Engineering Coexposed {001} and {101} Facets in Oxygen-Deficient TiO2 Nanocrystals for Enhanced CO2 Photoreduction under Visible Light

This work for the first time reports engineered oxygen-deficient, blue TiO2 nanocrystals with coexposed {101}-{001} facets (TiO2–x{001}-{101}) to enhance CO2 photoreduction under visible light. The TiO2–x{001}-{101} material demonstrated a relatively high quantum yield (0.31% under UV–vis light and 0.134% under visible light) for CO2 reduction to CO by water vapor and more than 4 times higher visible light activity in comparison with TiO2 with a single {001} plane or {101} plane and TiO2(P25). Possible reasons are the exposure of more active sites (e.g., undercoordinated Ti atoms and oxygen vacancies), the facilitated electron transfer between {001} and {101} planes, and the formation of a new energy state (Ti3+) within the TiO2 band gap to extend the visible light response. An in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study was applied to understand the roles of coexposed {001}-{101} facets and Ti3+ sites in activating surface intermediates. The in situ DRIFTS analysis ...

[1]  Dimitri D. Vaughn,et al.  Hybrid CuO-TiO(2-x)N(x) hollow nanocubes for photocatalytic conversion of CO2 into methane under solar irradiation. , 2012, Angewandte Chemie.

[2]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[3]  M. Wong,et al.  EPR investigation of TiO2 nanoparticles with temperature-dependent properties. , 2006, The journal of physical chemistry. B.

[4]  Nan Zhang,et al.  Defective TiO2 with oxygen vacancies: synthesis, properties and photocatalytic applications. , 2013, Nanoscale.

[5]  A. Mohamed,et al.  Facet-dependent photocatalytic properties of TiO(2) -based composites for energy conversion and environmental remediation. , 2014, ChemSusChem.

[6]  E. Carter,et al.  First principles scheme to evaluate band edge positions in potential transition metal oxide photocatalysts and photoelectrodes. , 2011, Physical chemistry chemical physics : PCCP.

[7]  Mark C Hersam,et al.  Minimizing graphene defects enhances titania nanocomposite-based photocatalytic reduction of CO2 for improved solar fuel production. , 2011, Nano letters.

[8]  G. Pacchioni,et al.  Reduced and n-Type Doped TiO2: Nature of Ti3+ Species , 2009 .

[9]  Hiromi Yamashita,et al.  Photocatalytic reduction of CO2 with H2O on various titanium oxide photocatalysts , 2012 .

[10]  Lianjun Liu,et al.  Integrated CO2 capture and photocatalytic conversion by a hybrid adsorbent/photocatalyst material , 2015 .

[11]  G. Mul,et al.  Artificial photosynthesis over crystalline TiO2-based catalysts: fact or fiction? , 2010, Journal of the American Chemical Society.

[12]  N. Umezawa,et al.  Anatase TiO2 Single Crystals Exposed with High-Reactive {111} Facets Toward Efficient H2 Evolution , 2013 .

[13]  H. Schobert,et al.  Quantum Chemical Modeling of Ground States of CO 2 Chemisorbed on Anatase (001), (101), and (010) TiO 2 Surfaces , 2008 .

[14]  Ying Yu,et al.  Ti 3+ in the surface of titanium dioxide: generation, properties and photocatalytic application , 2012 .

[15]  Wei Xiao,et al.  Enhanced photocatalytic CO₂-reduction activity of anatase TiO₂ by coexposed {001} and {101} facets. , 2014, Journal of the American Chemical Society.

[16]  Xiaoheng Liu,et al.  One-step and large-scale synthesis of anatase TiO2 mesocrystals along [001] orientation with enhanced photocatalytic performance , 2013 .

[17]  Yangen Zhou,et al.  Gold-plasmon enhanced solar-to-hydrogen conversion on the {001} facets of anatase TiO2 nanosheets , 2014 .

[18]  E. Grabowska,et al.  Decahedral TiO2 with exposed facets: Synthesis, properties, photoactivity and applications , 2014 .

[19]  A. Mohamed,et al.  Self-assembly of nitrogen-doped TiO2 with exposed {001} facets on a graphene scaffold as photo-active hybrid nanostructures for reduction of carbon dioxide to methane , 2014, Nano Research.

[20]  Jian Pan,et al.  Titanium dioxide crystals with tailored facets. , 2014, Chemical reviews.

[21]  Dong Liu,et al.  Photocatalytic CO2 reduction using an internally illuminated monolith photoreactor , 2011 .

[22]  Xiaobo Chen,et al.  Influence of the Amount of Hydrogen Fluoride on the Formation of (001)‐Faceted Titanium Dioxide Nanosheets and Their Photocatalytic Hydrogen Generation Performance , 2014 .

