Comprehensive Mechanism for CO Electroreduction on Dual-Atom-Catalyst-Anchored N-Doped Graphene.

Carbon neutrality has drawn increasing attention for realizing the carbon cyclization and reducing the greenhouse effect. Although the C1 products, such as CO, can be achieved with a high Faraday efficiency, the targeted production of C2 fuels as well as the mechanism have not been systematically investigated. In this work, we carry out a first-principles study to screen dual-atom catalysts (DACs) for producing C2 fuels through the electrocatalytic carbon monoxide reduction reaction (e-CORR). We find that methanol, ethanol and ethylene can be produced on both DAC-Co and DAC-Cu, while acetate can be achieved on DAC-Cu only. Importantly, methanol and ethylene are preferred on DAC-Co, while acetate and ethylene on DAC-Cu. Furthermore, we show that the explicit solvent can enhance the adsorption and influence the protonation steps, which subsequently affects the protonation and dimerization behavior as well as the performance and selectivity of e-CORR on DACs. We further demonstrate that the C-C coupling is easy to be formed and stabilized if the Integrated Crystal Orbital Hamilton Population (ICOHP) is low because of the low energy barrier. Our findings provide not only guidance on the design of novel catalysts for e-CORR, but an insightful understanding on the reduction mechanism.

Ultraviolet photodetector based on RbCu2I3microwire.

Copper-based halide perovskites have shown great potential in lighting and photodetection due to their excellent photoelectric properties, good stability and lead-free nature. However, as an important piece of copper-based perovskites, the synthesis and application of RbCu2I3have never been reported. Here, we demonstrate the synthesis of high-quality RbCu2I3microwires (MWs) by a fast-cooling hot saturated solution method. The prepared MWs exhibit an orthorhombic structure with a smooth surface. Optical measurements show the RbCu2I3MWs have a sharp ultraviolet absorption edge with 3.63 eV optical band gap and ultra-large stokes shift (300 nm) in photoluminescence. The subsequent photodetector based on a single RbCu2I3MW shows excellent ultraviolet detection performance. Under the 340 nm illumination, the device shows a specific detectivity of 5.0 × 109Jones and a responsivity of 380 mA·W-1. The synthesis method and physical properties of RbCu2I3could be a guide to the future optoelectronic application of the new material.

The fatigue effects in red emissive CdSe based QLED operated around turn-on voltage.

The operational stability is a current bottleneck facing the quantum dot light-emitting diodes (QLEDs). In particular, the device working around turn-on voltage suffers from unbalanced charge injection and heavy power loss. Here, we investigate the operational stability of red emissive CdSe QLEDs operated at different applied voltages. Compared to the rising luminance at higher voltages, the device luminance quickly decreases when loaded around the turn-on voltage, but recovers after unloading or slight heat treatment, which is termed fatigue effects of operational QLED. The electroluminescence and photoluminescence spectra before and after a period of operation at low voltages show that the abrupt decrease in device luminance derives from the reduction of quantum yield in quantum dots. Combined with transient photoluminescence and electroluminescence measurements, as well as equivalent circuit model analysis, the electron accumulation in quantum dots mainly accounts for the observed fatigue effects of a QLED during the operation around turn-on voltage. The underlying mechanisms at the low-voltage working regime will be very helpful for the industrialization of QLED.

Giant moiré trapping of excitons in twisted hBN.

Excitons in van der Waals (vdW) stacking interfaces can be trapped in ordered moiré potential arrays giving rise to the attractive phenomena of quantum optics and bosonic many-body effects. Compared to the prevalent transition metal dichalcogenides (TMDs) systems, due to the wide bandgap and low dielectric constant, excitons in twist-stacked hexagonal boron nitride (hBN) are anticipated trapped in deeper moiré potential, which enhances the strength of interactions. However, constrained by the common low detectivity of weak light-emitting in the deep-ultraviolet (DUV) bands, the moiré excitons in twist-hBN remain elusive. Here, we report that a remarkable DUV emitting band (peak located at ∼260 nm) only emerges at the twisted stacking area of hBN, which is performed by a high collection efficiency and spatially-resolved cathodoluminescence (CL) at room temperature. Significant peak red shifting contrast to defect-bound excitons of bulk hBN indicates the giant trapping effects of moiré potential for excitons. The observation of deeply trapped excitons motivates further studies of bosonic strongly correlation physics based on the twist-hBN system.

