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Lead halide perovskites (LHPs) have attracted a tremendous amount of attention because of their applications in solar cells, lighting, and optoelectronics. However, the atomistic principles underlying their decomposition processes remain in large part obscure, likely due to the lack of precise information about their local structures and composition along regions with dimensions on the angstrom scale, such as crystal interfaces. Aberration-corrected scanning transmission electron microscopy combined with X-ray energy dispersive spectroscopy (EDS) is an ideal tool, in principle, for probing such information. However, atomic-resolution EDS has not been achieved for LHPs because of their instability under electron-beam irradiation. We report the fabrication of CsPbBr

We would like to acknowledge King Abdullah University of Science and Technology for funding. We also acknowledge KAUST NMR core lab for their continuous help. We acknowledge as well the KAUST Imaging Core Lab, particularly Dr. Alessandro Genovese.

Graphite has become a critical material because of its essential role in the lithium-ion battery (LIB) industry. However, the synthesis of graphite requires an energy-intensive thermal treatment. Also, when used in sodium-ion and potassium-ion batteries (SIBs and PIBs), the graphite anode shows poor capacities and cycling stability, which hinders the development of next-generation battery technologies. Finding suitable anode materials for commercial alkali metal-ion batteries is not only urgent for the energy storage industry, but is also important for economic and sustainable development. In this work, we use fly ash carbon (FAC), a residue of crude oil combustion, as an anode material for alkali metal-ion batteries. The FAC anodes show relatively high capacities and excellent cycling stability. The charge storage mechanism of FAC anode is shown to be intercalation coupled with redox reactions of oxygen functional groups. This work shows that FAC is a promising scalable anode material for alkali metal-ion batteries.

Converting biomass waste into high-value products presents a challenging task in the environmental field. Growth of graphene from solid-state precursors is cost-effective and is becoming a hot research topic. However, the underlying mechanisms are as yet unclear. In this work, we report a novel method for directly growing adlayer-free large area graphene from cellulose acetate, the main component of cigarette filter waste. The evolution of cellulose acetate to reduced graphene oxide and finally to graphene is shown in this work for the first time. The effect of various growth parameters, hydrogen concentration and Cu grain boundaries on the size and qualities of the monolayer graphene domains is clarified. Finally, the mechanism for the growth of graphene from a solid-state precursor is proposed. The field-effect-transistor fabricated from transferred monolayer graphene demonstrated high electron and hole mobilities ∼1500 cm2/(V·s). This work presents a new opportunity for converting biomass waste into high-value graphene products.

Vanadium dioxide (VO2) has emerged as a promising micro-actuator material for its large amplitude and high work density across the transition between the insulating (M1 and M2) and metallic (R) phase. Even though M2–R transition offers about 70% higher transformation stress than M1–R structural phase transition, the application of the M2 phase in the micro-actuators is hindered by the fact that previously, M2 phase can only stay stable under tensile stress. In this work, we propose and verify that by synthesizing the VO2 nanowires under optimized oxygen-rich conditions, stoichiometry change can be introduced into the nanowires (NWs) which in turn yield a large number free-standing single-crystalline M2-phase NWs stable at room temperature. In addition, we demonstrate that the output stress of the M2-phase NWs is about 65% higher than that of the M1-phase NWs during their transition to R phase, quite close to the theoretical prediction. Our findings open new avenues towards enhancing the performance of VO2-based actuators by using M2–R transition.

High-performance chemiresistor gas sensor made of sulfide porous GaN decorated with Pt nanoparticles, which shows tunable sensor response and enhanced sensitivity. The fabricated gas sensors show detection of H2 down to 30 ppm at 23 °C after sulfide treatment and Pt decorated porous GaN. The response time and recovery time were equal to 47 s and 113 s, respectively. Density functional theory simulations were used to support the detection mechanism based on sulfide treatment. Adsorption energy calculations showed that H adsorption energy is lowered by the simultaneous presence of S and Pt on the GaN (0001) surface. The density of states (DOS) calculations revealed possibility of bond strengthening when Pt and S is adsorbed on GaN surface along with H, arising from the hybridization of d and p orbitals of Pt and S with that of H 1s orbitals.

Polyhydrido copper nanoclusters are an emerging class of nanomaterials. Unfortunately, insights into the structural evolution and structure–property relationship of such copper nanoclusters are sca...

Recent advancements in gallium oxide (Ga2O3)-based heterostructures have allowed optoelectronic devices to be used extensively in the fields of power electronics and deep-ultraviolet photodetection. While most previous research has involved realizing single-crystalline Ga2O3 layers on native substrates for high conductivity and visible-light transparency, presented and investigated herein is a single-crystalline β-Ga2O3 layer grown on an α-Al2O3 substrate through an interfacial γ-In2O3 layer. The single-crystalline transparent conductive oxide layer made of wafer-scalable γ-In2O3 provides high carrier transport, visible-light transparency, and antioxidation properties that are critical for realizing vertically oriented heterostructures for transparent oxide photonic platforms. Physical characterization based on X-ray diffraction and high-resolution transmission electron microscopy imaging confirms the single-crystalline nature of the grown films and the crystallographic orientation relationships among the monoclinic β-Ga2O3, cubic γ-In2O3, and trigonal α-Al2O3, while the elemental composition and sharp interfaces across the heterostructure are confirmed by Rutherford backscattering spectrometry. Furthermore, the energy-band offsets are determined by X-ray photoelectron spectroscopy at the β-Ga2O3/γ-In2O3 interface, elucidating a type-II heterojunction with conduction- and valence-band offsets of 0.16 and 1.38 eV, respectively. Based on the single-crystalline β-Ga2O3/γ-In2O3/α-Al2O3 all-oxide heterostructure, a vertically oriented DUV photodetector is fabricated that exhibits a high photoresponsivity of 94.3 A/W, an external quantum efficiency of 4.6 × 104%, and a specific detectivity of 3.09 × 1012 Jones at 250 nm. The present demonstration lays a strong foundation for and paves the way to future all-oxide-based transparent photonic platforms.

