Convenient Route for the Synthesis of Transition-Metal

Pnictides by Direct Reduction of Phosphate, Arsenate,

and Antimonate Precursors

J. Gopal akri shnan,* Sonal Pandey, and K. Kasthuri Rangan

Solid Stateand Structural Chemistry Unit, I ndian I nstituteof Science,
Bangalore560012, I ndia
Received March 27, 1997. Revised Manuscript Received J uly 21, 1997
X
Several transi ti on-metal phosphates, arsenates, and anti monates undergo di rect reducti on
i n hydrogen at rel ati vel y l ow temperatures (400-1050 C) to the correspondi ng phosphi des,
arseni des, and anti moni des, provi di ng a conveni ent route for the synthesi s of transi ti on-
metal pni cti des. We have synthesi zed by thi s route a vari ety of bi nary transi ti on-metal
phosphi des (MoP, WP, Fe
2
P, Ni
2
P, FeP, RuP), arseni des (Ni As, CoAs), and anti moni des
(Ni Sb
2
, CoSb
3
). We coul d not however synthesi ze pni cti des of manganese, vanadi um, and
gal l i um by thi s route, suggesti ng that the method i s appl i cabl e onl y to those metal s that
are l ess el ectroposi ti ve than hydrogen, that i s, those metal s whose bi nary oxi des are reduci bl e
by hydrogen to the metal l i c state.
Introduction
Sol i d-state chemi stry, for the most part, i s concerned
wi th synthesi s and characteri zati on of i norgani c sol i ds
of the ki nd, M
x
X
z
, M
x
M
y
X
z
, etc., contai ni ng metal l i c (M,
M) and nonmetal l i c (X) el ements.
1
The nonmetal l i c
el ements are usual l y drawn from the peri odi c groups
14, 15, 16, and 17, the correspondi ng sol i d compounds
bei ng the tetrel i des, pni cti des, chal cogeni des, and ha-
l i des. Among these sol i ds, metal oxi des have tradi ti on-
al l y attracted major attenti on,
2
not surpri si ngl y because
oxygen i s the most reacti ve consti tuent of the earths
atmosphere and most of the metal s i n the peri odi c tabl e
form stabl e oxi des rel ati vel y easi l y, wi th l arge negati ve
free energi es of formati on.
3
I nvesti gati ons of metal
oxi des over the past 3 decades or so have provi ded a
weal th of new materi al s and new knowl edge of i mpor-
tance to both materi al s sci ence and condensed matter
physi cs, the most wi del y known among them bei ng the
hi gh-T
c
superconducti ng cuprates.
4
Progress wi th other
fami l i es of sol i ds contai ni ng non-oxi de ani ons have been
rel ati vel y tardy, mai nl y because of the di ffi cul ti es
associ ated wi th synthesi s of these materi al s. Basi c
research i nto non-oxi de transi ti on-metal compounds i s
especi al l y attracti ve i n vi ew of the possi bi l i ty of novel
structures and el ectroni c properti es that have no paral -
l el among the oxi de anal ogues.
5
Among the non-oxi de sol i ds, transi ti on-metal pni c-
ti des consti tute a di sti nct fami l y exhi bi ti ng several
uni que structures and properti es. A speci al feature of
pni cti de (phosphi de, arseni de, and anti moni de) struc-
tures i s that, besi des normal val ence compounds con-
tai ni ng X
3-
ani ons, pol yani oni c compounds contai ni ng
X-X bonds as wel l as pol ycati oni c compounds contai n-
i ng M-M bonds are common.
5,6
Ni As, MnP, pyri te,
marcasi te, arsenopyri te, and skutterudi te are some of
the wel l -known structure types among transi ti on-metal
pni cti des. Exampl es for al most every type of el ectroni c
property can be found among members of thi s fami l y.
5
Thus, MnP and FeP are metal l i c ferromagnets, whi l e
the d
6
l ow-spi n pyri tes, PtX
2
(X ) P, As, Sb), are
di amagneti c semi conductors; the i sostructural AuSb
2
(d
7
) i s metal l i c and even superconducti ng. The l ow-spi n
d
6
Ni As
2
and Ni Sb
2
marcasi tes are semi conducti ng as
expected, but the d
5
arsenopyri tes (di storted marcasi tes)
CoAs
2
and CoSb
2
woul d have been metal l i c but for a
structural di storti on ari si ng from the hi ghest occupi ed
band of d
xy
parentage whi ch woul d be hal f-fi l l ed i n the
undi storted structure.
