Engineering Directional Charge Carrier Transport Using Ferroelectric Polarization for Enhanced Photoelectrochemical Water Oxidation.

Introducing ferroelectric polarization has shown great potential to facilitate interfacial charge separation in photoelectrochemical (PEC) water splitting. However, unambiguous evidence of the actual influence of spontaneous ferroelectric polarization, as compared to heterojunction formation, on electron extraction and PEC water splitting is still lacking to date. Herein, core-shell BaTiO3/TiO2 nanostructures are designed as photoanodes based on paraelectric cubic and ferroelectric tetragonal phases BaTiO3 (BTO) perovskite. The cubic and tetragonal crystalline phases are stabilized using selected elaboration methods. Compared to the paraelectric cubic (c-BTO), the ferroelectric tetragonal (t-BTO) leads to a favorable ferroelectric polarization, enhancing directional charge separation and as a consequence to increased photocurrent up to a factor of 1.95. More interestingly, the charge separation efficiency can be tuned by applying positive or negative polarization, with the highest charge separation obtained for the positive one. When loading Ni(OH)2 as a cocatalyst on the t-BTO@TiO2 photoanode, the Ni(OH)2/TiO2/t-BTO exhibits a high performance and superior stability toward PEC water oxidation with a photocurrent almost 6.7 times that of the reference SiO2@TiO2. The proposed facilitation may open an avenue to engineer charge separation and transport for high-performance PEC water oxidation.

TiO2 Films with Macroscopic Chiral Nematic-Like Structure Stabilized by Copper Promoting Light-Harvesting Capability for Hydrogen Generation.

Cellulose nanocrystals (CNCs) have inspired the synthesis of various advanced nanomaterials, opening opportunities for different applications. However, a simple and robust approach for transferring the long-range chiral nematic nanostructures into TiO2 photocatalyst is still fancy. Herein, a successful fabrication of freestanding TiO2 films maintaining their macroscopic chiral nematic structures after removing the CNCs biotemplate is reported. It is demonstrated that including copper acetate in the sol avoids the epitaxial growth of the lamellar-like structure of TiO2 and stabilizes the chiral nematic structure instead. The experimental results and optical simulation demonstrate an enhancement at the blue and red edges of the Fabry-Pérot reflectance peak located in the visible range. This enhancement arises from the light scattering effect induced by the formation of the chiral nematic structure. The nanostructured films showed 5.3 times higher performance in the photocatalytic hydrogen generation, compared to lamellar TiO2, and benefited from the presence of copper species for charge carriers' separation. This work is therefore anticipated to provide a simple approach for the design of chiral nematic photocatalysts and also offers insights into the electron transfer mechanisms on TiO2/CuxO with variable oxidation states for photocatalytic hydrogen generation.

Structure-Function Relationship of p-Block Bismuth for Selective Photocatalytic CO2 Reduction.

Selective photocatalytic reduction of CO2 to value-added fuels, such as CH4, is highly desirable due to its high mass-energy density. Nevertheless, achieving selective CH4 with higher production yield on p-block materials is hindered by non-ideal adsorption of *CHO key intermediate and an unclear structure-function relationship. Herein, we unlock the key reaction steps of CO2 and found a volcano-type structure-function relationship for photocatalytic CO2-to-CH4 conversion by gradual reduction of the p-band center of the p-block Bi element leading to formation of Bi-oxygen vacancy heterosites. The selectivity of CH4 is also positive correlation with adsorption energy of *CHO. The Bi-oxygen vacancy heterosites with an appropriate filled Bi-6p orbital electrons and p band center (-0.64) enhance the coupling between C-2p of *CHO and Bi-6p orbitals, thereby resulting in high selectivity (95.2 %) and productivity (17.4 µmol g-1 h-1) towards CH4. Further studies indicate that the synergistic effect between Bi-oxygen vacancy heterosites reduces Gibbs free energy for *CO-*CHO process, activates the C-H and C=O bonds of *CHO, and facilitates the enrichment of photoexcited electrons at active sites for multielectron photocatalytic CO2-to-CH4 conversion. This work provides a new perspective on developing p-block elements for selective photocatalytic CO2 conversion.

Selective Cocatalyst Decoration of Narrow-Bandgap Broken-Gap Heterojunction for Directional Charge Transfer and High Photocatalytic Properties.

