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Considering their superior charge-transfer characteristics, easy tenability of energy levels, and low production cost, organic semiconductors are ideal for photoelectrochemical (PEC) hydrogen production. However, organic-semiconductor-based photoelectrodes have not been extensively explored for PEC water-splitting because of their low stability in water. Herein, we report high-performance and stable organic-semiconductors photoanodes consisting of p-type polymers and n-type non-fullerene materials, which is passivated using nickel foils, GaIn eutectic, and layered double hydroxides as model materials. We achieve a photocurrent density of 15.1 mA cm−2 at 1.23 V vs. reversible hydrogen electrode (RHE) with an onset potential of 0.55 V vs. RHE and a record high half-cell solar-to-hydrogen conversion efficiency of 4.33% under AM 1.5 G solar simulated light. After conducting the stability test at 1.3 V vs. RHE for 10 h, 90% of the initial photocurrent density are retained, whereas the photoactive layer without passivation lost its activity within a few minutes., While organic semiconductors may be useful in photoelectrochemical water-splitting materials, they show low stability in water. Here, the authors report high-performance and stable organic-semiconductor-based photoanodes passivated using nickel foils, GaIn eutectic, and layered double hydroxides.

Spinel oxides are versatile and functional materials with physicochemical properties that are significantly influenced by their structural disorder. The transition from layered double hydroxides (LDHs) to mixed metal oxides (MMOs) containing spinel oxides is a powerful approach to create materials with tailored properties suitable for various applications. Herein, we report the control of structural ordering in spinels related to the crystallinity, cationic inversion, and coordination number of constituent atoms by varying the transformation energy. Transformation from LDHs to spinels with higher applied energy leads to higher crystallinity, lower degree of inversion, and lower ratios of low-coordinated atoms to fully coordinated atoms after treatment with acid. We provide a general framework for controlling structural ordering, that can be applied to other spinels and metal oxides. In addition, LDHs and MMOs possess many chemical and structural degrees of freedom, making it possible to create materials that suit the needs of different applications, such as memory, sensors, catalysis, and energy conversion.

Summary Phase transformation from layered double hydroxides (LDHs) into mixed metal oxides (MMOs) has been widely used in various catalytic applications owing to its numerous advantages over conventional synthesis methods. Herein we report the results of selective phase transformation of LDHs into spinels and delafossites for the preparation of phase-pure MMO catalysts. Pure cuprous delafossites and cupric spinels were selectively obtained through heat treatment of Cu-based LDHs followed by post-treatments. This enabled the study of the crystalline-phase-dependent CO oxidation activity of the MMO catalysts and their physicochemical properties. The spinel catalysts exhibited higher CO oxidation activities, in comparison with those of the delafossites, with greater redox properties and improved active sites for CO adsorption. Although the crystalline phases were derived from the same LDH precursors, the catalytic properties of the end product were greatly influenced by their crystal structures.

Noncentrosymmetric polar materials having polar facets exhibit unique and often useful physicochemical properties. However, the fraction of polar facets having a high specific surface energy is, generally, low because of free energy minimization during crystal growth. In this study, a mechanism for the spontaneous formation of polar ZnO crystals with high sphericity and a high fraction of polar ZnO facets, as supported by the results of material characterization, is proposed. Specifically, in a supersaturated solution of l -ascorbic acid, complexes of ZnO and organic species form nanoparticles, which then aggregate and merge to form large spherical structures. In these spherical structures, crystalline domains of polar ZnO oriented along [0001] dominate in the radial direction. In addition, during the growth period, the central part of the structure, which has a high curvature, releases strain by outward mass transfer and dissolution, and the spheres becomes hollow. The resulting hollow spherical particles having a high fraction of polar facets show higher activity for H2O2 generation via O2 reduction than rod-like ZnO structures, which have a dominant nonpolar surface, prepared in the absence of l -ascorbic acid.