5
The skutterudi te (CoAs
3
) struc-
ture, whi ch i s uni que to the pni cti de fami l y contai ni ng
cycl i c X
4
4-
ani ons, i s rel ated to the ReO
3
structure.
7
As
such, i t i s not surpri si ng to fi nd stuffed deri vati ves of
thi s structure, RM
4
X
12
(R ) rare earth),
8
members of
whi ch exhi bi t superconducti ng (LaFe
4
P
12
),
9
ferromag-
neti c (UFe
4
P
12
),
10
and ther moel ectr i c pr oper ti es
(LaFe
4-x
Co
x
Sb
12
);
11
the l atter are potenti al candi date

Contri buti on No. 1269 from the Sol i d State and Structural
Chemi stry Uni t.
X
Abstract publ i shed i n AdvanceACS Abstracts, September 1, 1997.
(1) (a) Solid StateChemistry: Compounds; Cheetham, A. K., Day,
P., Eds.; Cl arendon: Oxford, 1992. (b) Di Sal vo, F. J. Science 1990,
247, 649. (c) Rao, C. N. R.; Gopal akri shnan, J. NewDirections in Solid
State Chemistry, 2nd ed.; Cambri dge Uni versi ty Press: Cambri dge,
1997.
(2) (a) Goodenough, J. B. Prog. Solid State Chem. 1971, 5, 149-
399. (b) Rao, C. N. R. Annu. Rev. Phys. Chem. 1989, 40, 291-326.
(3) Weast, R. C., Ed. CRC Handbook of Chemistryand Physics, 68th
ed.; CRC Press: Boca Raton, FL, 1987; pp D:33-37.
(4) (a) Sl ei ght, A. W. Science1988, 242, 1519. (b) Cava, R. J. Science
1990, 247, 656.
(5) (a) Hul l i ger, F. Struct. Bonding 1968, 4, 83. (b) Goodenough,
J. B. J . Solid StateChem. 1972, 5, 144. (b) Hul l i ger, F. I n Structure
and Bondingin Crystals; OKeeffe, M., Navrotsky, A., Eds.; Academi c
Press: New York, 1981; Vol . 2, pp 297-352.
(6) Ni tri des are however di fferent from other pni cti des i n that they
do not i n general form pol yani oni c compounds, al though azi des are
excepti ons. See, for exampl e: (a) Brese, N. E.; OKeeffe, M. Struct.
Bonding 1992, 97, 307-378. (b) Di Sal vo, F. J.; Cl arke, S. J. Curr.
Opinion Solid StateMater. Sci. 1996, 1, 241-249.
(7) Wel l s, A. F. Structural I norganic Chemistry, 5th ed.; Cl aren-
don: Oxford, 1986; pp 267-268.
(8) Jei tschko, W.; Brown, D. J. Acta Crystallogr. 1977, B33, 3401.
(9) (a) Mei sner, G. P. Physica B 1981, 108, 763. (b) DeLong, L. F.;
Mei sner, G. P. Solid StateCommun. 1985, 53, 119.
(10) Mei sner, G. P.; Tori kachvi l i , M. S.; Yang, K. N.; Mapl e, M. B.;
Guerti n, R. P. J . Appl. Phys. 1985, 57, 3073.
(11) Sel es, B. C.; Mandrus, D.; Wi l l i ams, R. K. Science1996, 272,
1325.
2113 Chem. Mater. 1997, 9, 2113-2116
S0897-4756(97)00175-0 CCC: $14.00 1997 Ameri can Chemi cal Soci ety
materi al s for thermoel ectri c power generati on and
refri gerati on.
We bel i eve that nonavai l abi l i ty of a rapi d and con-
veni ent syntheti c route i s a major reason for the tardy
progress of research i n thi s area. A common method
empl oyed for the synthesi s of pni cti des i s the di rect
reacti on between the consti tuent el ements i n evacuated
and cl osed contai ners at el evated temperatures.
