Metal-free black phosphorus nanosheets-decorated graphitic carbon nitride nanosheets with CP bonds for excellent photocatalytic nitrogen fixation

Abstract Visible light photocatalytic nitrogen fixation, as a low-cost and mild technology, needs efforts to explore an economical photocatalyst with high activity and stability. In this study, a metal-free black phosphorus (BP) nanosheets-decorated graphitic carbon nitride nanosheets photocatalyst (BPCNS) has been successfully synthesized. With BP acting as the cocatalyst, BPCNS shows excellent performance in both visible light nitrogen photofixation and pollutant reduction owing to the increased number of excited electrons and enhanced separation efficiency of charge carriers through formation of C P covalent bonds. Besides, the chemical structure of the BPCNS with optimal content of BP remains the same after exposure to air for 30 days or after five cycles of photocatalytic nitrogen fixation, since the occupation of the lone pairs on phosphorus atoms largely improves the chemical stability of BP.

[1]  B. Pan,et al.  Promoting Photogenerated Holes Utilization in Pore‐Rich WO3 Ultrathin Nanosheets for Efficient Oxygen‐Evolving Photoanode , 2016 .

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

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

[4]  Xuping Sun,et al.  Au-nanoparticle-loaded graphitic carbon nitride nanosheets: green photocatalytic synthesis and application toward the degradation of organic pollutants. , 2013, ACS applied materials & interfaces.

[5]  Hironori Arakawa,et al.  Direct splitting of water under visible light irradiation with an oxide semiconductor photocatalyst , 2001, Nature.

[6]  Wei Huang,et al.  Black phosphorus quantum dots. , 2015, Angewandte Chemie.

[7]  B. Li,et al.  Effect of contact interface between TiO2 and g-C3N4 on the photoreactivity of g-C3N4/TiO2 photocatalyst: (0 0 1) vs (1 0 1) facets of TiO2 , 2015 .

[8]  Changfeng Chen,et al.  Phosphorene: Fabrication, Properties, and Applications. , 2015, The journal of physical chemistry letters.

[9]  Jimmy C. Yu,et al.  Graphene and g-C3N4 nanosheets cowrapped elemental α-sulfur as a novel metal-free heterojunction photocatalyst for bacterial inactivation under visible-light. , 2013, Environmental science & technology.

[10]  P. Chu,et al.  Surface Coordination of Black Phosphorus for Robust Air and Water Stability. , 2016, Angewandte Chemie.

[11]  Mohammad Ziaur Rahman,et al.  2D phosphorene as a water splitting photocatalyst: fundamentals to applications , 2016 .

[12]  Changcun Han,et al.  Enhanced visible light photocatalytic activity of novel polymeric g-C3N4 loaded with Ag nanoparticles , 2011 .

[13]  Likai Li,et al.  Black phosphorus field-effect transistors. , 2014, Nature nanotechnology.

[14]  M. Kraft,et al.  Unique PCoN Surface Bonding States Constructed on g‐C3N4 Nanosheets for Drastically Enhanced Photocatalytic Activity of H2 Evolution , 2017 .

[15]  Young-Chul Lee,et al.  Stable semiconductor black phosphorus (BP)@titanium dioxide (TiO2) hybrid photocatalysts , 2015, Scientific Reports.

[16]  Subhajyoti Samanta,et al.  Facile Synthesis of Au/g‐C3N4 Nanocomposites: An Inorganic/Organic Hybrid Plasmonic Photocatalyst with Enhanced Hydrogen Gas Evolution Under Visible‐Light Irradiation , 2014 .

[17]  S. Ogale,et al.  Doubling of photocatalytic H2 evolution from g-C3N4 via its nanocomposite formation with multiwall carbon nanotubes: Electronic and morphological effects , 2012 .

[18]  M. Jaroniec,et al.  Earth-abundant cocatalysts for semiconductor-based photocatalytic water splitting. , 2014, Chemical Society reviews.

[19]  M. Winter,et al.  Puzzling out the origin of the electrochemical activity of black P as a negative electrode material for lithium-ion batteries , 2013 .

[20]  Yongsheng Zhu,et al.  Layered nanojunctions for hydrogen-evolution catalysis. , 2013, Angewandte Chemie.

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

[22]  Chunying Wang,et al.  Photodegradation of bisphenol A by highly stable palladium-doped mesoporous graphite carbon nitride (Pd/mpg-C3N4) under simulated solar light irradiation , 2013 .

[23]  Jun Dai,et al.  Bilayer Phosphorene: Effect of Stacking Order on Bandgap and Its Potential Applications in Thin-Film Solar Cells. , 2014, The journal of physical chemistry letters.

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

[25]  Yi Luo,et al.  Single‐Atom Pt as Co‐Catalyst for Enhanced Photocatalytic H2 Evolution , 2016, Advanced materials.

[26]  Guangyuan Zheng,et al.  Formation of stable phosphorus-carbon bond for enhanced performance in black phosphorus nanoparticle-graphite composite battery anodes. , 2014, Nano letters.

[27]  Zhisheng Zhao,et al.  Flexible All‐Solid‐State Supercapacitors based on Liquid‐Exfoliated Black‐Phosphorus Nanoflakes , 2016, Advanced materials.

[28]  Yajun Wang,et al.  Enhanced oxidation ability of g-C3N4 photocatalyst via C60 modification , 2014 .

[29]  Ok-Kyung Park,et al.  Preparation and characterization of silica-coated TiO2 nanoparticle , 2005 .

[30]  L. Seefeldt,et al.  Substrate interactions with the nitrogenase active site. , 2005, Accounts of chemical research.

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

[32]  Xing Zhang,et al.  Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway , 2015, Science.

[33]  Jimmy C. Yu,et al.  A black–red phosphorus heterostructure for efficient visible-light-driven photocatalysis , 2015 .

[34]  P. Schmidt,et al.  Au3SnP7@black phosphorus: an easy access to black phosphorus. , 2007, Inorganic chemistry.

[35]  Gang Wu,et al.  High-Performance Electrocatalysts for Oxygen Reduction Derived from Polyaniline, Iron, and Cobalt , 2011, Science.

[36]  T. Nilges,et al.  A fast low-pressure transport route to large black phosphorus single crystals , 2008 .

[37]  M. Wasielewski,et al.  Photochemical nitrogen conversion to ammonia in ambient conditions with FeMoS-chalcogels. , 2015, Journal of the American Chemical Society.