Hydrogen peroxide (H2O2), the simplest peroxide consisting of only hydrogen and oxygen, is globally used as a green oxidant. It is also a promising fuel source, and it can be produced on large scales in centralized containers. H2O2 is mainly produced by the anthraquinone process, but it involves energy-consuming reactions and generates organic waste. As the demand for H2O2 continues to grow, alternative technologies that overcome these drawbacks are sought for its generation. The generation of H2O2 through the redox reaction of water and oxygen can be a low-cost, sustainable, and efficient production method. However, this reaction requires active and stable catalysts. In general, H2O2 can be generated by the oxidation of H2O at the anode of an electrochemical cell. Alternatively, H2O2 can also be formed by the reduction of O2 at the cathode. Despite the progress in the development and advancement of materials that catalyze these reactions, further research is required to increase the electron transport rates and active sites of the catalyst. In this article, we review the available catalytic materials for the electrochemical production of H2O2 and provide a summary and outlook of this field.

Highly porous thin films and nanostructure arrays are created by a simple process of selective dissolution of a water‐soluble material, Sr3Al2O6. Heteroepitaxial nanocomposite films with self‐separated phases of a target material and Sr3Al2O6 are first prepared by physical vapor deposition. NiO, ZnO, and Ni1− xMgxO are used as the target materials. Only the Sr3Al2O6 phase in each nanocomposite film is selectively dissolved by dipping the film in water for 30 s at room temperature. This gentle and fast method minimizes damage to the remaining target materials and side reactions that can generate impurity phases. The morphologies and dimensions of the pores and nanostructures are controlled by the relative wettability of the separated phases on the growth substrates. The supercapacitor properties of the porous NiO films are enhanced compared to plain NiO films. The method can also be used to prepare porous films or nanostructure arrays of other oxides, metals, chalcogenides, and nitrides, as well as films or nanostructures with single‐crystalline, polycrystalline, or amorphous nature.

Solid solutions have been widely investigated for solar energy conversion because of the ease to control properties (e.g., band edge positions, charge carrier transport, and chemical stability). In this study, we introduce a new method to investigate intrinsic solar energy conversion properties of solid solutions through fabricating high-quality single-crystalline solid solution films by pulsed laser deposition. This method rules out external factors, such as morphology, crystalline grain size, orientation, density and distribution, surface area, and particle–particle or particle–conducting layer connection, that have plagued previous studies on solid solution photoelectrodes. Perovskite BiFeO3 (BFO) and SrTiO3 (STO) were chosen as “end” members of the solid solutions (i.e., (BFO)x(STO)1–x (0 ≤ x ≤ 1)). Optical and photoelectrochemical (PEC) properties of the solid solutions significantly varied with changing compositions. Among the six studied compositions, BFO:STO (3:1 molar ratio) exhibited the highest...

Gold nanoparticle (Au NP)-mixed metal oxide (MMO) nanocomposite photocatalysts for efficient self-sensitized dye degradations under visible light were prepared by an electrostatically driven self-assembly. Dihydrolipoic acid (DHLA)-capped Au NPs (building block I) were synthesized through a room temperature reaction. Their hydrodynamic size was determined as being around 4.9 nm by dynamic light scattering measurements. MMO nanoplates with lateral dimensions of 100-250 nm (building block II) were prepared by a calcination of zinc aluminum layered double hydroxides at 750 °C for 2 h in air. In a pH 7.0 aqueous solution, the DHLA-capped Au NPs had a negative zeta potential (-22 ± 3 mV); on the other hand, the MMO nanoplates had a positive zeta potential (15 ± 2 mV). Electrostatic self-assembly was achieved by stirring an aqueous solution (pH 7.0) containing DHLA-capped Au NPs and MMO nanoplates at room temperature for 1 h. The self-assembled and sequentially calcined nanocomposites exhibited the superior self-sensitized dye degradation efficiency under visible light to that of ZnO, TiO(2) (P25), or pure MMO nanoplates. The enhanced degradation efficiency could be attributed to strong coupling interactions of ZnO and ZnAl(2)O(4) phases of the MMO and the role of Au as an electron sink and mediator for formations of reactive oxidation species and as a light concentrator.