12
I n
vi ew of the probl ems associ ated wi th the di rect el emen-
tal reacti on route, whi ch i ncl ude vol ati l i ty of nonmetal l i c
consti tuents, sl ow di ffusi on and l ong reacti on durati on,
i ncompl ete r eacti on, and for mati on of mi xtur e of
phases,
12,13
we consi dered i t i mportant to expl ore al ter-
nate syntheti c routes that woul d avoi d these probl ems.
One such route woul d be the di rect reduti on of metal
oxoani on precursor compounds such as M
x
(XO
y
)
z
(X )
P, As, Sb) to the desi red pni cti de.
14,15
We expl ored thi s
route at some l ength, and our i nvesti gati ons have
reveal ed that a surpri si ngl y l arge number of transi ti on-
metal phosphates, arsenates, and anti monates undergo
di rect reducti on i n hydrogen at not so very hi gh tem-
peratures (400-1050 C) to yi el d the correspondi ng
pni cti des. Our resul ts, whi ch are descri bed i n thi s
paper, show that hydrogen reducti on of oxoani on pre-
cursors not onl y provi des a conveni ent route for the
synthesi s of a wi de vari ety of transi ti on-metal pni cti des
but al so opens up new avenues for expl ori ng the sol i d-
state chemi stry of several fami l i es of transi ti on-metal
non-oxi de sol i ds. Our method appears to be compl e-
mentary to that descri bed by Kaner and co-workers
16
for the synthesi s of non-oxi de sol i ds. Thei r method i s
based on hi ghl y exothermi c metatheti cal (exchange)
reacti ons that enabl e synthesi s of thermal l y stabl e
pni cti des such as ZrP, GaP, and GaAs, among others.
Experimental Section
We i nvesti gated the formati on of pni cti des by di rect reduc-
ti on of several phosphate, arsenate, and anti monate precursors
i n hydrogen. The precursor compounds (Tabl e 1) were pre-
pared by standard methods reported i n the l i terature.
17
I n
addi ti on, the fol l owi ng new precursors were al so prepared:
RuP2O72H2O,
18
NH4Ni AsO4CH3CN2H2O,
18
and CoSb3O9.
19
We i nvesti gated the course of reducti on reacti ons of every
precursor by thermogravi metri c (TG, Cahn TG-131 system)
i n fl owi ng hydrogen or hydrogen:argon (1:1) mi xture (12 mL/
mi n) at a heati ng rate of 2 C/mi n. Bul k sampl es were
prepared by reduci ng 1 g quanti ti es of the precursor i n a
tubul ar furnace at temperatures determi ned by thermo-
gravi metry. The reducti on products were characteri zed by
EDX anal ysi s usi ng JEOL JSM 840A scanni ng el ectron
mi croscope and powder X-ray di ffracti on (XRD) usi ng JEOL
JDX-8P X-ray di ffractometer and Cu KR radi ati on. Uni t-cel l
parameters were deri ved by l east-squares refi nement of
powder XRD data usi ng PROSZKI program.
20
We l i st i n Tabl e
1 the precursors, the product pni cti des, condi ti ons for thei r
synthesi s together wi th thei r l atti ce parameters.
Results and Discussion
TG i nvesti gati ons showed that several transi ti on-
metal phosphates undergo faci l e reducti on i n hydrogen
at 650-1050 C to the correspondi ng phosphi des. For
exampl e, MoOPO
4
was reduced at 800 C to MoP
di rectl y (Fi gures 1a and 2a). The observed wei ght l oss
i n TG (38.57%) corresponded to the reacti on, MoOPO
4
+ 5H
2
fMoP + 5H
2
O (cal cul ated wei ght l oss, 38.66%),
i ndi cati ng that the reducti on to the phosphi de was
quanti tati ve. Powder XRD showed that the reducti on
product was i ndeed MoP havi ng the WC structure.
21
The
(12) (a) von Schneri ng, H. G. I n Encyclopedia of I norganic Chem-
istry; Ki ng, R. B. Ed. John Wi l ey & Sons: Chi chester, 1994; Vol . 6, pp
3110-3115. (b) Kjekshus, A. Acta Chem. Scand. 1971, 25, 411. (c)
Kjekshus, A.; Rakke, T.; Andersen, A. F. Acta Chem. Scand. 1974, 28,
996.
(13) (a) Cor bett, J. D. I n Solid State Chemistry-Techniques;
Cheetham, A. K., Day, P., Eds.; Cl arendon: Oxford, 1987; pp 1-38.
