Commonly Existing Hole-Capturer Organics Adsorption-Induced Recombination over Metal/Semiconductor Perimeters: A Possible Important Factor Affecting Photocatalytic Efficiencies.

Photocatalysis is a physiochemical effect arising from the relaxation of photoinduced electrons from the conduction band to the valence band. Controlling the electron relaxation to occur through photocatalytic pathways and prohibiting other relaxations is the main scientific thought for photocatalytic studies. It is needed to know the parallel relaxation pathways that can compete with photocatalytic reactions. By means of in situ photoconductances (PCs) and photoinduced absorptions (PAs), the current research studied the photoinduced electron relaxations of the Au/TiO2 in different atmospheres and at different temperatures. The PC and PA relaxations became different and fast when methanol, ethanol, isopropanol, and acetone were introduced; they also tend to decrease as temperature increases, while that of the undecorated TiO2 in all atmospheres and the Au/TiO2 in pure N2 increased. The results indicated that the organic adsorptions over the Au/TO2 perimeters change the relaxation pathway, and a hole-capturing organics adsorption-induced recombination over the Au/TiO2 perimeter was proposed to explain the relaxations. We found that this relaxation also exists for Ag/TiO2, Pt/TiO2, and Au/ZnO, so it is a commonly existing physical course for the metal/semiconductor (M/S) materials. The effect of the organics and M/S structures on the relaxation was discussed, and the relationship with photocatalytic reactions was also analyzed. Our finding means that blocking this relaxation pathway is an effective way to increase photocatalytic activities, which might open a door for highly active photocatalyst developments.

Facile preparation of a water-based antireflective SiO2 film with high transmittance for perovskite solar cells.

The synthesis of anti-reflective (AR) films has been increasingly focused on environmental friendliness and cost efficiency in order to realize green and sustainable development. Herein, a novel strategy for preparing a nanoporous SiO2 AR film with high transmittance by a sol-gel process is proposed based on a sodium silicate aqueous solution. Sodium ions in the as-prepared SiO2 AR film can be effectively removed by a facile washing process, and thus its refractive index can be regulated. Moreover, the pH value of the sol has a huge effect on the structure and properties of the SiO2 AR film. As a result, the AR film exhibited a high transmittance increase of 4.10% at 550 nm and an average transmittance increase by 3.51% in the wavelength range of 380-1100 nm compared with blank glass. In addition, the obtained water-based SiO2 AR film exhibited hydrophilicity and the water contact angle (WCA) can be regulated from 61° to 8.4°. When the AR film was applied to the upper surface of perovskite solar cells, the photoelectric conversion efficiency (PCE) revealed an improvement of 1.44% compared with the PCE of perovskite solar cells without the AR film. Therefore, this work can provide a facile and effective method to prepare water-based antireflective films with high transmittance for solar cells.

The Emerging Star of Carbon Luminescent Materials: Exploring the Mysteries of the Nanolight of Carbon Dots for Optoelectronic Applications.

Carbon dots (CDs), a class of carbon-based nanomaterials with dimensions less than 10 nm, have attracted significant interest since their discovery. They possess numerous excellent properties, such as tunability of photoluminescence, environmental friendliness, low cost, and multifunctional applications. Recently, a large number of reviews have emerged that provide overviews of their synthesis, properties, applications, and their composite functionalization. The application of CDs in the field of optoelectronics has also seen unprecedented development due to their excellent optical properties, but reviews of them in this field are relatively rare. With the idea of deepening and broadening the understanding of the applications of CDs in the field of optoelectronics, this review for the first time provides a detailed summary of their applications in the field of luminescent solar concentrators (LSCs), light-emitting diodes (LEDs), solar cells, and photodetectors. In addition, the definition, categories, and synthesis methods of CDs are briefly introduced. It is hoped that this review can bring scholars more and deeper understanding in the field of optoelectronic applications of CDs to further promote the practical applications of CDs.

Novel magneto-electrocatalyst Cr2CO2-MXene for boosting nitrogen reduction to ammonia.

