主题:【资料】Spectroscopic Signatures of Nitrogen-Substituted Zeolites,JACS上新文章

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行文很清晰,思路很直接,结果很有用
最新online的JACS文章中有标题所提一文DOI:10.1021/ja8044844
文章采用试验和计算结合的办法,提出了N进入分子筛(硅铝酸盐)骨架的有力证据。试验用的是室温单脉冲Si谱,我估计采样时间不会超过30min。
计算采用高斯,由于没有重原子,所以方法上也没什么特别的,算是较为简单的计算任务。
使用简单的方法为何可以发表在JACS呢?我认为有两点:
一是研究具有重要意义,酸性的zeolite经过N掺杂(一般为通氨气处理)可以作为固体碱使用,并且已经用在一些反应中了。
二是实验与计算符合的很好,给出了N进入骨架的直接证据
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Spectroscopic Signatures of Nitrogen-Substituted Zeolites
Karl D. Hammond,† Fulya Dogan,§ Geoffrey A. Tompsett,† Vishal Agarwal,† W. Curtis Conner Jr.,† Clare P. Grey,§ and Scott M. Auerbach*†‡
Department of Chemical Engineering, University of Massachusetts, Amherst, Massachusetts 01003

Abstract:
Nanoporous acid catalysts such as zeolites form the backbone of catalytic technologies for refining petroleum. With the promise of a biomass economy, new catalyst systems will have to be discovered, making shape-selective base catalysts especially important because of the high oxygen content in biomass-derived feedstocks. Strongly basic zeolites are attractive candidates, but such materials are notoriously difficult to make due to the strong inherent acidity of aluminosilicates. Several research groups have endeavored to produce strongly basic zeolites by treating zeolites with amines, but to date there is no compelling evidence that nitrogen is incorporated into zeolite frameworks. In this communication, we detail synthesis, NMR spectroscopy, and quantum mechanical calculations showing that nitrogen adds onto both surface and interior sites while preserving the framework structure of zeolites. This finding is crucial for the rational design of new biomass-refinement catalysts, allowing 50 years of zeolite science to be brought to bear on the catalytic synthesis of biofuels.



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