MOF-Based Catalysts for Selective Hydrogenolysis of Carbon Oxygen Ether Bonds

被引：80

作者：

Stavila, Vitalie ^{[1
]}

Parthasarathi, Ramakrishnan ^{[1
,2
]}

Davi, Ryan W. ^{[1
]}

El Gabaly, Farid ^{[1
]}

Sale, Kenneth L. ^{[1
,2
]}

Simmons, Blake A. ^{[1
,2
]}

Singh, Seema ^{[1
,2
]}

Allendorf, Mark D. ^{[1
]}

机构：

[1] Sandia Natl Labs, Livermore, CA 94550 USA

[2] Joint BioEnergy Inst, Emeryville, CA 94608 USA

来源：

ACS CATALYSIS | 2016年 / 6卷 / 01期

关键词：

metal-organic frameworks; catalysis; C-O bond cleavage; hydrogenolysis; aromatic ethers; METAL-ORGANIC FRAMEWORKS; NICKEL; ADSORPTION; NANOPARTICLES; HYDROGENATION; CONVERSION;

D O I：

10.1021/acscatal.5b02061

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We demonstrate that metal organic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74(I) and Mg-IRMOF-74(II) are stable under reducing conditions and can cleave phenyl ethers containing beta-O-4, alpha-O-4, and 4-O-5 linkages to the corresponding hydrocarbons and phenols. Reaction occurs at 10 bar H-2 and 120 degrees C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg2+ ions on the pore walls. Ti and Ni doping further increase conversions to as high as 82% with 96% selectivity for hydrogenolysis versus ring hydrogenation. Repeated cycling induces no loss of activity, making this a promising route for mild aryl-ether bond scission.

引用

页码：55 / 59

页数：5

共 30 条

[1] Catalysis with Metal Nanoparticles Immobilized within the Pores of Metal-Organic Frameworks [J].