Abstract: Vanadium-phosphorous oxide catalysts modified with bismuth were prepared by coprecipitation and characterized by X-ray diffraction（XRD），FTIR and SEM. Catalytic behavior of the prepared Bi-modified vanadium-phosphorous oxide catalysts for selective oxidation of cyclohexane with hydrogen peroxide as the oxidant was investigated with variations in Bi/V and P/V molar ratios，solvent and temperature. Results showed that cyclohexane conversion and selectivity for cyclohexanone were obviously improved with the increase in Bi/V molar ratio. The P/V molar ratio showed a great influence on catalyst structure and performance. The addition of P could significantely destroy the crystal structure of V2O5 by producing some phosphates. Under optimized conditions，n（Bi）/ n（V）=0.1，n（P）/ n（V）=0.92，acetone as the solvent at 65 ℃for 8 h， cyclohexane conversion，cyclohexanone and cyclohexanol yields were 81.4%，58.2% and 23.2%，respectively.

摘要： 采用共沉淀法制备了铋改性钒磷氧催化剂，并用X 射线衍射（XRD）、FTIR、SEM等技术对催化剂进行了表征。以环己烷为原料，H2O2为氧化剂，铋改性的钒磷氧化物为催化剂，研究了氧化合成环己醇和环己酮反应，研究了Bi/V比率、P/V比率、溶剂和反应温度等因素对其反应性能的影响。结果表明，Bi/V比率提高时，环己烷转化率，尤其是环己酮的选择性明显提高。P/V比对改性催化剂活性和结构影响较大，P的加入破坏了V2O5的晶型结构，形成大量磷酸盐物种。在Bi/V摩尔比为0.1、P/V摩尔比为0.92、丙酮为溶剂、65 ℃的反应条件下，反应8 h，环己烷转化率为81.4%，环己酮和环己醇的收率分别为58.2%和23.2%。