-page-title-main">Band gap</span> Energy range in a solid where no electron states exist

In solid-state physics and solid-state chemistry, a band gap, also called a bandgap or energy gap, is an energy range in a solid where no electronic states exist. In graphs of the electronic band structure of solids, the band gap refers to the energy difference between the top of the valence band and the bottom of the conduction band in insulators and semiconductors. It is the energy required to promote an electron from the valence band to the conduction band. The resulting conduction-band electron are free to move within the crystal lattice and serve as charge carriers to conduct electric current. It is closely related to the HOMO/LUMO gap in chemistry. If the valence band is completely full and the conduction band is completely empty, then electrons cannot move within the solid because there are no available states. If the electrons are not free to move within the crystal lattice, then there is no generated current due to no net charge carrier mobility. However, if some electrons transfer from the valence band to the conduction band, then current can flow. Therefore, the band gap is a major factor determining the electrical conductivity of a solid. Substances having large band gaps are generally insulators, those with small band gaps are semiconductor, and conductors either have very small band gaps or none, because the valence and conduction bands overlap to form a continuous band.

Benedict's reagent is a chemical reagent and complex mixture of sodium carbonate, sodium citrate, and copper(II) sulfate pentahydrate. It is often used in place of Fehling's solution to detect the presence of reducing sugars. The presence of other reducing substances also gives a positive result. Such tests that use this reagent are called the Benedict's tests. A positive test with Benedict's reagent is shown by a color change from clear blue to brick-red with a precipitate.

<span class="mw-page-title-main">Plasmon</span> Quasiparticle of charge oscillations in condensed matter

In physics, a plasmon is a quantum of plasma oscillation. Just as light consists of photons, the plasma oscillation consists of plasmons. The plasmon can be considered as a quasiparticle since it arises from the quantization of plasma oscillations, just like phonons are quantizations of mechanical vibrations. Thus, plasmons are collective oscillations of the free electron gas density. For example, at optical frequencies, plasmons can couple with a photon to create another quasiparticle called a plasmon polariton.

<span class="mw-page-title-main">Polariton</span> Quasiparticles arising from EM wave coupling

In physics, polaritons are quasiparticles resulting from strong coupling of electromagnetic waves with an electric or magnetic dipole-carrying excitation. They are an expression of the common quantum phenomenon known as level repulsion, also known as the avoided crossing principle. Polaritons describe the crossing of the dispersion of light with any interacting resonance. To this extent polaritons can also be thought of as the new normal modes of a given material or structure arising from the strong coupling of the bare modes, which are the photon and the dipolar oscillation. The polariton is a bosonic quasiparticle, and should not be confused with the polaron, which is an electron plus an attached phonon cloud.

Copper oxide is any of several binary compounds composed of the elements copper and oxygen. Two oxides are well known, Cu2O and CuO, corresponding to the minerals cuprite and tenorite, respectively. Paramelaconite (Cu4O3) is less well characterized.

<span class="mw-page-title-main">Quantum dot</span> Zero-dimensional, nano-scale semiconductor particles with novel optical and electronic properties

Quantum dots (QDs) or semiconductor nanocrystals are semiconductor particles a few nanometres in size with optical and electronic properties that differ from those of larger particles via quantum mechanical effects. They are a central topic in nanotechnology and materials science. When a quantum dot is illuminated by UV light, an electron in the quantum dot can be excited to a state of higher energy. In the case of a semiconducting quantum dot, this process corresponds to the transition of an electron from the valence band to the conductance band. The excited electron can drop back into the valence band releasing its energy as light. This light emission (photoluminescence) is illustrated in the figure on the right. The color of that light depends on the energy difference between the conductance band and the valence band, or the transition between discrete energy states when the band structure is no longer well-defined in QDs.

<span class="mw-page-title-main">Polaron</span> Quasiparticle in condensed matter physics

A polaron is a quasiparticle used in condensed matter physics to understand the interactions between electrons and atoms in a solid material. The polaron concept was proposed by Lev Landau in 1933 and Solomon Pekar in 1946 to describe an electron moving in a dielectric crystal where the atoms displace from their equilibrium positions to effectively screen the charge of an electron, known as a phonon cloud. This lowers the electron mobility and increases the electron's effective mass.