Ammonia (NH3) plays important roles in chemistry, the environment, and energy; however, the synthesis of NH3 relies heavily on the Haber-Bosch process, causing serious environmental pollution and energy consumption. A clean and effective strategy for the synthesis of NH3 involves nitrogen (N2) being transformed to ammonia (NH3) using electrocatalysis. Adjusting the magnetism of electrocatalysts may improve their performance, and therefore, four magnetic states, nonmagnetic (NM), ferromagnetic (FM), interlayer antiferromagnetic (Inter-AFM), and intra-layer antiferromagnetic (Intra-AFM) Cr2CO2-MXene were designed to explore magnetoelectrocatalysis performance using well-defined density functional theory (DFT) calculations in this study. Upon comparing the nitrogen reduction limiting potentials of N2 molecules on the surface of the four different magnetic states in Cr2CO2-MXene, and the selectivity calculations of the hydrogen evolution reaction (HER) and nitrogen reduction reaction (NRR), the Inter-AFM Cr2CO2-MXene is shown to be a better NRR electrocatalyst than the other three cases. This study paves way to unravel the mystery of the spin-catalytic mechanism and will lay a solid foundation for eNRR electrocatalysts with magnetic materials for environmental and energy applications.

Amorphization of MXenes: Boosting Electrocatalytic Hydrogen Evolution.

The emergence of amorphous 2D materials has opened up new avenue for materials science and nanotechnology in the recent years. Their unique disordered structure, excellent large-area uniformity, and low fabrication cost make them important for various industrial applications. However, there have no reports on the amorphous MXene materials. In this work, the amorphous Ti2C-MXene (a-Ti2C-MXene) model is built by ab initio molecular dynamics (AIMD) approach. This model is a unique amorphous model, which is totally different from continuous random network (CRN) model for silicate glass and amorphous model for amorphous 2D BN and graphene. The structure analysis shows that the a-Ti2C-MXene composited by [Ti5C] and [Ti6C] cluster, which are surrounded by the region of mixed cluster [TixC], [Ti-Ti] cluster, and [C-C] cluster. There is a high chemical activity for hydrogen evolution reaction (HER) in a-Ti2C-MXene with |ΔGH| 0.001 eV, implying that they serve as the potential boosting HER performance. The work provides insights that can pave the way for future research on novel MXene materials, leading to their increased applications in various fields.

Investigation of polyethylene glycol (PEG) assisted solvothermal synthesis of CuCoO2 nanosheets for efficient oxygen evolution reaction.

Water splitting to produce hydrogen is known as an effective way to alleviate the energy crisis, but the slow kinetics of the oxygen evolution reaction (OER) has been seriously restricting the development of water splitting technology. Therefore, low cost and high efficiency OER electrocatalysts have become substitutes for traditional noble metal-based catalysts. In this work, CuCoO2 nanosheets (denoted by CCO2) were successfully synthesized under the regulation of surfactants and a solvent polyethylene glycol (PEG) by a solvothermal route using Cu-BTC and Co(NO3)2·6H2O as reactants. The experimental results confirmed that PEG addition could further reduce significantly the crystal size of the CCO2 nanosheets, i.e., the size was about 150 nm and the thickness was 13 nm. The Ni@CCO2 electrode exhibits outstanding OER performance in 1.0 M KOH electrolyte, which shows the overpotential at 10 mA cm-2 is 378 mV, and the Tafel slope is 85 mV dec-1. Moreover, the CCO2 nanosheets exhibit good structural and compositional stability after the 18 h constant current OER test. Therefore, this work may offer a novel insight into enhancing the OER performance of CuCoO2 catalysts by decreasing their crystal size, and using a solvothermal route.

Enhanced Thermochromic Performance of VO2 Nanoparticles by Quenching Process.

