An Emerging Trend in the Synthesis of Iron Titanate Photocatalyst Toward Water Splitting.

Hydrogen gas is a prominent focus in pursuing renewable and clean alternative energy sources. The quest for maximizing hydrogen production yield involves the exploration of an ideal photocatalyst and the development of a simple, cost-effective technique for its generation. Iron titanate has garnered attention in this context due to its photocatalytic properties, affordability, and non-toxic nature. Over the years, different synthesis routes, different morphologies, and some modifications of iron titanate have been carried out to improve its photocatalytic performance by enhancing light absorption in the visible region, boosting charge carrier transfer, and decreasing recombination of electrons and holes. The use of iron titanate photocatalyst for hydrogen evolution reaction has seen an upward trend in recent times, and based on available findings, more can be done to improve the performance. This review paper provides a comprehensive overview of the fundamental principles of photocatalysis for hydrogen generation, encompassing the synthesis, morphology, and application of iron titanate-based photocatalysts. The discussion delves into the limitations of current methodologies and present and future perspectives for advancing iron titanate photocatalysts. By addressing these limitations and contemplating future directions, the aim is to enhance the properties of materials fabricated for photocatalytic water splitting.

Hollow Structured Transition Metal Phosphates and Their Applications.

Hollow nanostructures of transition metal phosphate are of immense interest in the existing and evolving areas of technology, due to their high surface area, presence of hollow void, and easy tuning of compositions and dimensions. Emerging synthesis methods such as template-free methods, hard-templating, and soft-templating are discussed in this review. Applications of these hollow metal phosphates dominate in energy storage and conversions, with specific advantages as supercapacitor materials. Other applications, including drug delivery, water splitting, catalysis, and adsorption, are reviewed. Finally, additional perspectives on the progress of these nanostructures, and their existing challenges related to the current synthesis routes are covered. Therefore, with the strategic modifications of the unique properties of these hollow metal phosphates, broader application requirements are fulfilled.

Porous Tungsten Oxide: Recent Advances in Design, Synthesis, and Applications.

Tungsten oxide (WO3 ) has received ever more attention and has been highly researched over the last decade due to its being a low-cost transition metal semiconductor with tunable, yet widely stable, band gaps. This minireview briefly highlights the challenges in the design and synthesis of porous WO3 including methods, precursors, solvent effects, crystal phases, and surface activities of the porous WO3 base material. These topics are explored while also drawing a connection of how the morphology and crystal phase affect the band gap. The shifts in band gap not only impact the optical properties of tungsten but also allow tuning to operate on different energy levels, which makes WO3 highly desirable in many applications such as supercapacitors, batteries, solar cells, catalysts, sensors, smart windows, and bioapplications.

Direct Synthesis of Polymer Vesicles on the Hundred-Nanometer-and-Beyond Scale Using Chemical Oscillations.

The direct synthesis of block copolymer vesicles on the scale of tens to hundreds of nanometers using reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization as an effect of chemical oscillations is reported. RAFT polymerization is successfully accomplished between polyethylene glycol containing a RAFT agent (PEG-CTA) and ethyl acrylate monomer in the presence of the Belousov-Zhabotinsky (B-Z) reaction in oscillatory mode. The self-assembly of poly(ethylene glycol)-b-poly(ethyl acrylate) unimers gives rise to spherical micelles. The self-assembled micelles reorganize and transform to vesicles. All the chemistry of polymerization, self-assembly and self-organization, of macromolecules takes place in a single pot using only a few simple raw materials in aqueous solution.

Tailored Design of Bicontinuous Gyroid Mesoporous Carbon and Nitrogen-Doped Carbon from Poly(ethylene oxide-b-caprolactone) Diblock Copolymers.

