Cl⁻介导 Fe/MgO-CaO 晶面工程与电子结构协同调控催化甘油氢解

Cl⁻ Mediated Facet Engineering and Electronic Modulation of Fe/MgO-CaO Catalysts for Glycerol Hydrogenolysis

摘要

针对传统浸渍法制备催化剂中活性组分易团聚、高活性晶面难以定向暴露等问题, 本文提出了一种Cl⁻介导的晶体定向生长与电子结构等多重调控策略, 有效提升了Fe/MgO-CaO的催化性能. 研究结果表明, 在宏观形貌上, NH₄Cl热解产生的气体刻蚀效应构建了催化剂的多孔特征, 并作为形貌调节剂诱导MgO-CaO由无序片状定向生长为(200)晶面择优暴露的棒状结构. 在微观物相上, Cl⁻的掺杂强化了Fe物种与MgO晶格的相互作用, 有效抑制了活性组分的团聚, 促进形成高分散的Mg-Fe-O固溶体. 此外, 还在催化剂表面衍生出均匀分布的Lewis酸位点. 且棒状固溶体结构在反应中表现出优异的稳定性, 有效避免了骨架坍塌. 当Fe/Cl摩尔比为1.00时, 与未掺杂的样品甘油转化率相比从60%提升至90%. 本文采用的Cl⁻多重调控策略为天然矿物资源的高值化利用及高效非贵金属氧化物催化剂的设计提供了新的研究思路.

Abstract

To overcome the limitations of active component aggregation and uncontrolled facet exposure typical of impregnation methods, we report a chloride-mediated engineering strategy to precisely tailor the morphology and electronic structure of Fe/MgO-CaO catalysts. Structural characterizations reveal that the gas-etching effect during NH₄Cl pyrolysis creates a porous architecture. Acting as a morphological modifier, NH₄Cl induces the directional growth of MgO-CaO from disordered sheets into a rod-like structure with preferentially exposed (200) facets. At the microstructural level, Cl⁻ doping strengthens the interaction between Fe species and the MgO lattice. This effectively inhibits the agglomeration of active components and promotes the formation of a highly dispersed Mg-Fe-O solid solution, while generating uniformly distributed Lewis acid sites on the catalyst surface. Consequently, the unique rod-like solid solution exhibits excellent structural stability during the catalytic reaction, successfully preventing framework collapse. Consequently, the optimized catalyst (Fe-Cl=1.00) boosted glycerol conversion from 60% to 90% relative to the Cl⁻ free benchmark. This chloride-mediated engineering strategy provides a blueprint for valorizing natural minerals and rationally designing robust non-noble metal catalysts.

关键词

甘油 / 铁氧化物 / 氯离子 / MgO-CaO / 1,2-丙二醇

Key words

Glycerol / Iron oxide / Chloride (Cl⁻) / MgO-CaO / 1,2-Propanediol

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基金资助

国家自然科学基金(42572045)

国家自然科学基金(22072136)

国家自然科学基金(W2433034)