Narrow-bandgap semiconductors are promising photocatalysts facing the challenges of low photoredox potentials and high carrier recombination. Here, a broken-gap heterojunction Bi/Bi2 S3 /Bi/MnO2 /MnOx , composed of narrow-bandgap semiconductors, is selectively decorated by Bi, MnOx nanodots (NDs) to achieve robust photoredox ability. The Bi NDs insertion at the Bi2 S3 /MnO2 interface induces a vertical carrier migration to realize sufficient photoredox potentials to produce O2 •- and • OH active species. The surface decoration of Bi2 S3 /Bi/MnO2 by Bi and MnOx cocatalysts drives electrons and holes in opposite directions for optimal photogenerated charge separation. The selective cocatalysts decoration realizes synergistic surface and bulk phase carrier separation. Density functional theory (DFT) calculation suggests that Bi and MnOx NDs act as active sites enhancing the absorption and reactants activation. The decorated broken-gap heterojunction demonstrates excellent performance for full-light driving organic pollution degradation with great commercial application potential.

Nanosized tubular clay minerals as inorganic nanoreactors for energy and environmental applications: A review to fill current knowledge gaps.

Modern society pays further and further attention to environmental protection and the promotion of sustainable energy solutions. Heterogeneous photocatalysis is widely recognized as one of the most economically viable and ecologically sound technologies to combat environmental pollution and the global energy crisis. One challenge is finding a suitable photocatalytic material for an efficient process. Inorganic nanotubes have garnered attention as potential candidates due to their optoelectronic properties, which differ from their bulk equivalents. Among them, clay nanotubes (halloysite, imogolite, and chrysotile) are attracting renewed interest for photocatalysis applications thanks to their low production costs, their unique physical and chemical properties, and the possibility to functionalize or dope their structure to enhance charge-carriers separation into their structure. In this review, we provide new insights into the potential of these inorganic nanotubes in photocatalysis. We first discuss the structural and morphological features of clay nanotubes. Applications of photocatalysts based on clay nanotubes across a range of photocatalytic reactions, including the decomposition of organic pollutants, elimination of NOx, production of hydrogen, and disinfection of bacteria, are discussed. Finally, we highlight the obstacles and outline potential avenues for advancing the current photocatalytic system based on clay nanotubes. Our aim is that this review can offer researchers new opportunities to advance further research in the field of clay nanotubes-based photocatalysis with other vital applications in the future.

A Facile Strategy for the Preparation of N-Doped TiO2 with Oxygen Vacancy via the Annealing Treatment with Urea.

Although titanium dioxide (TiO2) has a wide range of potential applications, the photocatalytic performance of TiO2 is limited by both its limited photoresponse range and fast recombination of the photogenerated charge carriers. In this work, the preparation of nitrogen (N)-doped TiO2 accompanied by the introduction of oxygen vacancy (Vo) has been achieved via a facile annealing treatment with urea as the N source. During the annealing treatment, the presence of urea not only realizes the N-doping of TiO2 but also creates Vo in N-doped TiO2 (N-TiO2), which is also suitable for commercial TiO2 (P25). Unexpectedly, the annealing treatment-induced decrease in the specific surface area of N-TiO2 is inhibited by the N-doping and, thus, more active sites are maintained. Therefore, both the N-doping and formation of Vo as well as the increased active sites contribute to the excellent photocatalytic performance of N-TiO2 under visible light irradiation. Our work offers a facile strategy for the preparation of N-TiO2 with Vo via the annealing treatment with urea.

Ba3(PO4)2 Photocatalyst for Efficient Photocatalytic Application.

Barium phosphate (Ba3(PO4)2) is a class of material that has attracted significant attention thanks to its chemical stability and versatility. However, the use of Ba3(PO4)2 as a photocatalyst is scarcely reported, and its use as a photocatalyst has yet to be reported. Herein, Ba3(PO4)2 nanoflakes synthesis is optimized using sol-gel and hydrothermal methods. The as-prepared Ba3(PO4)2 powders are investigated using physicochemical characterizations, including XRD, SEM, EDX, FTIR, DRS, J-t, LSV, Mott-Schottky, and EIS. In addition, DFT calculations are performed to investigate the band structure. The oxidation capability of the photocatalysts is investigated depending on the synthesis method using rhodamine B (RhB) as a pollutant model. Both Ba3(PO4)2 samples prepared by the sol-gel and hydrothermal methods display high RhB photodegradation of 79% and 68%, respectively. The Ba3(PO4)2 obtained using the sol-gel process exhibits much higher stability under light excitation after four regeneration cycles. The photocatalytic oxidation mechanism is proposed based on the active species trapping experiments where O2 •‒ is the most reactive species. The finding shows the promising potential of Ba3(PO4)2 photocatalysts and opens the door for further investigation and application in various photocatalytic applications.

Highly Dispersed Ni-Pt Bimetallic Cocatalyst: The Synergetic Effect Yields Pt-Like Activity in Photocatalytic Hydrogen Evolution.