Highly ordered mesoporous resol-type phenolic resin and the corresponding mesoporous carbon materials were synthesized by using poly(ethylene oxide-b-caprolactone) (PEO-b-PCL) diblock copolymer as a soft template. The self-assembled mesoporous phenolic resin was found to form only in a specific resol concentration range of 40-70 wt % due to an intriguing balance of hydrogen-bonding interactions in the resol/PEO-b-PCL mixtures. Furthermore, morphological transitions of the mesostructures from disordered to gyroid to cylindrical and finally to disordered micelle structure were observed with increasing resol concentration. By calcination under nitrogen atmosphere at 800 °C, the bicontinuous mesostructured gyroid phenolic resin could be converted to mesoporous carbon with large pore size without collapse of the original mesostructure. Furthermore, post-treatment of the mesoporous gyroid phenolic resin with melamine gave rise to N-doped mesoporous carbon with unique electronic properties for realizing high CO2 adsorption capacity (6.72 mmol g-1 at 0 °C).

Facile One-Pot Synthesis of Functional Giant Polymeric Vesicles Controlled by Oscillatory Chemistry.

We introduce a novel application of an oscillatory chemical reaction to the synthesis of block copolymers. The Belousov-Zhabotinsky (B-Z) reaction is coupled with the polymerization of an amphiphilic block copolymer. Radicals generated in the B-Z reaction initiate the polymerization between a polyethylene glycol (PEG) macroreversible addition-fragmentation chain-transfer agent and butyl acrylate monomers. The attachment of a hydrophobic block on PEG leads to self-assembly and formation of spherical micelles. The nanoscale micelles transform into submicrometer vesicles and grow to giant vesicles as a consequence of the oscillatory behavior of the B-Z reaction. The one-pot synthesis of an amphiphilic di-block copolymer and retention of oscillatory behavior for the B-Z reaction with the formation of giant vesicles bring a new insight into possible pathways for the synthesis of active functional microreactors in the range from hundreds of nanometers to tens of micrometers.

Direct Assembly of Mesoporous Silica Functionalized with Polypeptides for Efficient Dye Adsorption.

Herein, we introduce a new polypeptide-functionalized mesoporous silica template fabricated from a biodegradable poly(ethylene oxide-b-ɛ-caprolactone) (PEO-b-PCL) diblock copolymer and a poly(tyrosine) (PTyr) biopolymer. The crystallization behavior of the PEO-b-PCL diblock copolymer changes after blending, but the secondary structure of PTry remains stable. After selective solvent extraction in THF, the PEO-b-PCL is removed, but PTyr remains within the silica matrix due to its different solubility. Fourier-transform IR spectroscopic analysis (FTIR), thermal gravitometry analysis (TGA), small-angle X-ray scattering (SAXS), and X-ray diffraction (XRD) studies confirm the retention of PTyr to form a polypeptide-functionalized mesoporous material. The adsorption of methylene blue hydrate (MB) from aqueous solution into the polypeptide-functionalized mesoporous silica is investigated, thus revealing that the nanocomposite exhibits a high adsorption capacity relative to pure silica due to hydrogen-bonding interactions between the hydroxy phenolic group of PTyr and the N-containing aromatic ring from MB.

Synthesis of Mesoporous Transition-Metal Phosphates by Polymeric Micelle Assembly.

Mesoporous iron phosphate (FePO4 ) was synthesized through assembly of polymeric micelles made of asymmetric triblock co-polymer (polystyrene-b-poly-2-vinylpyridine-b-ethylene oxide; PS-PVP-PEO). The phosphoric acid solution stimulates the formation of micelles with core-shell-corona architecture. The negatively charged PO4 (3-) ions dissolved in the solution strongly interact with the positively charged PVP(+) units through an electrostatic attraction. Also, the presence of PO4 (3-) ions realizes a bridge between the micelle surface and the metal ions. The removal of polymeric template forms the robust framework of iron phosphate with 30 nm pore diameter and 15 nm wall thickness. Our method is applicable to other mesoporous metal phosphates by changing metal sources. The obtained materials were fully characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), N2 adsorption-desorption, Raman spectroscope, and other techniques.

Asymmetric block copolymers for supramolecular templating of inorganic nanospace materials.

