Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and Applications

TiO2 photocatalysis and related surface phenomena

As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and “earth-abundant” nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The constructi...

Graphitic Carbon Nitride (g-C3N4)-Based Photocatalysts for Artificial Photosynthesis and Environmental Remediation: Are We a Step Closer To Achieving Sustainability?

A review on g-C3N4-based photocatalysts

Tubular and fibrous nanostructures of titanates have recently been
synthesized and characterized. Three general approaches (template assisted, anodic oxidation, and alkaline hydrothermal) for the preparation of nanostructured titanate and TiO2 are reviewed. The crystal structures, morphologies, and mechanism of formation
of nanostructured titanates produced by the alkaline hydrothermal method are critically discussed. The physicochemical properties of nanostructured titanates are highlighted and the links between properties and applications are emphasized. Examples of early applications of nanostructured titanates in catalysis, photocatalysis, electrocatalysis, lithium batteries, hydrogen storage, and solar-cell technologies are reviewed. The stability of titanate nanotubes at elevated temperatures and in acid media is considered.

Protonated Titanates and TiO2 Nanostructured Materials: Synthesis, Properties, and Applications

Photocatalytic water splitting using semiconductors is attractive for converting solar energy into hydrogen. An efficient and scalable system based on particulate photocatalyst sheets is now shown to exhibit energy conversion efficiency exceeding 1%. Photocatalytic water splitting using particulate semiconductors is a potentially scalable and economically feasible technology for converting solar energy into hydrogen1,2,3. Z-scheme systems based on two-step photoexcitation of a hydrogen evolution photocatalyst (HEP) and an oxygen evolution photocatalyst (OEP) are suited to harvesting of sunlight because semiconductors with either water reduction or oxidation activity can be applied to the water splitting reaction4,5. However, it is challenging to achieve efficient transfer of electrons between HEP and OEP particles6,7. Here, we present photocatalyst sheets based on La- and Rh-codoped SrTiO3 (SrTiO3:La, Rh; ref. 8) and Mo-doped BiVO4 (BiVO4:Mo) powders embedded into a gold (Au) layer. Enhancement of the electron relay by annealing and suppression of undesirable reactions through surface modification allow pure water (pH 6.8) splitting with a solar-to-hydrogen energy conversion efficiency of 1.1% and an apparent quantum yield of over 30% at 419 nm. The photocatalyst sheet design enables efficient and scalable water splitting using particulate semiconductors.

Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy conversion efficiency exceeding 1%

The unprecedented impact of human activity on Earth’s climate and the ongoing increase in global energy demand have made the development of carbon-neutral energy sources ever more important. Hydrogen is an attractive and versatile energy carrier (and important and widely used chemical) obtainable from water through photocatalysis using sunlight, and through electrolysis driven by solar or wind energy1,2. The most efficient solar hydrogen production schemes, which couple solar cells to electrolysis systems, reach solar-to-hydrogen (STH) energy conversion efficiencies of 30% at a laboratory scale3. Photocatalytic water splitting reaches notably lower conversion efficiencies of only around 1%, but the system design is much simpler and cheaper and more amenable to scale-up1,2—provided the moist, stoichiometric hydrogen and oxygen product mixture can be handled safely in a field environment and the hydrogen recovered. Extending our earlier demonstration of a 1-m2 panel reactor system based on a modified, aluminium-doped strontium titanate particulate photocatalyst4, we here report safe operation of a 100-m2 array of panel reactors over several months with autonomous recovery of hydrogen from the moist gas product mixture using a commercial polyimide membrane5. The system, optimized for safety and durability, and remaining undamaged on intentional ignition of recovered hydrogen, reaches a maximum STH of 0.76%. While the hydrogen production is inefficient and energy negative overall, our findings demonstrate that safe, large-scale photocatalytic water splitting, and gas collection and separation are possible. To make the technology economically viable and practically useful, essential next steps are reactor and process optimization to substantially reduce costs and improve STH efficiency, photocatalyst stability and gas separation efficiency. Carbon-neutral hydrogen can be produced through photocatalytic water splitting, as demonstrated here with a 100-m2 array of panel reactors that reaches a maximum conversion efficiency of 0.76%.

Photocatalytic solar hydrogen production from water on a 100-m2 scale.

A Particulate Photocatalyst Water-Splitting Panel for Large-Scale Solar Hydrogen Generation

Electrochromism of Titanate‐Based Nanotubes

Nitrogen-doped TiO2 nanotubes were synthesized by a wet process. The nanotubes have an anatase crystal structure with nitrogen atoms substituted into oxygen sites of TiO2. These nanotubes exhibited...

Hiromasa Tokudome

Papers

Scalable water splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy conversion efficiency exceeding 1%

Photocatalytic solar hydrogen production from water on a 100-m2 scale.

A Particulate Photocatalyst Water-Splitting Panel for Large-Scale Solar Hydrogen Generation

Electrochromism of Titanate‐Based Nanotubes

N-doped TiO2 Nanotube with Visible Light Activity