A popular practice in Li-S battery research is to utilize highly nanostructured hosts and excessive electrolytes to enhance sulfur-specific capacities. However, from the perspective of commercialization, this is a less meaningful approach in the pursuit of high-energy Li-S batteries. Herein, we report the fabrication of a nanoskin composed of a conjugated microporous polymer by electropolymerization to create a closed system for a sulfur cathode. The nanoskin is ultrathin, conductive, continuous, and contains uniform micropores of approximately 0.8 nm. The nanoskin sealing prevents the shuttling of polysulfide species without using the absorption effect, enhances the utilization of electrolytes, and allows a fast transport of lithium ions. As a result, the Li-S batteries comprising the cathode with nanoskin exhibit superior stability (∼86% capacity retention) under lean electrolyte conditions and a prolonged lifetime (1000 cycles). At a low electrolyte/sulfur ratio of 4 μL mg-1, the designed cathode delivered a practical energy density of over 300 Wh kg-1 without using any sophisticated hosts.

Cesium lead halide perovskite nanocrystals (PNCs), while possessing facile chemical synthesis routes and high photoluminescence (PL) properties, are still challenged by issues of instability and de...

The electrochemical performance of aluminum-sulfur batteries is beset by poor stability and sluggish charge-storage properties. To address these issues, carbon allotropes have been used as electrod...

Solution-processed organic-inorganic hybrid perovskites have attracted attention as light-harvesting materials for solar cells and photonic applications. The present study focuses on cubic single crystals and microstructures of CH3NH3PbBr3 perovskite fabricated by a one-step solution-based self-assembly method. It is seen that, in addition to the nucleation from the precursor solution, crystallization occurs when the solution is supersaturated, followed by the formation of a small nucleus of CH3NH3PbBr3 that self-assembles into bigger hollow cubes. A three-dimensional (3D) fluorescence microscopy investigation of hollow cubes confirmed the formation of hollow plates on the bottom; then, the growth starts from the perimeter and propagates to the center of the cube. Furthermore, the growth in the (001) direction follows a layer-by-layer growth model to form a complete cube, confirmed by scanning electronic microscopy (SEM) observations. Two-dimensional (2D)-3D fluorescence microscopy and photoluminescence (PL) measurements confirm a peak emission at 535 nm. To get more insights into the structural and optical properties, density functional theory (DFT) simulations were conducted. The electronic and optical properties calculated by DFT are in agreement with the obtained experimental values. The density-of-state (DOS) calculations revealed that the valence band maximum (VBM) consists of states contributed by Br and Pb, which agrees with the X-ray photoelectron spectroscopy valence band (XPS VB) measurements.

This work was supported by Huawei Grant RGC/3/3513 and KAUST Baseline BAS/1/1375. The authors acknowledge the support from Cao Zhen for the DFT calculation.

Blue-emitting perovskites can be easily attained by precisely tuning the halide ratio of mixed halide (Br/Cl) perovskites (MHPs). However, the adjustable halide ratio hinders the passivation of Cl ...

We acknowledge the use of KAUST Core Lab and KAUST Solar Center facilities. This work was supported by KAUST and the Office of Sponsored Research (OSR) under award no. OSR-2017-CRG-3380. F.G. is a Wallenberg Academy Fellow.

The advantages of two dimensional covalent organic framework membranes to achieve high flux have been demonstrated, but the capability of easy structural modification to manipulate the pore size has not been fully explored yet. Here we report the use of the Langmuir–Blodgett method to synthesize two ultrathin covalent organic framework membranes (TFP–DPF and TFP–DNF) that have a similar framework structure to our previously reported covalent organic framework membrane (TFP–DHF) but different lengths of carbon chains aiming to rationally control the pore size. The membrane permeation results in the applications of organic solvent nanofiltration and molecular sieving of organic dyes showed a systematic shift of the membrane flux and molecular weight cut-off correlated to the pore size change. These results enhanced our fundamental understanding of transport through uniform channels at nanometer scales. Pore engineering of the covalent organic framework membranes was demonstrated for the first time., Pore surface engineering of ultrathin COF membranes by introducing different lengths of alkyl chains into the skeleton, which allows us to precisely control the pore size of COF membranes for OSN applications and molecular sieving.

