Chemical Physics 143 ( 1990) 459-467

North-Holland

“0 NMR IN SIMPLE OXIDES

T.J. BASTOW and S.N. STUART

Division of Materials Science and Technology, CSIRO Australia, L.ockedBag 33, Clayton, Victoria 3 168, Australia

Received 16 January 1990, in final form 2 February 1990

The following binary metal oxides have yielded high-resolution “0 nuclear magnetic resonance (NMR) spectra, obtained by
magic-angle spinning (MAS) without isotopic enrichment: a-Al,O,, TiOs (anatase and rutile), TirOr, monoclinic VOr, CurO,
ZnO, tetragonal and monoclinic Zr02, AgrO, tetragonal SnO, hexagonal Laz03, Ce02, HQ, a-Pm, also Na &41203 and cubic
MgO-Zr02. Detection sensitivity limits observation to cases where the nuclear quadrupole coupling is less than 4 MHz. Different
ceramic phases can readily be distinguished by their chemical shift. As empirical chemical shift correlation is sug~~estedbetween
“0 in the oxide MrO, and 19Fin the corresponding fluoride MF,,,.

1. Introduction rotation, have been developed to remove completely

* The possibility of characterizing metal oxides by
“0 NMR spectroscopy is an attractive goal due to
the industrial importance of these materials for ad-
vanced applications such as high-toughness ce-
ramics, high-temperature superconductors and cata-
lysts. The main obstacles to progress have been the
low natural abundance (0.037%) of “0, its small
magnetic moment and its nuclear quadrupole inter-
action. The latter, useful in its own right as a chemi-
cal fingerprint if spectroscopically resolved, acts also
to broaden powder spectra and so to obscure the
chemical shift information.
However, recent work by Oldfield and coworkers
[ l-5 ] on “O-enriched oxide materials has demon-
strated that well-resolved spectra, with good chemi-
cal shift dispersion, can be obtained at high magnetic
field by the magioangle spinning (MAS) technique
- not only where the oxygen atoms are in sites of cu-
bic symmetry (e.g. MgO), but also where the 0 sites
have lower symmetry (e.g. ZnO, A1203) and there is
quadrupole interaction. If the spinning frequency is
high enough, the dipolar and first-order quadrupolar
broadening is averaged out, leaving the ( l/2, - l/2)
powder line with some residual, second-order quad-
rupolar broadening [ 6 1.
Very recently more sophisticated spinning tech-
niques, viz. dynamic angle spinning and double axis
the second-order broadening which is severe in situ-
ations of large electric field gradient (e.g. cristobal-
ite, SiOz, and diopside, CaMgSi,O,) [ 7 1.
We are concerned to expand the class of technolog-
ically and scientifically interesting oxides that can be
characterized by “0 NMR, using the ordinary sin-
gle-axis MAS technique, with “0 in its natural iso-
topic abundance. What follows is a survey of some
commonly available simple oxides, mainly non-cu-
bic in structure, which supplements the above work
[ l-5 1. We examine the various phases of zirconia
which constitute the high-toughness zirconia ce-
ramics, and oxides having structural affinities with
zirconia (e.g. hafnia) or which are used as stabilizing
agents (e.g. ceria) in these ceramic systems. Others,
such as La203 and the two forms of Ti02, have cata-
lytic applications. Our first results, though by no
means exhaustive, are encouraging.
2. Experiment
The specimens were powders, mostly of analytical
grade from a variety of suppliers. The crystallo-
graphic form of the specimens of TiOz, VOz, ZQ,
HfQ, La203 and PbO was verified by powder X-ray
diffraction. The sodium &alumina was estimated by
powder X-ray diffraction to consist of 90% of one
460 T.J. Bastow, S. N. Stuart / “0 NMR in simple oxides
phase, viz. the standard NazO* 11Alz03 structure.
When necessary, samples were calcined to remove
hydroxide or carbonate contaminant. The magnesia-
fully-stabilized cubic zirconia was of eutectic com-
position ( 13 mol% MgO ) , fired at 1970 K for 4 h and
rapidly cooled, and then characterized by electron
diffraction. The magnesia-partially-stabilized zir-
conia (MgPSZ) was the material of spinners sup-
plied by Bruker. The composition of the nominal
T&O3 was analysed as Ti203.04 by thermogravimetry
during oxidation to the dioxide.
NMR spectra were obtained with a Bruker MSL
400 spectrometer operating in a nominal field of 9.4
T and at the frequency of 54.242 MHz. All experi-
ments were carried out at room temperature, 296 K.
Magic-angle spinning was done in a Bruker double
bearing gas turbine and a 7 mm outer diameter spin-
ner of 0.3 1 ml capacity. The MAS rotation frequency
was variously set between 3.5 and 4.9 kHz. The spec-
tra were obtained by Fourier transforming the free
induction decay following a 4 us rf pulse, accumulat-
ah
(a)
Ceo2
* *
4
Ag,O
6.9
Illlll’lLllf~‘l
1000 800 600 400 200
Ppm
Fig. I. MAS “0 absorption speeua of polyerystalline metal oxides: (a) CeO,, (b) Cu10, (c) Ag20, (d) a-PbO, (e) black SnO, ( f ) Na
P_A1203. Peaks due to (A) alumina spinner, (2) zirconia spinner, ( l ) spinning sidebands; additional line broadening (fwhm). Fre-
quency reference is H2”0.
ing typically 4000-8000 responses with the repeti-
tion period of 20 s. The x/2 pulse length for liquid
water was 9 and 6 us in two different probes. The
spinners supplied by Bruker for use in the former
probe were of alumina, and for the latter MgPSZ.
Each of them contributed a characteristic “0 NMR
signal which served as a frequency marker and inten-
sity calibrator. Spinner and probes were selected to
reduce spectral overlap with the specimen. The 170
resonance in distilled water was taken as the fre-
quency standard; its linewidth was 1.5 ppm ( fwhm ).
The spectra are shown in figs. t-3, relative fre-
quency (6) being expressed in parts per million
(ppm ). For display purposes additional line broad-
ening has been imposed on the raw spectra, as indi-
cated_ Nevertheless the figures demonstrate the sig-
nal-to-noise ratio that is available in these oxides
when the low natural abundance is compensated by
moderate patience. (Eleven other compounds that
were examined in the same way without any reso-
nance being detected are noted in section 4 below. )
1
15OHz
3ooHr
IIIIIII(I’~‘~~~
0 -200 -400 ,000 8W BOO 400 200 0 -200 -400
ppm
 T.J. &stow, S.N. Stuart I “0 NMR in simple oxides 461

