Flexible but Refractory Single-Crystalline Hyperbolic Metamaterials.

The fabrication of flexible single-crystalline plasmonic or photonic components in a scalable way is fundamentally important to flexible electronic and photonic devices with high speed, high energy efficiency, and high reliability. However, it remains a challenge. Here, we have successfully synthesized flexible single-crystalline optical hyperbolic metamaterials by directly depositing refractory nitride superlattices on flexible fluorophlogopite-mica substrates with magnetron sputtering. Interestingly, these flexible hyperbolic metamaterials show dual-band hyperbolic dispersion of dielectric constants with small dielectric losses and high figures of merit in the visible to near-infrared ranges. More importantly, the optical properties of these nitride-based flexible hyperbolic metamaterials show remarkable stability during 1000 °C heating or after being bent 1000 times. Therefore, the strategy developed in this work offers an easy and scalable route for fabricating flexible, high-performance, and refractory plasmonic or photonic components, which can significantly expand the applications of current electronic and photonic devices.

Constructing an Open-Structured J-Type ZnIn2S4/In(OH)3 Heterojunction for Photocatalytical Hydrogen Generation.

Constructing heterojunctions to separate photogenerated carriers is an effective strategy for improving the efficiency of photocatalytic reactions. A J-type heterojunction is a recently reported efficient anisotropic heterojunction. Herein, taking anisotropic ZnIn2S4 (ZIS) nanosheets as an example of a type-II heterojunction, we report for the first time the concept of open and closed structures (O and C structure) of J-type heterojunctions. A simple ammonia-post-treatment method was employed to prepare the O- and C-structured J-type ZnIn2S4/In(OH)3 (ZIS/IOH) heterojunctions. The O-structured J-type ZIS/IOH (OJ-ZIS/IOH) heterojunction exhibits a high hydrogen production activity, reaching 400 µmol·h-1, 2.67 times higher than that of pristine ZIS. However, the activity of the C-structured heterojunction (CJ-ZIS/IOH) is close to that of pristine ZIS. The findings emphasize the importance of the cooperation of photogenerated carrier separation and transport in J-type heterojunctions, providing insights into developing efficient heterojunction photocatalysts.

Modification of TiO2 with sulfate and phosphate for enhanced eosin Y-sensitized hydrogen evolution under visible light illumination.

TiO2 was modified with sulfate and phosphate (denoted as S/TiO2 and P/TiO2) through a simple sulfuric or phosphoric acid treatment. A strong coordination bond forms between sulfate or phosphate and Ti(4+) of TiO2. Eosin Y (EY)-sensitized S/TiO2 and P/TiO2 (Pt as a co-catalyst and triethanolamine as a sacrificial electron donor) exhibit enhanced photocatalytic activity for hydrogen evolution under visible light illumination (λ > 420 nm) compared to that of EY-sensitized TiO2. The conduction band (CB) edges of S/TiO2 and P/TiO2 shift toward the negative, and the hydrogen bond interaction between the reduced radical EY˙-H and S/TiO2 or P/TiO2 is enhanced due to the inducing effect of the bound sulfate and phosphate. Thus, the photocatalytic hydrogen evolution is promoted. The effects of the concentration of the sulfuric or phosphoric acid as well as concentration of EY on the sensitization hydrogen evolution were investigated. The possible mechanism was discussed.

Eosin Y-sensitized graphitic carbon nitride fabricated by heating urea for visible light photocatalytic hydrogen evolution: the effect of the pyrolysis temperature of urea.

Graphitic carbon nitride (g-C3N4) was prepared by pyrolysis of urea at different temperatures (450-650 °C), and characterized by thermogravimetric and differential thermal analysis (TG-DTA), elemental analysis (C/H/N), X-ray diffraction (XRD), UV-vis diffuse reflectance spectra (DRS), Brunauer-Emmett-Teller (BET) analysis, Fourier transform-infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectra. The samples prepared at low temperatures (450 and 500 °C) are a mixture of g-C3N4 and impurities, whereas the samples prepared at high temperatures (550, 600 and 650 °C) should be g-C3N4 (polymeric carbon nitride). The polymerization degree of g-C3N4 for the prepared samples increases to a maximum at 600 °C with increasing pyrolysis temperature and then decreases, whereas the defect concentration changes conversely, that is, g-C3N4 prepared at 600 °C has the lowest defect concentration. Using Eosin Y (EY) and the prepared sample as the sensitizer and the matrix, respectively, the photocatalytic activity for hydrogen evolution from aqueous triethanolamine solution was investigated. The g-C3N4 prepared at 600 °C exhibits the highest sensitization activity. Under optimum conditions (1.25 × 10(-5) mol L(-1) EY and 7.0 wt% Pt), the maximal apparent quantum yield of EY-sensitized g-C3N4 prepared at 600 °C for hydrogen evolution is 18.8%. The highest activity can be attributed to the pure composition, the higher dye adsorption amount and the lowest defect concentration.

