利用原位红外光谱研究若干过渡金属氧化物丙酸体系,Fe_2Cr(μ_3-O)(μ-O_2CC_2H_5)_6(H_2O)_3Cl·xH_2O及Cr_3(μ_3-O)(μ-O_2CC_2H_5)_6(H_2O)_3NO_3·xH_2O的反应行为

In Situ IR Study of the Reaction Behavior of Transition Metal Oxides-Propionic Acid System,Fe_2Cr(μ_3-O)(μ-O_2CC_2H_5)_6(H_2O)_3Cl·xH_2O and Cr_3(μ_3-O)(μ-O_2CC_2H_5)_6(H_2O)_3NO_3·xH_2O

利用原位红外光谱法研究标题化合作在N2 中的反应行为。发现它们在不同温度下能使丙酸分别转化为乙醛和戊酮。金属氧化物对丙酸的戊酮化反应活性顺序是 :Fe3O4 >MnO2 >Cr2 O3>Co2 O3>Ni2 O3,这顺序与下列簇合物对该反应的活性顺序类似 :[Fe2 MnOPH]>[Fe3OPH]>[Fe2 CrOPH]>[Fe2 CoOPH]>[Fe2 NiOPH]>[Cr3OPH][OPH =(μ3 O) (μ O2 CC2 H5) 6(H2 O) 3]。对于戊酮化反应 ,过渡金属氧化物的反应温度明显高于相应的 [Fe2 MOPH]的反应温度 ,这旁证了 [Fe2 MOPH]的活性组分不是其金属氧化物。还讨论了Fe3O4 ,Fe2 O3 对丙酸分别转化为乙醛和戊酮反应活性的明显差异。

The reaction behavior of the title complexes have been investigated by means of in situ IR in nitrogen atmosphere.It has been found that they enabled the propionic acid to convert to acetaldehyde and pentanone in different temperature.The sequence of the ketonization reaction activity for metal oxides Fe 3O 4>MnO 2>Cr 2O 3>Co 2O 3>Ni 2O 3 has analogy to that for metal clusters [Fe 2MnOPH]>[Fe 3OPH]>[Fe 2CrOPH]>[Fe 2CoOPH]>[Fe 2NiOPH]>[Cr 3OPH][OPH=(μ 3-O)(μ-O 2CC 2H 5) 6(H 2O) 3].For the ketonization reactions,the reaction temperatures of transition-metal oxides were much higher than that of corresponding metal clusters [Fe 2MOPH].It has been verified that the active component of metal cluster [Fe 2MOPH] is not the corresponding transition-metal oxides.The difference between Fe 3O 4 and Fe 2O 3 which catalyze the convertion of propionic acid to acetaldehyde and pentanone respectively were demonstrated.