Mesoporous carbon nitrides: synthesis, functionalization, and applications.

Mesoporous carbon nitrides (MCNs) with large surface areas and uniform pore diameters are unique semiconducting materials and exhibit highly versatile structural and excellent physicochemical properties, which promote their application in diverse fields such as metal free catalysis, photocatalytic water splitting, energy storage and conversion, gas adsorption, separation, and even sensing. These fascinating MCN materials can be obtained through the polymerization of different aromatic and/or aliphatic carbons and high nitrogen containing molecular precursors via hard and/or soft templating approaches. One of the unique characteristics of these materials is that they exhibit both semiconducting and basic properties, which make them excellent platforms for the photoelectrochemical conversion and sensing of molecules such as CO2, and the selective sensing of toxic organic acids. The semiconducting features of these materials are finely controlled by varying the nitrogen content or local electronic structure of the MCNs. The incorporation of different functionalities including metal nanoparticles or organic molecules is further achieved in various ways to develop new electronic, semiconducting, catalytic, and energy harvesting materials. Dual functionalities including acidic and basic groups are also introduced in the wall structure of MCNs through simple UV-light irradiation, which offers enzyme-like properties in a single MCN system. In this review article, we summarize and highlight the existing literature covering every aspect of MCNs including their templating synthesis, modification and functionalization, and potential applications of these MCN materials with an overview of the key and relevant results. A special emphasis is given on the catalytic applications of MCNs including hydrogenation, oxidation, photocatalysis, and CO2 activation.

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

[2]  K. Ariga,et al.  Coupling of soft technology (layer-by-layer assembly) with hard materials (mesoporous solids) to give hierarchic functional structures , 2009 .

[3]  Yao Zheng,et al.  Nanostructured metal-free electrochemical catalysts for highly efficient oxygen reduction. , 2012, Small.

[4]  Zhongkui Zhao,et al.  Highly-Ordered Mesoporous Carbon Nitride with Ultrahigh Surface Area and Pore Volume as a Superior Dehydrogenation Catalyst , 2014 .

[5]  Mohd Bismillah Ansari,et al.  Mesoporous carbon nitride as a metal-free base catalyst in the microwave assisted Knoevenagel condensation of ethylcyanoacetate with aromatic aldehydes , 2012 .

[6]  Markus Antonietti,et al.  Ionothermal synthesis of crystalline, condensed, graphitic carbon nitride. , 2008, Chemistry.

[7]  D. Dhawale,et al.  Synthesis of nitrogen-rich mesoporous carbon nitride with tunable pores, band gaps and nitrogen content from a single aminoguanidine precursor. , 2012, ChemSusChem.

[8]  Qing-fang Deng,et al.  Synthesis and CO2 capture properties of mesoporous carbon nitride materials , 2012 .

[9]  D. Zhao,et al.  Facile synthesis of mesoporous carbon nitrides using the incipient wetness method and the application as hydrogen adsorbent , 2011 .

[10]  Q. Huo,et al.  Mesostructure Design with Gemini Surfactants: Supercage Formation in a Three-Dimensional Hexagonal Array , 1995, Science.

[11]  Hongjian Yan Soft-templating synthesis of mesoporous graphitic carbon nitride with enhanced photocatalytic H2 evolution under visible light. , 2012, Chemical communications.

[12]  Pierre M. Petroff,et al.  Generalized synthesis of periodic surfactant/inorganic composite materials , 1994, Nature.

[13]  A. Vinu Two‐Dimensional Hexagonally‐Ordered Mesoporous Carbon Nitrides with Tunable Pore Diameter, Surface Area and Nitrogen Content , 2008 .

[14]  M. Antonietti,et al.  Metal-free activation of CO2 by mesoporous graphitic carbon nitride. , 2007, Angewandte Chemie.

[15]  Kazuhiko Maeda,et al.  Nature-Inspired, Highly Durable CO2 Reduction System Consisting of a Binuclear Ruthenium(II) Complex and an Organic Semiconductor Using Visible Light. , 2016, Journal of the American Chemical Society.

[16]  Young‐Kwon Park,et al.  Application of MCN-1 to the adsorptive removal of indoor formaldehyde , 2014 .

[17]  S. V. Priya,et al.  Transesterification of ethylacetoacetate catalysed by metal free mesoporous carbon nitride , 2013 .

[18]  Bing Xue,et al.  Mesostructured graphitic carbon nitride as a new base catalyst for the efficient synthesis of dimethyl carbonate by transesterification , 2013 .

[19]  Arne Thomas,et al.  Mesoporous carbon nitride–silica composites by a combined sol–gel/thermal condensation approach and their application as photocatalysts , 2011 .

