Metal-free photocatalytic graphitic carbon nitride on p-type chalcopyrite as a composite photocathode for light-induced hydrogen evolution.

Recently, it has been shown that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor. We present herein the preparation and characterization of graphitic carbon nitride (g-C(3)N(4)) films on p-type semiconducting CuGaSe(2) chalcopyrite thin-film substrates by thermal condensation of a dicyandiamide precursor under inert-gas conditions. Structural and surface morphological studies of the carbon nitride films suggest a high porosity of g-C(3)N(4) thin films consisting of a network of nanocrystallites. Photoelectrochemical investigations show light-induced hydrogen evolution upon cathodic polarization for a wide range of proton concentrations in the aqueous electrolyte. Additionally, synchrotron radiation-based photoelectron spectroscopy has been applied to study the surface/near-surface chemical composition of the utilized g-C(3)N(4) film photocathodes. For the first time, it has been shown that g-C(3)N(4) films coated on p-type CuGaSe(2) thin films can be successfully applied as new photoelectrochemical composite photocathodes for light-induced hydrogen evolution.

[1]  T. Schedel-Niedrig,et al.  Tunable optical transition in polymeric carbon nitrides synthesized via bulk thermal condensation , 2012, Journal of physics. Condensed matter : an Institute of Physics journal.

[2]  M. Antonietti,et al.  Phosphorus-doped carbon nitride solid: enhanced electrical conductivity and photocurrent generation. , 2010, Journal of the American Chemical Society.

[3]  Kazuhiro Takanabe,et al.  Synthesis of a carbon nitride structure for visible-light catalysis by copolymerization. , 2010, Angewandte Chemie.

[4]  R. Schlögl,et al.  Graphitic carbon nitride materials: variation of structure and morphology and their use as metal-free catalysts , 2008 .

[5]  A. Rheingold,et al.  Active-site models for iron hydrogenases: reduction chemistry of dinuclear iron complexes. , 2006, Inorganic chemistry.

[6]  M. Antonietti,et al.  Chemical synthesis of mesoporous carbon nitrides using hard templates and their use as a metal-free catalyst for Friedel-Crafts reaction of benzene. , 2006, Angewandte Chemie.

[7]  Arne Thomas,et al.  Chemische Synthese von mesoporösen Kohlenstoffnitriden in harten Templaten und ihre Anwendung als metallfreie Katalysatoren in Friedel‐Crafts‐Reaktionen , 2006 .

[8]  K. Domen,et al.  Photocatalyst releasing hydrogen from water , 2006, Nature.

[9]  M. Antonietti,et al.  Synthesis of g‐C3N4 Nanoparticles in Mesoporous Silica Host Matrices , 2005 .

[10]  A. Kudo,et al.  Visible-light-induced H2 evolution from an aqueous solution containing sulfide and sulfite over a ZnS-CuInS2-AgInS2 solid-solution photocatalyst. , 2005, Angewandte Chemie.

[11]  Kazuhiko Maeda,et al.  GaN:ZnO solid solution as a photocatalyst for visible-light-driven overall water splitting. , 2005, Journal of the American Chemical Society.

[12]  R. Riedel,et al.  Potassium melonate, K3[C6N7(NCN)3]·5H2O, and its potential use for the synthesis of graphite-like C3N4 materials , 2005 .

[13]  Hideki Kato,et al.  Photocatalytic H2 evolution reaction from aqueous solutions over band structure-controlled (AgIn)xZn2(1-x)S2 solid solution photocatalysts with visible-light response and their surface nanostructures. , 2004, Journal of the American Chemical Society.

[14]  E. Kroke,et al.  Novel group 14 nitrides , 2004 .

[15]  K. Domen,et al.  Oxysulfide Sm2Ti2S2O5 as a Stable Photocatalyst for Water Oxidation and Reduction under Visible Light Irradiation (λ ≤ 650 nm) , 2002 .

[16]  Tsuyoshi Takata,et al.  An oxynitride, TaON, as an efficient water oxidation photocatalyst under visible light irradiation (λ≤ 500 nm) , 2002 .

[17]  Hideki Kato,et al.  Visible-Light-Response and Photocatalytic Activities of TiO2 and SrTiO3 Photocatalysts Codoped with Antimony and Chromium , 2002 .

[18]  H. Arakawa,et al.  Stoichiometric water splitting into H2 and O2 using a mixture of two different photocatalysts and an IO3-/I- shuttle redox mediator under visible light irradiation. , 2001, Chemical communications.

[19]  Turner,et al.  A monolithic photovoltaic-photoelectrochemical device for hydrogen production via water splitting , 1998, Science.

[20]  V. DeRose,et al.  Where plants make oxygen: a structural model for the photosynthetic oxygen-evolving manganese cluster , 1993 .

[21]  T. Mallouk,et al.  Visible-light photolysis of hydrogen iodide using sensitized layered semiconductor particles , 1991 .

[22]  D. Kolb,et al.  The work function of emersed electrodes , 1979 .

[23]  R. Gomer,et al.  An experimental determination of absolute half‐cell emf’s and single ion free energies of solvation , 1977 .

[24]  M. Antonietti,et al.  A metal-free polymeric photocatalyst for hydrogen production from water under visible light. , 2009, Nature materials.

[25]  K. Domen,et al.  Zinc Germanium Oxynitride as a Photocatalyst for Overall Water Splitting under Visible Light , 2007 .

[26]  Freek Kapteijn,et al.  Evolution of nitrogen functionalities in carbonaceous materials during pyrolysis , 1995 .

[27]  K. Yoshino,et al.  Poly(p-phenylene)-catalysed photoreduction of water to hydrogen , 1985 .

[28]  Adam Heller,et al.  The absolute potential of the standard hydrogen electrode: a new estimate , 1985 .

[29]  Michael Grätzel,et al.  Photochemical cleavage of water by photocatalysis , 1981, Nature.