Ionic liquid promoted synthesis of conjugated carbon nitride photocatalysts from urea.

To allow for simultaneous textural engineering and doping of carbon nitride materials with heteroatoms, urea has been polymerized with an ionic liquid. The role of urea is to create a delamination effect during carbon nitride synthesis, whereas ionic liquid functions as texture modifier as well as B/F dopant source. This will result in the rational fabrication of boron- and fluorine-containing 2D carbon nitride nanosheets with enhanced optical harvesting and charge separation capabilities for hydrogen evolution catalysis using visible light. We believe that the innovative modification strategy developed herein can be coupled with the already known modification tools of 2D carbon nitride, thus further developing a new family of light-harvesting 2D platforms for the efficient and sustained utilization of solar radiation for a variety of advanced applications, including CO2 photofixation, organic photosynthesis, and pollutant controls.

[1]  Yong Wang,et al.  Polymeric graphitic carbon nitride as a heterogeneous organocatalyst: from photochemistry to multipurpose catalysis to sustainable chemistry. , 2012, Angewandte Chemie.

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

[3]  Xiufang Chen,et al.  Facile synthesis of phosphorus doped graphitic carbon nitride polymers with enhanced visible-light photocatalytic activity , 2013 .

[4]  Hans Lischka,et al.  Der Multiradikalcharakter ein‐ und zweidimensionaler Graphen‐Nanobänder , 2013 .

[5]  Miaofang Chi,et al.  A highly active titanium dioxide based visible-light photocatalyst with nonmetal doping and plasmonic metal decoration. , 2011, Angewandte Chemie.

[6]  D. Armstrong,et al.  Structure and properties of high stability geminal dicationic ionic liquids. , 2005, Journal of the American Chemical Society.

[7]  L. Wan,et al.  Synthesis of Hierarchically Structured Metal Oxides and their Application in Heavy Metal Ion Removal , 2008 .

[8]  M. Antonietti,et al.  Ordered Mesoporous SBA-15 Type Graphitic Carbon Nitride: A Semiconductor Host Structure for Photocatalytic Hydrogen Evolution with Visible Light , 2009 .

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

[10]  R. Asahi,et al.  Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides , 2001, Science.

[11]  Robin D. Rogers,et al.  Ionic Liquids--Solvents of the Future? , 2003, Science.

[12]  M. Antonietti,et al.  Synthesis of very small TiO2 nanocrystals in a room-temperature ionic liquid and their self-assembly toward mesoporous spherical aggregates. , 2003, Journal of the American Chemical Society.

[13]  M. Antonietti,et al.  Polymer semiconductors for artificial photosynthesis: hydrogen evolution by mesoporous graphitic carbon nitride with visible light. , 2009, Journal of the American Chemical Society.

[14]  Jinshui Zhang,et al.  Polycondensation of thiourea into carbon nitride semiconductors as visible light photocatalysts , 2012 .

[15]  Thomas Müller,et al.  The Multiradical Character of One- and Two-Dimensional Graphene Nanoribbons , 2013, Angewandte Chemie.

[16]  P. Wasserscheid,et al.  Highly Selective Aromatic Alkylation of Phenol and Anisole by Using Recyclable Brønsted Acidic Ionic Liquid Systems , 2013 .

[17]  M. Jaroniec,et al.  Facile oxygen reduction on a three-dimensionally ordered macroporous graphitic C3N4/carbon composite electrocatalyst. , 2012, Angewandte Chemie.

[18]  Xianzhi Fu,et al.  Molecular doping of carbon nitride photocatalysts with tunable bandgap and enhanced activity , 2014 .

[19]  Jing Kong,et al.  Photocatalytic patterning and modification of graphene. , 2011, Journal of the American Chemical Society.

[20]  A. Bond,et al.  Photoinduced oxidation of water to oxygen in the ionic liquid BMIMBF4 as the counter reaction in the fabrication of exceptionally long semiconducting silver-tetracyanoquinodimethane nanowires. , 2009, Journal of the American Chemical Society.

[21]  D. Weibel,et al.  Self-organized TiO2 nanotube arrays: synthesis by anodization in an ionic liquid and assessment of photocatalytic properties. , 2011, ACS applied materials & interfaces.

[22]  C. Zhi,et al.  Chemical peeling and branching of boron nitride nanotubes in dimethyl sulfoxide. , 2006, Angewandte Chemie.

[23]  C. Zhi,et al.  Deformation-driven electrical transport of individual boron nitride nanotubes. , 2007, Nano letters.