In recent years, β-Ga2O3/NiO heterojunction diodes have been studied, but reports in the literature lack an investigation of an epitaxial growth process of high-quality single-crystalline β-Ga2O3/NiO thin films via electron microscopy analysis and the fabrication and characterization of an optoelectronic device based on the resulting heterojunction stack. This work investigates the thin-film growth of a heterostructure stack comprising n-type β-Ga2O3 and p-type cubic NiO layers grown consecutively on c-plane sapphire using pulsed laser deposition, as well as the fabrication of solar-blind ultraviolet-C photodetectors based on the resulting p-n junction heterodiodes. Several characterization techniques were employed to investigate the heterostructure, including X-ray crystallography, ion beam analysis, and high-resolution electron microscopy imaging. X-ray diffraction analysis confirmed the single-crystalline nature of the grown monoclinic and cubic (201) β-Ga2O3 and (111) NiO films, respectively, whereas electron microscopy analysis confirmed the sharp layer transitions and high interface qualities in the NiO/β-Ga2O3/sapphire double-heterostructure stack. The photodetectors exhibited a peak spectral responsivity of 415 mA/W at 7 V reverse-bias voltage for a 260 nm incident-light wavelength and 46.5 pW/μm2 illuminating power density. Furthermore, we also determined the band offset parameters at the thermodynamically stable heterointerface between NiO and β-Ga2O3 using high-resolution X-ray photoelectron spectroscopy. The valence and conduction band offsets values were found to be 1.15 ± 0.10 and 0.19 ± 0.10 eV, respectively, with a type-I energy band alignment.

Although core–shell copper metal nanoclusters are important emerging materials for practical applications and fundamental scientific research, their synthesis lags behind that of gold and silver na...

We report a strong effect of the MXene flake size and surface termination on the dielectric permittivity of MXene polymer composites. Specifically, poly(vinylidene fluoride-trifluoro-ethylene-chlor...

We demonstrate a novel strategy to enhance sulfur loading and rate performance for Li–S battery by synchronously coupling a nanostructured cathode with an antifouling separator via a facile electrostatic self-assembly approach. The assembly of two dimensional (2D) MXene and positively charged 1D CNT-Polyethyleneimine was observed to controllably address the key issues of sluggish ionic transport, and produce an integrate cathode with dynamic crosslinking network. Moreover, an antifouling separator is proposed by this strategy for the first time, which features well-organized inter-lamellar porosity, dual polarity and high conductivity. The antifouling separator is found to play a pivotal role in: 1) low-order polysulfide activation, 2) high rate cyclability, and 3) Li dendrites inhibition. Our integrated design realizes a long-term capacity of 980 mAh g−1 at 5 mA cm−2 over 500 cycles (sulfur loading: 2.6 mg cm−2). Furthermore, a flexible self-assembled cathode with high loading (5.8 mg cm−2) and superb mechanical strength (13 MPa), demonstrates an appealing areal capacity of 7.1 mAh cm−2 and rate performance at nearly 10 mA cm−2.

Semiconductor quantum well structures have been critical to the development of modern photonics and solid-state optoelectronics. Quantum level tunable structures have introduced new transformative device applications and afforded a myriad of groundbreaking studies of fundamental quantum phenomena. However, noncolloidal, III–V compound quantum well structures are limited to traditional semiconductor materials fabricated by stringent epitaxial growth processes. This report introduces artificial multiple quantum wells (MQWs) built from CsPbBr3 perovskite materials using commonly available thermal evaporator systems. These perovskite-based MQWs are spatially aligned on a large-area substrate with multiple stacking and systematic control over well/barrier thicknesses, resulting in tunable optical properties and a carrier confinement effect. The fabricated CsPbBr3 artificial MQWs can be designed to display a variety of photoluminescence (PL) characteristics, such as a PL peak shift commensurate with the well/ba...

The rapid development of halide perovskite synthesis offers the opportunity to fabricate high-quality perovskite nanocrystals (NCs), whose structural uniformity can lead to assembled supra-structur...

Reduced graphene oxide (rGO) has inherited the outstanding electronic, optical, thermal and mechanical properties of graphene to a large extent, while maintaining sufficient chemically active sites. Therefore, it has attracted a great deal of research attention in the fields of energy storage, electronics, photonics, catalysis, environmental engineering, etc. Currently, the most popular way to prepare rGO is to reduce graphene oxide, which is obtained by modified Hummer methods using tedious treatments in a harsh environment, to rGO flakes. Industrial applications demand advanced preparation methods that can mass produce highly uniform rGO sheets on arbitrary substrates. In this work, a one-step growth process is introduced that utilizes cellulose acetate as a precursor, without any catalysts, to produce uniform ultrathin rGO films on various substrates and free-standing rGO powders. Systematic spectroscopic and microscopic studies on the resulting rGO are performed. Prototypes of electronic and optoelectronic devices, such as field effect transistors (FETs), photodetectors, and humidity sensors, are fabricated and tested, demonstrating the intriguing applications of our rGO materials across a wide range of fields.