We demonstrate selective growth of ZnO branched nanostructures: from nanorod clusters (with branches parallel to parent rods) to nanotrees (with branches perpendicular to parent rods). The growth of these structures was realized using a three-step approach: electrodeposition of nanorods (NRs), followed by the sputtering of ZnO seed layers, followed by the growth of branched arms using hydrothermal growth. The density, size and direction of the branches were tailored by tuning the deposition parameters. To our knowledge, this is the first report of control of branch direction. The photoelectrochemical (PEC) performance of the ZnO nanostructures follows the order: nanotrees (NTs) > nanorod clusters (NCs) > parent NRs. The NT structure with the best PEC performance also possesses the shortest fabrication period which had never been reported before. The photocurrent of the NT and NC photoelectrodes is 0.67 and 0.56 mA cm-2 at 1 V vs. Ag/AgCl, respectively, an enhancement of 139% and 100% when compared to the ZnO NR structures. The key reason for the improved performance is shown to be the very large surface-to-volume ratios in the branched nanostructures, which gives rise to enhanced light absorption, improved charge transfer across the nanostructure/electrolyte interfaces to the electrolyte and efficient charge transport within the material.

We report on spontaneously phase ordered heteroepitaxial SrTiO3 (STO):ZnFe2O4 (ZFO) nanocomposite films that give rise to strongly enhanced photoelectrochemical solar water oxidation, consistent with enhanced photoinduced charge separation. The STO:ZFO nanocomposite yielded an enhanced photocurrent density of 0.188 mA/cm2 at 1.23 V vs a reversible hydrogen electrode, which was 7.9- and 2.6-fold higher than that of the plain STO film and ZFO film cases under 1-sun illumination, respectively. The photoelectrode also produced stable photocurrent and Faradaic efficiencies of H2 and O2 formation that were more than 90%. Incident-photon-to-current-conversion efficiency measurements, Tauc plots, Mott–Schottky plots, and electrochemical impedance spectroscopy measurements proved that the strongly enhanced photogenerated charge separation resulted from vertically aligned pseudosingle crystalline components, epitaxial heterojunctions, and a staggered band alignment of the components of the nanocomposite films. This study presents a completely new avenue for efficient solar energy conversion applications.

We report the formation of ZnO structures with a bimodal distribution of aspect ratios in a one-batch reaction. In this synthesis, low aspect ratio (∼10) ZnO microrods were formed in the bulk solution, whereas high aspect ratio (∼1000) ZnO nanostructures formed on a ZnO thin film-coated substrate immersed in the bulk solution. The two types of structures were easily separated because the high aspect ratio ZnO nanostructures remained immobilized on the substrate. The distinct aspect ratios suggested that two types of ZnO structures formed by different growth mechanisms in the one-batch reaction. A systematic investigation led to the proposal of a formation mechanism. In the early stages of the reaction, Zn(OH)2 formed and was converted to ZnO in the bulk solution. The ZnO grew to form low aspect ratio ZnO mircorods via layer-by-layer growth. As the reaction proceeded, precursors were consumed, which decreased the degree of supersaturation. The high aspect ratio 1D ZnO nanostructures grew from defects in th...

We report a post-treatment method for modifying the crystalline nature and texture of ZnO nanostructure surfaces. Single crystalline ZnO structures were transformed using a solution-based reaction in an aqueous sodium selenite and hydrazine solution into single crystalline ZnO/polycrystalline ZnSe (core/shell) heterostructures (as an intermediate material), which were then used to texture the surfaces of ZnO nanostructures. The ZnO/ZnSe nanostructures were calcined to obtain pure ZnO nanostructures with a variety of surface crystalline natures and textures under controlled calcination conditions. Single crystalline ZnO core/polycrystalline ZnO shell nanostructures, single crystalline ZnO with wavy surfaces/ZnO nanoparticles, or single crystalline ZnO nanostructures with wavy surfaces were obtained by calcination at 550, 700, or 800 °C, respectively. The experimental results suggest a possible mechanism by which the surface of the ZnO nanostructures was modified. This method potentially may be extended to ...

We report a method for converting the surfaces of bulk metal substrates (pure iron or stainless steel) to metal oxide (hematite or Cr-doped hematite) nanostructures using microwave irradiation. When microwave radiation (2.45 GHz, single-mode) was applied to a metal substrate under the flow of a gas mixture containing O 2 and Ar, metal oxide nanostructures formed and entirely covered the substrate. The nanostructures were single crystalline, and the atomic ratios of the substrate metals were preserved in the nanostructures. When a pure iron sheet was used as a substrate, hematite nanowires (1000 W microwave radiation) or nanosheets (1800 W microwave radiation) formed on the surface of the substrate. When a SUS410 sheet was used as a substrate, slightly curved rod-like nanostructures were synthesized. The oxidation states of Fe and Cr in these nanorods were Fe 3+ and Cr 3+ . Quantitative analyses revealed an average Fe/Cr atomic ratio of 9.2, nearly identical to the ratio of the metals in the SUS410 substrate.