[20]  Dan Feng,et al.  A Family of Highly Ordered Mesoporous Polymer Resin and Carbon Structures from Organic−Organic Self-Assembly , 2006 .

[21]  M. Hartmann,et al.  Direct synthesis and catalytic evaluation of AlSBA-1. , 2002, Chemical communications.

[22]  C. Ziegler,et al.  Crystalline carbon nitride nanosheets for improved visible-light hydrogen evolution. , 2014, Journal of the American Chemical Society.

[23]  Huan Chen,et al.  Adsorption of Cr(VI) from aqueous solution on mesoporous carbon nitride , 2014 .

[24]  D. Dhawale,et al.  Facile synthesis and basic catalytic application of 3D mesoporous carbon nitride with a controllable bimodal distribution , 2012 .

[25]  A. Vinu,et al.  Bifunctional Mesoporous Carbon Nitride: Highly Efficient Enzyme-like Catalyst for One-pot Deacetalization-Knoevenagel Reaction , 2015, Scientific Reports.

[26]  A. Liu,et al.  Prediction of New Low Compressibility Solids , 1989, Science.

[27]  D. Zhao,et al.  Facile synthesis of porous carbon nitride spheres with hierarchical three-dimensional mesostructures for CO2 capture , 2010 .

[28]  M. Antonietti,et al.  Synthesis of ternary metal nitride nanoparticles using mesoporous carbon nitride as reactive template. , 2008, ACS nano.

[29]  Frank E. Osterloh,et al.  Inorganic Materials as Catalysts for Photochemical Splitting of Water , 2008 .

[30]  Hua Zhou,et al.  Facile one-pot synthesis of bimodal mesoporous carbon nitride and its function as a lipase immobilization support , 2011 .

[31]  Xinchen Wang,et al.  Molecular and textural engineering of conjugated carbon nitride catalysts for selective oxidation of alcohols with visible light , 2013 .

[32]  L. Yuliati,et al.  Photocatalytic removal of phenol under visible light irradiation on zinc phthalocyanine/mesoporous carbon nitride nanocomposites , 2014 .

[33]  Markus Antonietti,et al.  Mesoporous g-C3N4 nanorods as multifunctional supports of ultrafine metal nanoparticles: hydrogen generation from water and reduction of nitrophenol with tandem catalysis in one step , 2012 .

[34]  Akira Fujishima,et al.  Titanium dioxide photocatalysis , 2000 .

[35]  Yanqiu Zhu,et al.  Porous carbon-based materials for hydrogen storage: advancement and challenges , 2013 .

[36]  N. Logar,et al.  Nanoporous Materials: From Catalysis and Hydrogen Storage to Wastewater Treatment , 2006 .

[37]  D. Zhao,et al.  Carbon Materials for Chemical Capacitive Energy Storage , 2011, Advanced materials.

[38]  Mohd Bismillah Ansari,et al.  CO2 activation and promotional effect in the oxidation of cyclic olefins over mesoporous carbon nitrides , 2011 .

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

[40]  Yong Wang,et al.  A practical and benign synthesis of amines through Pd@mpg-C3N4 catalyzed reduction of nitriles , 2012 .

[41]  Gongxuan Lu,et al.  Enhanced Electron Transfer from the Excited Eosin Y to mpg-C3N4 for Highly Efficient Hydrogen Evolution under 550 nm Irradiation , 2012 .

[42]  Bradley F. Chmelka,et al.  Nonionic Triblock and Star Diblock Copolymer and Oligomeric Surfactant Syntheses of Highly Ordered, Hydrothermally Stable, Mesoporous Silica Structures , 1998 .

[43]  H. Cao,et al.  Carbon nitride-catalyzed oxidative cleavage of carbon–carbon bond of α-hydroxy ketones with visible light and thermal radiation , 2013 .

[44]  Mohd Bismillah Ansari,et al.  Carbon dioxide augmented oxidation of aromatic alcohols over mesoporous carbon nitride as a metal free catalyst , 2013 .

[45]  M. Antonietti,et al.  Facilitating room-temperature Suzuki coupling reaction with light: Mott-Schottky photocatalyst for C-C-coupling , 2013, Scientific Reports.

[46]  J. S. Beck,et al.  Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism , 1992, Nature.

[47]  A. Vinu,et al.  Highly ordered mesoporous carbon nitride nanoparticles with high nitrogen content: a metal-free basic catalyst. , 2009, Angewandte Chemie.

[48]  M. Antonietti,et al.  Mesoporous graphitic carbon nitride as a versatile, metal-free catalyst for the cyclisation of functional nitriles and alkynes , 2007 .

[49]  A. Fujishima,et al.  Heterogeneous photocatalysis: From water photolysis to applications in environmental cleanup , 2007 .