Synthesis of oriented J type ZnIn2S4@CdIn2S4 heterojunction by controllable cation exchange for enhancing photocatalytic hydrogen evolution.

Construction of semiconductor heterojunctions which promote the separation and transport of photogenerated carriers is an effective strategy for improving photocatalytic reaction efficiency. Based on the anisotropic electrical conductivity of layered ZnIn2S4 (ZIS) photocatalyst, an efficient heterojunction should be constructed along the layer plane of ZIS, that is, a J type heterojunction. However, achieving controllable synthesis of the oriented heterojunction of ZIS faces challenges. Herein, we develop a facile, cost-effective and spatially-selective cation exchange synthesis approach to construct J type ZnIn2S4@CdIn2S4 (J-ZIS@CIS) heterojunction using a flower-like hexagonal ZIS as the parent material. The developed synthesis approach can also control crystal structure of the heterojunction component CIS. This work presents a facile and controllable synthesis strategy to construct oriented anisotropic heterojunctions that are otherwise inaccessible. The as-prepared J-ZIS@CIS heterojunction displays a greatly enhanced photocatalytic hydrogen evolution activity with a rate of 183 µmol h-1, 2.77 times higher than that of pristine ZIS. Furthermore, the possible photocatalytic reaction mechanism is presented for the heterojunction.

Effect of molten-salt modulation on the composition and structure of g-C3N4-based photocatalysts.

Graphitic carbon nitride (g-C3N4), as an attractive metal-free polymer photocatalyst, has attracted extensive attention in energy and environmental fields in recent years. The photoactivity of bulk g-C3N4 is moderate on account of solid-phase thermal-condensation synthesis. This leads to inadequate light absorption, limited surface area, and easy recombination of charge carriers. The composition and nanostructure of g-C3N4 have been studied extensively. Molten-salt modulation is fascinating because of its "green" credentials and the properties of liquid-phase reaction systems. The review focuses mainly on molten-salt modulation of the composition and structure of g-C3N4 based-photocatalysts. We focus on elemental doping, molecular doping, and defect engineering, as well as control of the crystal structure, multi-dimensional structure, hom/heterostructures for photocatalytic applications. This review provides new insights to develop g-C3N4-based photocatalysts with control of composition and structure by facile molten-salt modulation in energy-conversion and environmental fields.

Construction of π-conjugated crystalline carbon dots with carbon nitride nanofragments for efficient photocatalytic H2 evolution.

Crystalline carbon dots (CCDs) embedded in carbon nitride (CN) nanofragments (CCDs-CN) have been developed through facile molten salt treatment. Molten salt treatment not only reconstructs CN layered sheets to form nanofragments, but also promotes the crystallization of CDs-CN. The π-conjugated electric field between CCDs and CN accelerates charge carrier separation for efficient photocatalytic H2 evolution.

Engineering Metal-Phenolic Networks for Solar Desalination with Directional Salt Crystallization.

Solar desalination is one of the most promising strategies to address the global freshwater shortage crisis. However, the residual salt accumulated on the top surface of solar evaporators severely reduces light absorption and steam evaporation efficiency, thus impeding the further industrialization of this technology. Herein, a metal-phenolic network (MPN)-engineered 3D evaporator composed of photothermal superhydrophilic/superhydrophobic sponges and side-twining hydrophilic threads for efficient desalination with directional salt crystallization and zero liquid discharge is reported. The MPN coatings afford the engineering of alternating photothermal superhydrophilic/superhydrophobic sponges with high heating efficiency and defined vapor escape channels, while the side-twining threads induce site-selective salt crystallization. The 3D evaporator exhibits a high and stable indoor desalination rate (≈2.3 kg m-2  h-1 ) of concentrated seawater (20 wt%) under simulated sun irradiation for over 21 days without the need for salt crystallization inhibitors. This direct desalination is also achieved in outdoor field operations with a production rate of clean water up to ≈1.82 kg m-2  h-1 from concentrated seawater (10 wt%). Together with the high affinity and multiple functions of MPNs, this work is expected to facilitate the rational design of solar desalination devices and boost the research translation of MPN materials in broader applications.

