Absorption and desorption of the oxygen can be controlled using pressure change, so-called
Pressure Swing Absorption (PSA) or temperature change, so-called
Temperature Swing Absorption (TSA). Cation ordered double
perovskites {{chem2|BaLnMn2O_{5+d} }} (Ln: Lanthanides and Y) are known oxygen storage materials working in PSA mode. The materials show practically complete and reversible change between fully reduced and oxidized , which occurs at moderate temperatures (300–500 °C) during changes of the oxygen partial pressure. The properties of the particular material depends on the substituted cation. In this type of material, oxygen
intercalation occurs into vacancies and is correlated with a change of the oxidation state of the manganese (
redox reaction). Another materials suitable for PSA operation are
brownmillerite-type materials such as {{chem2|La0.6Sr0.4Co0.2Fe0.8O_{3−d}, La0.5Sr0.5Co0.5Fe0.5O_{3−d} }}, commonly used as cathode materials for
SOFC exhibit some good oxygen storage properties such as high capacity and low oxidation temperature. However, cobalt-rich materials may suffer from instability in reducing conditions and higher temperatures such as 550 °C. Recently developed materials suitable for TSA applications are hexagonal {{chem2|LnMnO_{3+d} }} (Ln: Lanthanides and Y) materials. Oxygen stoichiometric phases (
δ = 0), denoted as Hex0, crystallize in the hexagonal
P63
cm symmetry which can be described as a layered structure in which layers of cations in eight-fold coordination are separated by layers of corner-sharing trigonal bipyramids. A very important property, from the viewpoint of TSA, is the possibility of the introduction of a significant amount of interstitial oxygen into the structure near the Mn site, which increases the Mn valence to above +3. This process leads to creation of a unique, maximally eightfold coordination of the manganese cations and changes the symmetry of the primitive cell. Introduction of interstitial oxygen into the structure results in the formation of oxygen-loaded phases having different symmetries:
R3
c (
δ ≈ 0.28, Hex1) and
Pca21 (
δ ≈ 0.41, Hex2). The operating temperature range of those type of materials in an air atmosphere, could be as low as 200-300 ˚C and as narrow as 20 ˚C. Scientists at the
University of Southern Denmark published a paper on oxygen storage by chemisorption. Two molecules of
dioxygen are stored into a crystalline salt {(bpbp)CoII2NO3}2(2-amino-1,4-benzenedicarboxylato)(NO3)2·2H2O. at 35 Celsius, and released by heating to 100 Celsius. "Bpbp" is 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-
tert-butylphenolato. An analogy of the function of
cobalt bound to their organic molecule was made to the function of
iron and
copper in
metalloproteins used for respiration by animals. The nitrate anions in the crystal are exchanged with neutral
dioxygen but remain in the crystal; other anions besides nitrate work similarly and exchange oxygen faster. 10 liters of crystals are "enough to suck up all the oxygen in a room", three times more oxygen than an equivalent sized steel tank. ==See also==