Fast Response Organic Tandem Photodetector for Visible and Near-Infrared Digital Optical Communications.

Organic photodetectors (OPDs), which usually work as photodiodes, photoconductors, or phototransistors, have emerged as candidates for next-generation light sensing. However, low response speed caused by low carrier mobility and resistance-capacitance (RC) time constant, severely hinders the commercialization of OPDs. Herein, the authors demonstrate a state-of-the-art OPD with a record response speed of 146.8 ns by employing tandem structure to simultaneously reduce both the carrier transit time and RC time constant of the device, which is faster than that of previously reported OPDs as far as they know. Moreover, benefitting from the multi-level barrier enhancement and voltage division engendered by tandem structure, an ultralow noise current of 7.82 × 10-14 A Hz-1/2 is obtained, as well as a wide detection range in 300-1000 nm. In addition, the tandem OPDs are successfully integrated into the optical communication system as signal receivers, demonstrating the precise digital signal communication from visible to near-infrared light. It is believed that tandem OPDs have promising application potential in the wireless transmission system.

Aligned Millineedle Arrays for Solar Power Seawater Desalination with Site-Specific Salt Formation.

As a sustainable and clean water production technology, solar thermal water evaporation has been extensively studied in the past few years. One challenge is that upon operation, salt would form on surface of the solar absorbers leading to inefficient water supply and light absorption and thus much reduced water vaporization rate. To address this problem, a simple solar evaporator based on an array of aligned millineedles for efficient solar water evaporation and controlled site-specific salt formation is demonstrated. The maximum solar evaporation rate achieved is 2.94 kg m-2 h-1 under one Sun irradiation in brine of high salinity (25 wt% NaCl), achieving energy conversion efficiency of 94.5% simultaneously. More importantly, the spontaneously site-specific salt formation on the tips of millineedles endows this solar evaporator with salt harvesting capacity. Rationally separating the clean water and salt from brine by condensation and gravity assistance, this tip-preferential crystallization solar evaporator is not affected by the salt clogging compared with conventional 2D solar evaporators. This study provides new insights on the design of solar evaporators and advances their applications in sustainable seawater desalination and wastewater management.

Stable and Efficient Blue-Emitting CsPbBr3 Nanoplatelets with Potassium Bromide Surface Passivation.

Colloidal all-inorganic perovskites nanocrystals (NCs) have emerged as a promising material for display and lighting due to their excellent optical properties. However, blue emissive NCs usually suffer from low photoluminescence quantum yields (PLQYs) and poor stability, rendering them the bottleneck for full-color all-perovskite optoelectronic applications. Herein, a facile approach is reported to enhance the emission efficiency and stability of blue emissive perovskite nano-structures via surface passivation with potassium bromide. By adding potassium oleate and excess PbBr2 to the perovskite precursor solutions, potassium bromide-passivated (KBr-passivated) blue-emitting (≈450 nm) CsPbBr3 nanoplatelets (NPLs) is successfully synthesized with a respectably high PLQY of 87%. In sharp contrast to most reported perovskite NPLs, no shifting in emission wavelength is observed in these passivated NPLs even after prolonged exposures to intense irradiations and elevated temperature, clearly revealing their excellent photo- and thermal-stabilities. The enhancements are attributed to the formation of K-Br bonding on the surface which suppresses ion migration and formation of Br-vacancies, thus improving both the PL emission and stability of CsPbBr3 NPLs. Furthermore, all-perovskite white light-emitting diodes (WLEDs) are successfully constructed, suggesting that the proposed KBr-passivated strategy can promote the development of the perovskite family for a wider range of optoelectronic applications.

Development of Perovskite Oxide-Based Electrocatalysts for Oxygen Evolution Reaction.

