CAJ | 학술논문

制备了多种金属-有机骨架(MOF)材料,采用浸渍-化学还原法制备了非晶态Ru-B/MOF催化剂,考察了它们在苯部分加氢反应中的催化性能.催化性能评价结果表明,这些催化剂的初始反应速率(r0)顺序为 Ru-B/MIL-53(Al)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO-66(Zr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-53(Cr)>Ru-B/MIL-101(Cr)>>Ru-B/MIL-100(Fe),环己烯初始选择性(S0)顺序为 Ru-B/MIL-53(Al)≈Ru-B/MIL-53(Cr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-101(Cr)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO-66(Zr)≈Ru-B/MIL-100(Fe).催化性能最好的Ru-B/MIL-53(Al)催化剂上的r0和S0分别为23 mmol?min-1?g-1和72%.采用多种手段,对催化性能差异最为显著的Ru-B/MIL-53(Al)和Ru-B/MIL-100(Fe)催化剂的物理化学性质进行了表征.发现MIL-53(Al)载体能够更好地分散Ru-B纳米粒子,粒子的平均尺寸为3.2 nm,而MIL-100(Fe)载体上Ru-B纳米粒子团聚严重,粒径达46.6 nm.更小的粒径不仅能够提供更多的活性位,而且也有利于环己烯选择性的提高.对Ru-B/MIL-53(Al)催化剂的反应条件进行了优化,在180°C和5 MPa的H2压力下,环己烯得率可达24%,展示了MOF材料用作苯部分加氢催化剂载体的良好前景.
제비료다충금속-유궤골가(MOF)재료,채용침지-화학환원법제비료비정태Ru-B/MOF최화제,고찰료타문재분부분가경반응중적최화성능.최화성능평개결과표명,저사최화제적초시반응속솔(r0)순서위 Ru-B/MIL-53(Al)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO-66(Zr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-53(Cr)>Ru-B/MIL-101(Cr)>>Ru-B/MIL-100(Fe),배기희초시선택성(S0)순서위 Ru-B/MIL-53(Al)≈Ru-B/MIL-53(Cr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-101(Cr)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO-66(Zr)≈Ru-B/MIL-100(Fe).최화성능최호적Ru-B/MIL-53(Al)최화제상적r0화S0분별위23 mmol?min-1?g-1화72%.채용다충수단,대최화성능차이최위현저적Ru-B/MIL-53(Al)화Ru-B/MIL-100(Fe)최화제적물이화학성질진행료표정.발현MIL-53(Al)재체능구경호지분산Ru-B납미입자,입자적평균척촌위3.2 nm,이MIL-100(Fe)재체상Ru-B납미입자단취엄중,립경체46.6 nm.경소적립경불부능구제공경다적활성위,이차야유리우배기희선택성적제고.대Ru-B/MIL-53(Al)최화제적반응조건진행료우화,재180°C화5 MPa적H2압력하,배기희득솔가체24%,전시료MOF재료용작분부분가경최화제재체적량호전경.
A series of metal-organic framework (MOF) materials were synthesized together with the corresponding amorphous Ru-B/MOF catalysts, which were prepared by the impregnation-chemical reduction method. These materials were subsequently evaluated for the first time as catalysts for the partial hydrogenation of benzene to cyclohexene. The results for the initial hydrogenation rate (r0) for the different catalysts fol owed the trend Ru-B/MIL-53(Al)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO-66(Zr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-53(Cr)>Ru-B/MIL-101(Cr)>>Ru-B/MIL-100(Fe), whereas the initial selectivity for cyclohexene (S0) was of the order of Ru-B/MIL-53(Al)≈Ru-B/MIL-53(Cr)>Ru-B/UIO-66(Zr)-NH2>Ru-B/MIL-101(Cr)>Ru-B/MIL-53(Al)-NH2>Ru-B/UIO- 66(Zr)≈Ru-B/MIL-100(Fe). The Ru-B/MIL-53(Al) catalyst exhibited the highest r0 and S0 values of 23mmol?min-1? g-1 and 72%, respectively. The characterization results demonstrated that the Ru-B amorphous alloy nanoparticles were highly dispersed on MIL-53(Al) with the average diameter of 3.2 nm. In contrast, the Ru-B nanoparticles on MIL-100(Fe) had an average diameter of 46.6 nm. The smaller Ru-B nanoparticles not only provided more active sites for the hydrogenation to occur, but could also be beneficial in the formation of cyclohexene. The reaction conditions were further optimized for the Ru-B/MIL-53(Al) catalyst. At 180 °C under a H2 pressure of 5 MPa, a cyclohexene yield of 24% was obtained, highlighting the potential of MOF materials as catalyst supports for the partial hydrogenation of benzene.