Confined Cu-OH single sites in SSZ-13 zeolite for the direct oxidation of methane to methanol

被引：26

作者：

Zhang, Hailong ^{[1
,2
]}

Han, Peijie ^{[1
]}

Wu, Danfeng ^{[1
]}

Du, Congcong ^{[1
]}

Zhao, Jiafei ^{[1
]}

Zhang, Kelvin H. L. ^{[1
]}

Lin, Jingdong ^{[1
]}

Wan, Shaolong ^{[1
]}

Huang, Jianyu ^{[3
]}

Wang, Shuai ^{[1
]}

Xiong, Haifeng ^{[1
]}

Wang, Yong ^{[4
]}

机构：

[1] Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, 422 South Siming Rd, Xiamen 361005, Peoples R China

[2] Sichuan Univ, Coll Carbon Neutral Future Technol, Chengdu 610064, Peoples R China

[3] Yanshan Univ, Clean Nano Energy Ctr, State Key Lab Metastable Mat Sci & Technol, Qinhuangdao 066004, Peoples R China

[4] Washington State Univ, Voiland Sch Chem Engn & Bioengn, Pullman, WA 99164 USA

来源：

NATURE COMMUNICATIONS | 2023年 / 14卷 / 01期

基金：

中国国家自然科学基金;

关键词：

INITIO MOLECULAR-DYNAMICS; TOTAL-ENERGY CALCULATIONS; ACTIVE-SITES; DIRECT CONVERSION; CRYSTAL-STRUCTURE; CU/SSZ-13; INSIGHTS; CATALYST; TRANSITION; CU-SSZ-13;

D O I：

10.1038/s41467-023-43508-4

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

The direct oxidation of methane to methanol (MTM) remains a significant challenge in heterogeneous catalysis due to the high dissociation energy of the C-H bond in methane and the high desorption energy of methanol. In this work, we demonstrate a breakthrough in selective MTM by achieving a high methanol space-time yield of 2678 mmol molCu-1 h-1 with 93% selectivity in a continuous methane-steam reaction at 400 degrees C. The superior performance is attributed to the confinement effect of 6-membered ring (6MR) voids in SSZ-13 zeolite, which host isolated Cu-OH single sites. Our results provide a deeper understanding of the role of Cu-zeolites in continuous methane-steam to methanol conversion and pave the way for further improvement. High yields of methanol are difficult to achieve with direct oxidation of methane to methanol. Here the authors report a high methanol space-time yield which is attributed to the confinement effect of 6-membered ring voids and the isolated Cu-OH single sites in SSZ-13 zeolite.

引用

页数：10

共 50 条

[1] Insights into the Speciation of Cu in the Cu-H-Mordenite Catalyst for the Oxidation of Methane to Methanol [J].

Brezicki, Gordon ;

Kammert, James D. ;

Gunnoe, T. Brent ;

Paolucci, Christopher ;

Davis, Robert J. .

ACS CATALYSIS, 2019, 9 (06) :5308-5319

[2] Continuous Partial Oxidation of Methane to Methanol Catalyzed by Diffusion-Paired Copper Dimers in Copper-Exchanged Zeolites [J].

Dinh, Kimberly T. ;

Sullivan, Mark M. ;

Narsimhan, Karthik ;

Serna, Pedro ;

Meyer, Randall J. ;

Dinca, Mircea ;

Roman-Leshkov, Yuriy .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2019, 141 (29) :11641-11650

[3] Understanding ammonia selective catalytic reduction kinetics over Cu/SSZ-13 from motion of the Cu ions [J].

Gao, Feng ;

Walter, Eric D. ;

Kollar, Marton ;

Wang, Yilin ;

Szanyi, Janos ;

Peden, Charles H. F. .

JOURNAL OF CATALYSIS, 2014, 319 :1-14

[4] Current Understanding of Cu-Exchanged Chabazite Molecular Sieves for Use as Commercial Diesel Engine DeNOx Catalysts [J].

Gao, Feng ;

Kwak, Ja Hun ;

Szanyi, Janos ;

Peden, Charles H. F. .

TOPICS IN CATALYSIS, 2013, 56 (15-17) :1441-1459

[5] VIBRATIONAL AND DIELECTRIC-PROPERTIES OF C-60 FROM DENSITY-FUNCTIONAL PERTURBATION-THEORY [J].

GIANNOZZI, P ;

BARONI, S .

JOURNAL OF CHEMICAL PHYSICS, 1994, 100 (11) :8537-8539

[6] Site-Specific Reactivity of Copper Chabazite Zeolites with Nitric Oxide, Ammonia, and Oxygen [J].

Godiksen, Anita ;

Isaksen, Oliver L. ;

Rasmussen, Soren B. ;

Vennestrom, Peter N. R. ;

Mossin, Susanne .

CHEMCATCHEM, 2018, 10 (02) :366-370

[7] Coordination Environment of Copper Sites in Cu-CHA Zeolite Investigated by Electron Paramagnetic Resonance [J].

Godiksen, Anita ;

Stappen, Frederick N. ;

Vennestrom, Peter N. R. ;

Giordanino, Filippo ;

Rasmussen, Soren Birk ;

Lundegaard, Lars F. ;

Mossin, Susanne .

JOURNAL OF PHYSICAL CHEMISTRY C, 2014, 118 (40) :23126-23138

[8]

Görne AL, 2017, INORGANICS, V5, DOI 10.3390/inorganics5010010

[9] A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu [J].

Grimme, Stefan ;

Antony, Jens ;

Ehrlich, Stephan ;

Krieg, Helge .

JOURNAL OF CHEMICAL PHYSICS, 2010, 132 (15)

[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

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