Stepwise Methane-to-Methanol Conversion on CuO/SBA-15

被引:42
作者
Le, Ha V. [1 ]
Parishan, Samira [2 ]
Sagaltchik, Anton [3 ]
Ahi, Hamideh [3 ,4 ]
Trunschke, Annette [4 ]
Schomaecker, Reinhard [2 ]
Thomas, Arne [1 ]
机构
[1] Tech Univ Berlin, Inst Chem Funct Mat, BA2,Hardenbergstr 40, D-10623 Berlin, Germany
[2] Tech Univ Berlin, Inst Chem Tech Chem, TC8,Str 17 Juni 124, D-10623 Berlin, Germany
[3] Tech Univ Berlin, BasCat UniCat BASF Joint Lab, EW K 01,Hardenbergstr 36, D-10623 Berlin, Germany
[4] Max Planck Gesell, Fritz Haber Inst, Dept Inorgan Chem, Faradayweg 4-6, D-14195 Berlin, Germany
关键词
copper; heterogeneous catalysis; mesoporous materials; oxidation; supported catalysts; ACTIVE-SITE; EXCHANGED ZEOLITES; COPPER; OXIDATION; CLUSTERS; OXIDE; MORDENITE; CU-ZSM-5; OXYGEN; ZSM-5;
D O I
10.1002/chem.201801135
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The direct partial oxidation of methane to methanol is a challenging scientific and economical objective to expand the application of this abundant fuel gas as a major resource for one-step production of value-added chemicals. Despite substantial efforts to commercialize this synthetic route, to date no heterogeneous catalyst can selectively oxidize methane to methanol by O-2 with an economically acceptable conversion. Cu-exchanged zeolites have been recently highlighted as one of the most promising bioinspired catalysts toward the direct production of methanol from methane under mild conditions. In this work, Cu-based catalysts were prepared using mesoporous silica SBA-15 as an alternative support and their activity for this conversion was investigated. The results demonstrate that highly dispersed CuO species on SBA-15 are able to react with methane and subsequently produce methanol with high selectivity (>84%) through water-assisted extraction. Furthermore, it was confirmed that the main intermediate formed after interaction of the catalyst with methane is a methoxyl species, which can be further converted to methanol or dimethyl ether on extraction with water or methanol, respectively.
引用
收藏
页码:12592 / 12599
页数:8
相关论文
共 49 条
[1]   Chemical looping combustion in a 10 kWth prototype using a CuO/Al2O3 oxygen carrier:: Effect of operating conditions on methane combustion [J].
Adanez, Juan ;
Gayan, Pilar ;
Celaya, Javier ;
de Diego, Luis F. ;
Garcia-Labiano, Francisco ;
Abad, Alberto .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 2006, 45 (17) :6075-6080
[2]   Reaction Conditions of Methane-to-Methanol Conversion Affect the Structure of Active Copper Sites [J].
Alayon, Evalyn Mae C. ;
Nachtegaal, Maarten ;
Bodi, Andras ;
van Bokhoven, Jeroen A. .
ACS CATALYSIS, 2014, 4 (01) :16-22
[3]   Oxidation of methane by a biological dicopper centre [J].
Balasubramanian, Ramakrishnan ;
Smith, Stephen M. ;
Rawat, Swati ;
Yatsunyk, Liliya A. ;
Stemmler, Timothy L. ;
Rosenzweig, Amy C. .
NATURE, 2010, 465 (7294) :115-U131
[4]   Structure of the key species in the enzymatic oxidation of methane to methanol [J].
Banerjee, Rahul ;
Proshlyakov, Yegor ;
Lipscomb, John D. ;
Proshlyakov, Denis A. .
NATURE, 2015, 518 (7539) :431-434
[5]   Oxidation of methane to methanol and formaldehyde over Co-ZSM-5 molecular sieves: Tuning the reactivity and selectivity by alkaline and acid treatments of the zeolite ZSM-5 agglomerates [J].
Beznis, Nadzeya V. ;
van Laak, Adri N. C. ;
Weckhuysen, Bert M. ;
Bitter, Johannes H. .
MICROPOROUS AND MESOPOROUS MATERIALS, 2011, 138 (1-3) :176-183
[6]   BIOCHEMISTRY Getting the metal right [J].
Bollinger, J. Martin, Jr. .
NATURE, 2010, 465 (7294) :40-41
[7]   Controlled oxidation of hydrocarbons by the membrane-bound methane monooxygenase: The case for a tricopper cluster [J].
Chan, Sunney I. ;
Yu, Steve S. -F. .
ACCOUNTS OF CHEMICAL RESEARCH, 2008, 41 (08) :969-979
[8]   The behavior of Cu/ZSM-5 in the oxide and reduced form in the presence of NO and methanol [J].
de Carvalho, MCNA ;
Passos, FB ;
Schmal, M .
APPLIED CATALYSIS A-GENERAL, 2000, 193 (1-2) :265-276
[9]   Selective oxidation of methane by the bis(μ-oxo)dicopper core stabilized on ZSM-5 and mordenite zeolites [J].
Groothaert, MH ;
Smeets, PJ ;
Sels, BF ;
Jacobs, PA ;
Schoonheydt, RA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (05) :1394-1395
[10]   Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol [J].
Grundner, Sebastian ;
Markovits, Monica A. C. ;
Li, Guanna ;
Tromp, Moniek ;
Pidko, Evgeny A. ;
Hensen, Emiel J. M. ;
Jentys, Andreas ;
Sanchez-Sanchez, Maricruz ;
Lercher, Johannes A. .
NATURE COMMUNICATIONS, 2015, 6