Pharmaceutical, chemical, and food industries are actively implementing membrane nanofiltration modules in their processes to separate valuable products and recover solvents. Interfacial polymerization (IP) is the most widely used method to produce thin-film composite membranes for nanofiltration and reverse osmosis processes. Although membrane processes are considered green and environmentally friendly, membrane fabrication has still to be further developed in such direction. For instance, the emission of volatile solvents during membrane production in the industry has to be carefully controlled for health reasons. Greener solvents are being proposed for phase-separation membrane manufacture. For the IP organic phase, the proposition of greener alternatives is in an early stage. In this work, we demonstrate the preparation of a high-performing composite membrane employing zero vapor pressure and naturally extracted oleic acid as the IP organic phase. Its long hydrophobic chain ensures intrinsic low volatility and acid monomer dissolution, while the polar head induces a unique self-assembly structure during the film formation. Membranes prepared by this technique were selective for small molecules with a molecular weight cutoff of 650 g mol-1 and a high permeance of ∼57 L m-2 h-1 bar-1.

Smart solar-blind UV-C band photodetectors suffer from low responsivity in a self-powered mode. Here, we address this issue by fabricating a novel enhanced solar-blind UV-C photodetector array based on solution-processed n-ZnO quantum dots (QDs) functionalized by p-CuO micro-pyramids. Self-assembled catalyst-free p-CuO micro-pyramid arrays are fabricated on a pre-ablated Si substrate by pulsed laser deposition without a need for a catalyst layer or seeding, while the solution-processed n-ZnO QDs are synthesized by the femtosecond-laser ablation in liquid technique. The photodetector is fabricated by spray-coating ZnO QDs on a CuO micro-pyramid array. The photodetector performance is optimized via a p-n junction structure as both p-ZnO QDs and p-CuO micro-pyramid layers are characterized by wide band gap energies. Two photodetectors (with and without CuO micro-pyramids) are fabricated to show the role of p-CuO in enhancing the device performance. The n-ZnO QD/p-CuO micro-pyramid/Si photodetector is characterized by a superior photo-responsivity of ∼956 mA/W at 244 nm with a faster photoresponse (

Iron-doped titanium dioxide nanoparticles, with Fe/Ti atomic ratios from 0% to 10%, were synthesized by flame spray pyrolysis (FSP), employing a single-step method. Ferrocene, being nontoxic and readily soluble in liquid hydrocarbons, was used as the iron source, while titanium tetraisopropoxide (TTIP) was used as the precursor for TiO2. The general particle characterization and phase description were examined using ICP-OES, XRD, BET, and Raman spectroscopy, whereas the XPS technique was used to study the surface chemistry of the synthesized particles. For particle morphology, HRTEM with EELS and EDS analyses were used. Optical and magnetic properties were examined using UV–vis and SQUID, respectively. Iron doping to TiO2 nanoparticles promoted rutile phase formation, which was minor in the pure TiO2 particles. Iron-doped nanoparticles exhibited a uniform iron distribution within the particles. XPS and UV–vis results revealed that Fe2+ was dominant for lower iron content and Fe3+ was common for higher iron content and the iron-containing particles had a contracted band gap of ~1 eV lower than pure TiO2 particles with higher visible light absorption. SQUID results showed that doping TiO2 with Fe changed the material to be paramagnetic. The generated nanoparticles showed a catalytic effect for dye-degradation under visible light.

High-resolution scanning transmission electron microscopy (HR-STEM) with spherical aberration correction enables researchers to peer into two-dimensional (2D) materials and correlate the material properties with those of single atoms. The maximum intensity of corrected electron beam is confined in the area having sub-angstrom size. Meanwhile, the residual threefold astigmatism of the electron probe implies a triangular shape distribution of the intensity, whereas its tails overlap and thus interact with several atomic species simultaneously. The result is the resonant modulation of contrast that interferes the determination of phase transition of 2D materials. Here, we theoretically reveal and experimentally determine the origin of resonant modulation of contrast and its unintended impact on violating the power-law dependence of contrast on coordination modes between transition metal and chalcogenide atoms. The finding illuminates the correlation between atomic contrast, spatially inequivalent chalcogenide orientation, and residual threefold astigmatism on determining the atomic structure of emerging 2D materials.

Solution-processed organic–inorganic hybrid perovskites have attracted attention as light-harvesting materials for solar cells and photonic applications. The present study focusses on cubic single crystal; microstructures of CH3NH3PbBr3 perovskite fabricated by a one-step solution based self-assembly method. It is seen that, in addition to the nucleation from the precursor solution, the crystallization occurs when the solution was supersaturated, followed by formation of small nucleus of CH3NH3PbBr3 that will self-assembled into bigger hollow cubes. A 3D fluorescence microscope investigation of hollow cubes confirmed the formation of hollow plates on the bottom, then the growth starts from the perimeter and propagate to the center of the cube. Furthermore, the growth in the (001) direction follows a layer-by-layer growth model to form a complete cube, confirmed by SEM observations. To get more insights into the structural and optical properties, density functional theory (DFT) simulations were conducted. The density of state (DOS) calculations revealed that the valence band maximum (VBM) consists of states contributed by Br and Pb, which agrees with the X-ray photoelectron spectroscopy valence band (XPSVB) measurements.

