Atomically dispersed Zn sites on N-doped carbon boosted transesterification of symmetrical organic carbonates with biomass-derived alcohols

IF 6.5 1区 化学 Q2 CHEMISTRY, PHYSICAL Journal of Catalysis Pub Date : 2024-09-17 DOI:10.1016/j.jcat.2024.115763
Yayun Pang , Long Tao , Ziyang Wang , Chenglei Xiao , Kaili Wang , Kongqian Liang , Jinliang Song , Tiejun Wang
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Abstract

Transesterification of symmetrical organic carbonates with alcohols to access the unsymmetrical ones is a highly attractive strategy for upgrading biomass-derived alcohols. Robust, facile-prepared, and cost-effective catalytic materials remain highly desirable for this route. Herein, we designed several Zn-based catalysts (denoted as Zn@C-T, where T represented the pyrolysis temperature) by the pyrolysis of Zn-based coordination polymer at different temperatures. Very interestingly, the prepared Zn@C-900 could efficiently catalyze the transesterification of diethyl carbonate (DEC) with various biomass-derived alcohols to synthesize the corresponding unsymmetrical organic carbonates with high yields (>95 %), resulting from the atomically dispersed ZnNx sites on the N-doped carbon. Notably, good catalytic activity could be obtained at a low temperature of 80 °C, representing the major breakthrough. Detailed investigations indicated that the excellent performance of Zn@C-900 originated mainly from the synergistic effect of Zn (to activate DEC) and N (to activate the alcohols) in the ZnNx sites. This work provided a promising efficient catalyst for low-temperature production of unsymmetrical organic carbonates via transesterification of DEC.

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掺杂 N 的碳上原子分散的 Zn 位点促进了对称有机碳酸盐与生物质衍生醇的酯交换反应
将对称的有机碳酸盐与醇类进行酯交换反应以获得不对称的有机碳酸盐,是一种极具吸引力的生物质衍生醇类升级策略。对于这条路线来说,稳健、易于制备且具有成本效益的催化材料仍然是非常理想的。在此,我们通过在不同温度下热解 Zn 基配位聚合物,设计了几种 Zn 基催化剂(称为 Zn@C-T,其中 T 代表热解温度)。有趣的是,所制备的 Zn@C-900 能有效催化碳酸二乙酯(DEC)与各种生物质衍生醇的酯交换反应,合成相应的非对称有机碳酸盐,产率高达 95%,这得益于掺杂 N 的碳上原子分散的 ZnNx 位点。值得注意的是,在 80 °C 的低温下就能获得良好的催化活性,这是一项重大突破。详细研究表明,Zn@C-900 的优异性能主要源于 ZnNx 位点中 Zn(活化 DEC)和 N(活化醇类)的协同效应。这项工作为通过 DEC 的酯交换反应低温生产不对称有机碳酸盐提供了一种前景广阔的高效催化剂。
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来源期刊
Journal of Catalysis
Journal of Catalysis 工程技术-工程:化工
CiteScore
12.30
自引率
5.50%
发文量
447
审稿时长
31 days
期刊介绍: The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes. The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods. The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.
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