Chatterjee Maya, Chatterjee Abhijit, Ishizaka Takayuki, Kawanami Hajime
Microflow Chemistry Group, Research Institute for Chemical Process Technology, AIST Tohoku 4-2-1, Nigatake, Miyagino-ku Sendai 983-8551 Japan
Materials Science, Dassault Systemes, BIOVIA K.K. Tokyo Think Park Tower, 2-1-1 Osaki Shinagawa-ku 141-6020 Japan.
RSC Adv. 2018 Jun 4;8(36):20190-20201. doi: 10.1039/c8ra03719a. eCollection 2018 May 30.
The development of a sustainable methodology for catalytic transformation of biomass-derived compounds to value-added chemicals is highly challenging. Most of the transitions are dominated by the use of additives, complicated reaction steps and large volumes of organic solvents. Compared to traditional organic solvents, alternative reaction media, which could be an ideal candidate for a viable extension of biomass-related reactions are rarely explored. Here, we elucidate a selective and efficient transformation of a biomass-derived aldehyde (furfural) to the corresponding alcohol, promoted in compressed CO using a Pt/AlO catalyst. Furfural contains a furan ring with C[double bond, length as m-dash]C and an aldehyde group, and is extremely reactive in a hydrogen atmosphere, resulting in several by-products and a threat to alcohol selectivity as well as catalyst life. The process described has a very high reaction rate (6000 h) with an excellent selectivity/yield (99%) of alcohol, without any organic solvents or metal additives. This strategy has several key features over existing methodologies, such as reduced waste, and facile product separation and purification (reduced energy consumption). Combining the throughput of experimental observation and molecular dynamics simulation, indeed the high diffusivity of compressed CO controls the mobility of the compound, and eventually maintains the activity of the catalyst. Results are also compared for different solvents and solvent-less conditions. In particular, combination of an effective Pt catalyst with compressed CO provides an encouraging alternative solution for upgradation of biomass related platform molecules.
开发一种将生物质衍生化合物催化转化为高附加值化学品的可持续方法极具挑战性。大多数转化过程主要依赖添加剂的使用、复杂的反应步骤以及大量有机溶剂。与传统有机溶剂相比，可作为生物质相关反应可行扩展的理想候选物的替代反应介质很少被探索。在此，我们阐明了在压缩CO中使用Pt/AlO催化剂促进生物质衍生醛（糠醛）选择性高效转化为相应醇的过程。糠醛含有一个带有C=C双键和醛基的呋喃环，在氢气气氛中极具反应性，会产生多种副产物，对醇的选择性以及催化剂寿命构成威胁。所描述的过程具有非常高的反应速率（6000 h），醇的选择性/产率极佳（99%），且无需任何有机溶剂或金属添加剂。该策略相对于现有方法具有几个关键特性，例如减少废物产生，以及便于产物分离和纯化（降低能耗）。结合实验观察和分子动力学模拟的通量，实际上压缩CO的高扩散性控制了化合物的迁移率，并最终维持了催化剂的活性。还比较了不同溶剂和无溶剂条件下的结果。特别是，有效的Pt催化剂与压缩CO的结合为生物质相关平台分子的升级提供了一种令人鼓舞的替代解决方案。