Vanadium dioxide (VO2) has been a promising energy-saving material due to its reversible metal-insulator transition (MIT) performance. However, the application of VO2 films has been seriously restricted due to the intrinsic low solar-energy modulation ability (ΔTsol) and low luminous transmittance (Tlum) of VO2. In order to solve the problems, the surface structure of VO2 particles was regulated by the quenching process and the VO2 dispersed films were fabricated by spin coating. Characterizations showed that the VO2 particles quenched in deionized water or ethanolreserved VO2(M) phase structure and they were accompanied by surface lattice distortion compared to the pristine VO2. Such distortion structure contributed to less aggregation and highly individual dispersion of the quenched particles in nanocomposite films. The corresponding film of VO2 quenched in water exhibited much higher ΔTsol with an increment of 42.5% from 8.8% of the original VO2 film, because of the significant localized surface plasmon resonance (LSPR) effect. The film fabricated from the VO2 quenched in ethanol presented enhanced thermochromic properties with 15.2% of ΔTsol and 62.5% of Tlum. It was found that the excellent Tlum resulted from the highly uniform dispersion state of the quenched VO2 nanoparticles. In summary, the study provided a facile way to fabricate well-dispersed VO2 nanocomposite films and to facilitate the industrialization development of VO2 thermochromic films in the smart window field.

Facile Synthesis of ZrO2-SiO2 Antireflective Films with Good Mechanical Performances for Perovskite Solar Cells.

Antireflective (AR) films are widely applied in solar cells to reduce the reflectivity toward sunlight, thus improving the photoelectric conversion efficiency (PCE) of solar cells. However, AR films are still suffering from poor mechanical properties and low transmittance in photovoltaic applications. Herein, a ZrO2-SiO2 composite film with enhanced mechanical properties was successfully synthesized by a facile sol-gel method, whose pencil hardness increased from less than 6B to B compared with the pure SiO2 film synthesized with the same alkali-catalyzed method. Moreover, the ZrO2-SiO2 film with a Zr/Si mole ratio (nZr/Si) of 0.06 exhibited a high transmittance gain (ΔT) of 3.0%, and an obvious increase (1.32%) in PCE was observed in a perovskite solar cell compared with the cell covered by a bare glass. Additionally, both the short-circuit current density (JSC) and PCE of perovskite solar cells have a non-linear increasing relationship with the average transmittance (Tavg) of the ZrO2-SiO2 composite film. In this sense, this work can provide a facile way to prepare AR films effectively improving performances of solar cells.

Fermi-level shift, electron separation, and plasmon resonance change in Ag nanoparticle-decorated TiO2 under UV light illumination.

Noble metal nanoparticles are widely used as co-catalysts for storing and separating electrons in semiconductor photocatalysis. Thus, evaluating this ability is important and meaningful to understand the photocatalytic mechanism. Employing Ag nanoparticles, the present study combined in situ photoconductance and theoretical analysis to evaluate the Fermi-level (EF) shift in a UV-illuminated Ag/TiO2 system under gaseous conditions. Based on this, the role of the Ag nanoparticles in storing and separating electrons was discussed. It was found that the EF of Ag/TiO2 is located deeper in the gap and a variation in temperature has less effect on the EF of Ag/TiO2 compared to the undecorated TiO2. The analysis showed that ∼46 electrons can be stored in 10 nm Ag nanoparticles under our experimental conditions, which does not change with temperature. The electron traps in TiO2 can affect the electron distribution in the TiO2 and Ag nanoparticles. It was observed that the localized surface plasmon resonance (LSPR) of the Ag nanoparticles exhibited a blue-shift under UV light illumination, which is generally ascribed to the electron storage in the Ag nanoparticles. However, we showed that the blue-shift is not related to the electron storage in the Ag nanoparticles, and thus it cannot be used as an indicator for evaluating their electron-storage ability. The in situ XPS analysis also does not support that the LSPR blue shift is associated with the reduction in the Ag2O layer and TiO2.

Unveiling Unconventional Luminescence Behavior of Multicolor Carbon Dots Derived from Phenylenediamine.

Fluorescence regulation of carbon dots (CDs) during their preparation has become a hot research topic. In this work, multicolor fluorescent CDs with unconventional luminescence behavior are prepared by using o-, m-, or p-phenylenediamine (o-PD, m-PD, or p-PD, respectively) and 2,3-dihydroxynaphthalene with rich hydroxyl groups as reaction precursors. Tunable multicolor fluorescent CDs with bright blue, yellow, and red colors can be obtained by a solvothermal method under the joint action of ethanol and hydrochloric acid. The fluorescence emission of the synthesized CDs follows a rule of o-PD to m-PD to p-PD from blue to red, which is contrary to most previously reported results (the luminescence from blue to red following an order of m-PD to o-PD to p-PD). Our results reveal that the differences in the polymerization, surface states, functional groups, and graphite N content of CDs might be the main reasons for the unconventional luminescence behavior. In addition, these multicolor CDs have good applications in the fields of light-emitting diode lighting and anticounterfeiting.