[50]  Bing Xue,et al.  A new and environmentally benign precursor for the synthesis of mesoporous g-C3N4 with tunable surface area. , 2013, Physical chemistry chemical physics : PCCP.

[51]  M. Antonietti,et al.  Porous materials via nanocasting procedures: innovative materials and learning about soft-matter organization. , 2002, Chemical communications.

[52]  Katsuhiko Ariga,et al.  Gold nanoparticles embedded in a mesoporous carbon nitride stabilizer for highly efficient three-component coupling reaction. , 2010, Angewandte Chemie.

[53]  T. Kyotani,et al.  Formation of New Type of Porous Carbon by Carbonization in Zeolite Nanochannels , 1997 .

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

[55]  Xiaohong Xu,et al.  Cosolvent-free nanocasting synthesis of ordered mesoporous g-C3N4 and its remarkable photocatalytic activity for methyl orange degradation , 2015 .

[56]  Angel T. Garcia-Esparza,et al.  Synthesis of tantalum carbide and nitride nanoparticles using a reactive mesoporous template for electrochemical hydrogen evolution , 2013 .

[57]  B. Kumar,et al.  Synthesis of highly efficient and recyclable visible-light responsive mesoporous g-C3N4 photocatalyst via facile template-free sonochemical route , 2014 .

[58]  D. Dhawale,et al.  Selective sensing performance of mesoporous carbon nitride with a highly ordered porous structure prepared from 3-amino-1,2,4-triazine , 2013 .

[59]  M. Antonietti,et al.  Fe-g-C3N4-catalyzed oxidation of benzene to phenol using hydrogen peroxide and visible light. , 2009, Journal of the American Chemical Society.

[60]  Yao Zheng,et al.  Graphitic carbon nitride materials: controllable synthesis and applications in fuel cells and photocatalysis , 2012 .

[61]  Xinchen Wang,et al.  Overall water splitting by Pt/g-C3N4 photocatalysts without using sacrificial agents† †Electronic supplementary information (ESI) available: Characterization and experimental detail. See DOI: 10.1039/c5sc04572j , 2016, Chemical science.

[62]  Xin Wang,et al.  Adsorption of Perfluorooctane Sulfonate and Perfluorooctanoic Acid on Magnetic Mesoporous Carbon Nitride , 2014 .

[63]  A. Corma,et al.  Lewis acids as catalysts in oxidation reactions: from homogeneous to heterogeneous systems. , 2002, Chemical reviews.

[64]  P. Ajayan,et al.  Exfoliated Graphitic Carbon Nitride Nanosheets as Efficient Catalysts for Hydrogen Evolution Under Visible Light , 2013, Advanced materials.

[65]  M. Antonietti,et al.  Metal-free catalysis of sustainable Friedel-Crafts reactions: direct activation of benzene by carbon nitrides to avoid the use of metal chlorides and halogenated compounds. , 2006, Chemical communications.

[66]  R. Schomäcker,et al.  Mesoporous carbon nitride-tungsten oxide composites for enhanced photocatalytic hydrogen evolution. , 2015, ChemSusChem.

[67]  Lei Liu,et al.  Direct synthesis of ordered mesoporous carbons. , 2013, Chemical Society reviews.

[68]  D. Anjum,et al.  Molybdenum carbide–carbon nanocomposites synthesized from a reactive template for electrochemical hydrogen evolution , 2014 .

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

[70]  Markus Antonietti,et al.  mpg-C(3)N(4)-Catalyzed selective oxidation of alcohols using O(2) and visible light. , 2010, Journal of the American Chemical Society.

[71]  Jong‐Sung Yu,et al.  Template-directed synthesis of highly ordered nanoporous graphitic carbon nitride through polymerization of cyanamide , 2007 .

[72]  M. Antonietti,et al.  Photocatalytic hydrogen evolution on dye-sensitized mesoporous carbon nitride photocatalyst with magnesium phthalocyanine. , 2010, Physical chemistry chemical physics : PCCP.

[73]  Yong Wang,et al.  A novel catalyst Pd@ompg-C3N4 for highly chemoselective hydrogenation of quinoline under mild conditions , 2013 .

[74]  Xinchen Wang,et al.  Synthesis of Ferrocene‐Modified Carbon Nitride Photocatalysts by Surface Amidation Reaction for Phenol Synthesis , 2014 .

[75]  M. Antonietti,et al.  Mesoporous, 2D Hexagonal Carbon Nitride and Titanium Nitride/Carbon Composites , 2009 .

[76]  Seung M. Oh,et al.  Synthesis of a new mesoporous carbon and its application to electrochemical double-layer capacitors , 1999 .

[77]  J. B. Higgins,et al.  A new family of mesoporous molecular sieves prepared with liquid crystal templates , 1992 .