Achieving high photocatalytic activity with the lowest possible platinum (Pt) consumption is crucial for reducing the cost of Pt-based cocatalysts and enabling large-scale applications. Bimetallic Ni-Pt cocatalysts exhibit excellent photocatalytic performance and are considered one of the most promising photocatalysts capable of replacing pure Pt for hydrogen evolution reaction (HER). However, the synergistic photocatalytic mechanism between bimetallic Ni-Pt cocatalysts needs to be further investigated. Herein, we deposit highly dispersed Ni-Pt bimetallic cocatalysts on the surface of TiO2 by radiolytic reduction. We study the dynamics of photogenerated charge carriers of the Ni-Pt-comodified TiO2 and propose their underlying electron transfer mechanisms, in which Pt acts as an electron trap, whereas Ni serves as an electron supplier. The synergistic effect is Ni/Pt ratio-dependent and can confer bimetallic Ni-Pt to pure Pt-like photocatalytic activity in HER. The Ni2-Pt1-comodified TiO2 is optimized to be the most cost-effective photocatalyst with robust stability, which exhibits about 40-fold higher performance than bare TiO2.

Ti-Modified Imogolite Nanotubes as Promising Photocatalyst 1D Nanostructures for H2 Production.

Imogolite nanotubes (INTs) are predicted as a unique 1D material with spatial separation of conduction and valence band edges but their large band gaps have inhibited their use as photocatalysts. The first step toward using these NTs in photocatalysis and exploiting the polarization-promoted charge separation across their walls is to reduce their band gap. Here, the modification of double-walled aluminogermanate INTs by incorporation of titanium into the NT walls is explored. The precursor ratio x = [Ti]/([Ge]+[Ti]) is modulated between 0 and 1. Structural and optical properties are determined at different scales and the photocatalytic performance is evaluated for H2 production. Although the incorporation of Ti atoms into the structure remains limited, the optimal condition is found around x = 0.4 for which the resulting NTs reveal a remarkable hydrogen production of ≈1500 µmol g-1 after 5 h for a noble metal-free photocatalyst, a 65-fold increase relative to a commercial TiO2 -P25. This is correlated to a lowering of the recombination rate of photogenerated charge carriers for the most active structures. These results confirm the theoretical predictions regarding the potential of modified INTs as photoactive nanoreactors and pave the way for investigating and exploiting their polarization properties for energy applications.

Getting Greener with the Synthesis of Nanoparticles and Nanomaterials.

The nanoscale level is bridging the gap between molecular level and crystal-based solid-state structures [...].

Facile Vacuum Annealing-Induced Modification of TiO2 with an Enhanced Photocatalytic Performance.

In this work, the photocatalytic performance enhancement of hydrothermally prepared TiO2 was achieved by facile vacuum annealing treatment. Calcination of TiO2 powder in air (CA-TiO2) maintained its white color, while gray powder was obtained when the annealing was performed under vacuum (CV-TiO2). Fourier transform infrared, total organic carbon, X-ray photoelectron spectroscopy, and electron paramagnetic resonance analyses proved that vacuum annealing transformed ethanol adsorbed on the surface of TiO2 into carbon-related species accompanied by the formation of surface oxygen vacancies (Vo). The residual carbon-related species on the surface of CV-TiO2 favored its adsorption of organic dyes. Compared with TiO2 and CA-TiO2, CV-TiO2 exhibited an improved charge carrier separation with surface Vo as trapping sites for electrons. Vacuum annealing-induced improvement of crystallinity, enhancement of adsorption capacity, and formation of surface Vo contributed to the excellent photocatalytic activity of CV-TiO2, which was superior to that of commercial TiO2 (P25, Degussa). Obviously, vacuum annealing-triggered decomposition of ethanol played an important role in the modification of TiO2. In the presence of ethanol, vacuum annealing was also suitable for the introduction of Vo into P25. Therefore, the current work offers an easy approach for the modification of TiO2 to enhance its photocatalytic performance by facile vacuum annealing in the presence of ethanol.

Nanocomposite Fiber Based on Natural Material for Water Disinfection under Visible Light Irradiation.

In the last decade, pathogenic bacteria and organic micropollutants have become a major issue in the water purification process. Heterogeneous photocatalysis is a low-cost and an ecofriendly process, which provides a sustainable solution for water treatment and its utilization in rural areas. In this context, we studied the generation and the surface engineering of polyacrylonitrile (PAN)/goethite composite nanofibers for photocatalytic water remediation under visible-light illumination. The photocatalytic activity was evaluated for dye (methylene blue) degradation and bacteria inactivation, as contaminant models, of the composite nanofibers. The PAN/goethite nanofibers were elaborated by an electrospinning technique, and the morphology and the composition, before and after spin coating, were investigated by Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray (EDX). The results showed partially intercalated structures of the PAN/goethite Composite-nano-fiber (CNF) were identified by SEM and EDX analysis. The composite nanofibers exhibited high photoefficiency upon dye bleaching (only 10% left after 5 h of illumination) and bacterial deactivation Escherichia coli and Clostridium perfringens (4.4- and 3.5-fold, respectively, in less than 5 h). The steadiness and pliancy of the generated nanofibers provide a promising application in the continuous flow system.