Tunable Afterglow and Self-Trapped Exciton Emissions in Zr (IV)-Based Organic-Inorganic Metal Halide Hybrids by Metal-Ion Doping.

Low-dimensional hybrid metal halide (LDHMH) materials have attracted considerable attention owing to their intriguing optical properties. To the best of the knowledge, this is the first study to successfully demonstrate both self-trap exciton (STE) and afterglow emissions in Zr-based LDHMH materials. The obtained pure (Ph3 S)2 ZrCl6 crystals showed near-ultraviolet phosphorescence and a green afterglow owing to the organic cation Ph3 S+ , while the Bi-doped and Sb-doped crystals exhibited both STE and afterglow emissions. However, the Te-doped crystals showed only a broad yellow STE emission owing to the [TeCl6 ]2- octahedron. In addition, all the crystals showed good stability. Notably, Sb-doped crystals produced white light, which can be adjusted between cold white and warm white using different excitations. Finally, this strategy for both STE and afterglow emissions can be applied to other LDHMH materials for optical applications.

Enhanced Luminescence of Dye-Decorated ZIF-8 Composite Films via Controllable D-A Interactions for White Light Emission.

Metal-organic frameworks (MOFs) constructed by metal ions/clusters and organic linkers are used to encapsulate fluorescent guest species with aggregation-caused quenching (ACQ) effects to enhance fluorescence properties due to their porous structures and high specific surface areas. However, there would be a problem of matching between MOF pores and guest molecules' sizes. In this paper, amorphous ZIF-8 was modified by carboxyl functional groups (H3BTC-ZIF-8) via introducing the 1,2,4-benzenetricarbonic acid (H3BTC) ligand into the ZIF-8 sol system. Moreover, H3BTC-ZIF-8 was used for the loading of organic fluorescent dyes rhodamine 6G (R6G) and coumarin 151 (C151) to prepare R6G/C151/H3BTC-ZIF-8 composite films. A white-light-emitting composite film (R6G/C151/H3BTC-ZIF-8) with CIE coordinates of (0.323, 0.347) was successfully prepared by compounding fluorescent dyes (R6G and C151) with H3BTC-modified ZIF-8, whose photoluminescence quantum yield (PLQY) can reach 64.0%. It was higher than the PLQY of the composite films prepared by crystalline ZIF-8 (40.2%) or amorphous ZIF-8 without H3BTC (48.0%) compounded with the same concentrations of dyes. The fluorescence enhancement was probably attributed to an increased amount of active sites of H3BTC-modified ZIF-8 interacting with dyes C151 and R6G. This can form hydrogen bonds between H3BTC-ZIF-8 and C151, and weak electron donor-acceptor (D-A) interactions between H3BTC-ZIF-8 and R6G molecules, respectively, thus enhancing the interactions between dyes and ZIF-8 and reducing the ACQ effect existing between dye molecules. Therefore, this strategy could provide an important guidance to develop white-light-emissive materials.

Targeted high-precision up-converting thermometer platform over multiple temperature zones with Er3.

Ratiometric luminescence thermometry based on trivalent erbium ions is a noninvasive remote sensing technique with high spatial and temporal resolution. The thermal coupling between two adjacent energy levels follows the Boltzmann statistics, whose effective range is related to the energy gap between the multi-excited states. However, the limitations of different thermally coupled levels (TCLs) in Er-based thermometers are rarely mentioned. Here, a type of targeted high-precision luminescence thermometer was designed using a lead-free double perovskite platform by selecting multiple TCLs of the Er3+ ion. According to the selection of different TCLs in a single system platform, more precise temperature resolution can be obtained in different temperature regions from 100 K to almost 880 K. This work provides a quantitative guideline that may pave the way for the development of the next generation of temperature sensor based on trivalent erbium ions.

Multimodal Luminescent Low-Dimension Cs2ZrCl6:xSb3+ Crystals for White Light-Emitting Diodes and Information Encryption.