Confined synthesis of condensed π-conjugation C-PAN/MS-CN nanotubes for efficient photocatalytic H2 evolution.

Condensed π-conjugation C-PAN/MS-CN nanotubes were obtained via a facile polyacrylonitrile (PAN)-confined molten salt (MS) thermal condensation of melamine. Carbonized PAN (C-PAN) nanosheets with a conjugate network structure in the molten salt system acted as partition plates confining the thermal condensation of melamine, which promoted the formation of condensed π-conjugation carbon nitride (CN) for the effective charge carrier separation and photocatalytic H2 evolution.

"Dancing Coins?" Unexpected Finding During microsurgery and Potential Risk of Sperm Damage: Intrascrotal Calculi: A Retrospective Analysis.

Objective: Microsurgery of andrology always brings unexpected findings. Scrotal calculi are rare and unique, which are easily confused with tumor. To understand its etiology and harm, our study retrospectively analyzed the clinical characteristics of men with scrotal calculi to provide a reference for clinical practice. Methods: The clinical data of patients who underwent microscopic testicular sperm extraction (MTESE) and microscopic epididymal sperm aspiration (MESA) from January 1, 2018 to December 31, 2021 were retrospectively analyzed. Data screening was performed on cases in which calculi were found or not, and the relationship between calculi and spermatogenesis was analyzed. Results: A total of 405 patients were recruited. After screening, 218 nonobstructive azoospermia (NOA), 83 obstructive azoospermia (OA), and 13 cryptozoospermia (CZ) patients were included in the study. Calculi were found in 3 patients [incidence was 0.74% (3/405)], in which 2 patients had obstructive azoospermia (1 was epididymal calculi, 1 was intrascrotal calculi) and 1 patient had cryptozoospermia (intrascrotal calculi). Pathological results showed that chronic granuloma with abscess infiltration appeared in epididymal tissue, basement membrane thickening and fibrosis appeared in seminiferous tubules, and fibrous hyperplasia with calcium deposition was found in scrotal calculus. White blood cells, lymphocytes, red blood cells, abstinence time and urethritis were closely related to the occurrence of calculi. While abstinence time might be a potential predictor, which increased the risk by approximately 1.2 times. Conclusion: Disturbance of the testicular microenvironment caused by lymphocyte infiltration may be the main reason for scrotal calculi and ultimately cause spermatogenesis disorders. Prolonged sexual abstinence was a potential risk.

Wafer-Scale Epitaxy of Flexible Nitride Films with Superior Plasmonic and Superconducting Performance.

Transition-metal nitrides (e.g., TiN, ZrN, TaN) are incredible materials with excellent complementary metal-oxide semiconductor compatibility and remarkable performance in refractory plasmonics and superconducting quantum electronics. Epitaxial growth of flexible transition-metal nitride films, especially at the wafer scale, is fundamentally important for developing high-performance flexible photonics and superconducting electronics, but the study is rare thus far. This work reports the high-quality epitaxy of 2-in. titanium nitride (TiN) films on flexible fluorophlogopite-mica (F-mica) substrates via reactive magnetron sputtering. Combined measurements of spectroscopic ellipsometry and electrical transport reveal the superior plasmonic and superconducting performance of TiN/F-mica films owing to the high single crystallinity. More interestingly, the superconductivity of these flexible TiN films can be manipulated by the bending states, and enhanced superconducting critical temperature TC is observed in convex TiN films with in-plane tensile strain. Density functional theory calculations reveal that the strain can tune the electron-phonon interaction strength and the resultant superconductivity of TiN films. This study provides a promising route toward integrating scalable single-crystalline transition-metal nitride films with flexible electronics for high-performance plasmonics and superconducting electronics.

Transformation of Fe-B@Fe into Fe-B@Ni for efficient photocatalytic hydrogen evolution.

