Enhanced dihydrogen adsorption in symmetry-lowered metal-porphyrin-containing frameworks

被引:19
作者
Kim, Yong-Hyun [1 ,2 ]
Sun, Y. Y. [3 ]
Choi, Woon Ih [1 ]
Kang, Joongoo [1 ]
Zhang, S. B. [3 ]
机构
[1] Natl Renewable Energy Lab, Golden, CO 80401 USA
[2] Korea Adv Inst Sci & Technol, Grad Sch Nanosci & Technol WCU, Taejon 305701, South Korea
[3] Rensselaer Polytech Inst, Dept Phys Appl Phys & Astron, Troy, NY 12180 USA
关键词
ORGANIC FRAMEWORKS; HYDROGEN STORAGE; SITES; HEMOGLOBIN; COMPLEXES; BINDING; HEME;
D O I
10.1039/b913711d
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
Porphyrin is a very important component of natural and artificial catalysis and oxygen delivery in blood. Here, we report that, based on first-principles density-functional calculations, a hydrogen molecule can be adsorbed non-dissociatively onto Ti-, V-, and Fe-porphyrins, similar to oxygen adsorption in heme-containing proteins, with a significant energy gain, greater than 0.3 eV per H(2). The dihydrogen-heme complex will be non-magnetic, as is oxyhemoglobin. In contrast to the backward electron donation of Fe(III)-O(2)(-) in oxyhemoglobin, the dihydrogen binding originates from electron donation from H(2) to the Fe(II). We have identified that the local symmetry of the transition metal center of porphyrins uniquely determines the binding strength, and, thus, one can even manipulate the strength by intentionally and systematically breaking symmetry.
引用
收藏
页码:11400 / 11403
页数:4
相关论文
共 25 条
  • [1] Antonini E., 1971, Hemoglobin and Myoglobin in. Their Reactions with Ligands
  • [2] Highly Tunable Heterometallic Frameworks Constructed from Paddle-Wheel Units and Metalloporphyrins
    Barron, Paul M.
    Son, Hyun-Tak
    Hu, Chunhua
    Choe, Wonyoung
    [J]. CRYSTAL GROWTH & DESIGN, 2009, 9 (04) : 1960 - 1965
  • [3] Highly tunable metal-organic frameworks with open metal centers
    Choi, Eun-Young
    Wray, Curtis A.
    Hu, Chunhua
    Choe, Wonyoung
    [J]. CRYSTENGCOMM, 2009, 11 (04): : 553 - 555
  • [4] Pillared Porphyrin Homologous Series: Intergrowth in Metal-Organic Frameworks
    Choi, Eun-Young
    Barron, Paul M.
    Novotny, Richard W.
    Son, Hyun-Tak
    Hu, Chunhua
    Choe, Wonyoung
    [J]. INORGANIC CHEMISTRY, 2009, 48 (02) : 426 - 428
  • [5] Hydrogen storage in microporous metal-organic frameworks with exposed metal sites
    Dinca, Mircea
    Long, Jeffrey R.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (36) : 6766 - 6779
  • [6] Hydrogen storage in a microporous metal-organic framework with exposed Mn2+ coordination sites
    Dinca, Mircea
    Dailly, Anne
    Liu, Yun
    Brown, Craig M.
    Neumann, Dan. A.
    Long, Jeffrey R.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (51) : 16876 - 16883
  • [7] Observation of Cu2+-H2 interactions in a fully desolvated sodalite-type metal-organic framework
    Dinca, Mircea
    Han, Won Seok
    Liu, Yun
    Dailly, Anne
    Brown, Craig M.
    Long, Jeffrey R.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (09) : 1419 - 1422
  • [8] Spin-dependent mechanism for diatomic ligand binding to heme
    Franzen, S
    [J]. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2002, 99 (26) : 16754 - 16759
  • [9] Nondissociative adsorption of H2 molecules in light-element-doped fullerenes -: art. no. 016102
    Kim, YH
    Zhao, YF
    Williamson, A
    Heben, MJ
    Zhang, SB
    [J]. PHYSICAL REVIEW LETTERS, 2006, 96 (01)
  • [10] Ab initio calculations predicting the existence of an oxidized calcium dihydrogen complex to store molecular hydrogen in densities up to 100 g/L
    Kim, Yong-Hyun
    Sun, Y. Y.
    Zhang, S. B.
    [J]. PHYSICAL REVIEW B, 2009, 79 (11)