(4
h-&&i 2oot-k
* l

A
tb%
160Hz

Z A
(d)
TiO, (h)
rutile 200Hz Mg c-Zr@ 2OOHz

I I II I I I 01 I 81 13 I
1000 800 600 400 200 0 -200 -400 moo 800 600 400 200 0 -200-400

fwm pm

Fig. 2. h4.4S I70 absorption spectra of polycrystalline metal oxides: (a) hexagonal La203, (b) TizOs, (c) TiOl anatase, (d) TiOz rutile,
(e) HfOz, (f) monoclinic ZrOz, (g) tetragonal ZrOl, (h) MgO-fully-stabilized cubic ZrO2. Peaks due to (A) alumina spinner, (Z)
zirconia spinner, ( s ) spinning sidebands; additional line broadening (fwhm). Frequency reference is Hz”O.

3. Method of analysis and results

In the cubic oxides, summarized in table 1, the high

symmetry of the oxygen sites ensures that both
shielding anisotropy and quadrupole coupling vanish
MAS 4.507 kHz for I70 (except in the vicinity of crystal defects).
Consequently the I70 MAS spectra of these oxides
can be highly resolved. All allowed transitions are ex-
cited together, and the isotropic chemical shift may
be read off directly. Some dispersion of chemical SW
can be expected in solid solution phases.
In the presence of magnetic dipole interaction (di-
.,. . pole-dipole, shielding anisotropy) and electric quad-
I I 1 I I I I I I