A soft-chemistry assisted strong metal-support interaction on a designed plasmonic core-shell photocatalyst for enhanced photocatalytic hydrogen production.

Engineering photocatalysts based on gold nanoparticles (AuNPs) has attracted great attention for the solar energy conversion due to their multiple and unique properties. However, boosting the photocatalytic performance of plasmonic materials for H2 generation has some limitations. In this study, we propose a soft-chemistry method for the preparation of a strong metal-support interaction (SMSI) to enhance the photocatalytic production of H2. The TiO2 thin overlayer covering finely dispersed AuNPs (forming an SMSI) boosts the photocatalytic generation of hydrogen, compared to AuNPs deposited at the surface of TiO2 (labelled as a classical system). The pathway of the charge carriers' dynamics regarding the system configuration is found to be different. The photogenerated electrons are collected by AuNPs in a classical system and act as an active site, while, unconventionally, they are injected back in the titania surface for an SMSI photocatalyst making the system highly efficient. Additionally, the adsorption energy of methanol, theoretically estimated using the density functional theory (DFT) methodology, is lower for the soft-chemistry SMSI photocatalyst accelerating the kinetics of photocatalytic hydrogen production. The SMSI obtained by soft-chemistry is an original concept for highly efficient photocatalytic materials, where the photon-to-energy conversion remains a major challenge.

Plasmonic core-shell nanostructure as an optical photoactive nanolens for enhanced light harvesting and hydrogen production.

Hydrogen production using plasmonic photocatalyst has attracted increasing attention since it improves light harvesting and photoefficiency. Herein, we have designed a plasmonic photocatalyst in a core-shell nanostructure that enabled an improvement of light harvesting and photocatalytic production of hydrogen using a very low amount of gold nanoparticles. The core-shell nanostructure was found to mimic the focusing of light observed for the lens-like epidermal cells. Thus, the core-shell nanostructure acts as a convex nanolens to reinforce the electromagnetic field at the nanostructure surface. The electric field was also found to be enhanced, which improves the energy absorbed for gold particles located in the core-shell nanostructure. Thus, by adjusting the diameter of the core-shell nanostructure, an optimal intensity for the localized surface plasmon resonance of gold was obtained. Tuning the size of the core-shell nanostructure enabled to improve the absorption at the reactive surface, thus increasing the photocatalytic hydrogen production efficiency by 5-fold.

Effect of SiN x diffusion barrier thickness on the structural properties and photocatalytic activity of TiO2 films obtained by sol-gel dip coating and reactive magnetron sputtering.

We investigate the effect of the thickness of the silicon nitride (SiN x ) diffusion barrier on the structural and photocatalytic efficiency of TiO2 films obtained with different processes. We show that the structural and photocatalytic efficiency of TiO2 films produced using soft chemistry (sol-gel) and physical methods (reactive sputtering) are affected differentially by the intercalating SiN x diffusion barrier. Increasing the thickness of the SiN x diffusion barrier induced a gradual decrease of the crystallite size of TiO2 films obtained by the sol-gel process. However, TiO2 obtained using the reactive sputtering method showed no dependence on the thickness of the SiN x barrier diffusion. The SiN x barrier diffusion showed a beneficial effect on the photocatalytic efficiency of TiO2 films regardless of the synthesis method used. The proposed mechanism leading to the improvement in the photocatalytic efficiency of the TiO2 films obtained by each process was discussed.

Study of mesoporous CdS-quantum-dot-sensitized TiO2 films by using X-ray photoelectron spectroscopy and AFM.

CdS quantum dots were grown on mesoporous TiO2 films by successive ionic layer adsorption and reaction processes in order to obtain CdS particles of various sizes. AFM analysis shows that the growth of the CdS particles is a two-step process. The first step is the formation of new crystallites at each deposition cycle. In the next step the pre-deposited crystallites grow to form larger aggregates. Special attention is paid to the estimation of the CdS particle size by X-ray photoelectron spectroscopy (XPS). Among the classical methods of characterization the XPS model is described in detail. In order to make an attempt to validate the XPS model, the results are compared to those obtained from AFM analysis and to the evolution of the band gap energy of the CdS nanoparticles as obtained by UV-vis spectroscopy. The results showed that XPS technique is a powerful tool in the estimation of the CdS particle size. In conjunction with these results, a very good correlation has been found between the number of deposition cycles and the particle size.