The achievement of H2 detection, up to 25 ppm, at room temperature using sulfur-treated, platinum (Pt)-decorated porous GaN is reported in this study. This achievement is attributed to the large lateral pore size, Pt catalyst, and surface treatment using organic sulfide. The performance of H2-gas sensors is studied as a function of the operating temperature by providing an adsorption activation energy of 22 meV at 30 ppm H2, confirming the higher sensitivity of the sulfide-treated Pt–porous GaN sensor. Furthermore, the sensing response of the sulfide-treated Pt–porous GaN gas sensor increases with the increase in porosity (surface-to-volume ratio) and pore radii. Using the Knudsen diffusion–surface reaction equation, the H2 gas concentration profile is simulated and fitted within the porous GaN layer, revealing that H2 diffusion is limited by small pore radii because of its low diffusion rate. The simulated gas sensor responses to H2 versus the pore diameter show the same trend as observed for the experimental data. The sulfide-treated Pt–porous GaN sensor achieves ultrasensitive H2 detection at room temperature for 125 nm pore radii.

The presence of localized trap states on the surface of CsPbCl3 perovskite nanocrystals (NCs) is one of the greatest challenges precluding the development of optoelectronic applications of these NCs. Passivation of these defect sites provides a promising pathway to remediating their electronic and optical properties, such as the photoluminescence quantum yield (PLQY). Herein, we demonstrate a postsynthetic dual-surface treatment using trivalent metal ion salts, i.e., YCl3, as a new passivation approach that enhances the PLQY up to 60% while preserving the NC size and crystal structure. Such remarkable enhancement of the PLQY along with prolongation of the average PL lifetimes of treated NCs samples indicates effective passivation of the surface defects and subsequent suppression of the formation of surface nonradiative recombination centers. As a segue toward optoelectronic applications, we probed the photoelectric performance of the NCs using ultraflexible devices; we found that YCl3-treated CsPbCl3 NC f...

In this work, we report a theoretical investigation of the structural, electronic and optical properties of InP1−xBix alloys. The study has been carried out by varying up the fraction x from 0 to 0.375. The calculations are performed using the density functional theory (DFT). The full potential linearized augmented plane wave (FPLAPW) scheme, as implemented in Wien2k package, is employed. The modified Becke-Johson potential with local density approximation (mBJLDA), which combines the Becke-Johson exchange potential with the local density approximation correlation potential, is used to evaluate the alloys band structure. We have studied the effect of bismuth composition on the structural and optoelectronic proprieties and found that lattice parameter of the compound increases with the bismuth composition which is in good agreement with Vegard’s law. A band gap reduction of the order 36 meV/%Bi with the Bi composition is observed giving rise to a semi-metallic behaviour beyond a composition about 47%. The effective masses of the binary compound InP and InP1−xBix alloys obtained, by our calculations, are in good agreement with the experimental results. Furthermore, the effects of the bismuth concentration on the dielectric function of the alloys is elucidated, suggesting that dopage of bismuth tunes the electronic and optical properties of the InP matrix. In addition, the calculated low value of the reflectivity in the visible and UV region of the InPBi alloys, together with the consistent behavior of the band gap and the reflective index variations with the composition of bismuth overall experimental results, shed light on the candidacy of InP1−xBix alloys as potential material for optoelectronic applications.

Insertion of alkali metal ions, especially Na, is a well-established method to significantly increase the power conversion efficiency of copper indium gallium selenide (CIGSe)-based photovoltaic devices. However, although it is known that Na ions mostly reside on the surface of CIGSe layer following diffusion, the exact mechanism of how Na affects the carrier dynamics of CIGSe still remains ambiguous. This is mainly due to the unavailability of suitable surface-sensitive techniques. Herein, we employ four-dimensional scanning ultrafast electron microscopy (4D S-UEM), which has the unique capability of mapping the charge carrier dynamics in real time and space selectively on the materials surfaces, to directly observe the effect of Na insertion on the carrier dynamics of shelled CIGSe film. It is found that an additional layer of NaF to the thin film of ZnS-shelled CIGSe nanocrystals not only increases the grain size and improves the texture of the film but, more importantly, reduces fast electron trap cha...

Ni and NiSn supported on zirconia (ZrO2) and on indium (In)-incorporated zirconia (InZrO2) catalysts were prepared by a wet chemical reduction route and tested for hydrogenation of CO2 to methanol in a fixed-bed isothermal flow reactor at 250 °C. The mono-metallic Ni (5%Ni/ZrO2) catalysts showed a very high selectivity for methane (99%) during CO2 hydrogenation. Introduction of Sn to this material with the following formulation 5Ni5Sn/ZrO2 (5% Ni-5% Sn/ZrO2) showed the rate of methanol formation to be 0.0417 μmol/(gcat·s) with 54% selectivity. Furthermore, the combination NiSn supported on InZrO2 (5Ni5Sn/10InZrO2) exhibited a rate of methanol formation 10 times higher than that on 5Ni/ZrO2 (0.1043 μmol/(gcat·s)) with 99% selectivity for methanol. All of these catalysts were characterized by X-ray diffraction, high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy, CO2-temperature-programmed desorption, and density functional theory (DFT) studies. Addition of Sn to Ni catalysts resulted in the formation of a NiSn alloy. The NiSn alloy particle size was kept in the range of 10–15 nm, which was evidenced by HRTEM study. DFT analysis was carried out to identify the surface composition as well as the structural location of each element on the surface in three compositions investigated, namely, Ni28Sn27, Ni18Sn37, and Ni37Sn18 bimetallic nanoclusters, and results were in agreement with the STEM and electron energy-loss spectroscopy results. Also, the introduction of “Sn” and “In” helped improve the reducibility of Ni oxide and the basic strength of catalysts. Considerable details of the catalytic and structural properties of the Ni, NiSn, and NiSnIn catalyst systems were elucidated. These observations were decisive for achieving a highly efficient formation rate of methanol via CO2 by the H2 reduction process with high methanol selectivity.