50 40 30 20 10 0 -10 -20 -30 rupole interaction, the static spectrum is broadened

kHz and the MAS spectrum may show rotational
Fig. 3. “0 absorption spectrum of tetragonal ZrOz with magi0 sidebands.
angle spinning, showing rotational sidebands at 4.507 KHz which The rotational centre band of the central (l/2,
are attributed to the first satellite transitions. Specimen is a spin-
ner made of magnesia-partially-stabilized zirconia. 12500 free
- l/2) transition has the same centroid frequency
induction decays have been accumulated for this spectrum. Ad- yL( 1+ 6’ ) as in the unspun spectrum [ 6,8], which is
ditional line broadening is 160 Hz.
462 T J. Bastow, S.N. Stuart /I70 NMR in simple oxides

Table 1
Cubic oxide structures

Structure Composition Space 0 packing 0 coordination 0 site

Brow symmetry

rocksalt MO Fm3m fee 6 m3m

fluorite MO2 FmJm sc 4 43m
cuprite MzO Pn3 bee 4 23

given for spin I= 5/2 by
s=s,- &(VQ/V#(l+$$).
Here, as usual, =&e2qQ/h is the nuclear quadru-
vQ
pole resonance frequency, and q the asymmetry pa-
rameter of the quadrupole interaction. Thus the der-
ivation of isotropic chemical shift & from centroid
frequency requires a second-order quadrupolar cor-
rection. The standard deviation (rms half-width) of
the centre-band absorption, relative to vL, has the
quadrupolar contribution [ 91
~Q=&vQ/vL)2(1+~tzz),
according to the adiabatic approximation [ 6 1. The
in terms of Cartesian tensor components, and where
dQ is defined by eq. (2 ) . A lower bound to M2 can be
(1) found from the amplitude of the sidebands visible
above the noise: with an upper bound for dQ, eq. (4)
gives a lower bound for 11 Aa]].
If the static broadening interactions are small
enough, then rotational sidebands of the satellite
transitions will be visible [ 8 1. Sidebands of the first
pair of satellites, + (3/2, i/2), are 7/24 as wide as
the centre band of the central transition (not count-
ing residual broadening) and are slightly shifted in
frequency. Sidebands of the second pair of satellites,
+ (5/2, 3/2), being 20 times weaker than the first,
(2)
are not important. A lower bound to the first side-
band amplitude provides an upper bound to if the
VQ

observed standard deviation d of the central line
therefore provides an upper bound to the quadrupole
coupling, thus,
KQ= ]e2qQ/h((1+fq2)‘/’
< +&(+t)“2,
The quadrupolar splitting of the centre band, which
is approximately $(vQ/~~)~(l-_) [6], has not
been seen in the present study.
Under certain conditions distinct rotational side-
bands of the central transition will be visible. The
pattern of centre band and sidebands has a variance
or second moment that is independent of the rota-
tion frequency, and to which the static broadening
mechanisms contribute independently. In the pres-
ence of shielding anisotropy Aa and quadrupole in-
teraction, the second moment, relative to I$ is [ 10,9]
M 2=&]lAal]2+~~&,
where
llW2= z C&d2, C %a=O,
(Y
sideband envelope is smooth. If, on the other hand,
vQ is much greater than about (1+1/2)/7=0.75
MHz, 7 being the rf pulse length, then the satellite
transitions are no longer excited.
Nonetheless, simple observation of rotational side-
bands does not permit direct inference about the static
(3)
broadening mechanisms unless the responsible tran-
sitions can positively be identified. The sidebands
might be those of the central transition broadened by
dipole interaction, those of the first satellite transi-
tions broadened by quadrupole interaction or some
combination of the two. In most cases where the sig-
nal-to-noise ratio is low we are unable to identify the
sidebands.
The results of our measurements are presented in
table 2. Both raw chemical shift 6’ and corrected
chemical shift & are given. The width of the central
line, fwhm = 2.3 55d (for equivalent Gaussian ) , de-
termines both the chemical shift correction and the
(4) stated error in So. In the cubic structures the error is
taken as id; in cases of lower site symmetry, where
the lineshape has some quadrupolar contribution, the
correction 2dQ is estimated conservatively as d, the
 T.J. Bastow, S.N. Stuart I “0 NMR in simple oxides 463

