Molten plastic induced noncovalent interactions for tunable cellulose fast pyrolysis
Molten plastic induced noncovalent interactions for tunable cellulose fast pyrolysis
复制标题
熔融塑料诱导非共价相互作用用于可调纤维素快速热解
DOI：
10.1039/d3gc01312j
复制
发表时间：
2023
期刊：
影响因子：
9.8
通讯作者：
Wong, Hsi-Wu
中科院分区：
文献类型：
--
作者：
Sakirler, Fuat;Tekbas, M. Doga;Wong, Hsi-Wu
木质纤维素生物质的快速热解是生产生物燃料和可再生化学品的一种有前景的方法，但由此产生的生物油质量和多样化的产品分布限制了其广泛应用。与此同时，废塑料（特别是聚烯烃热塑性塑料）在环境中的积累正成为一个日益严重的威胁。生物质与富氢热塑性塑料的共热解已显示出生产高质量生物油的前景，为废物管理提供了一种有吸引力的解决方案。然而，对于共热解过程中熔融相中两种组分的协同作用仍然缺乏分子水平的理解。在这项工作中，我们报告了熔融塑料诱导的非共价相互作用（NCI）对纤维素快速热解的催化和抑制作用的发现。我们的微反应器实验表明，由于聚酮、聚乙二醇或聚苯乙烯（这三种具有不同官能团的热塑性塑料）的存在，对纤维素衍生的脱水糖、小含氧化合物或呋喃的选择性分别增加。密度泛函理论计算表明，由于塑料官能团诱导的 NCI 引起的过渡态几何形状和部分电荷的扰动，导致产生主要产物的关键纤维素热解途径被催化或抑制。这一发现为使用一系列新的非常规熔融塑料催化剂或抑制剂通过 NCI 调节纤维素快速热解提供了见解和机会。
Fast pyrolysis of lignocellulosic biomass is a promising approach for producing biofuels and renewable chemicals, but the resultant bio-oil quality and diverse product distributions limit its widespread adaptation. Concurrently, the accumulation of waste plastics in the environment, particularly polyolefin thermoplastics, is becoming a growing threat. Co-pyrolysis of biomass with hydrogen-rich thermoplastics has shown promise for producing high-quality bio-oils, presenting an attractive solution to waste management. However, a molecular-level understanding of the synergy of the two components in the molten phase during co-pyrolysis is still lacking. In this work, we report the discovery of catalytic and inhibitory effects on cellulose fast pyrolysis caused by noncovalent interactions (NCIs) induced by molten plastics. Our microreactor experiments demonstrated that selectivity toward cellulose-derived anhydrosugars, small oxygenates, or furans increased due to the presence of polyketone, polyethylene glycol, or polystyrene, respectively, which are three thermoplastics with distinct functional groups. Density functional theory calculations reveal that key cellulose pyrolysis pathways leading to major products are catalyzed or inhibited due to perturbations of transition state geometries and partial charges caused by the NCIs induced by plastic functional groups. This discovery offers insights and opportunities for tuning cellulose fast pyrolysis via NCIs using a new family of unconventional molten plastic catalysts or inhibitors.