We propose hydroxyl-functionalized polytriazole as a precursor for the preparation of highly crosslinked membranes and carbon molecular sieves (CMS) for gas separation. We studied the effect of the treatment temperature on the chemical structure and gas separation properties. A progressing crosslinking structure was formed when polytriazole films were treated in the range of 300–400 °C. Above 425 °C, CMSs with multi-layered nitrogen-graphene-like structures were obtained. The CO2 permeability increased by increasing the temperature, while the CO2/CH4 selectivity was maintained. Permeability increases up to 37-fold compared to the untreated polymer film were obtained, aligned with a CO2/CH4 selectivity of 75. The single-gas CO2 permeability vs. CO2/CH4 selectivity data obtained for films treated at 475 and 550 °C are among the highest reported in the literature. Moreover, the mixed gas performance of these membranes is far above previously reported CO2/CH4 data plotted as mixed-gas trade-off curves, demonstrating the potential of polytriazole materials for these applications.

Graphite anodes are not stable in most noncarbonate solvents (e.g., ether, sulfoxide, sulfone) upon Li ion intercalation, known as an urgent issue in present Li ions and next-generation Li–S and Li–O2 batteries for storage of Li ions within the anode for safety features. The solid electrolyte interphase (SEI) is commonly believed to be decisive for stabilizing the graphite anode. However, here we find that the solvation structure of the Li ions, determined by the electrolyte composition including lithium salts, solvents, and additives, plays a more dominant role than SEI in graphite anode stability. The Li ion intercalation desired for battery operation competes with the undesired Li+–solvent co-insertion, leading to graphite exfoliation. The increase in organic lithium salt LiN(SO2CF3)2 concentration or, more effectively, the addition of LiNO3 lowers the interaction strength between Li+ and solvents, suppressing the graphite exfoliation caused by Li+–solvent co-insertion. Our findings refresh the knowled...

We report the effect of the Ti3C2Tx MXene flake thickness on its inherent electrochemistry and heterogeneous charge transfer characteristics. It is shown that Ti3C2Tx undergoes irreversible oxidation in a positive potential window, which strongly depends on the flake thickness and pH of the electrolyte. Few-layered Ti3C2Tx exhibits faster electron transfer kinetics (k0 = 0.09533 cm s−1) with a [Fe(CN)6]4−/3− redox mediator compared to multi-layered Ti3C2Tx (k0 = 0.00503 cm s−1). In addition, the few-layered free standing Ti3C2Tx film electrode remains intact after enduring irreversible oxidation.

Recent experimental and theoretical studies have demonstrated that two-dimensional (2D) transition metal dichalcogenide (TMDC) nanoflakes are one of the most promising candidates for non-noblemetal electrocatalysts for hydrogen evolution reaction (HER). However, it is still challenging to optimize their conductivity and enrich active sites for highly efficient electrochemical performance. Herein, we report a chemical vapor deposition (CVD) and thermal annealing two-step strategy to controllably synthesize hybrid electrocatalysts consisting of metallic NbS2 nanoflake backbones and a highly catalytic active MoSx nanocrystalline shell on polished commercial glass carbon (GC). In addition, the amount of MoSx in the hybrids can be easily adjusted. We first demonstrate that a small amount of MoSx significantly promotes the HER activity of 2D NbS2 nanoflakes, which is in good agreement with the density functional theory (DFT) calculation results. Moreover, the optimized MoSx@NbS2/GC electrocatalyst displays superior HER activity with overpotential of −164 mV at −10 mA cm−2, a small Tafel slope of 43.2 mV dec−1, and prominent electrochemical stability. This study provides a new path for enhancing the HER performance of 2D TMDC nanoflakes.

Xiangming Xu and Tianchao Guo contributed equally to this work. We appreciate Enze Xu, a 4-year-old boy, for providing his favorite toys to fabricate the home-made automatic spray system. Research reported in this publication was funded by King Abdullah University of Science and Technology (KAUST).

Engineering the surface energy through careful manipulation of the surface chemistry is a convenient approach to control quantum confinement and structure dimensionality during nanocrystal growth. Here, we demonstrate that the introduction of pyridine during the synthesis of methylammonium lead bromide (MAPbBr3) perovskite nanocrystals can transform three-dimensional (3D) cubes into two-dimensional (2D) nanostructures. Density functional theory (DFT) calculations show that pyridine preferentially binds to Pb atoms terminating the surface, driving the selective 2D growth of the nanostructures. These 2D nanostructures exhibit strong quantum confinement effects, high photoluminescence quantum yields in the visible spectral range, and efficient charge transfer to molecular acceptors. These qualities indicate the suitability of the synthesized 2D nanostructures for a wide range of optoelectronic applications.