Perovskite oxides are studied as electrocatalysts for oxygen evolution reactions (OER) because of their low cost, tunable structure, high stability, and good catalytic activity. However, there are two main challenges for most perovskite oxides to be efficient in OER, namely less active sites and low electrical conductivity, leading to limited catalytic performance. To overcome these intrinsic obstacles, various strategies are developed to enhance their catalytic activities in OER. In this review, the recent developments of these strategies is comprehensively summarized and systematically discussed, including composition engineering, crystal facet control, morphology modulation, defect engineering, and hybridization. Finally, perspectives on the design of perovskite oxide-based electrocatalysts for practical applications in OER are given.

Multi-Phase Heterostructure of CoNiP/Cox P for Enhanced Hydrogen Evolution Under Alkaline and Seawater Conditions by Promoting H2 O Dissociation.

Hydrogen evolution reaction (HER) is a key step for electrochemical energy conversion and storage. Developing well defined nanostructures as noble-metal-free electrocatalysts for HER is promising for the application of hydrogen technology. Herein, it is reported that 3D porous hierarchical CoNiP/Cox P multi-phase heterostructure on Ni foam via an electrodeposition method followed by phosphorization exhibits ultra-highly catalytic activity for HER. The optimized CoNiP/Cox P multi-phase heterostructure achieves an excellent HER performance with an ultralow overpotential of 36 mV at 10 mA cm-2 , superior to commercial Pt/C. Importantly, the multi-phase heterostructure shows exceptional stability as confirmed by the long-term potential cycles (30,000 cycles) and extended electrocatalysis (up to 500 h) in alkaline solution and natural seawater. Experimental characterizations and DFT calculations demonstrate that the strong electronic interaction at the heterointerface of CoNiP/CoP is achieved via the electron transfer from CoNiP to the heterointerface, which directly promotes the dissociation of water at heterointerface and desorption of hydrogen on CoNiP. These findings may provide deep understanding on the HER mechanism of heterostructure electrocatalysts and guidance on the design of earth-abundant, cost-effective electrocatalysts with superior HER activity for practical applications.

Theoretical evidence of the spin-valley coupling and valley polarization in two-dimensional MoSi2X4 (X = N, P, and As).

Very recently, the centimeter-scale MoSi2N4 monolayer was synthesized experimentally and exhibited a semiconducting nature with high mobility (Hong et al., Science, 2020, 369, 670-674). Here, we show that MoSi2N4 and its analogues, MoSi2P4 and MoSi2As4, are potential two-dimensional (2D) materials for valleytronics based on first-principles calculations. We demonstrate that the intrinsic inversion symmetry breaking and strong spin-orbital coupling lead to the remarkable spin-valley coupling in the inequivalent valleys at K and K' points, which result in not only the valley-contrasting transport properties, but also the spin and valley coupled optical selection rules. Moreover, the in-plane strain can tune the bandgaps and spin splitting or even induce an indirect-to-direct bandgap transition for promising application in the strain-tunable valleytronics. We find that the valley polarization can be generated by doping magnetic element. Our findings offer theoretical insight into the exotic physical properties of novel MoSi2N4-family materials beyond transition metal dichalcogenides.

A simple method for the preparation of multi-color carbon quantum dots by using reversible regulatory color transformation.

It is known that polychromatic carbon quantum dots (CQDs) can be obtained by doping and surface modification. The layer-wise synthesis of blue and green emitting CQDs (with typical sizes between 3 and 6 nm) is described here by adding oxalic acid and by introducing polycarboxy groups. By changing the external environment, the emission of CQDs can be adjusted in the blue-green spectral region (469-527 nm) under photoexcitation at 405 nm. The findings presented here provide new directions for the reversible regulatory transformation of polychromatic CQDs. The luminescence also is affected by a variety of conditions such as surface defects, degree of polymerization, polarity of external solutions, and hydrogen bonding which is studied in some detail. Graphical abstract Schematic presentation of the blue-green fluorescent transformation of the green carbon quantum dots(G-CQDs) to blue carbon quantum dots(B-CQDs).

