Class of chemical compounds
An oxyhydride is a
mixed anion compound containing both
oxide O2− and
hydride ions H− . These compounds may be unexpected as the
hydrogen and
oxygen could be expected to react to form water. But if the metals making up the
cations are
electropositive enough, and the conditions are
reducing enough, solid materials can be made that combine hydrogen and oxygen in the negative ion role.
[1]
Production
The first oxyhydride to be discovered was lanthanum oxyhydride, a 1982 discovery. It was made by heating
lanthanum oxide in an atmosphere of hydrogen at 900 °C.
[2] However, heating transition metal oxides with hydrogen usually results in water and the reduced metal.
[2]
Topochemical synthesis retains the basic structure of the parent compound, and only does the minimum rearrangements of atoms to convert to the final product.
[2]
Topotactic transitions retain the original crystal symmetry.
[2] Reactions at lower temperatures do not distort the existing structure. Oxyhydrides in a topochemical synthesis can be produced by heating oxides with
sodium hydride NaH or
calcium hydride CaH2 at temperatures from 200–600 °C.
[3]
TiH2 or
LiH can also be used as an agent to introduce hydride.
[2] If
calcium hydroxide or
sodium hydroxide is formed, it might be able to be washed away.
[2] However for some starting oxides, this kind of hydride reduction might just yield an oxygen-deficient oxide.
[2]
Reactions under hot high-pressure hydrogen can result from heating hydrides with oxides. A suitable seal for the lid on the container is required, and one such substance is
sodium chloride .
[4]
Oxyhydrides all contain an
alkali metal ,
alkaline earth metal , or
rare-earth element , which are needed in order to put electronic charge on hydrogen.
[4]
Properties
The hydrogen bonding in oxyhydrides can be
covalent ,
metallic , and
ionic bonding , depending on the metals present in the compound.
[4]
Oxyhydrides lose their hydrogen less than the pure metal hydrides.
[3]
The hydrogen in oxyhydrides is much more exchangeable. For example
oxynitrides can be made at much lower temperatures by heating the oxyhydride in
ammonia or
nitrogen gas (say around 400 °C rather than 900 °C required for an oxide)
[3] Acidic attack can replace the hydrogen, for example moderate heating in
hydrogen fluoride yields compounds containing oxide, fluoride, and hydride ions (
oxyfluorohydride .
[5] ) The hydrogen is more
thermolabile , and can be lost by heating yielding a reduced valence metal compound.
[3]
Changing the ratio of hydrogen and oxygen can modify electrical or magnetic properties. Then
band gap can be altered.
[3] The hydride atom can be mobile in a compound undergoing electron coupled hydride transfer.
[4] The hydride ion is highly polarisable, so it presence raised the
dielectric constant and
refractive index .
[4]
Some oxyhydrides have
photocatalytic capability. For example BaTiO2.5 H0.5 can function as a catalyst for ammonia production from hydrogen and nitrogen.
[3]
The hydride ion is quite variable in size, ranging from 130 to 153
pm .
[4]
The hydride ion actually does not only have a −1 charge, but will have a charge dependent on its environment, so it is often written as Hδ− .
[4] In oxyhydrides, the hydride ion is much more compressible than the other atoms in compounds.
[4] Hydride is the only anion with no
π orbital , so if it is incorporated into a compound, it acts as a π-blocker, reducing dimensionality of the solid.
[4]
Oxyhydride structures with
heavy metals cannot be properly studied with
X-ray diffraction , as hydrogen hardly has any effect on X-rays.
Neutron diffraction can be used to observe hydrogen, but not if there are heavy neutron absorbers like Eu, Sm, Gd, Dy in the material.
