Approaches to efficient molecular catalyst systems for photochemical H2 production using [FeFe]-hydrogenase active site mimics.

State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), Dalian, 116024, China.
Dalton Transactions (Impact Factor: 4.1). 12/2011; 40(48):12793-800. DOI: 10.1039/c1dt11166c
Source: PubMed

ABSTRACT The research on structural and functional biomimics of the active site of [FeFe]-hydrogenases is in an attempt to elucidate the mechanisms of H(2)-evolution and uptake at the [FeFe]-hydrogenase active site, and to learn from Nature how to create highly efficient H(2)-production catalyst systems. Undoubtedly, it is a challenging, arduous, and long-term work. In this perspective, the progresses in approaches to photochemical H(2) production using mimics of the [FeFe]-hydrogenase active site as catalysts in the last three years are reviewed, with emphasis on adjustment of the redox potentials and hydrophilicity of the [FeFe]-hydrogenase active site mimics to make them efficient catalysts for H(2) production. With gradually increasing understanding of the chemistry of the [FeFe]-hydrogenases and their mimics, more bio-inspired proton reduction catalysts with significantly improved efficiency of H(2) production will be realized in the future.

  • [Show abstract] [Hide abstract]
    ABSTRACT: Three comparable hybrid photocatalytic systems, comprising semiconductor g-C3N4, end-group-functionalized cobaloxime complexes (carboxy-functionalized cobaloxime, C1; pyrene-functionalized cobaloxime, C2; and non-functionalized cobaloxime, C3), and triethanolamine (TEOA), are active for visible-light-driven hydrogen production in CH3CN-H2O (9/1, v/v) solution. Upon irradiation for 12 h, the turnover numbers of hydrogen evolution are 234, 281 and 195 for the hybrid systems C1/g-C3N4, C2/g-C3N4 and C3/g-C3N4, respectively. The highest hydrogen evolution efficiency of the C2/g-C3N4 system can be attributed to the strongest π-π interactions between the pyrene moiety and g-C3N4. Based on electrochemical properties, steady-state photoluminescence spectra and theoretical analyses, the visible light absorption of g-C3N4, the catalytic H2-evolving ability of cobaloxime as well as the efficient charge separation of the excited g-C3N4 in the presence of both TEOA and cobaloxime, are responsible for the high activity of these hybrid systems.
    RSC Advances 01/2014; 4(36):18853. · 3.71 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: Dendrimers are regularly and hierarchically branched synthetic macromolecules with numerous chain ends all emanating from a single core, which makes them attractive candidates for energy conversion applications. During photosynthesis and photocatalysis, photoinduced electron transfer and energy transfer are the main processes involved. Studies on these processes in dendritic systems are critical for the future applications of dendrimers in photochemical energy conversion and other optoelectronic devices. In this Perspective, the recent advances of photofunctional dendrimers in energy conversion based on light-harvesting systems, solar cells, and photochemical production of hydrogen will be discussed. The electron-transfer and energy-transfer characteristics in light-harvesting photofunctional dendrimers and the regulation of the electron-transfer process and the stabilization of the charge separation state in hydrogen photoproduction are emphasized.
    Journal of Physical Chemistry Letters 06/2014; 5(13):2340–2350. · 6.69 Impact Factor
  • [Show abstract] [Hide abstract]
    ABSTRACT: A membrane electrode assembled with electrospun-fibers derived from a composite of cellulose acetate (CA) functionalised with carboxylated multiwall carbon nanotubes (cMWCNTs), polyvinyl pyrrolidone (PVP), and diiron model ([Fe2(edt)(CO)6], edt = ethanedithiolate) catalyses proton reduction in water with the presence of acetic acid.
    RSC Advances 01/2012; 2(27):10171. · 3.71 Impact Factor