Fluorometric determination of pesticides and organophosphates using nanoceria as a phosphatase mimic and an inner filter effect on carbon nanodots.

Nanoceria with a remarkable phosphatase mimicking activity was synthesized and used to catalyze the hydrolysis of phosphate esters in pH 10 solution. The catalytic effect of nanoceria was firstly investigated by selecting p-nitrophenyl phosphate as a model substrate. The pH value, incubation temperature, reaction time, and concentration of nanoceria were optimized. The catalytic effect was then confirmed by using methyl-paraoxon as a substrate. The p-nitrophenol anion released by the enzyme mimic is yellow and exerts an inner filter effect on the fluorescence of the carbon dots (with excitation/emission maxima at 400/520 nm). Response to methyl-paraoxon is linear in the 1.125-26.25 µmol L-1 concentration range. The method was applied to the determination of pesticides in spiked Panax quinquefolius and water samples. Recoveries ranged from 85 to 103% (n = 3). The technique is rapid, reliable, and can be used for on-site detection of pesticides and organophosphates. Graphical abstract Schematic presentation of a fluorometric technique for the detection of organophosphate compound and pesticide using nanoceria as a phosphatase mimic and an inner filter effect on the blue fluorescence of carbon dots (with excitation/emission maxima at 400/520 nm).

Mixed Two-Dimensional Organic-Inorganic Halide Perovskites for Highly Efficient and Stable Photovoltaic Application.

Solar cells made of hybrid organic-inorganic perovskite (HOIP) materials have attracted ever-increasing attention due to their high efficiency and easy fabrication. However, issues regarding their poor stability remain a challenge for practical applications. Engineering the composition and structure of HOIP can effectively enhance the thermal stability and improve the power conversion efficiency (PCE). In this work, mixed two-dimensional (2D) HOIPs are systematically investigated for solar-power harvesting using first-principles calculations. We find that their electronic properties depend strongly on the mixed atoms (Cs, Rb, Ge and Pb) and the formation energy is related to the HOIP's composition, where the atoms are more easily mixed in SnI-2D-HOIPs due to low formation energy at the same composition ratio. We further show that optimal solar energy harvesting can be achieved on the solar cells composed of mixed SnI-2D-HOIPs because of reduced bandgaps, enhanced mobility and improved stability. Importantly, we find that the mixed atoms (Cs, Rb, Ge and Pb) with the appropriate composition ratios can effectively enhance the solar-to-power efficiency and show greatly improved resistance to moisture. The findings demonstrate that mixed 2D-HOIPs can replace the bulk HOIPs or pure 2D-HOIPs for applications into solar cells with high efficiency and stability.

Transparent ultraviolet photovoltaic cells.

Photovoltaic cells have been fabricated from p-GaN/MgO/n-ZnO structures. The photovoltaic cells are transparent to visible light and can transform ultraviolet irradiation into electrical signals. The efficiency of the photovoltaic cells is 0.025% under simulated AM 1.5 illumination conditions, while it can reach 0.46% under UV illumination. By connecting several such photovoltaic cells in a series, light-emitting devices can be lighting. The photovoltaic cells reported in this Letter may promise the applications in glass of buildings to prevent UV irradiation and produce power for household appliances in the future.

Black-colored ZnO nanowires with enhanced photocatalytic hydrogen evolution.

Black-colored ZnO nanowires have been prepared in a metal-organic chemical vapor deposition system by employing a relatively low growth temperature and oxygen-deficient conditions. X-ray photoelectron spectroscopy reveals the incorporation of carbon into the nanowires. The photocatalytic hydrogen evolution activity of the black-colored ZnO nanowires is over 2.5 times larger than that of the pristine ZnO nanowires under simulated solar illumination conditions, and the enhanced photocatalytic activity can be attributed to the higher absorption of visible light by the black color and better carrier separation at the ZnO/carbon interface.

Ultra-low threshold avalanche gain from solar-blind photodetector based on graded-band-gap-cubic-MgZnO.