We report a method for growing aligned single-crystalline ZnO nanoneedles on single-crystalline Zn plates via a solution-phase reaction. An Al film deposited on a Si wafer was immersed and maintained in an aqueous ammonia solution containing Zn ions at 90 °C. After 30 min, the substrate surface was found to be covered with hierarchical ZnO nanoneedles/Zn heterostructures. ZnO nanoneedles evolved epitaxially from the surface of a hexagonal “mother” Zn disk. The mother Zn crystals were thin, hexagonal disks with lateral dimensions on the order of 2−8 μm. The nanoneedles had an average diameter of 100 nm and an average length of 700 nm. The mechanism of formation of the hierarchical ZnO/Zn structures was investigated by characterizing the crystalline nature, morphology, and composition of the synthesized materials as a function of the reaction time. In this way, the evolution of structures could be determined. The role of the Al layer in this method is also discussed. On the basis of the experimental results...

We report a novel method for the synthesis of fractal Zn structures through a solution phase reaction. An Al-film-deposited substrate was immersed in an aqueous ammonia solution containing Zn ions and maintained at 95 degrees C for 5 min. After the reaction, the Al-deposited side of the substrate was found to be covered with fractal Zn structures. These Zn structures are highly oriented, and the Zn(002) planes are parallel to the substrate. They are single-crystalline and the average thickness of the plates is approximately 50 nm. On the basis of our results, we propose a mechanism for the spontaneous growth of such fractal Zn structures. Single-crystalline fractal ZnO structures can also be obtained by calcination of the as-synthesized fractal Zn crystals at 500 degrees C for 5 h in air. These fractal ZnO structures are highly oriented and inherit their morphologies from the Zn structures.

Amorphous zinc phosphate nanospheres were prepared via a sonochemical route. Zinc phosphate nanospheres were uniform in shape with an average diameter of 210 nm. The average diameter of nanospheres could be controlled by changing the pH of a precursor solution. This sonochemical method is simple, facile, economical, and environmentally benign. Non-crystalline characteristics of as-prepared zinc phosphate nanospheres were confirmed by X-ray diffraction, transmission electron microscopy, and FT-IR spectroscopy analyses. We believe this technique will be readily adopted in realizing other forms of zinc phosphate nanostructures.

Layered double hydroxide-quantum dot (LDH-QD) composites are synthesized via a room temperature LDH formation reaction in the presence of QDs. InP/ZnS (core/shell) QD, a heavy metal free QD, is used as a model constituent. Interactions between QDs (with negative zeta potentials), decorated with dihydrolipoic acids, and inherently positively charged metal hydroxide layers of LDH during the LDH formations are induced to form the LDH-QD composites. The formation of the LDH-QD composites affords significantly enhanced photoluminescence quantum yields and thermal- and photostabilities compared to their QD counterparts. In addition, the fluorescence from the solid LDH-QD composite preserved the initial optical properties of the QD colloid solution without noticeable deteriorations such as red-shift or deep trap emission. Based on their advantageous optical properties, we also demonstrate the pseudo white light emitting diode, down-converted by the LDH-QD composites.

We report the synthesis of porous ZnO-ZnSe nanocomposites for use in visible light photocatalysis. Porous ZnO nanostructures were synthesized by a microwave-assisted hydrothermal reaction then converted into porous ZnO-ZnSe nanocomposites by a microwave-assisted dissolution-recrystallization process using an aqueous solution containing selenium ions. ZnO and ZnSe nanocrystallites of the nanocomposites were well-mixed (rather than forming simple core-shell (ZnO-ZnSe) structures), particularly, in the outer regions. Both ZnO and ZnSe were present at the surface and exposed to the environment. The porous ZnO-ZnSe nanocomposites showed absorption bands in the visible region as well as in the UV region. The porous ZnO-ZnSe nanocomposites had much higher activities than the porous ZnO nanostructures. Control experiments using cutoff filters revealed that the main photocatalytic activity of the synthesized nanostructures arose from photo-excitation of the semiconductor (ZnO or ZnSe) via absorption of light of an energy equal to or exceeding the band gap energy.

