Formic Acid Photoreforming for Hydrogen Production on Shape-Controlled Anatase TiO2 Nanoparticles: Assessment of the Role of Fluorides, {101}/{001} Surfaces Ratio, and Platinization

Hydrogen production via formate photoreforming on TiO2 is characterized by marked dependence on the ratio between {101} and {001} surfaces for anatase nanoparticles. We observed higher rates of hydrogen evolution with the increase of the {101} facets presence, owing to their reductive nature. This helps the Pt photodeposition in the early stages of irradiation and, then, the hydrogen ion reduction reaction. The selective photodeposition of 2 nm Pt nanoparticles on {101} facets was confirmed by transmission electron microscopy (TEM) micrographs. The results are confirmed also by experiments carried out without the use of Pt as cocatalyst and by photoelectrochemical measurements. The work also explains the marginal effect of the fluorination on the H2 evolution.

[1]  J. Grunwaldt,et al.  One step flame-made fluorinated Pt/TiO2 photocatalysts for hydrogen production , 2014 .

[2]  Hongwei Lu,et al.  Constructing Anatase TiO2 Nanosheets with Exposed (001) Facets/Layered MoS2 Two-Dimensional Nanojunctions for Enhanced Solar Hydrogen Generation , 2016 .

[3]  Lan-sun Zheng,et al.  Enhancing the photocatalytic activity of anatase TiO2 by improving the specific facet-induced spontaneous separation of photogenerated electrons and holes. , 2013, Chemistry, an Asian journal.

[4]  J. Keum,et al.  Quantitative Analysis of the Morphology of {101} and {001} Faceted Anatase TiO2 Nanocrystals and Its Implication on Photocatalytic Activity , 2017 .

[5]  Maria Vittoria Dozzi,et al.  Crystal Surfaces and Fate of Photogenerated Defects in Shape-Controlled Anatase Nanocrystals: Drawing Useful Relations to Improve the H2 Yield in Methanol Photosteam Reforming , 2015 .

[6]  A. Selloni,et al.  Surface Structure and Reactivity of Anatase TiO2 Crystals with Dominant {001} Facets , 2013 .

[7]  R. Gómez,et al.  Electrochemical Method for Studying the Kinetics of Electron Recombination and Transfer Reactions in Heterogeneous Photocatalysis: The Effect of Fluorination on TiO2 Nanoporous Layers , 2008 .

[8]  P. Fornasiero,et al.  Nonaqueous synthesis of TiO2 nanocrystals using TiF4 to engineer morphology, oxygen vacancy concentration, and photocatalytic activity. , 2012, Journal of the American Chemical Society.

[9]  M. Matsumura,et al.  Formation of new crystal faces on TiO2 particles by treatment with aqueous HF solution or hot sulfuric acid , 2003 .

[10]  T. Lana-Villarreal,et al.  Effect of surface fluorination on the electrochemical and photoelectrocatalytic properties of nanoporous titanium dioxide electrodes. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[11]  Vincenzo Balzani,et al.  The future of energy supply: Challenges and opportunities. , 2007, Angewandte Chemie.

[12]  P. Schmuki,et al.  Intrinsic Au Decoration of Growing TiO2 Nanotubes and Formation of a High‐Efficiency Photocatalyst for H2 Production , 2013, Advanced materials.

[13]  R. Andreozzi,et al.  Hydrogen production by photoreforming of formic acid in aqueous copper/TiO2 suspensions under UV-simulated solar radiation at room temperature , 2013 .

[14]  Vasile-Dan Hodoroaba,et al.  Beyond Shape Engineering of TiO2 Nanoparticles: Post-Synthesis Treatment Dependence of Surface Hydration, Hydroxylation, Lewis Acidity and Photocatalytic Activity of TiO2 Anatase Nanoparticles with Dominant {001} or {101} Facets , 2018, ACS Applied Nano Materials.

[15]  S. Nikitenko,et al.  Photothermal Hydrogen Production Using Noble-Metal-Free Ti@TiO2 Core–Shell Nanoparticles under Visible–NIR Light Irradiation , 2015 .