This review focuses on polymeric micelles consisting of asymmetric block copolymers as designed templates for several inorganic nanospace materials with a wide variety of compositions. The presence of chemically distinct domains of asymmetric triblock and diblock copolymers provide self-assemblies with more diverse morphological and functional features than those constructed by EOn POm EOn type symmetric triblock copolymers, thereby affording well-designed nanospace materials. This strategy can produce unprecedented nanospace materials, which are very difficult to prepare through other conventional organic templating approaches. Here, the recent development on the synthesis of inorganic nanospace materials are mainly focused on, such as hollow spheres, tubes, and porous oxides, using asymmetric triblock copolymers.

Smart soft-templating synthesis of hollow mesoporous bioactive glass spheres.

Hollow bioactive glass spheres with mesoporous shells were prepared by using dual soft templates, a diblock co-polymer poly(styrene-b-acrylic acid) (PS-b-PAA) and a cationic surfactant cetyltrimethylammonium bromide (CTAB). Hollow mesoporous bioactive glass (HMBG) spheres comprise the large hollow interior with vertical mesochannels in shell, which realize large uptake of drugs and their sustained release. The formation of hydroxyapatite layer on the surface of HMBG particles shows the clear evidence for promising application in bone regeneration.

Multi-Stimuli-Responsive Polymeric Materials.

Stimuli-responsive materials are of immense importance because of their ability to undergo alteration of their properties in response to their environment. The properties of such materials can be tuned by subtle adjustments in temperature, pH, light, and so forth. Among such smart materials, multi-stimuli-responsive polymeric materials are of pronounced significance as they offer a wide range of applications and their properties can be tuned through several mechanisms. Here, we aim to highlight some recent studies showcasing the multi-stimuli-responsive character of these polymers, which are still relatively little known compared to their single-stimuli-responsive counterpart.

Dual soft-template system based on colloidal chemistry for the synthesis of hollow mesoporous silica nanoparticles.

A new dual soft-template system comprising the asymmetric triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) is used to synthesize hollow mesoporous silica (HMS) nanoparticles with a center void of around 17 nm. The stable PS-b-P2VP-b-PEO polymeric micelle serves as a template to form the hollow interior, while the CTAB surfactant serves as a template to form mesopores in the shells. The P2VP blocks on the polymeric micelles can interact with positively charged CTA(+) ions via negatively charged hydrolyzed silica species. Thus, dual soft-templates clearly have different roles for the preparation of the HMS nanoparticles. Interestingly, the thicknesses of the mesoporous shell are tunable by varying the amounts of TEOS and CTAB. This study provides new insight on the preparation of mesoporous materials based on colloidal chemistry.

Polymeric micelle assembly for the smart synthesis of mesoporous platinum nanospheres with tunable pore sizes.

A facile method for the fabrication of well-dispersed mesoporous Pt nanospheres involves the use of a polymeric micelle assembly. A core-shell-corona type triblock copolymer [poly(styrene-b-2-vinylpyridine-b-ethylene oxide), PS-b-P2VP-b-PEO] is employed as the pore-directing agent. Negatively charged PtCl4 (2-) ions preferably interact with the protonated P2VP(+) blocks while the free PEO chains prevent the aggregation of the Pt nanospheres. The size of the mesopores can be finely tuned by varying the length of the PS chain. Furthermore, it is demonstrated that the metallic mesoporous nanospheres thus obtained are promising candidates for applications in electrochemistry.

Polymeric micelle assembly with inorganic nanosheets for construction of mesoporous architectures with crystallized walls.

Here we propose a novel way to construct mesoporous architectures through evaporation-induced assembly of polymeric micelles with crystalline nanosheets. As a model study, we used niobate nanosheets exfoliated by the direct reaction of K4Nb6O17⋅3 H2O crystals with an aqueous solution of propylamine. The electrostatic interaction between negatively charged nanosheets and positively charged polymeric micelles enable us to form composite micelles with the nanosheets. Removal of the micelles by calcination results in robust mesoporous oxides with the original crystalline structure.

Mesoporous silica particles as topologically crosslinking fillers for poly(N-isopropylacrylamide) hydrogels.

Here it is demonstrated that mesoporous silicas (MPSs) can be used as effective "topological crosslinkers" for poly(N-isopropylacrylamide) (PNIPA) hydrogels to improve the mechanical property. Three-dimensional bicontinuous mesporous silica is found to effectively reinforce the PNIPA hydrogels, as compared to nonporous silica and two-dimensional hexagonally ordered mesoporous silica.

