Grand Julien, Talapaneni Siddulu Naidu, Vicente Aurélie, Fernandez Christian, Dib Eddy, Aleksandrov Hristiyan A, Vayssilov Georgi N, Retoux Richard, Boullay Philippe, Gilson Jean-Pierre, Valtchev Valentin, Mintova Svetlana
Laboratoire Catalyse et Spectrochimie (LCS) Normandie Univ, ENSICAEN, UNICAEN, CNRS, 14000 Caen, France.
Faculty of Chemistry and Pharmacy, University of Sofia, 1126 Sofia, Bulgaria.
Nat Mater. 2017 Oct;16(10):1010-1015. doi: 10.1038/nmat4941. Epub 2017 Jul 31.
The synthesis of nanostructured zeolites enables modification of catalytically relevant properties such as effective surface area and diffusion path length. Nanostructured zeolites may be synthesized either in alkaline media, and so contain significant numbers of hydrophilic silanol groups, or in expensive and harmful fluoride-containing media. Here, we report and characterize, using a combination of experimental and theoretical techniques, the one-pot synthesis of silanol-free nanosized MFI-type zeolites by introducing atomically dispersed tungsten; this prevents silanol group occurrence by forming flexible W-O-Si bridges. These W-O-Si bonds are more stable than Si-O-Si in the all-silica MFI zeolite. Tungsten incorporation in nanosized MFI crystals also modifies other properties such as structural features, hydrophobicity and Lewis acidity. The effect of these is illustrated on the catalytic epoxidation of styrene and separation of CO and NO. Silanol-free nanosized W-MFI zeolites open new perspectives for catalytic and separation applications.
纳米结构沸石的合成能够改变与催化相关的性质,如有效表面积和扩散路径长度。纳米结构沸石可以在碱性介质中合成,因此含有大量亲水性硅醇基团,也可以在昂贵且有害的含氟介质中合成。在此,我们结合实验和理论技术,报道并表征了通过引入原子分散的钨一锅法合成无硅醇的纳米尺寸MFI型沸石;这通过形成柔性的W-O-Si桥来防止硅醇基团的出现。在全硅MFI沸石中,这些W-O-Si键比Si-O-Si键更稳定。钨掺入纳米尺寸的MFI晶体中还会改变其他性质,如结构特征、疏水性和路易斯酸性。这些性质对苯乙烯催化环氧化以及CO和NO分离的影响得到了说明。无硅醇的纳米尺寸W-MFI沸石为催化和分离应用开辟了新的前景。