[16]  Claudio Minero,et al.  Photocatalytic Transformation of Organic Compounds in the Presence of Inorganic Anions. 1. Hydroxyl-Mediated and Direct Electron-Transfer Reactions of Phenol on a Titanium Dioxide−Fluoride System , 2000 .

[17]  Huijun Zhao,et al.  Preparation and characterization of hydrophobic TiO(2) pillared clay: the effect of acid hydrolysis catalyst and doped Pt amount on photocatalytic activity. , 2008, Journal of colloid and interface science.

[18]  G. Peharz,et al.  Solar hydrogen production by water splitting with a conversion efficiency of 18 , 2007 .

[19]  A. Mohamed,et al.  Highly reactive {001} facets of TiO2-based composites: synthesis, formation mechanism and characterization. , 2014, Nanoscale.

[20]  H. Kominami,et al.  Preparation of Au/TiO2 with Metal Cocatalysts Exhibiting Strong Surface Plasmon Resonance Effective for Photoinduced Hydrogen Formation under Irradiation of Visible Light , 2013 .

[21]  F. Sordello,et al.  The Role of Surface Texture on the Photocatalytic H2 Production on TiO2 , 2019, Catalysts.

[22]  M. Langlet,et al.  Influence of platinum nano-particles on the photocatalytic activity of sol–gel derived TiO2 films , 2009, Journal of Materials Science.

[23]  Yi Zhou,et al.  Three-dimensional sea-urchin-like hierarchical TiO2 microspheres synthesized by a one-pot hydrothermal method and their enhanced photocatalytic activity , 2013 .

[24]  Somnath C. Roy,et al.  Toward solar fuels: photocatalytic conversion of carbon dioxide to hydrocarbons. , 2010, ACS nano.

[25]  F. Illas,et al.  Relative Stability of F-Covered TiO2 Anatase (101) and (001) Surfaces from Periodic DFT Calculations and ab Initio Atomistic Thermodynamics , 2014 .

[26]  R. Naidu,et al.  Tailored titanium dioxide photocatalysts for the degradation of organic dyes in wastewater treatment: A review , 2009 .

[27]  Helmut Tributsch,et al.  Photovoltaic hydrogen generation , 2008 .

[28]  Peter K. J. Robertson,et al.  Mechanisms of Simultaneous Hydrogen Production and Formaldehyde Oxidation in H2O and D2O over Platinized TiO2 , 2017 .

[29]  A. Stavropoulos,et al.  Role of Photoinduced Charge Carrier Separation Distance in Heterogeneous Photocatalysis: Oxidative Degradation of CH3OH Vapor in Contact with Pt/TiO2 and Cofumed TiO2−Fe2O3 , 1996 .

[30]  C. Haisch,et al.  Insights into Different Photocatalytic Oxidation Activities of Anatase, Brookite, and Rutile Single-Crystal Facets , 2018, ACS Catalysis.

[31]  D. Ceresoli,et al.  Exploiting the Photonic Crystal Properties of TiO2 Nanotube Arrays To Enhance Photocatalytic Hydrogen Production , 2016 .

[32]  D. Nocera,et al.  Wireless Solar Water Splitting Using Silicon-Based Semiconductors and Earth-Abundant Catalysts , 2011, Science.

[33]  M. Okumura,et al.  Effects of halogens on interactions between a reduced TiO2 (110) surface and noble metal atoms: A DFT study , 2017 .

[34]  J. Yi,et al.  Effect of TiO2 nanoparticle shape on hydrogen evolution via water splitting. , 2011, Journal of nanoscience and nanotechnology.

[35]  J. Vohs,et al.  The Influence of Surface Platinum Deposits on the Photocatalytic Activity of Anatase TiO2 Nanocrystals , 2019, Journal of Physical Chemistry C.

[36]  M. Beller,et al.  Solar Hydrogen Production by Plasmonic Au-TiO2 Catalysts: Impact of Synthesis Protocol and TiO2 Phase on Charge Transfer Efficiency and H2 Evolution Rates , 2015 .

[37]  H. Tributsch,et al.  Material research challenges towards a corrosion stable photovoltaic hydrogen-generating membrane , 2007 .