Direct growth of cobalt hydroxide rods on nickel foam and its application for energy storage.

The present work reports synthesis of cobalt hydroxide (Co(OH)2) rods on nickel foam and its supercapacitor application. Hierarchical Co(OH)2 rods with length of approximately 3.5 µm and diameter of approximately 400 nm were prepared by one-step, simple, and inexpensive chemical-bath-deposition method. The direct growth of Co(OH)2 rods on the Ni foam gave three dimensional (3D) structure for easy access of electrolyte throughout material surface. Also, well-adhered interface between Co(OH)2 rods and Ni-foam surface gave better conduction channels. Detailed electrochemical study was performed by using cyclic voltammetry and galvanostatic charge/discharge measurements. The results demonstrate that Co(OH)2 rods on Ni foam are efficient electrodes for supercapacitor application.

Synthesis of mesoporous TiO2/SiO2 hybrid films as an efficient photocatalyst by polymeric micelle assembly.

Thermally stable mesoporous TiO2/SiO2 hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle-assembly method. A triblock copolymer, poly(styrene-b-2-vinyl pyridine-b-ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles. The effective interaction of titanium tetraisopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) with the polymeric micelles enabled us to fabricate stable mesoporous films. By changing the molar ratio of TEOS and TTIP, several mesoporous TiO2/SiO2 hybrid films with different compositions can be synthesized. The presence of amorphous SiO2 phase effectively retards the growth of anatase TiO2 crystal in the pore walls and retains the original mesoporous structure, even at higher temperature (650 °C). These TiO2/SiO2 hybrid films are of very high quality, without any cracks or voids. The addition of SiO2 phase to mesoporous TiO2 films not only adsorbs more organic dyes, but also significantly enhances the photocatalytic activity compared to mesoporous pure TiO2 film without SiO2 phase.

Polymeric micelle assembly for preparation of large-sized mesoporous metal oxides with various compositions.

Here we report the synthesis of mesoporous metal oxide materials with various compositions by assembly of spherical polymeric micelles consisting of triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-PVP-b-PEO) with three chemically distinct units. The PVP block interacts strongly with the inorganic precursors for the target compositions. The hydrophobic PS block is kinetically frozen in the precursor solutions, enabling the spherical micelles to remain in a stable form. The frozen PS cores serve as templates for preparing robust mesoporous materials. The PEO corona helps the micelles to stay well dispersed in the precursor solutions, which plays a key role in the orderly arrangement of the micelles during solvent evaporation. This approach is based on assembly of the stable micelles using a simple, highly reproducible method and is widely applicable toward numerous compositions that are difficult for the formation of mesoporous structures.

Direct synthesis of a mesoporous TiO2-RuO2 composite through evaporation-induced polymeric micelle assembly.

Here we report a direct synthesis of a mesoporous TiO2-RuO2 composite. Titanium tetraisopropoxide (TTIP) and RuCl3 are used as inorganic precursors for TiO2 and RuO2, respectively. Evaporation-induced assembly of spherical micelles made of an asymmetric poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) triblock copolymer enables the fabrication of a mesoporous TiO2-RuO2 composite with a uniform pore size of 30 nm.

Chemical design of a smart chitosan-polypyrrole-magnetite nanocomposite toward efficient water treatment.

A magnetic chitosan-polypyrrole-magnetite (Cs-PPy-Fe3O4) nanocomposite is prepared in a simple one-step method via in situ chemical polymerization of pyrrole using anhydrous FeCl3 as an oxidant in the presence of Cs. Magnetic Fe3O4 nanoparticles of size in the range of 10-20 nm are successfully introduced into the Cs-PPy matrix. Adsorption of an anionic dye (acid green 25, AG) from aqueous solution into the Cs-PPy-Fe3O4 nanocomposite is investigated. The nanocomposite exhibits high adsorption capacity compared to PPy and Cs themselves. After the adsorption, the Cs-PPy-Fe3O4 nanocomposite is easily separated from the reaction solution using an external magnet, which is very useful for practical applications.