International audience; Converting photon energy into chemical energy using inorganic materials requires the successful capture of photons, exciton dissociation, and the charge carrier diffusion. This study reports a thorough analysis of the optoelectronic properties of visible-light-responsive SrTaO2N perovskites to quantify their absorption coefficient and the generated charge carriers' effective masses, dielectric constants, and electronic structures. The measurements on such intrinsic properties were attempted using both epitaxial and polycrystalline SrTaO2N films deposited by radiofrequency magnetron sputtering under N-2 reactive plasma. Density functional theory calculations using the HSE06 functional provided reliable values of these optoelectronic properties. Such quantities obtained by both measurements and calculations gave excellent correspondence and provide possible variations that account for the small discrepancies observed. One of the significant factors determining the optical properties was found to be the anion ordering in the perovskite structure imposed by the cations. As a result, the different anion ordering has a noticeable influence on the optical properties and high sensitivity of the hole effective mass. Determination of relative band positions with respect to the water redox properties was also attempted by Mott-Schottky analysis. All these results offer the opportunity to understand why SrTaO2N possesses intrinsically all the ingredients needed for an efficient water splitting device.

Water splitting driven by electricity or sunlight is one of the most promising ways to address the global terawatt energy needs of future societies; however, its large-scale application is limited by the sluggish kinetics of the oxygen evolution reaction (OER). NiFe-based compounds, mainly oxides and hydroxides, are well-known OER catalysts and have been intensively studied; however, the utilization of the synergistic effect between two different NiFe-based materials to further boost the OER performance has not been achieved to date. Here, we report the rapid conversion of NiFe double hydroxide into metallic NiFeP using PH3 plasma treatment and further construction of amorphous NiFe hydroxide/NiFeP/Ni foam as efficient and stable oxygen-evolving anodes. The strong electronic interactions between NiFe hydroxide and NiFeP significantly lower the adsorption energy of H2O on the hybrid and thus lead to enhanced OER performance. As a result, the hybrid catalyst can deliver a geometrical current density of 300 ...

Ultrathin layers of native oxides on the surface of photovoltaic materials may act as very efficient carrier trapping/recombination centers, thus significantly affecting their interfacial photophysical properties. How ultrathin oxide layers affect the surface and interface carrier dynamics cannot be selectively accessed by conventional ultrafast transient spectroscopic methods due to the deep penetration depth (tens to thousands of nanometers) of the pump/probe laser pulses. Herein, scanning ultrafast electron microscopy (S-UEM) at a low voltage of 1 keV electrons was recently developed at KAUST to selectively map the ultrafast charge carrier dynamics of a few layers on the top surfaces of photovoltaic materials. Unlike high-voltage 30 keV experiments, at 1 keV, the depth of detected secondary electrons (SEs) underneath the surface is significantly reduced 5 times, thus making it possible to visualize the dynamics of charge carrier from the uppermost surface of photoactive layers. More specifically, this new approach has been employed to explore and decipher the tremendous impact of native oxide layers and oxygen defect states on charge carrier dynamics in space and time simultaneously at sub-nanometer levels on several photovoltaic material surfaces, including Si, GaAs, CdTe, and CdZnTe single crystals. Interestingly, the contrast in the SEs time-resolved difference images switched from a dark "energy-loss mechanism" to a bright "energy-gain mechanism" only by removing the layers of surface oxides. Moreover, the charge carrier recombination was estimated and found to be dramatically affected by the native oxide layers. The density functional theory (DFT) calculations demonstrate that the work function of oxygen-terminated Si surface also increases slightly upon optical excitation and makes for less SE intensity, providing another piece of evidence that the origin of the dark contrast observed on these material surfaces should be assigned to the surface oxide formation, mainly oxygen defect states in the band gap and/or work function increment. Our findings provide a new method and pave the way for evaluating the effect of surface morphology and defects, including but not limited to native oxide, on charge carrier dynamics, and interfacial properties of photovoltaic absorber layers.

MXenes are a class of two-dimensional (2D) transition metal carbides, nitrides and carbonitrides that have shown promise for high-rate pseudocapacitive energy storage. However, the effects that irreversible oxidation have on the surface chemistry and electrochemical properties of MXenes are still not understood. Here we report on a controlled anodic oxidation method which improves the rate performance of titanium carbide MXene (Ti3 C2 Tx, Tx refers to -F, =O, -Cl and -OH) electrodes in acidic electrolytes. The capacitance retention at 2000 mV s-1 (with respect to the lowest scan rate of 5 mV s-1 ) increases gradually from 38 % to 66 % by tuning the degree of anodic oxidation. At the same time, a loss in the redox behavior of Ti3 C2 Tx is evident at high anodic potentials after oxidation. Several analysis methods are employed to reveal changes in the structure and surface chemistry while simultaneously introducing defects, without compromising electrochemically active sites, are key factors for improving the rate performance of Ti3 C2 Tx . This study demonstrates improvement of the electrochemical performance of MXene electrodes by performing a controlled anodic oxidation.