Table 2
“0 NMR at 54.242 MHz with magic-angle spinning of about 4 kHz. Centroid frequency and corrected chemical shift (ppm with respect
to water); linewidth (fwhm, ppm) of centr&and absorption; upperbound of quadrupole coupling (MHz) derived from linewidth,
relative intensity of sidebands; extent of visible sideband pattern (standard deviation, ppm)

Composition structure s Width so Kh-= P Qf

Al203 corundum 60 14 66( 9) ” 2.4 0.3 38

TiOz anatase 557 3 558(2) 1.1
rutile 588 5 590(3) *) 1.5 0.5 44
T&O, corundum 496 16 503( 10) 2.6 -
v02 monoclinic 755 13 - 7 230
815 13 - 7 270
cu20 cuprite -193 22 - 193(5)
ZnO wurtzite - 18.4 1.1 -17.9(7) 0.2 b’ 1.6 150
Zt.02 tetragonal 378 11 383(7) 1.4 b’ >2.0 >380
baddeleyite 324 1.8 325( 1) 0.9 0.5 48
401 2 402(2) 1.0 0.5 50
420 cuprite -277 24 -277(5) -
SnO litharge 246 13 251(8) 2.3 1.3 110
J&O, hexagonal (act ) 467 4 469( 3) 1.4
hexagonal (tet ) 584 11 590(7) 2.2 0.7 50
Ce02 fluorite 878 9 878(2) 0.5 46
HfO2 baddeleyite 266 3 267(2) 1.1 0.4 35
334 2 335( 1) 0.9 0.9 54
PbO litharge 293 2 294(l) 0.9 1.3 100
1 lA120s: NazO hexagonal 71 12 76(8) 2.2 -
87Zr02: 13MgO (fluorite) 355 84 -

al See text for informed correction. b, Derived from positions of satellite sidebands.