It is highly desirable to develop efficient and cost-effective composite catalysts to replace noble metal Pt for hydrogen evolution reaction (HER). For an excellent HER catalyst, both the adsorption and desorption of intermediate H atoms on it should be easy. However, except metal platinum, most individual species cannot satisfy this requirement. Fe-B is an active HER catalyst with strong ability to adsorb H atoms. In our previous work, we found that when Fe-B alloy was decorated with metal Fe particles (Fe-B@Fe), the resultant composite displayed a significant synergic effect for HER compared to single Fe-B and Fe. The role of the decorated Fe on Fe-B is to improve H2 desorption. Because the desorption of H2 molecule from Ni is easier than from Fe, we expect Fe-B@Ni to be a more efficient HER catalyst than Fe-B@Fe. Herein, we transform Fe-B@Fe into Fe-B@Ni by a facile displacement reaction. As a proof of concept, the as-prepared Fe-B@Ni catalyst exhibits much higher electrocatalytic and photocatalytic activity for hydrogen production than the pristine Fe-B@Fe. At the current density of -100 mA cm-2, the overpotential of Fe-B@Ni in 1.0 mol L-1 KOH is close to that of 20 wt% Pt/C. The highest apparent quantum yield (AQY) for dye-sensitized photocatalytic hydrogen evolution reaches 51% at 420 nm. The possible mechanisms have been proposed. These findings provide new insights for designing and fabricating new HER composite catalysts for electrocatalytic and photocatalytic hydrogen evolution.

Two-dimensional polar metals in KNbO3/BaTiO3 superlattices: first-principle calculations.

Polar metals, commonly defined by the coexistence of polar structure and metallicity, are thought to be scarce because free carriers eliminate internal dipoles that may arise owing to asymmetric charge distributions. By using first-principle electronic structure calculations, we explored the possibility of producing metallic states in the polar/nonpolar KNbO3/BaTiO3 superlattice (SL) composed of two prototypical ferroelectric materials: BaTiO3 (BTO) and KNbO3 (KNO). Two types of polar/nonpolar interfaces, p-type (KO)-/(TiO2)0 and n-type (NbO2)+/(BaO)0, which can be constituted into two symmetric NbO2/BaO-NbO2/BaO (NN-type) and KO/TiO2-KO/TiO2 (PP-type) SL, as well as one asymmetric KO/TiO2-NbO2/BaO (PN-type) SL. The spatial distribution of ferroelectric distortions and their conductive properties are found to be extraordinarily sensitive to the interfacial configurations. An insulator-to-metal transition is found in each unit cell of the symmetric interfacial SL models: one exhibiting quasi-two-dimensional n-type conductivity for NN-type SL, while the other being quasi-two-dimensional p-type conductivity for PP-type SL. The anisotropic coexistence of in-plane orientation of free carriers and out-of-plane orientation of ferroelectric polarization in KNO/BTO SL indicates that in-plane free carriers can not eliminate the out-of-plane dipoles. Our results provide a road map to create two-dimensional polar metals in insulating perovskite oxide SL, which is expected to promote applications of new quantum devices.

Photocatalytic hydrogen generation in the presence of chloroacetic acids over Pt/TiO2.

In the presence of chloroacetic acids, the photocatalytic hydrogen evolution and decomposition of the pollutants over Pt/TiO2 have been investigated. The Pt/TiO2 was prepared by photodeposition. Monochloroacetic acid and dichloroacetic acid enhance photocatalytic hydrogen generation, whereas trichloroacetic acid does not. The photocatalytic oxidation of monochloroacetic acid and dichloroacetic acid mainly produces CO2, HCl and formaldehyde, whereas the photocatalytic oxidation of trichloroacetic acid mainly produces CO2 and HCl. The effect of the concentration of monochloroacetic acid and dichloroacetic acid on the hydrogen generation rate is consistent with a Langmuir-Hinshelwood kinetic model. A possible reaction mechanism was discussed.

Facile Synthesis of Graphene Sponge from Graphene Oxide for Efficient Dye-Sensitized H2 Evolution.