A larger ratio of conduction-band offset to valence-band offset is the unique character for Mg(x)Zn(1-x)O alloys. For this reason, it is feasible to build a quasi-electric forces, caused by the spatial gradient of the conduction edge, exerting on the electrons. In this paper, a novel graded band gap cubic-MgZnO-based solar-blind photodetector is successfully fabricated from Graded-Band-Gap-Cubic-MgZnO/i-MgO/p-Si heterojunction, via changing stoichiometry spatial gradient. Due to quasi-electric fields in non-uniform MgZnO, the multiple carriers are generated under ultra-low threshold bias voltage. The photodetector showed high performance, namely, high responsivity, quantum efficiency, high sensitivity and selectivity towards the solar-blind spectrum, and fast response times.

[Optical Properties Investigation of p-Type ZnO Film Based on Doping by Diffusion].

The main purpose of this paper is to investigate the optical properties of p-type ZnO film based on P doping. ZnO film was grown by Atomic layer deposition (ALD) on InP subsrate in this experiment, and phosphorus diffused into ZnO lattice by annealing treatment at different temperature (500, 700 °C). The optical properties of samples were investigated by photoluminescence (PL) spectroscopy, which indicated that the annealing temperature is the important factor influencing the phosphorus diffusion doping. The low-temperature PL spectra of the sample which annealed at 700 °C for 1 h exhibited acceptor related emission peaks located at 3.351, 3.311, 3.246 and 3.177 eV, which were attributed to A °X, FA, DAP and DA-1LO, respectively. The acceptor binding energy is estimated to be about 122 meV, which is agreed with the theoretic values in phosphorus-doped ZnO films. In this paper, through thermal diffusion method to realize the p-type doped ZnO thin films, it solved the main problems which limited the development of ZnO based optoelectronic devices, and has an important significance for the development of the ZnO semiconductor materials and ZnO based photoelectric device.

Graphene induced high-Q hybridized plasmonic whispering gallery mode microcavities.

A novel hybridized plasmonic whispering gallery mode (WGM) microcavities composed of graphene monolayer coated ZnO microrod with hexagonal cross section were proposed that operates in the ultraviolet region. π and π + σ surface plasmon modes in graphene monolayer at 4.7 eV and 14.6 eV can be used to achieve the near field coupling interaction between surface plasmonic modes and the conventional WGM microcavity modes in the ultraviolet band. Significantly, the coupling, happened in the evanescent wave field excited along the interface between ZnO and graphene, can lead to distinct optical field confinement and lasing enhancement experimentally, so as well as WGM lasing characteristics, such as the higher cavity quality factor (Q), narrower linewidth, lasing intensities enhancement. The results could provide a platform to study hybridized plasmonic cavity dynamics, and also provides the building blocks to construct graphene based novel microcavity for high performance ultraviolet laser devices with potential application to optical signal processing, biological monitoring, and so on.

Enhanced solar-blind responsivity of photodetectors based on cubic MgZnO films via gallium doping.

We report on gallium (Ga) doped cubic MgZnO films, which have been grown by metal organic chemical vapor deposition. It was demonstrated that Ga doping improves the n-type conduction of the cubic MgZnO films. A two-orders of magnitude enhancement in lateral n-type conduction have been achieved for the cubic MgZnO films. The responsivity of the cubic MgZnO-based photodetector has been also enhanced. Depletion region electric field intensity enhanced model was adopted to explain the improvement of quantum efficiency in Ga doped MgZnO-based detectors.

Pure ultraviolet emission from ZnO nanowire-based p-n heterostructures.

Well-aligned ZnO nanowires have been prepared on sapphire substrate, and structural and optical characterizations indicate that the nanowires are of single crystalline and have relatively high luminescent quality. By employing the ZnO nanowires as an active layer, p-Zn0.68Mg0.32O:N/n-ZnO nanowire heterostructure light-emitting devices (LEDs) have been fabricated. The LEDs show pure ultraviolet emission when a forward bias is applied, while the deep-level emission frequently observed in ZnO p-n junctions is almost totally invisible. The devices can work continuously for over 27 h under the injection of a current density of 500 mA/cm2, indicating their good stability.