[24]  M. Jaroniec,et al.  Ionic-liquid-assisted synthesis of uniform fluorinated B/C-codoped TiO2 nanocrystals and their enhanced visible-light photocatalytic activity. , 2013, Chemistry.

[25]  Hui‐Ming Cheng,et al.  Graphene‐Like Carbon Nitride Nanosheets for Improved Photocatalytic Activities , 2012 .

[26]  Jong-Sung Yu,et al.  Hierarchical nanostructured carbons with meso-macroporosity: design, characterization, and applications. , 2013, Accounts of chemical research.

[27]  Hideki Kato,et al.  Highly efficient water splitting into H2 and O2 over lanthanum-doped NaTaO3 photocatalysts with high crystallinity and surface nanostructure. , 2003, Journal of the American Chemical Society.

[28]  Masa Ishigami,et al.  Observation of the giant stark effect in boron-nitride nanotubes. , 2005, Physical review letters.

[29]  M. Antonietti,et al.  Boron- and fluorine-containing mesoporous carbon nitride polymers: metal-free catalysts for cyclohexane oxidation. , 2010, Angewandte Chemie.

[30]  R. Kaner,et al.  Honeycomb carbon: a review of graphene. , 2010, Chemical reviews.

[31]  Qing Tang,et al.  Molecular Charge Transfer: A Simple and Effective Route To Engineer the Band Structures of BN Nanosheets and Nanoribbons , 2011 .

[32]  Xinchen Wang,et al.  Polymeres graphitisches Kohlenstoffnitrid als heterogener Organokatalysator: von der Photochemie über die Vielzweckkatalyse hin zur nachhaltigen Chemie , 2012 .

[33]  A. Amassian,et al.  Correlation between the sp2-phase nanostructure and the physical properties of unhydrogenated carbon nitride , 2005 .

[34]  Markus Antonietti,et al.  Bioinspired hollow semiconductor nanospheres as photosynthetic nanoparticles , 2012, Nature Communications.

[35]  M. Antonietti,et al.  Facile one-pot synthesis of nanoporous carbon nitride solids by using soft templates. , 2010, ChemSusChem.

[36]  Wei Chen,et al.  Simple pyrolysis of urea into graphitic carbon nitride with recyclable adsorption and photocatalytic activity , 2011 .

[37]  Xiaoqing Qiu,et al.  Iodine Modified Carbon Nitride Semiconductors as Visible Light Photocatalysts for Hydrogen Evolution , 2014, Advanced materials.

[38]  M. Antonietti,et al.  Synthesis of boron doped polymeric carbon nitride solids and their use as metal-free catalysts for aliphatic C–H bond oxidation , 2011 .

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

[40]  M. Antonietti,et al.  Activation of carbon nitride solids by protonation: morphology changes, enhanced ionic conductivity, and photoconduction experiments. , 2009, Journal of the American Chemical Society.

[41]  M. Antonietti,et al.  Polymeric Graphitic Carbon Nitride for Heterogeneous Photocatalysis , 2012 .

[42]  Robin D. Rogers,et al.  Materials science: Reflections on ionic liquids , 2007, Nature.

[43]  M. Antonietti,et al.  Ionic Liquid Monomers and Polymers as Precursors of Highly Conductive, Mesoporous, Graphitic Carbon Nanostructures , 2010 .

[44]  Z. Zou,et al.  Photodegradation performance of g-C3N4 fabricated by directly heating melamine. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[45]  T. Tang,et al.  Direct observation of a widely tunable bandgap in bilayer graphene , 2009, Nature.

[46]  Nianwu Li,et al.  Fabrication of Hierarchical Macroporous/Mesoporous Carbons via the Dual-Template Method and the Restriction Effect of Hard Template on Shrinkage of Mesoporous Polymers , 2013 .

[47]  Hongzheng Chen,et al.  Graphene-like two-dimensional materials. , 2013, Chemical reviews.

[48]  Jeunghee Park,et al.  X-ray photoelectron spectroscopy and first principles calculation of BCN nanotubes. , 2007, Journal of the American Chemical Society.

[49]  Xinchen Wang,et al.  A facile synthesis of covalent carbon nitride photocatalysts by Co-polymerization of urea and phenylurea for hydrogen evolution , 2013 .

[50]  Jinshui Zhang,et al.  An Optimized and General Synthetic Strategy for Fabrication of Polymeric Carbon Nitride Nanoarchitectures , 2013 .

[51]  Yunhui Huang,et al.  Ionic-Liquid-Assisted Synthesis of Self-Assembled TiO2-B Nanosheets under Microwave Irradiation and Their Enhanced Lithium Storage Properties , 2013 .