[2]
List
Formula
Structure
Space group
Unit cell
Volume
Density
Comments
Reference
Na3 SO4 H
tetrahedral
P 4/nmm
a=7.0034 c=4.8569
[6]
[η1 -3,5-t Bu2 pz(η-Al)H)2 O]2 pz=pyrazolato
triclinic
P 1
a=10.202 b=13.128 c=13.612 α=112.39 β=101.90 γ=96.936 Z=1
1608.7
1.162
[7]
(Me LAlH)2 (μ-O)
Me L = HC[(CMe)N(2,4,6-Me3 C6 H2 )]2 –
white
[8]
[9]
CaTiO3−x Hx (x ≤ 0.6)
Conducting; H in disordered position
[3]
Mg2 AlNiX HZ OY
[10]
Sr2 LiH3 O
ionic conductor
[11]
Sr3 AlO4 H
tetragonal
I4/mcm
a =6.7560 c =11.1568
[12]
Sr2 CaAlO4 H
tetragonal
I4/mcm
a= 6.6220 c= 10.9812
481.531
[12]
Sr21 Si2 O5 H14
cubic
[13]
Sr5 (BO3 )3 H
orthorhombic
Pnma
a= 7.1982, b= 14.1461, c= 9.8215
1000.10
decomposed by water
[14]
LiSr2 SiO4 H
monoclinic
P 21 /m
a = 6.5863, b = 5.4236, c = 6.9501, β = 112.5637
air stable
[15]
Sr21 Si2 O5 H12+x
cubic
Fd 3 m
a = 19.1190
[16]
Sr5 (PO4 )3 H
hexagonal
P 63 /m
a = 9.7169, c = 7.2747
594.83
for deuteride
[17]
SrTiO3−x Hx (x ≤ 0.6)
Conducting; H in disordered position
[3]
SrVO2 H
[3]
Sr2 VO3 H
[3]
Sr3 V2 O5 H2
[3]
SrCrO2 H
cubic
produced under 5GPa 1000 °C
[3]
Sr3 Co2 O4.33 H0.84
insulator
[3]
YHO
orthorhombic
Pnma
a = 7.5367, b = 3.7578, c = 5.3249
[18]
YOx Hy
photochromic ; band gap 2.6 eV
[19]
Zr3 V3 OD5
[2]
Zr5 Al3OH5
[2]
Ba3 AlO4 H
orthorhombic
Pnma
Z =4,a =10.4911,b =8.1518,c =7.2399
[20]
BaTiO3−x Hx (x ≤ 0.6)
Conducting; H in disordered position
[3]
Ba2 NaTiO3 H3
cubic
Fm 3 m
a= 8.29714
[21]
BaVO3−x Hx (x = .3)
5 GPa hexagonal, 7GPa cubic
[3]
Ba2 NaVO2.4 H3.6
cubic
Fm 3 m
a= 8.22670
[21]
BaCrO2 H
hexagonal
P 63 /mmc
a =5.6559 c =13.7707
[22]
Ba2 NaCrO2.2 H3.8
cubic
Fm 3 m
a= 8.17470
[21]
Ba21 Zn2 O5 H12
cubic
Fd 3 m
a = 20.417
[13]
Sr2 BaAlO4 H
tetragonal
I4/mcm
a =6.9093 c =11.2107
[12]
Ba21 Cd2 O5 H12
cubic
Fd 3 m
a=20.633
[13]
Ba21 Hg2 O5 H12
cubic
Fd 3 m
a=20.507
[13]
Ba21 In2 O5 H12
cubic
Fd 3 m
a=20.607
[13]
Ba21 Tl2 O5 H12
cubic
Fd 3 m
a=20.68
[13]
Ba21 Si2 O5 H14
cubic
Fd 3 m
a=20.336
[13]
Ba21 Ge2 O5 H14
cubic
Fd 3 m
a=20.356
[13]
Ba21 Sn2 O5 H14
cubic
Fd 3 m
a=20.532
[13]
Ba21 Pb2 O5 H14
cubic
Fd 3 m
a=20.597
[13]
Ba21 As2 O5 H16
cubic
Fd 3 m
a=20.230
[13]
Ba21 Sb2 O5 H16
cubic
Fd 3 m
a=20.419
[13]
BaScO2 H
Cubic
Pm 3̅m
a=4.1518
[23]
Ba2 ScHO3
H− conductor
[24]
