新型限域结构多功能纳米催化剂构筑及其催化生物质基呋喃衍生物胺化性能研究

Biomass-derived furan derivatives are favorable feedstocks for the synthesis of C5, C6 amino alcohols and diamines by catalytic amination, but the present heterogeneous amination metal catalysts still encounter the drawbacks of low activity (or stability) and poor selectivity. This project intends to construct novel multifunctional nanometal catalysts with confined structure to achieve the effective and directional conversion of biomass-derived furan derivatives to the target linear chain C5、C6 amino alcohols or diamines under mild conditions. The strategies for the construction of such catalysts are by using the synergistic effects between the subject (confined support, stabilizing active metals and adjusting product selectivity) and the object (metals with hydrogenation/dehydrogenation) and between metals, and by coupling the in situ generation of ω-hydroxy aldehydes or ω-amino alcohols (aldehydes) and their further amination. The properties of the active metal sites of the catalysts, the confine effect of the support, the reaction pathways and catalytic mechanisms were revealed by the studying of the deep relationships between catalyst structure, compositions and surface properties and catalytic performances, as well as the understanding of the laws of the adsorption and activation of reactant molecules and the highly active reaction intermediates. The effective methods for the control of reaction routes and product selectivity were thus established. These studies will lay the experimental and theoretical foundations for the development of novel stable catalysts with high efficiency in the amination of special oxygen-containing compounds with multifunctional groups from the molecular or atomic level.

生物质基呋喃衍生物是催化胺化合成C5、C6氨基醇和二元胺的良好原料，但目前的多相胺化金属催化剂还存在活性(或稳定性)不高和选择性较低等问题。本项目拟通过构筑新型限域结构多功能纳米催化剂，利用主体（限域载体，稳定活性金属并调控产物选择性）与客体（具有加/脱氢活性的双（多）金属）协同、双（多）金属之间协同并耦合ω-羟基醛或ω-氨基醇（醛）的原位生成与胺化，实现生物质基呋喃衍生物在温和条件下高效定向转化为目标直链C5、C6氨基醇或二元胺产物。通过对催化剂结构、组成和表面性质与性能之间内在关联的研究，反应物分子及高活性反应中间体在催化剂表面的吸附活化规律认识，深入揭示催化剂活性金属位特性、载体限域效应、反应路径和催化机理，建立有效调控反应路径和C=O、C-OH键高选择性胺化的方法，为从分子/原子水平创制针对特定多官能团含氧化学品高效胺化的新型稳定催化剂体系提供实验和理论依据。

围绕可再生生物质资源的高值化利用，开展了系列非贵金属特别是镍基催化剂催化生物糠醛衍生2-羟基四氢吡喃、5-氨基-2-戊酮还原胺化制备高附加值5-氨基戊醇和1,4-戊二胺性能研究，并深入研究了催化剂结构、组成、表面酸碱性、活性金属价态及尺寸等对催化性能影响。研究发现构筑性能匹配并能形成协同作用的特定结构和尺寸的纳米Ni（加氢部分）-固体酸（C=O、C=N吸附活化）双功能催化剂是选择性还原胺化糠醛衍生物合成氨基戊醇和戊二胺的关键。基于2-羟基四氢吡喃可原位异构化为高活性5-羟基戊醛，发展了5-氨基戊醇清洁高效合成新方法。以层状水滑石限域的纳米Ni-Mg3AlOx催化剂实现了2-羟基四氢吡喃高效还原胺化制备5-氨基戊醇，5-氨基戊醇收率可达93%，催化剂寿命超过90 h。为克服水滑石类材料在水热条件下因记忆效应发生重构，继而发生活性Ni0烧结及表面氧化，合成了兼具水滑石和尖晶石前体的高分散纳米Ni-Al2O3催化剂，将2-羟基四氢吡喃连续还原胺化的寿命提高至150 h以上。以该类催化剂发展了5-氨基-2-戊酮一步高效还原胺化制备磷酸氯喹关键侧链化合物N1,N1-二乙基-1,4-戊二胺的新方法，目标戊二胺收率高达99%，连续运行200小时未出现失活。通过构筑Ni-M（M=Fe、Co或Cu）双金属合金催化剂，提升催化剂的抗烧结、抗氧化性，将氯喹侧链化合物合成的寿命提升至500 h以上。此外，以羟基磷灰石纳米棒、纳米凹凸棒为载体负载限域的高分散纳米镍催化剂在系列生物质基醛、酮还原胺化反应中也表现出优异的催化活性。基于对纳米Ni催化剂加氢活性的认识，以NiCu合金催化剂实现高碳醛低温长寿命（超过1500 h）液相加氢制高碳醇，显示良好的工业应用前景。研究工作对发展高效稳定的纳米非贵金属催化剂具有重要的参考借鉴意义。