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.

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.

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.

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.

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.

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.

Defective Nature of CdSe Quantum Dots Embedded in Inorganic Matrices.

Quantum dots (QDs) embedded in inorganic matrices have been extensively studied for their potential applications in lighting, displays, and solar cells. While a significant amount of research studies focused on their experimental fabrication, the origin of their relatively low photoluminescence quantum yield has not been investigated yet, although it severely hinders practical applications. In this study, we use time-dependent density functional theory (TDDFT) to pinpoint the nature of excited states of CdSe QDs embedded in various inorganic matrices. The formation of undercoordinated Se atoms and nonbridging oxygen atoms at the QD/glass interface is responsible for the localization of a hole wave function, leading to the formation of low-energy excited states with weak oscillator strength. These states provide pathways for nonradiative processes and compete with radiative emission. The photoluminescence performance is predicted for CdSe QDs in different matrices and validated by experiments. The results of this study have significant implications for understanding the underlying photophysics of CdSe QDs embedded in inorganic matrices that would facilitate the fabrication of highly luminescent glasses.

Ionic Liquid-Assisted Fast Synthesis of Carbon Dots with Strong Fluorescence and Their Tunable Multicolor Emission.

Conventional synthesis of carbon dots (CDs) mostly involves a hydrothermal or solvent-thermal reaction which needs relatively high temperature and pressure. In this work, ionic liquid is used to assist in fast synthesizing CDs with an ultrahigh photoluminescent quantum yield (98.5%) by heating at a low temperature (≤100 °C) and at atmospheric pressure. In addition, through this approach, tunable multicolor emissive CDs can be successfully achieved and used for preparing high-performance white light-emitting diodes. Theoretical computation proves that the activity of synthesis reaction can be significantly enhanced by ionic liquids. Density functional theory calculation reveals that the size and graphite nitrogen ratios of CDs have an effect on bandgap reduction, resulting in a redshift of the emission, which is in good agreement with the experimental results. This simple and promising approach for fast synthesis of tunable emissive CDs using ionic liquid affords the facilitation of CDs-based luminescent materials for fast manufacturing of functional devices.

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.

A light-heat synergism in the sub-bandgap photocatalytic response of pristine TiO2: a study of in situ diffusion reflectance and conductance.

Pristine TiO2 materials are mainly used as photocatalysts under super-bandgap light illumination. The sub-bandgap (SBG) photocatalytic response has seldom been investigated and the mechanism of action remains unclear. In the current research, we firstly study the SBG light electronic transition of pristine P25 TiO2 by means of in situ diffusion reflectance and (photo)conductance measurements under finely controllable conditions. It is revealed that the SBG light can promote valence band (VB) electrons to the exponentially-distributed gap states of the TiO2, which can then be thermally activated to the CB states. A hole in the VB and an electron in the CB can be generated by the synergism of a SBG photon and heat. It is also seen that the photoinduced electrons can transfer to O2 through the CB states, and that the holes can be captured by isopropanol molecules. As a result, isopropanol dehydrogenation can occur over pristine TiO2 under SBG light illumination. It is seen that the photocatalytic activity increases with temperature and the energy of the SBG photons, in agreement with the light-heat synergistic electric transition via the exponential gap states. The present research reveals a mechanism for the SBG light photocatalytic response of pristine TiO2 materials, which is important in designing highly-active visible light active photocatalysts.

Kinetics and energetic analysis of the slow dispersive electron transfer from nano-TiO2 to O2 by in situ diffusion reflectance and Laplace transform.

Electron transfer to O2 is a universally existing process for the physiochemistry of many materials. Electron transfer to O2 is also an inevitable process for photocatalytic reactions over TiO2 and other materials. In the present research, a diffusion reflectance system was developed to measure in situ optical diffusion reflectances caused by photoinduced electrons in nano-TiO2 under a steady light illumination; in situ absorption decays can be obtained to study the electron transfer from their trapped states to O2. It is seen that the kinetics of electron transfer to O2 is persistent and dispersive; this lasts for several minutes and approximately agrees with a stretched exponential kinetics. The result implies that variable apparent energy barriers (Eis) are involved in the electron transfer. The effects of O2 amount, light intensity, and temperature are studied and the results mean the trap-filling effect should be involved in the electron transfer to O2. A Laplace transform is used to derive the Ei distributions. It is found that the Ei dispersion shape almost does not change; this indicates that the physical reason causing the Ei dispersion is the same for different experimental conditions and possibly comes from the trap-filling effect. It is shown that the slow kinetics of the electron transfer is also dependent on the slow rate for an electron transferring from a trap to O2, in additional to the trapping-filling effect. The results indicate that the photocatalytic activity can be increased through a modulation in trap distribution.

The effect of Cu dopants on electron transfer to O2 and the connection with acetone photocatalytic oxidations over nano-TiO2.

Modifying TiO2 with the Cu element has been shown to be useful for photocatalysis. Although it had been known that Cu species could trap electrons from TiO2, whether they can affect the kinetics of electron transfer and how this can contribute to photocatalysis still remain unknown. In the current research, Cu-TiO2 samples were firstly prepared with a hydrothermal reaction and characterized in detail. It was shown that Cu elements were doped in the TiO2 lattice in +1/0 valence states and have a minor effect on the TiO2 structure. By means of photoconductances, it is shown that the Cu dopants could catalyze the electron transfer from TiO2 to O2 by reducing the apparent activation energy (Eapp) by about 2 times. The photocatalytic experiments conducted at different temperatures showed that the Eapp of the acetone photocatalytic oxidations could be decreased by ∼2 times; this implies that the Cu dopants change the photocatalytic pathway. First-principles computation showed that the surface Cu dopants, along with the compensated oxygen vacancies, can mediate both of the electron and hole transfer. By combining other studies, we proposed that the Cu sites could act as Lewis acid and base pairs that could combine with acetone and O2 molecules under UV light illumination; this allows electron transfer to O2via the Cu sites that then react with acetone. As compared to pure TiO2 surfaces, the different chemical environment of the Cu sites leads to the decrease in the Eapp of photocatalysis.