<span class="mw-page-title-main">Copper(II) oxide</span> Chemical compound – an oxide of copper with formula CuO

Copper(II) oxide or cupric oxide is an inorganic compound with the formula CuO. A black solid, it is one of the two stable oxides of copper, the other being Cu2O or copper(I) oxide (cuprous oxide). As a mineral, it is known as tenorite. It is a product of copper mining and the precursor to many other copper-containing products and chemical compounds.

<span class="mw-page-title-main">Copper(I) chloride</span> Chemical compound

Copper(I) chloride, commonly called cuprous chloride, is the lower chloride of copper, with the formula CuCl. The substance is a white solid sparingly soluble in water, but very soluble in concentrated hydrochloric acid. Impure samples appear green due to the presence of copper(II) chloride (CuCl2).

David W. Snoke is a physics professor at the University of Pittsburgh in the Department of Physics and Astronomy. In 2006 he was elected a Fellow of the American Physical Society "for his pioneering work on the experimental and theoretical understanding of dynamical optical processes in semiconductor systems." In 2004 he co-wrote a controversial paper with prominent intelligent design proponent Michael Behe. In 2007, his research group was the first to report Bose-Einstein condensation of polaritons in a trap. David Snoke and theoretical physicist Jonathan Keeling recently published an article announcing a new era for polariton condensates saying that polaritons are arguably the "...best hope for harnessing the strange effects of quantum condensation and superfluidity in everyday applications."

<span class="mw-page-title-main">Multiple exciton generation</span> A concept in quantum electronics

In solar cell research, carrier multiplication is the phenomenon wherein the absorption of a single photon leads to the excitation of multiple electrons from the valence band to conduction band. In the theory of a conventional solar cell, each photon is only able to excite one electron across the band gap of the semiconductor, and any excess energy in that photon is dissipated as heat. In a material with carrier multiplication, high-energy photons excite on average more than one electron across the band gap, and so in principle the solar cell can produce more useful work.

Copper(I) hydroxide is the inorganic compound with the chemical formula of CuOH. Little evidence exists for its existence. A similar situation applies to the monohydroxides of gold(I) and silver(I). Solid CuOH has been claimed however as an unstable yellow-red solid. The topic has been the subject of theoretical analysis. Copper(I) hydroxide would also be expect to easily oxidise to copper(II) hydroxide:

<span class="mw-page-title-main">Delafossite</span> Copper iron oxide mineral

Delafossite is a copper iron oxide mineral with formula CuFeO2 or Cu1+Fe3+O2. It is a member of the delafossite mineral group, which has the general formula ABO2, a group characterized by sheets of linearly coordinated A cations stacked between edge-shared octahedral layers (BO6). Delafossite, along with other minerals of the ABO2 group, is known for its wide range of electrical properties, its conductivity varying from insulating to metallic. Delafossite is usually a secondary mineral that crystallizes in association with oxidized copper and rarely occurs as a primary mineral.

Copper(I) sulfate, also known as cuprous sulfate, is an inorganic compound with the chemical formula Cu2SO4. It is a white solid, in contrast to copper(II) sulfate, which is blue in hydrous form. Compared to the commonly available reagent, copper(II) sulfate, copper(I) sulfate is unstable and not readily available.

Bose–Einstein condensation can occur in quasiparticles, particles that are effective descriptions of collective excitations in materials. Some have integer spins and can be expected to obey Bose–Einstein statistics like traditional particles. Conditions for condensation of various quasiparticles have been predicted and observed. The topic continues to be an active field of study.

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<span class="mw-page-title-main">Copper(I) thiocyanate</span> Chemical compound

Copper(I) thiocyanate is a coordination polymer with formula CuSCN. It is an air-stable, white solid used as a precursor for the preparation of other thiocyanate salts.

<span class="mw-page-title-main">Chevreul's salt</span> Chemical compound

Chevreul's salt (copper(I,II) sulfite dihydrate, Cu2SO3•CuSO3•2H2O or Cu3(SO3)2•2H2O), is a copper salt which was prepared for the first time by a French chemist Michel Eugène Chevreul in 1812. Its unusual property is that it contains copper in both of its common oxidation states, making it a mixed-valence complex. It is insoluble in water and stable in air. What was known as Rogojski's salt is a mixture of Chevreul's salt and metallic copper.

References

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  12. Bellini, Emiliano (2021-12-22). "Toshiba claims 8.4% efficiency for transparent cuprous oxide solar cell". pv magazine. Retrieved 2021-12-22.
  13. "Paramelaconite".
  14. "List of Minerals". 21 March 2011.