Synthesis and photocatalytic application of visible-light active β-Fe2O3/g-C3N4 hybrid nanocomposites

Abstract Hybrid organic/inorganic nanocomposites comprised of nanocrystalline iron oxide at the metastable β-phase and graphitic carbon nitride (g-C 3 N 4 ) were prepared via a facile in-situ growth strategy embedded in a solid state process. The hybridized β-Fe 2 O 3 /g-C 3 N 4 nanomaterials were thoroughly characterized by a variety of techniques, including UV–vis absorption, nitrogen physisorption, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM). Their photocatalytic activity was evaluated under both simulated solar light and pure visible light irradiation against the photodegradation of methyl orange (MO), rhodamine B (RhB) and phenol. The prepared β-Fe 2 O 3 /g-C 3 N 4 nanocomposites were proven durable and significantly more efficient than the single components. The β-Fe 2 O 3 content in the final material was tuned to optimize the photocatalytic performance, with particular attention to the activity under visible light. The enhanced photoactivity was attributed to a) the improved optical properties of the prepared nanocomposites, presenting narrower band-gap energies and increased visible light absorption efficiency, and b) to the efficient separation of the photoinduced charge carriers driven by the matched band edges in the heterostructure. The predominant active species responsible for the photodegradation activity were determined and a possible mechanism is proposed.

[1]  Yuxin Yang,et al.  Preparation and enhanced visible-light photocatalytic activity of graphitic carbon nitride/bismuth niobate heterojunctions. , 2013, Journal of hazardous materials.

[2]  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.

[3]  Zaizhu Lou,et al.  Temperature-controlled morphology evolution of graphitic carbon nitride nanostructures and their photocatalytic activities under visible light , 2015 .

[4]  Li Xu,et al.  Preparation of sphere-like g-C3N4/BiOI photocatalysts via a reactable ionic liquid for visible-light-driven photocatalytic degradation of pollutants , 2014 .

[5]  R. Amal,et al.  Z-schematic water splitting into H2 and O2 using metal sulfide as a hydrogen-evolving photocatalyst and reduced graphene oxide as a solid-state electron mediator. , 2015, Journal of the American Chemical Society.

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

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

[8]  M. Antonietti,et al.  Synthesis of transition metal-modified carbon nitride polymers for selective hydrocarbon oxidation. , 2010, ChemSusChem.

[9]  Hui Gu,et al.  Photochemical synthesis of noble metal (Ag, Pd, Au, Pt) on graphene/ZnO multihybrid nanoarchitectures as electrocatalysis for H2O2 reduction. , 2013, ACS applied materials & interfaces.

[10]  Di Zhang,et al.  Tailoring the Morphology of g‐C3N4 by Self‐Assembly towards High Photocatalytic Performance , 2014 .

[11]  Junfa Zhu,et al.  Facile fabrication of magnetically separable graphitic carbon nitride photocatalysts with enhanced photocatalytic activity under visible light , 2013 .

[12]  M. Antonietti,et al.  Making MetalCarbon Nitride Heterojunctions for Improved Photocatalytic Hydrogen Evolution with Visible Light , 2010 .

[13]  J. Lee,et al.  Optoelectronic properties of β-Fe2O3 hollow nanoparticles , 2008 .

[14]  Caroline Sunyong Lee,et al.  Photoelectrochemical properties and photodegradation of organic pollutants using hematite hybrids modified by gold nanoparticles and graphitic carbon nitride , 2015 .

[15]  M. Ashokkumar,et al.  Photocatalytic and photoelectrochemical studies of visible-light active α-Fe2O3–g-C3N4 nanocomposites , 2014 .

[16]  T. Peng,et al.  Effect of graphitic carbon nitride microstructures on the activity and selectivity of photocatalytic CO2 reduction under visible light , 2013 .

[17]  Yucheng He,et al.  A facile method to crystallize amorphous anodized TiO₂ nanotubes at low temperature. , 2011, ACS applied materials & interfaces.

[18]  Hua-ming Li,et al.  Visible-light-induced WO3/g-C3N4 composites with enhanced photocatalytic activity. , 2013, Dalton transactions.

[19]  Hongjun Lin,et al.  Enhanced photodegradation activity of methyl orange over Z-scheme type MoO3–g-C3N4 composite under visible light irradiation , 2014 .

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

[21]  E. Oliveros,et al.  Advanced Oxidation Processes for Organic Contaminant Destruction Based on the Fenton Reaction and Related Chemistry , 2006 .

[22]  F. Chang,et al.  Photocatalytic degradation of 2,4,6-trichlorophenol over g-C3N4 under visible light irradiation , 2013 .

[23]  M. Fernández-García,et al.  Iron–sulfur codoped TiO2 anatase nano-materials: UV and sunlight activity for toluene degradation , 2012 .

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

[25]  G. Adami,et al.  Enhanced Hydrogen Production by Photoreforming of Renewable Oxygenates Through Nanostructured Fe2O3 Polymorphs , 2014 .