We report a method for synthesizing quasi-single crystalline porous ZnO nanostructures containing a single large cavity. The microwave-assisted route consists of a short (about 2 min) temperature ramping stage (from room temperature to 120 °C) and a stage in which the temperature is maintained at 120 °C for 2 h. The structures produced by this route were 200–480 nm in diameter. The morphological yields of this method were very high. The temperature- and time-dependent evolution of the synthesized powders and the effects of an additive, vitamin C, were studied. Spherical amorphous/polycrystalline structures (70–170 nm in diameter), which appeared transitorily, may play a key role in the formation of the single crystalline porous hollow ZnO nanostructures. Studies and characterization of the nanostructures suggested a possible mechanism for formation of the quasi-single crystalline porous ZnO nanostructures with an interior space.

We report a method for synthesizing zinc citrate spheres at a low temperature (90 °C) under normal atmospheric pressure. The spherical structures were amorphous and had an average diameter of ∼1.7 μm. The amorphous zinc citrate spheres could be converted into crystalline ZnO nanostructures in aqueous solutions by heating at 90 °C for 1 h. By local dissolution of the zinc citrate spheres, nucleation and growth of ZnO occurred on the surfaces of the amorphous zinc citrate spheres. The morphologies and exposed crystal faces of the crystalline ZnO nanostructures (structure I: oblate spheroid; structure II: prolate spheroid; structure III: hexagonal disk; structure IV: sphere) could be controlled simply by varying the solution composition (solutions I, II, III, or IV) in which the as-prepared amorphous zinc citrate spheres were converted. The concentration of citrate anions and solution pH played a decisive role in determining the morphologies and exposed crystal faces of the crystalline ZnO nanostructures. On the basis of experimental results, we propose a plausible mechanism for the conversion of amorphous zinc citrate spheres into the variety of observed ZnO structures.

We report a novel method for covering a substrate with highly-oriented single crystalline hexagonal zinc structures under atmospheric pressure and room temperature without an external source of electric current, any templates or the use of epitaxial growth on the substrate.

We report a method for converting the surface of pure iron or stainless steel sheets (SUS304 or SUS410) to α-(FexCr1−x)2O3 (x = 0.80, 0.92 or 1) nanostructure arrays by performing microwave irradiation (1000 W, 2.45 GHz, single-mode) under an O2 and Ar atmosphere. When the iron, SUS304 and SUS410 sheets were irradiated, large-scale vertically aligned α-Fe2O3, α-(Fe0.80Cr0.20)2O3, and α-(Fe0.92Cr0.08)2O3 nanostructures, respectively, were found covering these substrates. The synthesized nanostructures were single crystalline. The Fe/Cr atomic ratios of the substrate were almost preserved in the nanostructures synthesized by the microwave irradiation. The morphology and size of the nanostructures can also be controlled by varying the microwave power or the irradiation time. This method requires only a relatively short reaction time (7 min), and does not require the supply of metallic species from the vapour phase, a template, or a catalyst. On the basis of the results, we speculate a possible mechanism for the formation of these α-(FexCr1−x)2O3 nanostructures by microwave irradiation.

We report the synthesis of carbon-doped zinc oxide nanostructures using vitamin C, and their visible light photocatalytic activity. Amorphous/crystalline vitamin C–ZnO (VitC–ZnO) structures were obtained from a solution of zinc nitrate hexahydrate, HMT, and vitamin C through heating at 95 °C for 1 h. VitC–ZnO structures were calcined in air at 500 °C for 2 h to create C-doped ZnO nanostructures. Calcined structures were polycrystalline, with an average crystal domain size of 7 nm. EDS, XPS, and XRD analysis revealed the substitution of oxygen with carbon and the formation of Zn–C bonds in the C-doped ZnO nanostructures. The carbon concentrations, in the form of carbide, were controlled by varying the concentrations of vitamin C (more than 1 mM) added to reaction solutions. On the basis of these experimental results, we propose a possible formation mechanism for C-doped ZnO nanostructures. The C-doped ZnO nanostructures exhibited visible light absorption bands that were red-shifted relative to the UV exciton absorption of pure ZnO nanostructures. The visible light (λ ≥ 420 nm) photocatalytic activities of C-doped ZnO nanostructures were much better than the activities of pure ZnO nanostructures.