Copper Oxides

Mixed Valence

Index © M. Hewat 1998 Help

Oxides like silica are normally insulators because the electrons are intimately associated with the individual bonds or ions. Metals can conduct because the electrons are relatively free. But there are oxides that can become metallic conductors, or even superconductors. The most interesting contain "mixed valence" atoms such as copper that can give up a variable number of electrons when bonding. According to Pauling's ideas about chemical bonds, by looking at the co-ordination of these atoms, we can usually tell something about their valence.

Copper is often divalent (Cu++), and the the usual form of divalent copper oxide is the monoclinic mineral ¶tenorite (CuO). The tenorite structure illustrates how Cu++ (green) is typically surrounded by 4 oxygen atoms (red), with possibly 1 or 2 additional oxygens at greater distances. The drawing of CuO shows how these 1-dimensional chains of copper oxide extend indefinitely, with alternate chains in opposing directions.

Otherwise copper may be monovalent (Cu+) as in the cubic mineral ¶cuprite (CuO). Cu+ (green) is then co-ordinated to only 2 oxygen atoms (red) on either side, and the cuprite structure shows how this is possible with 4 copper now surrounding each oxygen.

Not surprisingly, we can find copper oxides such as ¶Paramelaconite (Cu4O3) which contain both Cu+ and Cu++; these are called mixed valence oxides, since we can write Cu4O3 as 2CuO.Cu2O. In the drawing, we see that Cu4O3 contains two kinds of copper, Cu+ surrounded by only 2 oxygen atoms on either side as in Cu2O, and Cu++ surrounded by a square of 4 oxygen atoms as in CuO.

But we can also find trivalent copper (Cu+++) as in monoclinic ¶LiCuO3. Li is monovalent (Li+) and oxygen divalent (O2-) so formally Cu must be Cu+++, and this is confirmed if we consider the short Cu-O bond lengths, even though Cu still has only 4 oxygen atoms surrounding it in a square, as in Cu++.

Another interesting structure containing Cu+++ is ¶SrCuO2.5, where Sr is Sr++. In this structure, copper is co-ordinated by the usual square of 4 oxygen atoms, but there is now a 5th oxygen atom at the apex of a pyramid around copper. Such 'apical' oxygen atoms were thought to be important for 'high temperature superconductivity' in copper oxide materials.

The first high temperature superconductor, which earned Bednorz and Muller the Nobel prize, was ¶(Sr,La)2CuO4. In La2CuO4, we have La+++ and O2-, so copper should be Cu++. But if we replace some of the La+++ by an equal quantity of Sr++, then some of the Cu++ must be 'oxidised' to Cu+++.

Bednorz and Muller thought that this mixed valence Cu++/Cu+++ compound might result in valence fluctuations, which could couple pairs of electrons to produce a superconductor. They discovered a new kind of material, superconducting at what had previously been thought to be impossibly high temperatures ! Inspired by this astonishing discovery, chemists soon found other copper oxides with even higher superconducting temperatures well above that of ordinary liquid air, which can be readily produced !


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