Lewis-Bronsted Acid Pairs in Ga/H-ZSM-5 To Catalyze Dehydrogenation of Light Alkanes

被引：242

作者：

Schreiber, Moritz W. ^{[1
,2
]}

Plaisance, Craig P. ^{[1
]}

Baumgaertl, Martin ^{[1
]}

Reuter, Karsten ^{[1
]}

Jentys, Andreas ^{[1
]}

Bermejo-Deval, Ricardo ^{[1
]}

Lercher, Johannes A. ^{[1
]}

机构：

[1] Tech Univ Munich, Dept Chem, Catalysis Res Ctr, Lichtenbergstr 4, D-85747 Garching, Germany

[2] TOTAL Res & Technol Feluy, Zone Ind Feluy C, B-7181 Seneffe, Belgium

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2018年 / 140卷 / 14期

关键词：

DENSITY-FUNCTIONAL THEORY; AB-INITIO; AROMATIZATION; CONVERSION; ZEOLITES; GALLIUM; CATIONS; CRACKING; HYDRIDE; PROPANE;

D O I：

10.1021/jacs.7b12901

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The active sites for propane dehydrogenation in Ga/H-WZSM-5 with moderate concentrations of tetrahedral aluminum in the lattice were identified to be Lewis-Bronsted acid pairs. With increasing availability, Ga+ and Bronsted acid site concentrations changed inversely, as protons of Bronsted acid sites were exchanged with Ga+. At a Ga/Al ratio of 1/2, the rate of propane dehydrogenation was 2 orders of magnitude higher than with the parent H-ZSM-5, highlighting the extraordinary activity of the Lewis-Bronsted acid pairs. Density functional theory calculations relate the high activity to a bifunctional mechanism that proceeds via heterolytic activation of the propane C-H bond followed by a monomolecular elimination of H-2 and desorption of propene.

引用

页码：4849 / 4859

页数：11

共 33 条

[1] X-RAY WAVELENGTHS [J].

BEARDEN, JA .

REVIEWS OF MODERN PHYSICS, 1967, 39 (01) :78-&

[2] Structure and function of metal cations in light alkane reactions catalyzed by modified H-ZSM5 [J].

Biscardi, JA ;

Iglesia, E .

CATALYSIS TODAY, 1996, 31 (3-4) :207-231

[3] PROJECTOR AUGMENTED-WAVE METHOD [J].

BLOCHL, PE .

PHYSICAL REVIEW B, 1994, 50 (24) :17953-17979

[4] AROMATIZATION OF PROPANE OVER GA/H-ZSM-5 - AN EXPLANATION OF THE SYNERGY OBSERVED BETWEEN GA3+ AND H+ [J].

BUCKLES, G ;

HUTCHINGS, GJ ;

WILLIAMS, CD .

CATALYSIS LETTERS, 1991, 11 (01) :89-94

[5]

DAVIES EE, 1979, Patent No. 509285

[6] Ab initio study of the adamantonium cations:: the protonated adamantane [J].

Esteves, PM ;

Alberto, GGP ;

Ramírez-Solís, A ;

Mota, CJA .

JOURNAL OF PHYSICAL CHEMISTRY A, 2001, 105 (17) :4308-4311

[7] Organometallic model complexes elucidate the active gallium species in alkane dehydrogenation catalysts based on ligand effects in Ga K-edge XANES [J].

Getsoian, Andrew Bean ;

Das, Ujjal ;

Camacho-Bunquin, Jeffrey ;

Zhang, Guanghui ;

Gallagher, James R. ;

Hu, Bo ;

Cheah, Singfoong ;

Schaidle, Joshua A. ;

Ruddy, Daniel A. ;

Hensley, Jesse E. ;

Krause, Theodore R. ;

Curtiss, Larry A. ;

Miller, Jeffrey T. ;

Hock, Adam S. .

CATALYSIS SCIENCE & TECHNOLOGY, 2016, 6 (16) :6339-6353

[8] A density functional theory study of hydrogen recombination and hydrogen-deuterium exchange on Ga/H-ZSM-5 [J].

Gonzales, NO ;

Chakraborty, AK ;

Bell, AT .

TOPICS IN CATALYSIS, 1999, 9 (3-4) :207-213

[9] Catalytic hydrogenation of alkenes on acidic zeolites: Mechanistic connections to monomolecular alkane dehydrogenation reactions [J].

Gounder, Rajamani ;

Iglesia, Enrique .

JOURNAL OF CATALYSIS, 2011, 277 (01) :36-45

[10] Catalytic Consequences of Spatial Constraints and Acid Site Location for Monomolecular Alkane Activation on Zeolites [J].

Gounder, Rajamani ;

Iglesia, Enrique .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (05) :1958-1971

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