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水滑石负载钯催化剂上的醇无氧脱氢反应

ISSN号：0253-9837
期刊名称：《催化学报》
时间：0
分类：O643[理学—物理化学;理学—化学]
作者机构：[1]厦门大学化学化工学院固体表面物理化学国家重点实验室,醇醚酯化工清洁生产国家工程实验室,福建厦门361005, [2]中国科学院福建物质结构研究所结构化学国家重点实验室,福建福州350002
相关基金：国家自然科学基金（20873110 20625310 20923004）; 国家重点基础研究发展计划（973计划 2010CB732303）; 高等学校博士学科点专项科研基金（20090121110007）; 福建省重大研究专项（2009HZ0002-1）

作者：陈静[1,2], 张庆红[1], 方文浩[1], 王野[1], 万惠霖[1]

关键词：绿色催化, 醇, 脱氢反应, 水滑石, 钯, 纳米粒子, 酸碱双功能, green catalysis, alcohol, dehydrogenation, hydrotalcite, palladium, nanoparticle, acid-base bifunctionality

中文摘要：

研究了多种载体负载Pd催化剂上苯甲醇无氧脱氢反应.结果发现,以兼具较强酸性和碱性的水滑石（HT）为载体时,Pd催化剂具有优异的苯甲醇转化活性和苯甲醛选择性,当Pd含量为0.32%～0.55%时催化性能最佳.Pd/HT催化剂可重复使用,且对于含推电子取代基的芳香醇、2-噻吩甲醇、α,β-不饱和醇与环状脂肪醇等的直接脱氢反应均具有较好催化性能.HT表面的Pd（II）物种反应后转变为平均粒径为2.0～2.5nm的Pd纳米粒子或纳米簇.具有较高分散度的Pd（II）物种易转变为较小的Pd纳米粒子,从而具有较佳的催化性能.本文推测,催化剂表面的碱性位可促进苯甲醇O-H键的活化,形成Pd-苯甲氧基中间体,该中间体进一步脱氢生成苯甲醛和Pd-H物种;而催化剂表面的质子酸位可与Pd-H作用,促进H2的脱除.

英文摘要：

Pd catalysts supported on various supports have been studied for the oxidant-free dehydrogenation of alcohols.The Pd catalyst loaded on hydrotalcite （HT）,which is an acid-base bifunctional support,demonstrates superior benzyl alcohol conversion and benzaldehyde selectivity.Detailed studies using the Pd/HT catalyst reveal that the best performance can be obtained over the catalyst with w（Pd）=0.32%-0.55%.The Pd/HT can be used repeatedly without significant deactivation and can efficiently catalyze the dehydrogenation of various alcohols including the substituted benzylic alcohols,2-thiophenemethanol,α,β-unsaturated alcohols,and cyclic aliphatic alcohols.The characterization results show that the Pd（II） species over the HT are transformed into Pd nanoparticles or nanoclusters with mean size of 2.0-2.5 nm during the reaction.The highly dispersed Pd（II） species in the catalyst precursors can lead to the formation of smaller Pd nanoparticles,favoring the catalytic performance.We speculate that the basicity of the catalyst may promote the activation of the O-H bond of alcohol to form a Pd-benzyl alcoholate intermediate,which undergoes β-H abstraction by Pd nanoparticles,and the Brnsted acid sites on the catalyst surface may facilitate the release of H2 by the interaction with the formed hydride species on Pd nanoparticles.