(b) Rao, C. N. R.; Gopal akri shnan, J. Acc. Chem. Res. 1987, 20, 228.
(c) Stei n, A.; Kel l er, S. W.; Mal l ouk, T. E. Science1993, 259, 1558.
(14) To our knowl edge, reducti on of Fe2P2O7 to FeP seems to be
the onl y defi ni ti ve report i n the l i terature of hydrogen reducti on of a
phosphate to a phosphi de. See: von Schneri ng, H. G.; Honl e, W. Chem.
Rev. 1988, 88, 243.
(15) El ectrol yti c reducti on of fused sal ts contai ni ng al kal i -metal
phosphates/arsenates and transi ti on-metal oxi des and/or chl ori des i s
known to yi el d transi ti on-metal phosphi des and arseni des. See: Wol d,
A.; Bel l avance, D. I n Preparative Methods in Solid State Chemistry;
Hagenmul l er, P., Ed.; Academi c Press: New York, 1972; pp 279-307.
(16) (a) Wi l ey, J. B.; Kaner, R. B. Science 1992, 225, 1093. (b)
Gi l l an, E. G.; Kaner, R. B. Chem. Mater. 1996, 8, 333-343.
(17) (a) MoOPO4: Ki erkegaard, P.; Westerl and, M. Acta Chem.
Scand. 1964, 18, 2217. (b) MoO2HPO4H2O: Ki erkegaard, P. Acta
Chem. Scand. 1960, 14, 657. (c) NH4MPO4H2O (M ) Mn, Fe, Co,
Ni ): Carl i ng, S. G.; Day, P.; Vi sser, D. I norg. Chem. 1995, 34, 3917.
(d) FePO4: Standard X-ray Di ffracti on Powder Patterns, NBS Mono-
graph 25, Secti on 15; U.S. Department of Commerce, 1978; p 33. (e)
VOPO42H2O: Johnson, J. W.; Jacobson, A. J.; Brody, J. F.; Ri ch, S.
M. I norg. Chem. 1982, 21, 3820. (f) GaPO4: Mooney, R. C. L. Acta
Crystallogr. 1956, 9, 728. (g) CoAs2O6: Tayl or, J. B.; Heydi ng, R. D.
Can. J . Chem. 1958, 36, 597. (h) CoSb2O6: Standard X-ray Di ffracti on
Powder Patterns, NBS Monograph 25, Secti on 5; U.S. Department of
Commerce, 1967; p 26.
(18) RuP2O72H2O was prepared by di rect reacti on of RuO2 and
NH4H2PO4 in the required proportion in air at 600 C. NH4NiAsO4CH3-
CN2H2O was prepared by refl uxi ng a sol uti on of Ni (NO3)26H2O (10
mmol ), H3AsO43H2O (10 mmol ) and concentrated NH3 (200 mmol ) i n
60 mL of CH3CN for 3 days.
(19) CoSb3O9 was prepared by reacti ng CoC2O42H2O and Sb2O3
i n the stoi chi ometri c proporti on at 1000 C for 24 h. Powder XRD
pattern of the phase reveal ed a tri ruti l e structure si mi l ar to that of
CoSb2O6.
(20) Losocha, W.; Lewi nski , K. J . Appl. Crystallogr. 1994, 27, 437.
(21) Rundqvi st, S.; Lundstro m, T. Acta Chem. Scand. 1963, 17, 37.