[78]  A. Vinu,et al.  Morphological control of mesoporous CN based hybrid materials and their excellent CO2 adsorption capacity , 2015 .

[79]  Xinchen Wang,et al.  Helical graphitic carbon nitrides with photocatalytic and optical activities. , 2014, Angewandte Chemie.

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

[81]  M. Antonietti,et al.  Highly-active Tantalum (V) nitride nanoparticles prepared from a mesoporous carbon nitride template for photocatalytic hydrogen evolution under visible light irradiation , 2010 .

[82]  O. Ikkala,et al.  Functional Porous Structures Based on the Pyrolysis of Cured Templates of Block Copolymer and Phenolic Resin , 2006 .

[83]  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.

[84]  J. Xu,et al.  Chemical exfoliation of graphitic carbon nitride for efficient heterogeneous photocatalysis , 2013 .

[85]  D. Dhawale,et al.  Highly ordered macro-mesoporous carbon nitride film for selective detection of acidic/basic molecules. , 2014, Chemical communications.

[86]  Huan Chen,et al.  Enhanced catalytic hydrogenation of aqueous bromate over Pd/mesoporous carbon nitride , 2013 .

[87]  Yueping Fang,et al.  Mesoporous polymeric semiconductor materials of graphitic-C3N4: general and efficient synthesis and their integration with synergistic AgBr NPs for enhanced photocatalytic performances , 2013 .

[88]  K. Ariga,et al.  Preparation and Characterization of Well‐Ordered Hexagonal Mesoporous Carbon Nitride , 2005 .

[89]  Mohd Bismillah Ansari,et al.  Mesoporous carbon nitride synthesized by nanocasting with urea/formaldehyde and metal-free catalytic oxidation of cyclic olefins , 2013 .

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

[91]  Yi Xie,et al.  Polyoxometalates immobilized in ordered mesoporous carbon nitride as highly efficient water oxidation catalysts. , 2012, ChemSusChem.

[92]  Fredrickson,et al.  Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores , 1998, Science.

[93]  Rong Xu,et al.  Mesoporous carbon nitride with in situ sulfur doping for enhanced photocatalytic hydrogen evolution from water under visible light , 2012 .

[94]  M. Antonietti,et al.  mpg-C3N4 as a solid base catalyst for Knoevenagel condensations and transesterification reactions , 2012 .

[95]  K. Zhao,et al.  Carbon self-doping induced high electronic conductivity and photoreactivity of g-C3N4. , 2012, Chemical communications.

[96]  M. Antonietti,et al.  Synthesis of bulk and nanoporous carbon nitride polymers from ammonium thiocyanate for photocatalytic hydrogen evolution , 2011 .

[97]  B. Wood,et al.  Cage type mesoporous carbon nitride with large mesopores for CO2 capture , 2015 .

[98]  Sang Hoon Joo,et al.  Synthesis of highly ordered carbon molecular sieves via template-mediated structural transformation , 1999 .

[99]  K. Ariga,et al.  New families of mesoporous materials , 2006 .

[100]  Katsuhiko Ariga,et al.  Three-Dimensional Cage Type Mesoporous CN-Based Hybrid Material with Very High Surface Area and Pore Volume , 2007 .

[101]  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.

[102]  Ashin Marin Thomas,et al.  Growth Confined by the Nitrogen Source: Synthesis of Pure Metal Nitride Nanoparticles in Mesoporous Graphitic Carbon Nitride , 2007 .

[103]  L. Yuliati,et al.  A urea precursor to synthesize carbon nitride with mesoporosity for enhanced activity in the photocatalytic removal of phenol. , 2012, Chemistry, an Asian journal.

[104]  Yuyu Bu,et al.  Using electrochemical methods to study the promotion mechanism of the photoelectric conversion performance of Ag-modified mesoporous g-C3N4 heterojunction material , 2014 .

[105]  Yongxin Li,et al.  Preparation of mesoporous graphitic carbon nitride using hexamethylenetetramine as a new precursor and catalytic application in the transesterification of β-keto esters , 2014 .

[106]  Yuanjian Zhang,et al.  Soft and hard templating of graphitic carbon nitride , 2015 .

[107]  B. Kumar,et al.  News from the Biomaterials Science editors. , 2013, Biomaterials science.

[108]  Hui-Ming Cheng,et al.  Unique electronic structure induced high photoreactivity of sulfur-doped graphitic C3N4. , 2010, Journal of the American Chemical Society.

[109]  Z. Wen,et al.  Mesoporous carbon nitride loaded with Pt nanoparticles as a bifunctional air electrode for rechargeable lithium-air battery , 2012, Journal of Solid State Electrochemistry.

[110]  E. Haque,et al.  Superior adsorption capacity of mesoporous carbon nitride with basic CN framework for phenol , 2010 .