Parasitic absorption in transparent electrodes is one of the main roadblocks to enabling power conversion efficiencies (PCEs) for perovskite‐based tandem solar cells beyond 30%. To reduce such losses and maximize light coupling, the broadband transparency of such electrodes should be improved, especially at the front of the device. Here, the excellent properties of Zr‐doped indium oxide (IZRO) transparent electrodes for such applications, with improved near‐infrared (NIR) response, compared to conventional tin‐doped indium oxide (ITO) electrodes, are shown. Optimized IZRO films feature a very high electron mobility (up to ≈77 cm2 V−1 s−1), enabling highly infrared transparent films with a very low sheet resistance (≈18 Ω □−1 for annealed 100 nm films). For devices, this translates in a parasitic absorption of only ≈5% for IZRO within the solar spectrum (250–2500 nm range), to be compared with ≈10% for commercial ITO. Fundamentally, it is found that the high conductivity of annealed IZRO films is directly linked to promoted crystallinity of the indium oxide (In2O3) films due to Zr‐doping. Overall, on a four‐terminal perovskite/silicon tandem device level, an absolute 3.5 mA cm−2 short‐circuit current improvement in silicon bottom cells is obtained by replacing commercial ITO electrodes with IZRO, resulting in improving the PCE from 23.3% to 26.2%.

The facile synthesis of hierarchically functional, catalytically active, and electrochemically stable nanostructures holds a tremendous promise for catalyzing the efficient and durable oxygen evolution reaction (OER) and yet remains a formidable challenge. Herein, we report the scalable production of core-shell nanostructures composed of carbon-coated cobalt diphosphide nanosheets, C@CoP

The electronic, optical, and thermoelectric properties of RbYbX3 (X = Cl, Br) are investigated with density functional theory based Modified Becke and Johnson (mBJ) potential which is executed in Wien2K code. The tolerance factors (0.96, 0.98) and formation energies favor their structural and thermodynamic stabilities. The direct bandgaps of 1.42 eV and 1.30 eV for RbYbCl3, and RbYbBr3 address the visible region of spectrum for solar cells. The optical properties are explored comprehensively in terms of dielectric constants, refractive index, absorption coefficient, and reflection. The absorption bands of light are in the visible region, and light is plane-polarized. Furthermore, the thermoelectric properties are analyzed in terms of thermal and electrical conductivities, Seebeck coefficient, and figure of merit. The room temperature ZT turns out to be 0.78 for RbYbCl3 and 0.75 for RbYbBr3. The maximum absorption in the visible region and high ZT make them excellent materials for renewable energy applications.

D.G. and F.M. contributed equally to this work. This work was supported by the KAUST Baseline BAS/1/1375-01 and KAUST competitive research grant URF/1/3769-01.

We study the band discontinuity at the GaN/single-layer (SL) WSe2 heterointerface. The GaN thin layer is epitaxially grown by molecular beam epitaxy on chemically vapor deposited SL-WSe2/c-sapphire. We confirm that the WSe2 was formed as an SL from structural and optical analyses using atomic force microscopy, scanning transmission electron microscopy, micro-Raman, absorbance, and microphotoluminescence spectra. The determination of band offset parameters at the GaN/SL-WSe2 heterojunction is obtained by high-resolution X-ray photoelectron spectroscopy, electron affinities, and the electronic bandgap values of SL-WSe2 and GaN. The valence band and conduction band offset values are determined to be 2.25 ± 0.15 and 0.80 ± 0.15 eV, respectively, with type II band alignment. The band alignment parameters determined here provide a route toward the integration of group III nitride semiconducting materials with transition metal dichalcogenides (TMDs) for designing and modeling of their heterojunction-based electr...

There exists a strong demand to replace expensive noble metal catalysts with efficient and earth-abundant catalysts for hydrogen evolution reaction (HER). Recently the Co- and Mo-based sulfides such as CoS2, Co9S8, and MoSx have been considered as several promising HER candidates. Here, a highly active and stable hybrid electrocatalyst 3D flower-like hierarchical Co9S8 nanosheets incorporated with MoSx has been developed via a one-step sulfurization method. Since the amounts of Co9S8 and MoSx are easily adjustable, we verify that small amounts of MoSx promotes the HER activity of Co9S8, and vise versa. In other words, we validate that symmetric synergy for HER in the Co- and Mo-based sulfide hybrid catalysts, a long-standing question requiring clear experimental proofs. Meanwhile, the best electrocatalyst Co9S8-30@MoSx/CC in this study exhibits excellent HER performance with an overpotential of −98 mV at −10 mA/cm2, a small Tafel slope of 64.8 mV/dec, and prominent electrochemical stability.

Strategies to synthesize reduced graphene oxide (rGO) abound but, in most studies, research teams select one particular oxidation-reduction method without providing a methodic reasoning for doing so. Herein, it is analyzed how diverse oxidation-reduction strategies commonly used can result in considerable performance differences of rGO for supercapacitor applications. Depending on the graphite oxidation method followed, the surface chemistry analysis of the products confirms that there is a marked disparity in the degree of oxidation and the nature of the oxygen functional groups present. Subsequent reduction of the oxidized graphite (using three different methods) showed that the maximum specific capacitance of rGOs produced from the classical Hummers' method was 128 F g−1 whereas an analogous material obtained from an improved Hummers' method reached ∼274 F g−1 (both via an hydrothermal reduction route). Besides showing that the improved oxidation method results in superior capacitance performance, explained by the higher number of structural defects allied to a surface chemistry where residual hydroxyl and epoxy functional groups predominate, this study highlights the need to rationalize the oxidation-reduction strategies followed when investigating applications of rGO materials.