Ba2 YHO3
a=4.38035 c=13.8234
H− conductor
[25]
Ba3 AlO4 H
[2]
Ba21 Si2 O5 H24
cubic
Fd 3 m
a = 20.336
Zintl phase
[2]
Ba21 Zn2 O5 H24
cubic
Fd 3 m
a = 20.417
[26]
Ba21 Ge2 O5 H24
cubic
Fd 3 m
a = 20.356
Zintl phase
[2]
Ba21 Ga2 O5 H24
cubic
Fd 3 m
Zintl phase
[2]
Ba21 As2 O5 H24
cubic
Fd 3 m
a = 20.230
[26]
Ba21 Cd2 O5 H24
cubic
Fd 3 m
a = 20.633
[26]
Ba21 In2 O5 H24
cubic
Fd 3 m
a = 20.607
Zintl phase
[2]
Ba21 Sn2 O5 H24
cubic
Fd 3 m
a = 20.532
[26]
Ba21 Sb2 O5 H24
cubic
Fd 3 m
a = 20.419
[26]
La2 LiHO3
orthorhombic
Immm
a =3.57152 b =3.76353 c =12.9785
[4]
[27]
La0.6 Sr1.4 LiH1.6 O2
H− conductor
[4]
LaSr3 NiRuO4 H4
[3]
LaSrMnO3.3 H0.7
high-pressure fabrication
[3]
LaSrCoO3 H0.7
insulator
[3]
Nd0.8 Sr0.2 NiO2 Hx (x = 0.2–0.5)
superconductor for x between 0.22 and 0.28
[28]
EuTiO3−x Hx (x ≤ 0.6)
Conducting; H in disordered position
[3]
LiEu2 HOCl2
orthorhombic
Cmcm
a = 14.923, b = 5.7012, c = 11.4371, Z = 8
density 5.444; yellow
[29]
LaHO
[30]
CeHO
[30]
PrHO
[30]
NdHO
P 4/nmm
a=7.8480, c=5.5601 V=342.46
[30]
GdHO
Fmm
a = 5.38450
[31]
HoHO
F 4̅3m
a = 5.2755
light-yellow under the sun; pink indoors
[32]
DyHO
cubic
F4̅3m
a=5.3095
[33]
ErHO
cubic
F4̅3m
a=5.24615
[33]
LuHO
cubic
F4̅3m
a=5.17159
[33]
LuHO
orthorhombic
Pnma
a = 7.3493, b = 3.6747, c = 5.1985
[33]
CeNiHZ OY
Catalyse
ethanol to H2
[34]
Ba21 Tl2 O5 H24
cubic
Fd 3 m
a = 20.68
Zintl phase
[2]
Ba21 Hg2 O5 H24
cubic
Fd 3 m
a = 20.507
[26]
Ba21 Pb2 O5 H24
cubic
Fd 3 m
a = 20.597
[26]
Ba21 Bi2 O5 H16
cubic
Fd 3 m
a=20.459
[13]
PuHO
Formed during corrosion of plutonium metal in water
[35]
Three or more anions
Formula
Structure
Space group
Unit cell
Comments
Reference
Li
Eu2 HOCl2
orthorhombic
Cmcm
a = 14.923 b = 5.7012 c = 11.4371 Z = 8
yellow
[36]
Sr2 LiHOCl2
orthorhombic
Cmcm
a = 15.0235 b = 5.69899 c = 11.4501
synthesized at ambient pressure and 2 GPa; ordered H/O
[37]
Sr2 LiHOCl2
tetragonal
I 4/mmm
a = 4.04215 c = 15.04359
synthesized at 5 GPa; disordered H/O
[37]
Sr2 LiHOBr2
tetragonal
I 4/mmm
a = 4.1097 c = 16.1864
synthesized at 5 GPa; disordered H/O
[37]
Ba2 LiHOCl2
tetragonal
I 4/mmm
a = 4.26816 c = 15.6877
synthesized at 5 GPa; disordered H/O
[37]
See also
References
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