A visible-light active catechol–metal oxide carbonaceous polymeric material for enhanced photocatalytic activity

Designing new materials for sustainable energy and environmental applications is one of the prime focuses in chemical science. Here, an unprecedented visible-light active catechol–TiO2 carbonaceous polymer based organic–inorganic hybrid material was synthesized by a photosynthetic route. The visible light induced (>400 nm) photosynthetic polymerization of catechol led to the formation of carbonaceous polymeric deposits on the surface of TiO2. The band gap energy of hybrids was shifted to the visible region by orbital hybridization between 3d(Ti) of TiO2 and 2p(O), π(C) of catechol. The Tauc plot clearly revealed that 1.0 wt% catechol–TiO2 carbonaceous polymer remarkably tailored the optical band gap of TiO2 from 3.1 eV to 1.9 eV. The synthesized hybrid materials were thoroughly characterized and their photocatalytic activity was evaluated towards toxic Cr(VI) to relatively less toxic Cr(III) reduction under visible light irradiation (>400 nm), and solar light-driven H2 production through water splitting. Very interestingly, the hybrid material showed 5- and 10-fold enhanced activity for photocatalytic Cr(VI) reduction and solar light-driven H2 production respectively compared with pure TiO2. Moreover, the hybrid materials showed enhanced stability during photocatalysis. Thus, the simple photosynthetic strategy for developing light harvesting organic–inorganic hybrid materials can open up potential applications in energy and environmental remediation.

[1]  Xue-mei Gao,et al.  Phenylethanoids from the Flowers of Rosa rugosa and Their Biological Activities , 2013 .

[2]  H. Eskandarloo,et al.  Minimization of electrical energy consumption in the photocatalytic reduction of Cr(VI) by using immobilized Mg, Ag co-impregnated TiO2 nanoparticles , 2014 .

[3]  D. Chatterjee.  Effect of excited state redox properties of dye sensitizers on hydrogen production through photo-splitting of water over TiO2 photocatalyst , 2010 .

[4]  Ling Wu,et al.  Electrostatically derived self-assembly of NH2-mediated zirconium MOFs with graphene for photocatalytic reduction of Cr(VI) , 2014 .

[5]  Masakazu Saito,et al.  Visible-Light-Promoted Photocatalytic Hydrogen Production by Using an Amino-Functionalized Ti(IV) Metal–Organic Framework , 2012 .

[6]  Zisheng Zhang,et al.  Graphene-wrapped hierarchical TiO2 nanoflower composites with enhanced photocatalytic performance , 2013 .

[7]  Li Wang,et al.  Morphology evolution of TiO2 facets and vital influences on photocatalytic activity. , 2012, ACS applied materials & interfaces.

[8]  E. Wolfrum,et al.  Heterogeneous Photocatalytic Reduction of Cr(VI) in UV-Irradiated Titania Suspensions: Effect of Protons, Ammonium Ions, and Other Interfacial Aspects , 2000 .

[9]  H. Yamashita,et al.  Synthesis of highly visible light active TiO2-2-naphthol surface complex and its application in photocatalytic chromium(VI) reduction , 2015 .

[10]  J. Nedeljković,et al.  Surface modification of anatase nanoparticles with fused ring catecholate type ligands: a combined DFT and experimental study of optical properties. , 2012, Nanoscale.

[11]  U. Pal,et al.  Effects of crystallization and dopant concentration on the emission behavior of TiO2:Eu nanophosphors , 2012, Nanoscale Research Letters.

[12]  Wen Zhu,et al.  Photogenerated electron reservoir in hetero-p–n CuO–ZnO nanocomposite device for visible-light-driven photocatalytic reduction of aqueous Cr(VI) , 2015 .

[13]  Jiaqiang Wang,et al.  Significantly enhanced photocatalytic hydrogen evolution under visible light over CdS embedded on metal-organic frameworks. , 2013, Chemical communications.

[14]  Jiaqiang Wang,et al.  A dye-sensitized Pt@UiO-66(Zr) metal-organic framework for visible-light photocatalytic hydrogen production. , 2014, Chemical communications.

[15]  Jinhua Ye,et al.  An Amine‐Functionalized Iron(III) Metal–Organic Framework as Efficient Visible‐Light Photocatalyst for Cr(VI) Reduction , 2015, Advanced science.

[16]  T. Lana-Villarreal,et al.  A spectroscopic and electrochemical approach to the study of the interactions and photoinduced electron transfer between catechol and anatase nanoparticles in aqueous solution. , 2005, Journal of the American Chemical Society.

[17]  H. Kisch,et al.  Daylight photocatalysis by carbon-modified titanium dioxide. , 2003, Angewandte Chemie.

[18]  Hong‐Ying Zang,et al.  Organic–inorganic hybrid assemblies based on Ti-substituted polyoxometalates for photocatalytic dye degradation , 2015 .

[19]  Weifeng Zhang,et al.  Core/shell-shaped CdSe/PbS nanotetrapods for efficient organic-inorganic hybrid solar cells , 2014 .

