碳热还原一步构建氧化铝修饰CuNi合金催化剂及其乙酰丙酸转移加氢性能  

Alumina-modified CuNi Alloy Catalyst Prepared by One-step Carbothermic Reduction and Its Levulinic Acid Transfer Hydrogenation Properties

作　　者：俞南汐 鲁厚芳[2] 吴可荆 YU Nan-xi;LU Hou-fang;WU Ke-jing(Institute of New Energy and Low-Carbon Technology,Chengdu 610065,China;School of Chemical Engineering,Sichuan University,Chengdu 610065,China)

机构地区：[1]四川大学新能源与低碳技术研究院,四川成都610065 [2]四川大学化学工程学院,四川成都610065

出　　处：《化学试剂》2022年第12期1747-1755,共9页Chemical Reagents

基　　金：国家自然科学基金资助项目(21808148)。

摘　　要：在以异丙醇为氢供体的乙酰丙酸转移加氢反应中,催化剂需同时具有用于氢转移的加氢位点和用于乙酰丙酸与醇酯化的酸性位点。以氧化铝为酸性位点,铜镍为加氢位点,以碳热还原法一步构建了酸修饰的CuNi合金催化剂。碳热还原温度大于450℃时,能得到CuNi合金;过高的还原温度下,部分铜还没有进入合金相就已经被还原成Cu_(2)O,不利于铜镍合金的形成。还原温度较低的催化剂上虽然零价金属较少,但反应过程中异丙醇能把金属氧化物还原至零价金属;还原温度较高时,得到的零价金属较多,但颗粒团聚更严重。这些作用拉平了还原温度的影响,在300~600℃下碳热还原得到的催化剂表现出相近的催化活性。In the transfer hydrogenation reaction of levulinic acid with isopropanol as hydrogen donor,the catalyst should have both a metal site for hydrogen transfer and an acid site for the esterification of levulinic acid with alcohol.Acid modified CuNi alloy catalyst was constructed by carbothermic reduction with alumina as acid site and copper and nickel as hydrogenation site.CuNi alloy can be obtained when the reduction temperature was higher than 450℃.At high reduction temperature,part of copper had been reduced to Cu_(2)O before entering the alloy phase,which was not conducive to the formation of CuNi alloy.Catalysts with lower reduction temperatures had less zero-valent metals,but isopropanol can reduce metal oxides to metals in the reaction.When the calcination temperature was higher,more zero-valent metals were obtained,but the agglomeration of particles were more serious.These effects smoothen the effect of reduction temperature,and the catalyst obtained by carbothermic reduction at 300~600℃ exhibits similar catalytic activity.

关 键 词：转移加氢 乙酰丙酸 酸性位 CuNi合金 碳热还原 

分 类 号：O69[理学—化学]