Ab Initio Molecular Dynamics of CdSe Quantum-Dot-Doped Glasses.

We have probed the local atomic structure of the interface between a CdSe quantum dot (QD) and a sodium silicate glass matrix. Using ab initio molecular dynamics simulations, we determined the structural properties and bond lengths, in excellent agreement with previous experimental observations. On the basis of an analysis of radial distribution functions, coordination environment, and ring structures, we demonstrate that an important structural reconstruction occurs at the interface between the CdSe QD and the glass matrix. The incorporation of the CdSe QD disrupts the Na-O bonds, while stronger SiO4 tetrahedra are reformed. The existence of the glass matrix breaks the stable 4-membered (4MR) and 6-membered (6MR) Cd-Se rings, and we observe a disassociated Cd atom migrated in the glass matrix. Besides, the formation of Se-Na and Cd-O linkages is observed at the CdSe QD/glass interface. These results significantly extend our understanding of the interfacial structure of CdSe QD-doped glasses and provide physical and chemical insight into the possible defect structure origin of CdSe QD, of interest to the fabrication of the highly luminescent CdSe QD-doped glasses.

Surfactant-Modified Hydrothermal Synthesis of Ca-Doped CuCoO2 Nanosheets with Abundant Active Sites for Enhanced Electrocatalytic Oxygen Evolution.

It is urgent to explore cost-effective, high-efficiency, and durable electrocatalysts for electrochemical water splitting due to the rapidly increasing energy consumption. In this work, we successfully synthesize Ca-doped CuCoO2 nanosheets (CCCO-P NSs) with different Ca2+ dopants (such as 3, 5, and 10 atom %) by a surfactant-modified hydrothermal reaction with polyvinylpyrrolidone (PVP) addition. The oxygen evolution reaction (OER) performances of these CCCO-P NSs in 1.0 M KOH are investigated. An optimal nickel foam supported CCCO-P2 NSs (Ni@CCCO-P2, 5 atom % Ca-doped) electrode requires low overpotential of 470 mV to afford the current density of 10 mA cm-2 and small Tafel slope of 96.5 mV dec-1. Furthermore, the Ni@CCCO-P2 electrode displays outstanding long-term stability during the galvanostatic OER electrolysis for 18 h with a little degradation of 32 mV. The improvement of OER performances for CCCO-P2 NSs could be attributed to their higher active surface area, more active sites (Co vacancies defect and Co3+/Co4+ redox pairs), and higher electrical conductivity. This work highlights the joint effect of surfactant and Ca doping for preparing CuCoO2 with nanosheet-like morphology and porous crystal structure, which is favorable for enhancing their OER performance.

Durable Self-Cleaning Surfaces with Superhydrophobic and Highly Oleophobic Properties.

Functional surfaces with superhydrophobic and superoleophobic properties are of great interest in many applications. However, such surfaces are generally difficult to obtain. Although a few superamphiphobic surfaces have been developed recently, a challenge still remains in preparing such a surface with good durability which is a critical issue in practical application. In this study, we demonstrate a facile method for preparing durable superhydrophobic and highly oleophobic surfaces using two kinds of nanoparticles. Epoxy resin is used as the adhesive material to improve the wear resistance of the surfaces. ZnO nanoparticles and SiO2 nanoparticles are used to create high surface roughness. The prepared surfaces exhibit excellent superhydrophobicity and high oleophobicity once the nanoparticles are treated with 1 H,1 H,2 H,2 H-perfluorodecyltriethoxydsilane (FAS-17). Water and ethylene glycol contact angles of the coatings can reach up to 172 ? 2? and 157 ? 2?, respectively. After undergoing strong adhesive tape peeling and mechanical abrasion, the coatings still maintain good amphiphobicity.

Near-infrared anti-Stokes photoluminescence of PbS QDs embedded in glasses.

Near-infrared photoluminescence properties of PbS QDs embedded in glasses were investigated upon below-bandgap excitation. PbS QDs were precipitated in the glasses upon thermal treatment. Near-infrared anti-Stokes photoluminescence (ASPL) from PbS QDs was observed. Dependence of the ASPL on size and excitation power indicated that ASPL was phonon-assisted one-photon process. These near-infrared anti-Stokes photoluminescence of PbS QDs in glasses have potential applications for light conversion and laser cooling.

The role of electron interfacial transfer in mesoporous nano-TiO2 photocatalysis: a combined study of in situ photoconductivity and numerical kinetic simulation.

In this research, a combination of in situ photoconductivity (σ) and kinetic simulations was used to study the role of electron interfacial transfer (IT) in the gaseous photocatalysis of formic acid by mesoporous nanocrystalline TiO2. The effects of light intensity, initial formic acid concentrations, oxygen amounts, and temperature on the in situ σ and the photocatalytic courses were studied in detail. The temperature dependence of in situ σ clearly shows that the electron transfer is determined by the IT of electrons to O2 rather than by the transport. It was seen that the electron IT limits the photocatalysis by correlating with the recombination and the hole IT via the dynamic change in electron densities. The numerical simulation of in situ σ shows that the IT of electrons belongs to a thermally activated process that presents a thermal barrier of 0.5 eV. It is considered that this high thermal barrier limits the IT of electrons. It was also seen that the thermal activation of photocatalysis does not relate to that of the electron IT, although the overall photocatalysis is limited by the IT of electrons. Our finding shows that it is an effective way to increase the photocatalytic activity by reducing the thermal barrier of electron IT.