制备具有丰富 VO/VCo 的 CuCo2O4@NFs 纳米花材料：氧化断裂木质素 β-O-4 键的优良催化剂

IF 4.7 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General Pub Date : 2024-10-18 DOI:10.1016/j.apcata.2024.119983

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引用次数: 0

摘要

通过简单的方法制备了一种具有丰富氧空位（VO）和钴空位（VCo）的中空纳米花材料 CuCo2O4@NFs。这种新型材料 CuCo2O4@NFs 具有优异的氧化活性，能裂解木质素模型化合物中的β-O-4 键。底物的转化率高达 99.02%，主要产物苯酚的产率达到 49.50%。结构分析表明，该材料的花瓣和空腔形式增加了其比表面积，有利于其与氧气分子充分接触。此外，退火过程中晶格氧脱离产生的 VO 有利于 O2 的吸附，而掺杂铜金属引起的晶格畸变产生的 VCo 则促进了氧中间产物的脱离。这两种缺陷的协同作用提高了限速步骤的速率。密度泛函理论计算显示，VO 和 VCo 的协同效应缩小了费米能级与 d 带中心之间的间隙，从而提高了电子迁移率。最后，通过循环实验证实了 CuCo2O4@NFs 极佳的可回收性。该材料的应用为木质素高效裂解为高附加值化学品提供了技术支持，实现了木质生物质资源的有效利用。

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Preparation of CuCo2O4@NFs nanoflower material with abundant VO/VCo: An excellent catalyst for oxidative breakage of the β-O-4 bond of lignin

A hollow nanoflower material CuCo₂O₄@NFs with abundant oxygen vacancies (V_O) and cobalt vacancies (V_Co) was prepared by a simple method. The novel material CuCo₂O₄@NFs showed excellent oxidation activity, cleaving the β-O-4 bond in lignin model compounds. Conversion of the substrate was as high as 99.02 %, and the yield of the main product, phenol, reached 49.50 %. Structural analysis showed that the petal and cavity form of the material increased its specific surface area, which facilitated its full contact with O₂ molecules. Moreover, the V_O generated by lattice oxygen detachment during annealing favor the adsorption of O₂, and the V_Co generated through lattice distortion induced by Cu-metal doping promoted the detachment of oxygen intermediates. The synergy of these two defects improved the rate of the rate-limiting step. Density functional theory calculations revealed that the synergistic effect of V_O and V_Co narrowed the gap between the Fermi energy levels and the d-band center, thereby enhancing electron mobility. Finally, excellent recyclability of CuCo₂O₄@NFs was confirmed through cycling experiments. The application of this material provided technical support for the efficient cracking of lignin into high-value-added chemicals and realized the effective utilization of woody biomass resources.

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来源期刊

Applied Catalysis A: General 化学-环境科学

CiteScore

9.00

自引率

5.50%

发文量

415

审稿时长

24 days

期刊介绍： Applied Catalysis A: General publishes original papers on all aspects of catalysis of basic and practical interest to chemical scientists in both industrial and academic fields, with an emphasis onnew understanding of catalysts and catalytic reactions, new catalytic materials, new techniques, and new processes, especially those that have potential practical implications. Papers that report results of a thorough study or optimization of systems or processes that are well understood, widely studied, or minor variations of known ones are discouraged. Authors should include statements in a separate section "Justification for Publication" of how the manuscript fits the scope of the journal in the cover letter to the editors. Submissions without such justification will be rejected without review.