Table 1. Synthesis of Transition-Metal Pnictides by Reduction of Phosphate, Arsenate, and Antimonate Precursors
precursor synthesi s condi ti ons pni cti de structure type and l atti ce parameters ()
MoOPO4 800 C, H2, 1 h MoP WC, hexagonal , a ) 3.214(2), c ) 3.198(2)
MoO2HPO4H2O 870 C, H2 + Ar, 1 h MoP
W2O3(PO4)2 800 C, H2, 2 h WP MnP, orthorhombi c, a ) 5.729(1), b ) 3.250(5), c ) 6.220(1)
NH4FePO4H2O 800 C, H2 + Ar, 7 h FeP MnP, orthorhombi c, a ) 5.185(4), b ) 5.788(1), c ) 3.096(1)
NH4CoPO4H2O 980 C, H2 + Ar, 2 h Co2P anti -PbCl 2, orthorhombi c, a ) 5.666(1), b ) 6.301(9), c ) 3.528(2)
NH4Ni PO4H2O 820 C, H2 + Ar, 2 h Ni 2P Fe2P, hexagonal , a ) 5.863(2), c ) 3.377(7)
NH4MnPO4H2O 1000 C, H2 + Ar, 3 h no phosphi de
FePO4 1000 C, H2 + Ar, 9 h Fe2P Fe2P, hexagonal , a ) 5.876(1), c ) 3.454(1)
RuP2O72H2O 600 C, H2, 6 h RuP MnP, orthorhombi c, a ) 5.499(2), b ) 3.160(1), c ) 6.100(3)
VOPO42H2O 1000 C, H2, 3 h no phosphi de
GaPO4 1000 C, H2, 3 h no phosphi de
NH4Ni AsO4CH3CN2H2O 400 C, H2, 2 h Ni As Ni As, hexagonal , a ) 3.618(1), c ) 5.037(2)
CoAs2O6 420 C, H2 + Ar, 6 h CoAs MnP, orthorhombi c, a ) 3.470(1), b ) 5.862(1), c ) 5.287(1)
CoSb2O6 600 C, H2, 6 h CoSb2 FeAsS (arsenopyri te), orthorhombi c, a ) 6.486(6), b ) 6.353(6), c ) 6.516(6)
Ni Sb2O6 500 C, H2, 6 h Ni Sb2 FeS2 (marcasi te), orthorhombi c, a ) 5.177(2), b ) 6.295(3), c ) 3.827(2)
CoSb3O9 575 C, H2, 6 h CoSb3 CoAs3 (skutterudi te), cubi c, a ) 9.017(2)
2114 Chem. Mater., Vol. 9, No. 10, 1997 Gopalakrishnan et al.
hexagonal l atti ce parameters of the sampl e prepared by
us (a ) 3.214(2); c ) 3.198(2) ) are i n agreement wi th
the val ues of MoP reported i n the l i terature.
21
MoP
coul d al so be prepared starti ng from MoO
2
HPO
4
H
2
O
(Fi gure 1b). Si mi l arl y, WP havi ng the MnP structure
coul d be obtai ned by the reducti on of W
2
O
3
(PO
4
)
2
at
800 C (Fi gures 1c and 2b). The el emental rati os of MoP
and WP as determi ned by EDX anal ysi s were 1:1 wi thi n
a rel ati ve error of 2%.
Next, we i nvesti gated the formati on of fi rst-row
transi ti on-metal phosphi des from precursor phosphates
of the general formul a NH
4
MPO
4
H
2
O (M ) Mn, Fe, Co,
Ni ). Whi l e we obtai ned FeP from NH
4
FePO
4
H
2
O, we
coul d obtai n onl y Ni
2
P and Co
2
P by the reducti on of the
correspondi ng ni ckel and cobal t phosphates. Reducti on
of FePO
4
on the other hand yi el ds Fe
2
P. From the TG
data (Fi gure 3a), the reacti on sequence for the formati on
of FeP from NH
4
FePO
4
H
2
O, for exampl e, coul d be
wri tten as fol l ows:
EDX anal ysi s and powder XRD data showed that the
products were si ngl e-phase phosphi des havi ng the
expected stoi chi ometry and structure, the l atti ce pa-
rameters (Tabl e 1) bei ng i n agreement wi th the val ues
reported i n the l i terature.
22
Reducti on of RuP
2
O
7
H
2
O
yi el ded RuP i nstead of the expected RuP
2
(Fi gures 2d
and 3d):
I t i s si gni fi cant that for Co
2
P, Ni
2
P, Fe
2
P, and RuP, the
precursor phosphate composi ti ons do not match wi th the
product phosphi des, i ndi cati ng that part of phosphorus
i s l ost duri ng the reducti on process.
I nteresti ngl y, we coul d not obtai n a manganese phos-
phi de by reducti on of NH
4
MnPO
4
H
2
O (Fi gure 3c). Al so,
both VOPO
4
2H
2
O and GaPO
4
di d not yi el d phosphi des
on reducti on up to 1000 C. Our i nabi l i ty to prepare
phosphi des of manganese, vanadi um, and gal l i um i s
si gni fi cant. The i mpl i cati on of thi s resul t i s di scussed
l ater.
