MOF衍生Rh/ZrO_2@C催化剂的制备及氢甲酰化性能研究
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摘要
以UIO-66为前驱体,通过高温惰性气氛下焙烧得到ZrO_2@C载体,采用吸附还原方法制备了1%Rh/ZrO_2@C催化剂。通过X射线衍射、热重、高分辨透射电镜等对催化剂结构进行分析,结果表明,金属Rh在载体上高度分散。将所合成的催化剂用于1-十二烯的氢甲酰化反应,考察了反应温度和反应压力对催化剂性能的影响。结果表明,当反应温度为90℃、反应压力为4 MPa时,催化剂具有较好的催化性能,1-十二烯转化率为94. 2%,十三醛选择性达到98. 9%,且催化剂循环使用4次后,活性无明显下降。
ZrO_2@ C carrier is obtained by calcining UIO-66 materials under inert atmosphere at high temperature.The 1% Rh/ZrO_2@ C catalyst is prepared through adsorption reduction method.XRD,TG and HRTEM measurements are used to characterize the obtained catalysts. The results indicate that metal Rh disperses highly on the carrier.Hydroformylation reaction of 1-dodecene is applied to evaluate the catalytic performance of 1% Rh/ZrO_2@ C catalyst.Influences of reaction temperature and pressure on the performance of catalyst are investigated. It is shown that the catalyst exhibits good catalytic performance at 90℃ and 4 MPa,the conversion of 1-dodecene can achieve about 94. 2%and the selectivity of tridecylic aldehyde reaches 98. 9%.Moreover,there is no obvious loss in catalytic activity after the catalyst has been reused 4 times.
ZrO_2@ C carrier is obtained by calcining UIO-66 materials under inert atmosphere at high temperature.The 1% Rh/ZrO_2@ C catalyst is prepared through adsorption reduction method.XRD,TG and HRTEM measurements are used to characterize the obtained catalysts. The results indicate that metal Rh disperses highly on the carrier.Hydroformylation reaction of 1-dodecene is applied to evaluate the catalytic performance of 1% Rh/ZrO_2@ C catalyst.Influences of reaction temperature and pressure on the performance of catalyst are investigated. It is shown that the catalyst exhibits good catalytic performance at 90℃ and 4 MPa,the conversion of 1-dodecene can achieve about 94. 2%and the selectivity of tridecylic aldehyde reaches 98. 9%.Moreover,there is no obvious loss in catalytic activity after the catalyst has been reused 4 times.
引文
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[2]Bortenschlager M,Mayr M,Nuyken O,et al.Hydroformylation of 1-octene using rhodium-1,3-R 2-3,4,5,6-tetrahydropyrimidin-2-ylidenes(R=2-Pr,mesityl)[J]. Journal of Molecular Catalysis A:Chemical,2005,233(1):67-71.
[3]Frank R,Setle D,Borner A.Applied hydroformylation[J].Chemical Reviews,2012,112(11):5675-5732.
[4]胡嵩霜,郑明芳.铑催化剂在1-辛烯氢甲酰化反应中的应用[J].现代化工,2018,7(38):172-175.
[5]Behr A,Obst D,Turkowski B.Isomerizing hydroformylation of trans-4-octene to n-nonanal in multiphase systems:Acceleration effect of propylene carbonate[J]. Journal of Molecular Catalysis A:Chemical,2005,226(2):215-219.
[6]贺德华,马兰,彭庆蓉.一种从烯烃和合成气制造醛的方法.中国:CN101279900[P].2008-04-11.
[7]Jiang M,Yan L,Ding Y,et al.Ultrastable 3V-PPh3polymers supported single Rh sites for fixed-bed hydroformylation of olefins[J].Journal of Molecular Catalysis A:Chemical,2015,s404-405:211-217.
[8]马昱博,高志贤,吾满江·艾力.Rh/SiO2催化剂上双环戊二烯氢甲酰化[J].工业催化,2012,20(11):52-56.
[9]Lang R,Li T,Matsumura D,et al.Hydroformylation of olefins by a rhodium single-atom catalyst with activity comparable to RhCl(PPh3)3[J].Angewandte Chemie International Edition,2016,55(52):16054.
[10]Li C,Sun K,Wang W,et al. Xantphos doped Rh/POPs-PPh3catalyst for highly selective long-chain olefins hydroformylation:Chemical and DFT insights into Rh location and the roles of Xantphos and PPh3[J].Journal of Catalysis,2017,353:123-132.
[11]Lee J Y,Farha O K,Roberts J,et al.Metal-organic framework materials as catalysts[J]. Chemical Society Reviews,2009,38(5):1450-1459.
[12]Cao W,Luo W,Ge H,et al. UIO-66 derived Ru/Zr O2@C as a highly stable catalyst for hydrogenation of levulinic acid toγ-valerolactone[J].Green Chemistry,2017,19(9):2201-2211.
[13]Guo Z,Xiao C,Maligalganesh R V,et al.Pt nanoclusters confined within metal-organic framework cavities for chemoselective cinnamaldehyde hydrogenation[J]. ACS Catalysis,2014,4(5):1340-1348.
[14]Hou C,Zhao G,Ji Y,et al. Hydroformylation of alkenes over rhodium supported on the metal-organic framework ZIF-8[J].Nano Research,2014,7(9):1364-1369.
[15]刘倩,刘伯潭.新型Rh-Ni@MOF-5催化剂催化烯烃氢甲酰化反应的研究[J].现代化工,2017,37(5):71-75.
[16]Li X,Zhang B,Tang L,et al.Cooperative multifunctional catalysts for nitrone synthesis:Platinum nanoclusters in amine-functionalized metal-organic frameworks[J]. Angewandte Chemie International Edition,2017,129(51):16589-16593.
[17]Rsler C,Dissegna S,Rechac V L,et al.Encapsulation of bimetallic metal nanoparticles into robust zirconium-based metal-organic frameworks:Evaluation of the catalytic potential for size-selective hydrogenation[J]. Chemistry-A European Journal,2017,23(15):3583-3594.
[18]Sun D,Xu M,Jiang Y,et al.Small-sized bimetallic CuPd nanoclusters encapsulated inside cavity of NH2-UIO-66(Zr)with superior performance for light-induced suzuki coupling reaction[J]. The Journal of Physical Chemistry,2016,120(35):1-27.
[19]Cavka J H,Jakobsen S,Olsbye U,et al.A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability[J]. Journal of the American Chemical Society,2008,130(42):13850-13851.
[20]Liu S,Yue Z,Liu Y.Mesoporous carbon-ZrO2composites prepared using thermolysis of zirconium based metal-organic frameworks and their adsorption properties[J].Journal of Porous Materials,2015,22(2):465-471.