error as $A.No correction is made for bulk magnetic 4. Discussion

susceptibility. The upper bound to the quadrupole
coupling x$ is that of eq. (3), except as noted. All
the spinning sidebands have about the same width as
their centre band, with the exception of tetragonal
ZrOz (fig. 3 ) where satellite sidebands can be iden-
tified. Only a rough description of the sideband pat-
terns can be given. The ratio of total visible sideband
amplitude to centre-band amplitude is denoted in ta-
ble 2 by p. The standard deviati0n.o’ of the visible
pattern includes the central line as well as the
sidebands.
The sensitivity of the present experimental ar-
rangement is such that the central resonance would
not be seen at all if X, were greater than about 7 MHz,
while it ought to be detected if & were less than about
4 MHz. The accumulated number of free induction
decays required to detect an absorption line whose
centre-band amplitude is twice the peak-to-peak noise
is of order 20x ( 1064)2.
4.1. Cubic oxides
The high-resolution spectra of oxides with the
rocksalt structure have been reported by Oldfield and
co-workers [ 1,3]. We report Ce02 which has the
fluorite structure, CuzO and Ag,O which have the cu-
prite structure.
In Ce02 the chemical shift agrees with that of
Oldfield et al. [ 5 1, and since nuclear dipole-dipole
interaction is negligible, the occurrence of sidebands
is attributed to first-order quadrupolar broadening
associated with crystal defects; the sidebands are those
of the satellite transitions.
In the group IB oxides the oxygen shieldings are
the largest yet recorded. This is reminiscent of the ex-
treme shielding of fluorine in AgF [ 11). The source
of the line-broadening is not obvious in view of the
high symmetry of the oxygen site (table 1): a possi-
ble cause is nonstoichiometry which would give rise
464 T.J. Bastow. S. N. Stuart / ’ 7ONMR in simple oxides
to a distribution of chemical shift. In the case of CutO,
it must be in spite of the coherent Cu environment,
since a clearly defined 63Cu nuclear quadrupole res-
onance signal was measured previously in the same
material [ 12 1. The chemical shift in Cu,O is lower
than that reported by Oldfield et al. [ 5 1.
There is appreciable complexity in magnesia cubic
zirconia, which is a solid solution having the average
structure of fluorite with oxygen vacancies (Zr,
Mg) (0, 0 )2_ The fully stabilized material ( 13 mol%
MgO) gives a broad band (fig. 2h) indicating the
range of oxygen chemical shift. In MgPSZ (9 mol%
MgO, in typical commercial grades ) such a spectrum
is apparently swamped by the signal from the accom-
panying tetragonal phase (fig. 3, discussed in section
4.4 below). In neither material is there any trace of
the MgO line at 47 ppm [ 31.
4.2. Uniaxial monoxides
In the tetragonal structure of litharge, oxygen at-
oms occupy a tetrahedral site of axial symmetry.
Strong sideband patterns are observed in the spectra
of black SnO and a-PbO (figs. 1d, 1e ). Static dipole-
dipole broadening is expected to be minor. If the
sidebands should be attributed to the central transi-
tion, it would follow from eq. (4) that the shielding
anisotropy ]]Aa]] is at least 300 and 270 ppm, respec-
tively. The chemical shift of SnO agrees with a recent
report, but our value for PbO is higher [ 5 1.
Our measurement of ZnO (spectrum not shown)
gives a sharp central line at S’ = - 18.4 ppm, which
agrees with Oldfield et al., value [ 3 1. The centre band
is sharp enough to ensure that the satellites are ex-
cited also. The strong sidebands have a symmetrical
envelope, which indicates a first-order quadrupolar
powder pattern with q=O (in accordance with site
symmetry) and small shielding anisotropy; the stan-
dard deviation (excluding the centre band) is at least
10 kHz. On that interpretation, the observation of
sidebands equidistant from the centre places an up-
per bound on the quadrupole coupling constant [ 81
of about 0.2 MHz. Other such bounds derived from
eq. (3) and from the first sideband amplitude [8]
are less stringent. Further, if the static broadening
were purely quadrupolar, the coupling constant would
be at least 0.15 MHz [ 13 1. These estimates are rea-
sonably consistent with a reported value of 0.13 MHz
[ 3 ] and an order-of-magnitude calculation of 0.16
MHz [ 141.
4.3. Sesquioxides
In hexagonal Laz03 the oxygen atoms occupy two
distinct sites, one with octahedral coordination, one
tetrahedral, both of axial symmetry. The two ob-
served (centre-band) resonances (fig. 2a) can be as-
signed on the basis of their integrated intensity. The
site of higher 6 has the lower coordination. This line
shows evidence of low-level satellite sidebands, rather
like ZnO; from the shape of the envelope the quad-
rupole coupling constant may be about 0.37 MHz; the
prominence of the first sidebands is presumably due