[23]  Kai Jiang,et al.  Anatase TiO2 hierarchical structures composed of ultra-thin nano-sheets exposing high percentage {0 0 1} facets and their application in quantum-dot sensitized solar cells , 2015 .

[24]  John P. Baltrus,et al.  Visible Light Photoreduction of CO2 Using CdSe/Pt/TiO2 Heterostructured Catalysts , 2009 .

[25]  Xiaobo Chen,et al.  Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals , 2011, Science.

[26]  B. Viswanathan,et al.  Visible light driven reduction of carbon dioxide with water on modified Sr3Ti2O7 catalysts , 2015 .

[27]  J. Yates,et al.  Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results , 1995 .

[28]  M. Xing,et al.  Highly-dispersed Boron-doped Graphene Nanosheets Loaded with TiO2 Nanoparticles for Enhancing CO2 Photoreduction , 2014, Scientific Reports.

[29]  Mohammad Mansoob Khan,et al.  Band gap engineered TiO2 nanoparticles for visible light induced photoelectrochemical and photocatalytic studies , 2014 .

[30]  T. Peng,et al.  Pt-loading reverses the photocatalytic activity order of anatase TiO2 {0 0 1} and {0 1 0} facets for photoreduction of CO2 to CH4 , 2014 .

[31]  Congjun Wang,et al.  Size-dependent photocatalytic reduction of CO2 with PbS quantum dot sensitized TiO2 heterostructured photocatalysts , 2011 .

[32]  Kesong Yang,et al.  First-principles GGA+U study of the different conducting properties in pentavalent-ion-doped anatase and rutile TiO2 , 2014 .

[33]  John P. Perdew,et al.  Physical Content of the Exact Kohn-Sham Orbital Energies: Band Gaps and Derivative Discontinuities , 1983 .

[34]  Mietek Jaroniec,et al.  Anatase TiO2 with Dominant High-Energy {001} Facets: Synthesis, Properties, and Applications , 2011 .

[35]  Lianjun Liu,et al.  Porous microspheres of MgO-patched TiO2 for CO2 photoreduction with H2O vapor: temperature-dependent activity and stability. , 2013, Chemical communications.

[36]  Zaicheng Sun,et al.  A facile and versatile method for preparation of colored TiO2 with enhanced solar-driven photocatalytic activity. , 2014, Nanoscale.

[37]  Hong Liu,et al.  Recent progress in design, synthesis, and applications of one-dimensional TiO2 nanostructured surface heterostructures: a review. , 2014, Chemical Society reviews.

[38]  Pratim Biswas,et al.  Size and structure matter: enhanced CO2 photoreduction efficiency by size-resolved ultrafine Pt nanoparticles on TiO2 single crystals. , 2012, Journal of the American Chemical Society.

[39]  Xiaobo Chen,et al.  Titanium dioxide nanomaterials: self-structural modifications. , 2014, Chemical reviews.

[40]  Jianmeng Chen,et al.  Photocatalytic Reduction of CO2 in Aqueous Solution on Surface-Fluorinated Anatase TiO2 Nanosheets with Exposed {001} Facets , 2014 .

[41]  T. Chen,et al.  Surface Phases of TiO2 Nanoparticles Studied by UV Raman Spectroscopy and FT-IR Spectroscopy , 2008 .

[42]  T. Andreu,et al.  Slightly hydrogenated TiO2 with enhanced photocatalytic performance , 2014 .

[43]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[44]  Debabrata Pradhan,et al.  Synergy of low-energy {101} and high-energy {001} TiO₂ crystal facets for enhanced photocatalysis. , 2013, ACS nano.

[45]  Muhammad Tahir,et al.  Photocatalytic CO2 reduction and kinetic study over In/TiO2 nanoparticles supported microchannel monolith photoreactor , 2013 .

[46]  Lauren R. Grabstanowicz,et al.  Facile oxidative conversion of TiH2 to high-concentration Ti(3+)-self-doped rutile TiO2 with visible-light photoactivity. , 2013, Inorganic chemistry.

[47]  Ruifeng Li,et al.  Effect of heating temperature on photocatalytic reduction of CO2 by N–TiO2 nanotube catalyst , 2012 .

[48]  J. Barber,et al.  Recent advances in hybrid photocatalysts for solar fuel production , 2012 .

[49]  Xiaoming Xie,et al.  H‐Doped Black Titania with Very High Solar Absorption and Excellent Photocatalysis Enhanced by Localized Surface Plasmon Resonance , 2013 .

[50]  G. Lu,et al.  Hollow Anatase TiO2 Single Crystals and Mesocrystals with Dominant {101} Facets for Improved Photocatalysis Activity and Tuned Reaction Preference , 2012 .

[51]  A. Takshi,et al.  Toward a Visible Light-Driven Photocatalyst: The Effect of Midgap-States-Induced Energy Gap of Undoped TiO2 Nanoparticles , 2015 .