Graphene is an advanced carbon energy material due to its excellent properties. Reduction of graphene oxide (GO) is the most promising mass production route of graphene/reduced graphene oxide (rGO). To maintain graphene's properties and avoid restacking of rGO sheets in bulk, the preparation of 3-dimensional porous graphene sponge via 2-dimensional rGO sheets is considered as a good strategy. This article presents a facile route to synthesize graphene sponge by thermal treating GO powder at low temperature of 250 °C under N2 atmosphere. The sponge possesses macroporous structure (5-200 nm in size) with BET specific surface area of 404 m(2) g(-1) and high conductivity. The photocatalytic H2 production activity of the rGO sponge with a sensitizer Eosin Y (EY) and cocatalyst Pt was investigated. The rGO sponge shows highly efficient dye-sensitized photocatalytic H2 evolution compared to that obtained via a chemical reduction method. The maximum apparent quantum yield (AQY) reaches up to 75.0% at 420 nm. The possible mechanisms are discussed. The synthesis method can be expanded to prepare other graphene-based materials.

Synergetic effect of metal nickel and graphene as a cocatalyst for enhanced photocatalytic hydrogen evolution via dye sensitization.

Exploiting new, low-cost and efficient electrocatalysts for hydrogen evolution reaction (HER) is important to resolve the energy crisis and environment pollution. In this work, graphene decorated with Ni nanoparticles (NPs) were synthesized via one-pot reduction using graphene oxide (GO, the obtained composite was denoted as GN) as a precursor. The as-prepared composite GN exhibits much better electrocatalytic and dye-sensitized HER activities than single Ni and reduced graphene oxide (RGO), namely, a great synergetic effect of RGO and Ni for HER. The coupling of metal Ni with the defect carbons of RGO plays a key role in the synergetic effect. The structure of GN composites is another key factor to the synergetic effect. The highest apparent quantum yield (AQY) for dye-sensitized photocatalytic hydrogen evolution at 470 nm reaches 30.3% under the optimal conditions.

Enhancement of photocatalytic H2 evolution of eosin Y-sensitized reduced graphene oxide through a simple photoreaction.

A graphene oxide (GO) solution was irradiated by a Xenon lamp to form reduced graphene oxide (RGO). After irradiation, the epoxy, the carbonyl and the hydroxy groups are gradually removed from GO, resulting in an increase of sp(2) π-conjugated domains and defect carbons with holes for the formed RGO. The RGO conductivity increases due to the restoration of sp(2) π-conjugated domains. The photocatalytic activity of EY-RGO/Pt for hydrogen evolution was investigated with eosin Y (EY) as a sensitizer of the RGO and Pt as a co-catalyst. When the irradiation time is increased from 0 to 24 h the activity rises, and then reaches a plateau. Under optimum conditions (pH 10.0, 5.0 × 10(-4) mol L(-1) EY, 10 µg mL(-1) RGO), the maximal apparent quantum yield (AQY) of EY-RGO24/Pt for hydrogen evolution rises up to 12.9% under visible light irradiation (λ ≥ 420 nm), and 23.4% under monochromatic light irradiation at 520 nm. Fluorescence spectra and transient absorption decay spectra of the EY-sensitized RGO confirm that the electron transfer ability of RGO increases with increasing irradiation time. The adsorption quantity of EY on the surface of RGO enhances, too. The two factors ultimately result in an enhancement of the photocatalytic hydrogen evolution over EY-RGO/Pt with increasing irradiation time. A possible mechanism is discussed.

Nitrogen-doped TiO2 modified with NH4F for efficient photocatalytic degradation of formaldehyde under blue light-emitting diodes.

A nitrogen-doped TiO(2) (N-TiO(2)) photocatalyst was prepared by calcination of the hydrolysis precipitate of Ti(SO(4))(2) with aqueous ammonia. The prepared N-TiO(2) was treated with NH(4)F (F-N-TiO(2)) by an impregnation-calcination method. The photocatalyst (F-N-TiO(2)) was characterized by X-ray diffraction (XRD), Fourier Transform Infrared (FT-IR), UV-vis diffusive reflectance spectroscopy (DRS), BET and X-ray photoelectron spectroscopy (XPS). With blue light-emitting diode (LED) as the light source, its photocatalytic activity for the degradation of formaldehyde was investigated. NH(4)F treatment enhances markedly photocatalytic activity of N-TiO(2). The treatment increases the visible absorption of N-TiO(2), decreases its specific surface area and influences the concentration of oxygen vacancies in N-TiO(2). Photocatalytic activity of F-N-TiO(2) depends on the visible absorption, the specific surface area, and the concentration of oxygen vacancies. The preparation conditions, such as the calcination temperature and the initial molar ratio of NH(4)F to N-TiO(2), have a significant influence on the photocatalytic activity. The doping mechanism of NH(4)F was investigated.