to the central transition_ An observation of lower res-
olution has been reported [ 5 1.
The solid alumina spinners give the same spectrum
(marked A in figs. 1 and 2 ) as a powder specimen of
a-Al,O, (in a zirconia spinner). The centre-band
lineshape is approximately Gaussian. First side-
bands are visible with about the same width as the
centre band: they may be attributed to the central
transition. Now the I70 quadrupole interaction has
been measured in a single crystal of ruby as
le2qQ/hl =2.167(5) MHz, ~=0.517(5) [15]. Us-
ing those parameters, the chemical shift correction in
eq. ( 1) amounts to 10.4 ppm, giving the corrected
shift S,= 7 1 ppm. At the frequency of 67.8 MHz em-
ployed by Oldfield et al., the reported position (6’ )
[ 1 ] is subject to a correction of 6.7 ppm, which leads
to &= 73 (2 ) ppm; and another report [ 4 ] gives the
corrected value 75 (2) ppm. From eq. (2) the quad-
rupolar contribution to the width of the centre band
is 12.3 ppm (fwhm of equivalent Gaussian); the ob-
served linewidth of 14 ppm is just enough to blur the
quadrupolar splitting of about 5.6 ppm. The second
moment A42 of the static central transition is esti-
mated from the sidebands to be at least 1460 ppm2.
Of this, 358 ppm2 is due to the above quadrupole in-
teraction, 490 ppm* to dipole-dipole interaction from
27Al (according to Walter and Oldfield [ 41) , leaving
at least 6 10 ppm* which may be attributed to shield-
ing anisotropy. This corresponds via eq. (4) to
I]Aa]l> 68 ppm. At the frequency employed by Old-
field et al. the three interactions would combine
slightly differently, and the static spectrum would be
about 5.2 kHz wide (fwhm of equivalent Gaussian ),
 T.J. Bastow, S.N. Stuart / “0 NMR in simple oxides
which is in agreement with the reported observation
[ 41. Sidebands of the satellite transitions are too weak
to be visible [ 8 1.
The chemical shift in Tiz03 shows more shielding
than in TiOz (see section 4.4 below), which is possi-
bly due to the greater coordination at the oxygen, but
no very pronounced, paramagnetic shift. This sup-
ports the Goodenough view that the titanium elec-
tronic spins (3d’ ) are strongly paired in the ses-
quioxide [ 16,17 1. The resonance in Ti203 has about
the same width as the centre band in u-A&O,. The
isomorphic V203 showed no resonance.
No resonances were observed in the bixbyite struc-
tures, Scz03, Y203, In203 (in which the oxygen at-
oms are not close packed). None of the three sites in
&Ga203 was detected.
4.4. Tetragonal and monoclinic dioxides
Two forms of TiOa show distinct chemical shifts,
the oxygen being trigonally coordinated in both. Ru-
tile, the denser of the two, produces the higher value
of 6. Our value for rutile is similar to that recently
attributed to TiOz [ 5 1. The “0 quadrupole interac-
tion in x-utile has been measured as e2qQ/h=
1.497(4) MHz, ~=0.868(5) [ 18 J. Using those pa-
rameters, the chemical shift correction in eq. ( 1)
amounts to 5.7 ppm, giving the corrected shift
&,= 594 ppm; the quadrupolar linewidth predicted by
eq. (2) is marginally greater than that observed. The
sidebands (fig. 2d) are due to the central transition,
as in alumina, and their observed extent implies via
eq. (4)) if static dipole-dipole broadening is negligi-
ble, that llAall> 120 ppm. It would be surprising if
the shielding anisotropy were greater in r-utile than in
alumina, considering that the quadrupole interaction
is smaller. The narrower line of anatase implies a
smaller quadrupole coupling than in rutile; there are
no obvious sidebands, presumably because of an in-
sufficient magnetic dipole interaction. No reso-
nances were detected in a third form of TiOz, natural
brookite, or in other oxides with the rutile structure,
Ge02, SnOz and Pb02.
In monoclinic VOz ( V204), a distorted rutile
structure, the oxygen atoms occupy two sites of three-
fold coordination. The spectrum exhibits two series
of spinning sidebands without intense centre bands,
the stronger series extending from 400 to 1300 ppm.
465
The centre bands have been identified from several
long runs at different rotational frequencies. Signal-
to-noise ratio is inadequate for close analysis (spec-
trum not shown).
Pure tetragonal zirconia shows the same spectrum
(fig. 2g) as the Bruker spinners (marked Z in figs. 1
and 2) made of MgPSZ, which contains precipitates
of tetragonal Zr02. The sidebands, being mostly nar-
rower than the centre band (fig. 3)) are attributed to
the first pair of satellites [ 81. Their uniform ampli-
tude is indicative of a first-order quadrupolar pow-
der pattern with an asymmetry parameter that is not
too large. Their position is not significantly displaced
from the centre band, which implies an upper bound
to the quadrupole coupling constant of about 1.4 MHz
[ 8 ] ; other bounds, as in the case of ZnO above, are
less stringent. The full extent of the sideband pattern
