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| Compared with VO2 oxidation , V2O5 reduction by CO occurred at somewhat higher temperature .Nonstoichiometric V2O5 is an n-type semiconductor : vanadium ions in o.s.£¼5 compensate the oxygen vacancies formed in the reduction process .Assuming that at least in the first reduction step the main process is V5+¡úV4+ , the semiconducting properties arise from a hopping process between V4+ and V5+ ions [27] . The above-mentioned problems in EPR recording ( phase inversion , difficulty of tuning and effect of oxygen ) , the small values of [V4+]EPR/e and its strong decrease with reduction time (Fig.6) , are consistent with the suggestion that most of the electrons acquired in the reduction process were delocalized in the conduction band. A similar discrepancy between EPR and analytical data was found by others in non-stoichiometric V2O5-¦Ä ( d = 0.07 ) prepared by vacuum decomposition of AMV and explained with two consecutive reduction processes ( V5+¡úV4+¡úV3+ ) having two rate constants [9] .£¨Moreover , they found that non-stoichiometric and stoichiometric V2O5 ( obtained by heating V2O5-¦Ä in oxygen at 573K ) , submitted to reduction treatments with propylene , had the same dependence of the V4+ concentration detected by EPR vs. reductiontime . In the run at the highest temperature ( 573K ) the V4+ detected by EPR had time dependence similar to that we found at 773K . Our results suggest that the two rate constants originate from the different formation rate of V4+ ions and of electrons delocalized in the conduction band . |
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ganguihua1983(½ð±Ò+10,VIP+0):ºÜÊǸÐл! 1-16 11:40
ganguihua1983(½ð±Ò+10,VIP+0):ºÜÊǸÐл! 1-16 11:40
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kingoddess
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ganguihua1983(½ð±Ò+10,VIP+0): 1-16 12:53
ganguihua1983(½ð±Ò+10,VIP+0): 1-16 12:53
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kingoddess
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