[52]  M. Xing,et al.  Enhanced Photocatalysis by Au Nanoparticle Loading on TiO2 Single-Crystal (001) and (110) Facets , 2013 .

[53]  Yunbin He,et al.  Evidence for the predominance of subsurface defects on reduced anatase TiO2(101). , 2009, Physical review letters.

[54]  Nathan T. Hahn,et al.  Enhancing visible light photo-oxidation of water with TiO2 nanowire arrays via cotreatment with H2 and NH3: synergistic effects between Ti3+ and N. , 2012, Journal of the American Chemical Society.

[55]  A. Mohamed,et al.  Band gap engineered, oxygen-rich TiO2 for visible light induced photocatalytic reduction of CO2. , 2014, Chemical communications.

[56]  E. Xie,et al.  Preparation of black TiO2 by hydrogen plasma assisted chemical vapor deposition and its photocatalytic activity , 2014 .

[57]  Yajun Wang,et al.  Facile in situ synthesis of graphitic carbon nitride (g-C3N4)-N-TiO2 heterojunction as an efficient photocatalyst for the selective photoreduction of CO2 to CO , 2014 .

[58]  F. Bechstedt,et al.  Linear optical properties in the projector-augmented wave methodology , 2006 .

[59]  A. Xu,et al.  Stable blue TiO2−x nanoparticles for efficient visible light photocatalysts , 2014 .

[60]  S. Trasatti The absolute electrode potential: an explanatory note (Recommendations 1986) , 1986 .

[61]  Jian Shi,et al.  One-dimensional titanium dioxide nanomaterials: nanowires, nanorods, and nanobelts. , 2014, Chemical reviews.

[62]  Lianjun Liu,et al.  Spontaneous Dissociation of CO2 to CO on Defective Surface of Cu(I)/TiO2–x Nanoparticles at Room Temperature , 2012 .

[63]  Photocatalytic CO2 reduction by TiO2 and related titanium containing solids , 2012 .

[64]  R. Asahi,et al.  Nitrogen-doped titanium dioxide as visible-light-sensitive photocatalyst: designs, developments, and prospects. , 2014, Chemical reviews.

[65]  G. Spoto,et al.  CO2 Capture by TiO2 Anatase Surfaces: A Combined DFT and FTIR Study , 2014 .

[66]  John Robertson,et al.  Calculation of TiO2 Surface and Subsurface Oxygen Vacancy by the Screened Exchange Functional , 2015 .

[67]  G. Marcì,et al.  Photocatalytic CO2 reduction in gas–solid regime in the presence of H2O by using GaP/TiO2 composite as photocatalyst under simulated solar light , 2014 .

[68]  Weiqiang Wu,et al.  Photoinduced reactions of surface-bound species on titania nanotubes and platinized titania nanotubes: An in situ FTIR study , 2013 .

[69]  Wenguang Tu,et al.  Robust Hollow Spheres Consisting of Alternating Titania Nanosheets and Graphene Nanosheets with High Photocatalytic Activity for CO2 Conversion into Renewable Fuels , 2012 .

[70]  Prathamesh Pavaskar,et al.  Photocatalytic Conversion of CO2 to Hydrocarbon Fuels via Plasmon-Enhanced Absorption and Metallic Interband Transitions , 2011 .

[71]  F. Gao,et al.  Tailoring Cu valence and oxygen vacancy in Cu/TiO2 catalysts for enhanced CO2 photoreduction efficiency , 2013 .

[72]  Lianjun Liu,et al.  Photocatalytic CO2 Reduction with H2O on TiO2 Nanocrystals: Comparison of Anatase, Rutile, and Brookite Polymorphs and Exploration of Surface Chemistry , 2012 .

[73]  Avelino Corma,et al.  Photocatalytic reduction of CO2 for fuel production: Possibilities and challenges , 2013 .

[74]  E. Baeissa Green synthesis of methanol by photocatalytic reduction of CO2 under visible light using a graphene and tourmaline co-doped titania nanocomposites , 2014 .

[75]  M. Marelli,et al.  Effect of nature and location of defects on bandgap narrowing in black TiO2 nanoparticles. , 2012, Journal of the American Chemical Society.

[76]  D. Shen,et al.  Hydrogenation and disorder in engineered black TiO2. , 2013, Physical review letters.

[77]  F. Solymosi,et al.  Infrared spectroscopic study of the photoinduced activation of CO2 on TiO2 and Rh/TiO2 Catalysts , 1994 .

[78]  G. Lu,et al.  Synthesis of anatase TiO2 rods with dominant reactive {010} facets for the photoreduction of CO2 to CH4 and use in dye-sensitized solar cells. , 2011, Chemical communications.

[79]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.