[26]  M. Fernández-García,et al.  Advanced nanoarchitectures for solar photocatalytic applications. , 2012, Chemical reviews.

[27]  M. Antonietti,et al.  Metal‐Containing Carbon Nitride Compounds: A New Functional Organic–Metal Hybrid Material , 2009 .

[28]  F. Dong,et al.  Graphitic carbon nitride based nanocomposites: a review. , 2015, Nanoscale.

[29]  N. Keller,et al.  Single-Step Synthesis of SnS₂ Nanosheet-Decorated TiO₂ Anatase Nanofibers as Efficient Photocatalysts for the Degradation of Gas-Phase Diethylsulfide. , 2015, ACS applied materials & interfaces.

[30]  Z. Zou,et al.  Photodegradation of rhodamine B and methyl orange over boron-doped g-C3N4 under visible light irradiation. , 2010, Langmuir : the ACS journal of surfaces and colloids.

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

[32]  Kiyoshi Okada,et al.  Preparation of graphitic carbon nitride (g-C₃N₄)/WO₃ composites and enhanced visible-light-driven photodegradation of acetaldehyde gas. , 2013, Journal of hazardous materials.

[33]  Michael Grätzel,et al.  Identifying champion nanostructures for solar water-splitting. , 2013, Nature materials.

[34]  Michael Grätzel,et al.  Solar water splitting: progress using hematite (α-Fe(2) O(3) ) photoelectrodes. , 2011, ChemSusChem.

[35]  Jianlin Shi,et al.  Highly selective CO2 photoreduction to CO over g-C3N4/Bi2WO6 composites under visible light , 2015 .

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

[37]  Santosh Kumar,et al.  Fe-doped and -mediated graphitic carbon nitride nanosheets for enhanced photocatalytic performance under natural sunlight , 2014 .

[38]  D. Peeters,et al.  Solar H2generation via ethanol photoreforming on ε-Fe2O3nanorod arrays activated by Ag and Au nanoparticles , 2014 .

[39]  Zhongbiao Wu,et al.  An Advanced Semimetal-Organic Bi Spheres-g-C3N4 Nanohybrid with SPR-Enhanced Visible-Light Photocatalytic Performance for NO Purification. , 2015, Environmental science & technology.

[40]  J. Tuček,et al.  ε-Fe2O3: An Advanced Nanomaterial Exhibiting Giant Coercive Field, Millimeter-Wave Ferromagnetic Resonance, and Magnetoelectric Coupling , 2010 .

[41]  Binbin Chang,et al.  Novel C3N4–CdS composite photocatalysts with organic–inorganic heterojunctions: in situ synthesis, exceptional activity, high stability and photocatalytic mechanism , 2013 .

[42]  X. Qiu,et al.  Selective oxidation of benzene to phenol by Fe-CN/TS-1 catalysts under visible light irradiation , 2014 .

[43]  Maurizio Prato,et al.  Multiwalled carbon nanotubes drive the activity of metal@oxide core-shell catalysts in modular nanocomposites. , 2012, Journal of the American Chemical Society.

[44]  Tatsuo Fujii,et al.  Crystal Structure of β-Fe2O3 and Topotactic Phase Transformation to α-Fe2O3 , 2013 .

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

[46]  Xiaoyun Li,et al.  Photo-assisted synthesis of Ag3PO4/reduced graphene oxide/Ag heterostructure photocatalyst with enhanced photocatalytic activity and stability under visible light , 2014 .

[47]  Shaozheng Hu,et al.  The properties and photocatalytic performance comparison of Fe3+-doped g-C3N4 and Fe2O3/g-C3N4 composite catalysts , 2014 .

[48]  Jun Jiang,et al.  Two-dimensional g-C(3)N(4): an ideal platform for examining facet selectivity of metal co-catalysts in photocatalysis. , 2014, Chemical communications.

[49]  T. Tzanov,et al.  Predicting Dye Biodegradation from Redox Potentials , 2004, Biotechnology progress.

[50]  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.

[51]  M. Fernández-García,et al.  Photoactivity and charge trapping sites in copper and vanadium doped anatase TiO2 nano-materials , 2016 .

[52]  Ming Yan,et al.  In-situ synthesis of direct solid-state Z-scheme V2O5/g-C3N4 heterojunctions with enhanced visible light efficiency in photocatalytic degradation of pollutants , 2016 .

[53]  B. Kumar,et al.  Synthesis of magnetically separable and recyclable g‑C3N4−Fe3O4 hybrid nanocomposites with enhanced photocatalytic performance under visible-light irradiation , 2013 .

[54]  Dieter Söll,et al.  Cover Picture: Recoding the Genetic Code with Selenocysteine (Angew. Chem. Int. Ed. 1/2014) , 2014 .

[55]  Xinchen Wang,et al.  Ferrocene-modified carbon nitride for direct oxidation of benzene to phenol with visible light. , 2014, ChemSusChem.

[56]  Hui Yang,et al.  An orthophosphate semiconductor with photooxidation properties under visible-light irradiation. , 2010, Nature materials.