Hydrogen spillover mechanism on covalent organic frameworks as investigated by ab initio density functional calculation

被引:26
作者
Guo, Jing-hua [1 ]
Zhang, Hong [1 ]
Tang, Yongjian [2 ]
Cheng, Xinlu [3 ]
机构
[1] Sichuan Univ, Coll Phys Sci & Technol, Chengdu 610065, Peoples R China
[2] China Acad Engn Phys, Res Ctr Laser Fus, Mianyang 621900, Peoples R China
[3] Sichuan Univ, Inst Atom & Mol Phys, Chengdu 610065, Peoples R China
基金
中国国家自然科学基金; 高等学校博士学科点专项科研基金;
关键词
RETICULAR SYNTHESIS; STORAGE CAPACITY; CARBON; ENERGY; METALS; DFT;
D O I
10.1039/c2cp44007e
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
The hydrogen spillover mechanism, including the H chemisorption, diffusion, and H-2 associative desorption on the surface of COFs and H atoms migration from metal catalyst to COFs, have been studied via density functional theory (DFT) calculation. The results described herein show that each sp(2) C atom on COFs' surface can adsorb one H atom with the bond length d(C-H) between 1.11 and 1.14 angstrom, and the up-down arrangement of the adsorbed H atoms is the most stable configuration. By counting the chemisorption binding sites for these COFs, we can predict the saturation storage densities. High hydrogen storage densities show that the gravimetric uptakes of COFs are in the range of 5.13-6.06 wt%. The CI-NEB calculations reveal that one H atom diffusing along the C-C path on HHTP surface should overcome the 1.41-2.16 eV energy barrier. We chose tetrahedral Pt-4 cluster and HHTP as the representative catalyst and substrate, respectively, to study the H migration from metal cluster to COFs. At most, two H atoms can migrate from Pt-4 cluster to HHTP substrate. The migration reaction is an endothermic process, undergoing an activation barrier of 1.87 eV and 0.57 eV for the first and second H migration process, respectively. Three types of H-2 associative desorption from hydrogenated COFs were studied: (I) the two H adatoms recombining to one H-2 molecule with a recombination barrier of 4.28 eV, (II) the abstraction of adsorbed H atoms by gas-phase hydrogen atoms through ER type recombination reactions with a recombination barrier of 1.05 eV, (III) the H-2 desorption through the reverse spillover mechanism with an energy barrier of 2.90 eV.
引用
收藏
页码:2873 / 2881
页数:9
相关论文
共 40 条
[1]   Mechanistic study on hydrogen spillover onto graphitic carbon materials [J].
Chen, Liang ;
Cooper, Alan C. ;
Pez, Guido P. ;
Cheng, Hansong .
JOURNAL OF PHYSICAL CHEMISTRY C, 2007, 111 (51) :18995-19000
[2]   SPILLOVER IN HETEROGENEOUS CATALYSIS [J].
CONNER, WC ;
FALCONER, JL .
CHEMICAL REVIEWS, 1995, 95 (03) :759-788
[3]   Reticular synthesis of microporous and mesoporous 2D covalent organic frameworks [J].
Cote, Adrien P. ;
El-Kaderi, Hani M. ;
Furukawa, Hiroyasu ;
Hunt, Joseph R. ;
Yaghi, Omar M. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (43) :12914-+
[4]   Porous, crystalline, covalent organic frameworks [J].
Côté, AP ;
Benin, AI ;
Ockwig, NW ;
O'Keeffe, M ;
Matzger, AJ ;
Yaghi, OM .
SCIENCE, 2005, 310 (5751) :1166-1170
[5]   Challenges in hydrogen adsorptions: from physisorption to chemisorption [J].
Ding, Feng ;
Yakobson, Boris I. .
FRONTIERS OF PHYSICS, 2011, 6 (02) :142-150
[6]   Designed synthesis of 3D covalent organic frameworks [J].
El-Kaderi, Hani M. ;
Hunt, Joseph R. ;
Mendoza-Cortes, Jose L. ;
Cote, Adrien P. ;
Taylor, Robert E. ;
O'Keeffe, Michael ;
Yaghi, Omar M. .
SCIENCE, 2007, 316 (5822) :268-272
[7]  
Frisch MJ, 2003, GAUSSIAN 03 REVISION
[8]   Storage Capacity of Metal-Organic and Covalent-Organic Frameworks by Hydrogen Spillover [J].
Ganz, Eric ;
Dornfeld, Matthew .
JOURNAL OF PHYSICAL CHEMISTRY C, 2012, 116 (05) :3661-3666
[9]   Covalent organic frameworks as exceptional hydrogen storage materials [J].
Han, Sang Soo ;
Furukawa, Hiroyasu ;
Yaghi, Omar M. ;
Goddard, William A., III .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (35) :11580-+
[10]   Stability of hydrogenation states of graphene and conditions for hydrogen spillover [J].
Han, Sang Soo ;
Jung, Hyun ;
Jung, Dong Hyun ;
Choi, Seung-Hoon ;
Park, Noejung .
PHYSICAL REVIEW B, 2012, 85 (15)