[20]  A. Zaban,et al.  The TiO2–Catechol Complex: Coupling Type II Sensitization with Efficient Catalysis of Water Oxidation , 2014 .

[21]  S. Armes,et al.  Polystyrene−Silica Colloidal Nanocomposite Particles Prepared by Alcoholic Dispersion Polymerization , 2007 .

[22]  Shun Mao,et al.  A new reducing agent to prepare single-layer, high-quality reduced graphene oxide for device applications. , 2011, Nanoscale.

[23]  Guan Zhang,et al.  Visible light driven photocatalysis mediated via ligand-to-metal charge transfer (LMCT): an alternative approach to solar activation of titania , 2014 .

[24]  Jiaguo Yu,et al.  Rapid synthesis of mesoporous TiO2 with high photocatalytic activity by ultrasound-induced agglomeration , 2002 .

[25]  Jincai Zhao,et al.  Conjugation-grafted-TiO(2) nanohybrid for high photocatalytic efficiency under visible light. , 2014, ACS applied materials & interfaces.

[26]  J. Fujisawa,et al.  Interfacial charge-transfer transitions in a TiO2-benzenedithiol complex with Ti-S-C linkages. , 2015, Physical chemistry chemical physics : PCCP.

[27]  J. Ying,et al.  Tunable Release of Proteins with Polymer–Inorganic Nanocomposite Microspheres , 2008 .

[28]  M. Ashokkumar,et al.  Graphene oxide based Pt-TiO2 photocatalyst: ultrasound assisted synthesis, characterization and catalytic efficiency. , 2012, Ultrasonics sonochemistry.

[29]  Jacqueline M. Cole,et al.  Anchoring groups for dye-sensitized solar cells. , 2015, ACS applied materials & interfaces.

[30]  S. Armes,et al.  Efficient preparation of polystyrene/silica colloidal nanocomposite particles by emulsion polymerization using a glycerol-functionalized silica sol. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[31]  Ling Wu,et al.  Multifunctional NH2-mediated zirconium metal-organic framework as an efficient visible-light-driven photocatalyst for selective oxidation of alcohols and reduction of aqueous Cr(VI). , 2013, Dalton transactions.

[32]  Feng Wu,et al.  Effective TiO2 hybrid heterostructure fabricated on nano mesoporous phenolic resol for visible-light photocatalysis , 2012 .

[33]  P. R. Deshmukh,et al.  Chemical synthesis of PANI–TiO2 composite thin film for supercapacitor application , 2015 .

[34]  Chuanhao Li,et al.  Improving photocatalytic hydrogen production of metal–organic framework UiO-66 octahedrons by dye-sensitization , 2015 .

[35]  K. Vinodgopal,et al.  Influence of electron storing, transferring and shuttling assets of reduced graphene oxide at the interfacial copper doped TiO2 p-n heterojunction for increased hydrogen production. , 2015, Nanoscale.

[36]  Y. Tachibana,et al.  Photoinduced Formation of Polythiophene/TiO2 Nanohybrid Heterojunction Films for Solar Cell Applications , 2008 .

[37]  Yan Gao,et al.  Synthesis of polypyrrole–titanium dioxide brush-like nanocomposites with enhanced supercapacitive performance , 2014 .

[38]  B. Mei,et al.  Surface-Modified TiO2 Photocatalysts Prepared by a Photosynthetic Route: Mechanism, Enhancement, and Limits. , 2014, ChemPlusChem.

[39]  H. Einaga.  Heterogeneous photocatalytic oxidation of benzene, toluene, cyclohexene and cyclohexane in humidified air: comparison of decomposition behavior on photoirradiated TiO2 catalyst , 2002 .

[40]  W. Choi,et al.  Visible-light-induced photocatalytic degradation of 4-chlorophenol and phenolic compounds in aqueous suspension of pure titania: demonstrating the existence of a surface-complex-mediated path. , 2005, The journal of physical chemistry. B.

[41]  Yadong Yin,et al.  Photocatalytic Surface-Initiated Polymerization on TiO2 toward Well-Defined Composite Nanostructures. , 2016, ACS applied materials & interfaces.

[42]  Caruso,et al.  Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating , 1998, Science.

[43]  O. Ayyad,et al.  Copper@polypyrrole nanocables , 2012, Nanoscale Research Letters.

[44]  S. Siddiqi,et al.  Synthesis of polypyrrole/zinc oxide composites and study of their structural, thermal and electrical properties , 2012 .

[45]  Omid Akhavan,et al.  Flash photo stimulation of human neural stem cells on graphene/TiO2 heterojunction for differentiation into neurons. , 2013, Nanoscale.

[46]  N. Zhang,et al.  Waltzing with the Versatile Platform of Graphene to Synthesize Composite Photocatalysts. , 2015, Chemical reviews.

[47]  S. Hecht,et al.  Vacuum-processable ladder-type oligophenylenes for organic–inorganic hybrid structures: synthesis, optical and electrochemical properties upon increasing planarization as well as thin film growth , 2012 .