Low-dimension perovskite materials have attracted wide attention due to their excellent optical properties and stability. Herein, Sb3+-doped Cs2ZrCl6 crystals are synthesized by a coprecipitation method in which Sb3+ ions partially replace Zr4+ ions. The Cs2ZrCl6:xSb3+ powder shows blue and orange-red emissions under a 254 and 365 nm light, respectively, due to the [ZrCl6]2- octahedron and [SbCl6]3- octahedron. The photoluminescence quantum yield (PLQY) of Cs2ZrCl6:xSb3+ (x = 0.1) crystals is up to 52.5%. According to experimental and computational results, the emission mechanism of the Cs2ZrCl6:xSb3+ crystals is proposed. On the one hand, a wide blue emission with a large Stokes shift is caused by the self-trapping excitons of [ZrCl6]2- octahedra under a 260 nm excitation. On the other hand, the luminescence mechanism of [SbCl6]3- octahedron is divided into two parts: 1P1 → 1S0 (490 nm) and 3P1 → 1S0 (625 nm). The broad-band emission, high PLQY, and excellent stability endow the Cs2ZrCl6:xSb3+ powders with the potential for the fabrication of white light-emitting diodes (WLEDs). A WLED device is fabricated using a commercial 310 nm NUV chip, which shows a high color rendering index of 89.7 and a correlated color temperature of 5333 K. In addition, the synthesized Cs2ZrCl6:xSb3+ crystals can be also successfully used for information encryption. Our work will provide a deep understanding of the photophysical properties of Sb3+-doped perovskites and facilitate the development of Cs2ZrCl6:xSb3+ crystals in encrypting multilevel optical codes and WLEDs.

Achieving High-Efficiency Large-Area Luminescent Solar Concentrators.

Luminescent solar concentrators (LSCs) are semitransparent windows that are able to generate electricity from sunlight absorption. LSCs have shown huge promise for realizing building-integrated photovoltaics (BIPV). Unfortunately, to date, the power conversion efficiency (PCE) of LSCs is still very low which dramatically hampers their practical applications. In this Perspective, We summarize and review the latest developments of LSCs by looking at different structures. Among others, we focus more on the next developments in the field of LSCs, i.e., the possibility of high PCE, large area, mass production, and durability needed for future industrial development. We hope to promote the application of uniform testing standards and to draw attention to industrial development, toxicity, and durability. Then, we will provide a critical assessment of the field of LSCs. Finally, the challenge and solution will be discussed.

High Verdet Constant Glass for Magnetic Field Sensors.

Due to the high transparency, high Verdet constant, as well as easy processing properties, rare-earth ion-doped glasses have demonstrated great potential in magneto-optical (MO) applications. However, the variation in the valence state of rare-earth ions (Tb3+ to Tb4+) resulted in the decreased effective concentration of the paramagnetic ions and thus degraded MO performance. Here, a strategy was proposed to inhibit the oxidation of Tb3+ into Tb4+ as well as improve the thermal stability by tuning the optical basicity of glass networks. Moreover, the depolymerization of the glass network was modulated to accommodate more Tb ions. Thus, a record high effective concentration (14.19 × 1021/cm3) of Tb ions in glass was achieved, generating a high Verdet constant of 113 rad/(T·m) at 650 nm. Lastly, the first application of MO glass for magnetic field sensors was demonstrated, achieving a sensitivity of 0.139 rad/T. We hope our work provides guidance for the fabrication of MO glass with high performance and thermal stability and could push MO glass one step further for magnetic sensing applications.

Boosting efficiency of luminescent solar concentrators using ultra-bright carbon dots with large Stokes shift.