We coul d readi l y synthesi ze a number of transi ti on
metal arseni des and anti moni des as wel l by the reduc-
ti on route. For exampl e, NH
4
Ni AsO
4
CH
3
CN2H
2
O and
CoAs
2
O
6
undergo faci l e reducti on around 400 C i n
hydrogen to yi el d the wel l -known Ni As (Fi gure 4a) and
CoAs. Si mi l arl y, we coul d synthesi ze CoSb
2
and Ni Sb
2
possessi ng the arsenopyri te and marcasi te structures,
(22) (a) FeP: Kjekshus, S. K. Acta Chem. Scand. 1972, 26, 1276.
(b) Co2P: Standard X-ray Di ffracti on Powder Paterns, NBS Monograph
25, Secti on 18; U.S. Department of Commerce, 1981; p 32. (c) Ni 2P:
Nowotny, H.; Hengl ei n, E. Z. Phys. Chem. 1938, 40, 281. (d) Fe2P:
Fuji i , H.; Komura, S.; Takeda, T.; Okamoto, T.; I to, Y.; Aki mi tsu, J. J .
Phys. Soc. J pn. 1979, 46, 1616.
Figure1. Thermogravi metri c curves for the reducti on of (a)
MoOPO4, (b) MoO2HPO4H2O, and (c) W2O3(PO4)2.
Figure2. Powder XRD patterns of (a) MoP, (b) WP, (c) Ni 2P,
and (d) RuP.
Figure3. Thermogravi metri c curves for the reducti on of (a)
NH4FePO4H2O, (b) NH4Ni PO4H2O, (c) NH4MnPO4H2O, and
(d) Ru2P2O72H2O.
NH
4
FePO
4
H
2
O f FeHPO
4
+ NH
3
+ H
2
O (1)
FeHPO
4
f
1
/
2
Fe
2
P
2
O
7
+
1
/
2
H
2
O (2)
1
/
2
Fe
2
P
2
O
7
+
7
/
2
H
2
f FeP +
7
/
2
H
2
O (3)
RuP
2
O
7
+
17
/
2
H
2
f RuP + P +
3
/
2
H
2
+ 7H
2
O (4)
Synthesis of Transition-Metal Pnictides Chem. Mater., Vol. 9, No. 10, 1997 2115
respecti vel y,
5
by the reducti on of tri ruti l e-l i ke CoSb
2
O
6
and Ni Sb
2
O
6
precursor anti monates. Reducti on of ar-
senates and anti monates occurs at rel ati vel y l ow tem-
peratures (400-650 C) to yi el d the pni cti des and cl ean
si ngl e-phase products coul d be prepared wi thi n a few
hours, whereas syntheses of these phases by di rect
reacti on route requi re several days of repeti ti ve reacti on
i n cl osed systems at hi gher temperatures.
12
We coul d
al so synthesi ze CoSb
3
possessi ng the skutterudi te struc-
ture
5
by reducti on of a new precursor, CoSb
3
O
9
. Agai n,
si ngl e-phase CoSb
3
was obtai ned at 575 C wi thi n a few
hours. We bel i eve thi s resul t i s qui te si gni fi cant
because of the recentl y di scovered thermoel ectri c ma-
teri al s based on the skutterudi te structure.
11
The fol l owi ng general observati ons coul d be made on
the basi s of the data gi ven i n Tabl e 1. We see that i n
general arsenates and anti monates undergo reducti on
at much l ower temperatures (400-650 C) than phos-
phates (700-1050 C). Thi s i s not surpri si ng i n vi ew
of the fact that pentaval ent arsenates and anti monates
are oxi di zi ng agents, whereas phosphates are stabl e
toward reducti on.
23
Another i mportant observati on i s
that whi l e most of the phosphates i nvesti gated yi el d
phosphi des on reducti on, there are three excepti ons,
namel y VOPO
4
2H
2
O, NH
4
MnPO
4
H
2
O, and GaPO
4
,
whi ch do not yi el d phosphi des on reducti on up to 1000
C. Thi s resul t i s si gni fi cant because i t gi ves an i nsi ght
i nto the thermodynami cs of the reducti on process.