[48]  J. Xin,et al.  Fabrication of UV-blocking nanohybrid coating via miniemulsion polymerization. , 2006, Journal of colloid and interface science.

[49]  F. Kapteijn,et al.  Co@NH2-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H2 production , 2015 .

[50]  Ling Wu,et al.  NH2-mediated indium metal–organic framework as a novel visible-light-driven photocatalyst for reduction of the aqueous Cr(VI) , 2015 .

[51]  Yadong Yin,et al.  Magnetically Tunable Colloidal Photonic Structures in Alkanol Solutions , 2008 .

[52]  Nan Zhang,et al.  One-dimensional CdS nanowires–CeO2 nanoparticles composites with boosted photocatalytic activity , 2015 .

[53]  Yi Li,et al.  Efficient visible light photocatalytic degradation of 17α-ethinyl estradiol by a multifunctional Ag–AgCl/ZnFe2O4 magnetic nanocomposite , 2016 .

[54]  Ling Wu,et al.  Highly dispersed palladium nanoparticles anchored on UiO-66(NH₂) metal-organic framework as a reusable and dual functional visible-light-driven photocatalyst. , 2013, Nanoscale.

[55]  Yi‐Jun Xu,et al.  Heterostructured semiconductor nanowire arrays for artificial photosynthesis , 2016 .

[56]  Cheng Wang,et al.  Pt nanoparticles@photoactive metal-organic frameworks: efficient hydrogen evolution via synergistic photoexcitation and electron injection. , 2012, Journal of the American Chemical Society.

[57]  A free radical assisted strategy for preparing ultra-small Pt decorated CNTs as a highly efficient counter electrode for dye-sensitized solar cells , 2014 .

[58]  Hanqing Yu,et al.  Light-triggered reversible sorption of azo dyes on titanium xerogels with photo-switchable acetylacetonato anchors. , 2014, Chemical communications.

[59]  H. Yamashita,et al.  A visible-light-harvesting assembly with a sulfocalixarene linker between dyes and a Pt-TiO2 photocatalyst. , 2013, Angewandte Chemie.

[60]  Yupeng Yuan,et al.  Dye-sensitized MIL-101 metal organic frameworks loaded with Ni/NiOx nanoparticles for efficient visible-light-driven hydrogen generation , 2015 .

[61]  Claudio Ciavatta,et al.  Catechol polymerization in the presence of silver surface , 2001 .

[62]  G. Stucky,et al.  In situ photopolymerization of pyrrole in mesoporous TiO2. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[63]  Shaozheng Hu,et al.  Properties and photocatalytic performance of polypyrrole and polythiophene modified g-C3N4 nanocomposites , 2015 .

[64]  Xinyong Li,et al.  Controllable synthesis of ZnO nanoflowers and their morphology-dependent photocatalytic activities , 2008 .

[65]  Synthesis of Bi nanowire networks and their superior photocatalytic activity for Cr(vi) reduction. , 2014, Nanoscale.

[66]  Zhuo. Sun,et al.  Sol–gel synthesis of Au/N–TiO2 composite for photocatalytic reduction of Cr(VI) , 2012 .

[67]  Jinlin Li,et al.  Controllable synthesis and morphology-dependent photocatalytic performance of anatase TiO2 nanoplates , 2015 .

[68]  N. Parveen,et al.  Route to High Surface Area, Mesoporosity of Polyaniline–Titanium Dioxide Nanocomposites via One Pot Synthesis for Energy Storage Applications , 2016 .

[69]  Rosanna Larciprete,et al.  Dual path mechanism in the thermal reduction of graphene oxide. , 2011, Journal of the American Chemical Society.

[70]  Brian C. Smith.  Infrared Spectral Interpretation: A Systematic Approach , 1998 .

[71]  Zhuo. Sun,et al.  Microwave-assisted synthesis of CdS-reduced graphene oxide composites for photocatalytic reduction of Cr(VI). , 2011, Chemical communications.

[72]  Guan Zhang,et al.  A low-cost sensitizer based on a phenolic resin for charge-transfer type photocatalysts working under visible light. , 2012, Chemical communications.

[73]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[74]  David F. Ollis,et al.  Benzene and toluene gas-phase photocatalytic degradation over H2O and HCL pretreated TiO2: by-products and mechanisms , 1998 .

[75]  M. Gratzel,et al.  Photochemical hydrogen generation by visible light. Sensitization of titanium dioxide particles by surface complexation with 8-hydroxyquinoline , 1983 .

[76]  J. Nedeljković,et al.  Surface modification of anatase nanoparticles with fused ring salicylate-type ligands (3-hydroxy-2-naphthoic acids): a combined DFT and experimental study of optical properties. , 2013, Nanoscale.

[77]  B. Mei,et al.  Enhanced performance of surface-modified TiO2 photocatalysts prepared via a visible-light photosynthetic route. , 2012, Chemical communications.

[78]  Nan Zhang,et al.  Structural diversity of graphene materials and their multifarious roles in heterogeneous photocatalysis , 2016 .

[79]  Andrew G. Glen,et al.  APPL , 2001 .