Vv. Guliants et al., THE EFFECT OF THE PHASE-COMPOSITION OF MODEL VPO CATALYSTS FOR PARTIAL OXIDATION OF N-BUTANE, Catalysis today, 28(4), 1996, pp. 275-295
X-ray diffraction, Raman spectroscopy, P-31 MAS-NMR and spin-echo NMR
indicated that model vanadium phosphorus oxide (VPO) precursors and ca
talysts contained various minor phases depending on both the synthetic
approach and P/V ratios used. Raman spectroscopy revealed the presenc
e of a number of micro-crystalline and amorphous V(IV) and V(V) phases
not evident by XRD, The presence of VOPO4 phases was detrimental to t
he performance of the VPO catalysts for M-butane oxidation. The best m
odel organic VPO catalyst contained only vanadyl pyrophosphate with th
e highest degree of stacking order and virtually no VOPO, phase impuri
ty. Raman spectroscopy detected vanadyl metaphosphate, VO(PO3)(2), in
the catalysts derived from aqueous precursors possessing P/V ratios gr
eater than 1. Pure vanadyl metaphosphate catalyst was inactive in n-bu
tane oxidation. P-31 NMR demonstrated the absence of vanadyl metaphosp
hate and other impurity phases in the best catalyst derived from organ
ic precursors at P/V = 1.18. The experimental data strongly indicate t
hat the best VPO catalysts for n-butane oxidation contain only vanadyl
pyrophosphate with well-ordered stacking of the (200) planes.