When el ectrons and protons (hydrogen) are pumped i nto
the precursor phosphates at el evated temperatures, i t
i s l i kel y that the el ectrons fi rst go to the l owest
unoccupi ed (LUMO-l i ke) states whi ch are essenti al l y
deri ved from the metal d orbi tal s. Si mul taneousl y,
oxi de i ons woul d be removed by the protons, destabi l i z-
i ng the ani oni c P(V) states; accordi ngl y, P(V) becomes
suscepti bl e to reducti on. El ectron-ri ch M and P speci es
thus formed i n si tu duri ng the reducti on process even-
tual l y transforms to the appropri ate phosphi de under
the reacti on condi ti on. We therefore bel i eve that addi -
ti on of el ectrons to metal -l i ke LUMO states i s an
essenti al fi rst step that tri ggers reducti on of the phos-
phate i n the precursor. A si mi l ar process woul d be
operati ve for the reducti on of the arsenates and anti -
monates as wel l , except that the l atter are more easi l y
reduci bl e than the phosphates. These consi derati ons
al so expl ai n why phosphates l i ke GaPO
4
, VOPO
4
2H
2
O,
and NH
4
MnPO
4
H
2
O do not undergo reducti on to phos-
phi des; Ga (I I I ), V(I I I ), and Mn(I I ) cannot be reduced
by hydrogen to l ower oxi dati on states. Accordi ngl y, the
reducti on route i s appl i cabl e to the synthesi s of pni cti des
of onl y those transi ti on metal s whose bi nary oxi des are
reduci bl e by hydrogen; MoO
3
, WO
3
, FeO, CoO, and Ni O
are reduci bl e to the metal l i c state by H
2
, whi l e MnO,
V
2
O
3
, and Ga
2
O
3
are not.
We bel i eve that the resul ts of thi s paper have a much
wi der si gni fi cance i n the l i ght of the rel ati ve stabi l i ti es
of oxoani ons of nonmetal l i c el ements of groups 14 (Si ,
Ge, Sn), 15 (P, As, Sb), 16 (S, Se, Te), and 17 (Cl , Br, I ).
I t i s general l y known from the standard reducti on
potenti al data
24
that the stabi l i ty of XO
y
n-
(X ) non-
metal l i c el ement) ani ons decreases as we move from l eft
to ri ght and from top to bottom i n the peri odi c tabl e,
Si O
4
4-
bei ng most stabl e and I O
4
-
l east stabl e (hi ghl y
oxi di zi ng). Accordi ngl y, we suggest that the method
descri bed i n thi s paper coul d be extended to the syn-
thesi s of transi ti on-metal chal cogeni des (especi al l y se-
l eni des and tel l uri des) and even tetrel i des (stanni des
and pl umbi des). Further work to real i ze these objec-
ti ves i s i n progress. Fi nal l y, we i ndi cate i n a peri odi c
tabl e (Fi gure 5) the metal s and nonmetal s whose bi nary
and ternary compounds coul d be synthesi zed by hydro-
gen reducti on of oxoani on precursors.
Acknowledgment. We thank Professor C. N. R. Rao
for encouragement and support. We al so thank the
I ndo-French Centre for the Promoti on of Advanced
Research, New Del hi and the Department of Sci ence &
Technol ogy, Government of I ndi a, for fi nanci al support.
CM970175G
(23) Shri ver, D. F.; Atki ns, P. W.; Langford, C. H. I norganic
Chemistry; Oxford Uni versi ty Press: Oxford, 1991; p 337. (24) Reference 3, p D:158.
Figure4. Thermogravi metri c curves for the reducti on of (a)
NH4Ni AsO4CH3CN2H2O, (b) Ni Sb2O6, (c) CoSb2O6, and (d)
CoSb3O9.
Figure5. Peri odi c tabl e of el ements showi ng the appl i cabi l i ty
of oxoani on precursor reducti on route for the synthesi s of
metal -nonmetal compounds. Open tri angl es denote metal s
and nonmetal s for whi ch the route has been found appl i cabl e;
open ci rcl es denote metal s and nonmetal s for whi ch the route
i s l i kel y to be appl i cabl e but not i nvesti gated; fi l l ed ci rcl es
denote metal s for whi ch phosphate reducti on does not yi el d
phosphi de.
2116 Chem. Mater., Vol. 9, No. 10, 1997 Gopalakrishnan et al.