Luminescent solar concentrators (LSCs) are able to collect sunlight from a large-area to generate electric power with a low cost, showing great potential in building-integrated photovoltaics. However, the low efficiency of large-area LSCs caused by the reabsorption losses is a critical issue that hampers their practical applications. In this work, we synthesized novel yellow emissive carbon dots (CDs) with a large Stokes shift of 193 nm, which exhibit nearly zero reabsorption. The quantum yield (QY) of the yellow emitting CDs is up to 61%. The yellow emitting CDs can be employed to fabricate high-performance large-area LSCs due to successful suppression of the reabsorption losses. The as-prepared LSCs are able to absorb 14% of the sunlight as the absorption of the CDs matches well with the sun's spectrum. The large-area LSC (10 × 10 cm2) with a laminated structure based on the yellow emitting CDs achieves an optical conversion efficiency (ηopt) of 4.56% and power conversion efficiency (ηPCE) of 4.1% under natural sunlight (45 mW cm-2), which are significantly higher than other previously reported works with similar sizes. Furthermore, the prepared high-performance LSCs show good stability. This method of synthesizing novel CDs for high-efficiency LSCs provides a useful platform for future study and practical application of LSCs.

Percolative Channels for Superionic Conduction in an Amorphous Conductor.

All-solid-state batteries greatly rely on high-performance solid electrolytes. However, the bottlenecks in solid electrolytes are their low ionic conductivity and stability. Here we report a new series of amorphous xAgI·(1-x)Ag3PS4 (x = 0∼0.8 with interval of 0.1) conductors, among which the sample with x = 0.8 exhibits the highest ionic conductivity (about 1.1 × 10-2 S cm-1) and ultrahigh chemical stability. We discovered the existence of mixed disordered Ag3PS4 and AgI clusters in the amorphous conductors using solid-state nuclear magnetic resonance spectroscopy. The high ionic conductivity was ascribed to the formation of the interconnecting AgI clusters, i.e., the percolative channels for superionic conduction. The composition dependence of the ionic conductivity for this series of amorphous conductors was clarified by a continuum percolation model. These findings provide fundamental guidance for designing and fabricating high-performance amorphous solid electrolytes for all-solid-state batteries.

Achieving Ultrahigh Efficiency Vacancy-Ordered Double Perovskite Microcrystals via Ionic Liquids.

Lead-free perovskites have gained much interest for photovoltaic and optoelectronic applications. But instability and low quantum efficiency significantly limit their prospects for future applications. Here, a general route is reported to synthesize highly stable lead-free perovskites on a large scale with remarkably enhanced quantum efficiency. Two typical vacancy-ordered double perovskites (Cs2 ZrCl6 and Cs2 SnCl6 ) and their corresponding Bi3+ or Sb3+ doped samples are synthesized in ionic liquids (ILs) solutions via a simple solution method. These prepared perovskite samples all exhibit high-quality crystalline structures and their photoluminescence quantum yields (PLQYs) all show an increase close to 200% compared to the samples prepared in the hydrochloric acid system. The PLQY of Sb-doped Cs2 ZrCl6 with excellent thermal stability can reach up to 90.2%, which is the highest value reported for this system (Cs2 ZrCl6 :Sb). Density functional theory calculations reveal that the corresponding interaction between the ILs and the samples can effectively improve the crystal quality and reduce energy loss. The potential applications of the prepared samples for high-performance white light-emitting diodes and optical anti-counterfeiting are also demonstrated. The findings provide a straightforward way to obtain ultrahigh quantum efficiency vacancy-ordered double perovskites with good thermal stability and excellent optoelectronic properties.

Fast HCl-free Synthesis of Lead-free Rb2ZrCl6:xSb3+ Perovskites.

Due to the toxicity and instability issues of lead halide perovskites, lead-free perovskites have recently emerged as a viable alternative. However, significant optical band gaps of lead-free perovskites exert influence on their luminescent properties. Fortunately, the addition of dopants becomes an efficacious solution. The current widely utilized methods for synthesizing perovskites almost require high temperatures, a long period, and atmosphere protection, which cost more energy and resources. In this paper, we report that Rb2ZrCl6:xSb3+ perovskite phosphors can be easily prepared by a wet grinding approach at room temperature, which is a more efficient and facile process. Due to the self-trapped excitons of the host structure and Sb3+ ions, the produced samples display blue-white and orange fluorescence under UV lamp irradiation at 254 and 365 nm, respectively. In the photoluminescence spectrum, the doped perovskite exhibits an emission peak at 630 nm under excitation at 365 nm. Importantly, the prepared phosphors have tunable emissions related to the excitation wavelength. In addition, our produced powders show remarkable stability at room temperature, laying the foundations for this approach to be widely used in perovskite production.