Product Protection, the Key to Developing High Performance Methane Selective Oxidation Catalysts

被引：111

作者：

Ahlquist, Marten ^{[1
]}

Nielsen, Robert J. ^{[1
]}

Periana, Roy A. ^{[2
]}

Goddard, William A., III ^{[1
]}

机构：

[1] CALTECH, Mat & Proc Simulat Ctr MC 139 74, Pasadena, CA 91125 USA

[2] Scripps Res Inst, Jupiter, FL 33458 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 47期

关键词：

CONTINUUM DIELECTRIC THEORY; EFFECTIVE CORE POTENTIALS; PLATINUM CATALYSTS; LOW-TEMPERATURE; CH ACTIVATION; SOLVATION; MECHANISM; DENSITY; THERMOCHEMISTRY; CATALYTICA;

D O I：

10.1021/ja903930e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Selective, direct conversion of methane to methanol might seem an impossible task since the C-H bond energy of methane is 105 kcal mol(-1) compared to the C-H bond energy for methanol of 94. We show here that the Catalytica catalyst is successful because the methanol is protected as methyl bisulfate, which is substantially less reactive than methanol toward the catalyst. This analysis suggests a limiting performance for systems that operate by this type of protection that is well above the Catalytica system.

引用

页码：17110 / 17115

页数：6

共 21 条

[1] C-H activation in strongly acidic media. The co-catalytic effect of the reaction medium [J].

Ahlquist, Marten ;

Periana, Roy A. ;

Goddard, William A., III .

CHEMICAL COMMUNICATIONS, 2009, (17) :2373-2375

[2] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

[3] Direct methane conversion to methanol by ionic liquid-dissolved platinum catalysts [J].

Cheng, Jihong ;

Li, Zaiwei ;

Haught, Mark ;

Tang, Yongchun .

CHEMICAL COMMUNICATIONS, 2006, (44) :4617-4619

[4] Transition-State Charge Transfer Reveals Electrophilic, Ambiphilic, and Nucleophilic Carbon-Hydrogen Bond Activation [J].

Ess, Daniel H. ;

Nielsen, Robert J. ;

Goddard, William A., III ;

Periana, Roy A. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (33) :11686-+

[5]

Glendening E. D., 2001, Nbo 5.0

[6]

HAY PJ, 1985, J CHEM PHYS, V82, P299, DOI [10.1063/1.448799, 10.1063/1.448800]

[7] The possible role of SO3 as an oxidizing agent in methane functionalization by the catalytica process.: A density functional theory study [J].

Hristov, IH ;

Ziegler, T .

ORGANOMETALLICS, 2003, 22 (08) :1668-1674

[8] DEVELOPMENT OF THE COLLE-SALVETTI CORRELATION-ENERGY FORMULA INTO A FUNCTIONAL OF THE ELECTRON-DENSITY [J].

LEE, CT ;

YANG, WT ;

PARR, RG .

PHYSICAL REVIEW B, 1988, 37 (02) :785-789

[9]

Lutsyk AI, 2002, RUSS J PHYS CHEM+, V76, P1962

[10] New model for calculation of solvation free energies: Correction of self-consistent reaction field continuum dielectric theory for short-range hydrogen-bonding effects [J].

Marten, B ;

Kim, K ;

Cortis, C ;

Friesner, RA ;

Murphy, RB ;

Ringnalda, MN ;

Sitkoff, D ;

Honig, B .

JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (28) :11775-11788

← 1 2 3 →