has not been determined.
There are two oxygen sites in the monoclinic bad-
deleyite structure, one of tetrahedral and one of tri-
gonal coordination. These show up clearly both in
monoclinic ZrOz (fig. 2f) and in HfQ, (fig. 2e). The
site of higher 6 may be the one of lower coordination
and shorter bondlength, according to a well-known
principle [ 19,201. These lines are not found in the
MgPSZ (fig. 3).
Oxygen shielding in the solid oxides of zirconium
and hafnium is greater than has been found in their
p-0x0 complexes in solution, where the coordination
is two fold [ 2 11. This also may be a matter of ionic-
ity, coordination and bondlength.
4.5. Other oxides
In sodium p-alumina the strength of the observed
line (fig. 1f ) indicates that most of the “0 nuclei in
the sample are contributing to the signal. The bulk of
the material has the hexagonal structure of the ca-
nonical Na20: 1 1A1203, which involves five distinct
oxygen sites (with non-cubic point symmetry). We
conclude that possibly two of the most populated sites
have (a) nearly equal chemical shift and (b ) small
quadrupole coupling. The shift is not far from that of
a-A&OS and other OAld sites [ 41.
V,O, (which has three oxygen sites) and CuO were
examined without success.
466 T.J. Bastow, S. N. Stuart / “0 NMR in simple oxides
4.6. Chemical shift
In fig. 4 the chemical shift of I70 in binary oxides
(M,O,) is compared with that of 19F in the corre-
sponding fluorides (MF,). In this comparison, the
valence of the electropositive element is the same in
a pair of compounds, while coordination about the
electronegative atom is in general different. The col-
lection of 38 diamagnetic compounds ranges across
the periodic table from ionic solids (BaO, BaF,) to
associated liquids (H20, HF). A broadly positive
correlation between the two shifts may be discerned,
especially with regard to the oxidation states I to III.
The effect may be compared with the chemical shift
correlation between I70 in ethers ORR’ and 13Cin
the corresponding hydrocarbons CH,RR’ [ 22 1. The
primary variation of both oxygen and fluorine shifts
is probably related to variation in the size of the an-
ion; and it is possible that relative electronegativity
has an additional but secondary effect.
l C
-100 0 100 200 300
IF
Fig. 4. NMR chemical shift (ppm) of “0 in binary oxides MzO,
compared with that of “F in the corresponding fluorides MF,,,,
taking reference frequencies from Hz0 and C6FS, respectively.
Valence m is indicated by symbol, thus: I ( 0 ) , II ( 0 ), III ( A ),
IV (*) or VI (0). Values for Ag20, ZnO, PbO, A1203, La203,
ZrQ, HfO, are present measurements. Other values are taken
from published reports as follows: BeO, MgO, CaO, SrO, CdO,
BaO, HgO [3]; CO2 [24]; SiO2 [2]; SO1, SOa [25]; HF [26];
BeFz [27]; MgFz, ZnFz, HgF2 [28]; CaF2 [29-311; SrF2, CdFt,
BaF,[30,31];AgF,AlF3,HfF4[11];LaFj[32];ZrF.,[33];PbF2
[31,34]; CF4, SiF,, SF,, SFs [35]. Conversions: &(F,)-
&(C,F,)=589 ppm [11,32]; G,(CF,CO,H)-$(C,F,)=
84.4 ppm [29].
5. Conclusions
The NMR of I70 can successfully be detected by
the MAS technique in well-ordered oxides, without
special isotopic enrichment, provided the nuclear
quadrupole coupling is less than about 4 MHz. A
promising range of industrially useful oxides are
found in this category. The resolution is quite suffl-
cient to reveal the inequivalent sites. To obtain such
resolution, in cases where the quadrupole coupling is
much greater than that, would seem to call for the
technique of specimen double rotation [ 71 or some
multiple-pulse equivalent. In a few cases the spectral
sidebands, which carry information about static
broadening mechanisms, can be interpreted.
There is a broad correlation between the chemical
shift of I70 in binary oxides MzO, and that of 19Fin
the corresponding fluorides MF,, as might be ex-
pected of isoelectronic anions. The span of oxygen
shifts is about three times larger than fluorine.
Interesting chemical shift effects are seen where the
same system exhibits different phases or inequiva-
lent sites. In zirconia-based ceramics “0 NMR MAS
clearly distinguishes the monoclinic, tetragonal and
cubic solution phases. The latter two are difficult to
separate by routine X-ray diffraction powder meth-
ods [ 231. For La203, Ti,03, Ti02, ZrOz and HQ
the results appear to be consistent with the general
rule [20] that 6 varies inversely with coordination.
But it is too early to say whether the shifts are fully
accounted for by the mechanism of overlap.
Acknowledgement
We wish to thank I. Grey, R.H.J. Hannink, D. Hay,
R.J. Hill, M. Hoang, H.J. Rossell, S.L. Segel and H.J.
Whitfield for generously providing us with well-char-
acterized materials. We are further grateful to Henry
Rossell for enlightening discussions on the structural
chemistry of zirconia ceramics.
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