Suppressing Jahn-Teller distortion and locking lattice water with doped Fe(III) in birnessite toward fast and stable zinc-ion batteries.

Birnessite has been regarded as a promising cathode material for aqueous zinc-ion batteries (ZIBs), but severe Jahn-Teller distortion and abrupt lattice collapse at deep charged states lead to serious problems such as poor capacity retention and short cycle life, which severely impede its practical applications. We herein report the construction of an advanced layered Fe-doped Na0.55Mn2O4·xH2O (Fe-NMO·xH2O) cathode to promote zinc-ion storage performance and electrochemical stability. An outstanding capacity of 102 mA h g-1 at a high current density of 20 A g-1 and a long cycle life of 6000 cycles have been achieved, comparable to the state-of-the-art manganese oxide-based cathodes. Both experimental measurements and theoretical calculations reveal that Fe3+ substitution and lattice water cooperatively stabilize the interlayer structure, accelerate zinc-ion diffusion, and improve electronic conductivity. Notably, Fe doping is conducive to alleviating the Jahn-Teller effect and locking lattice water, which effectively prevents phase transformation and lattice collapse during the (de)intercalation process. This work sheds light on the synergistic interplay between dopants and structural water in zinc-ion storage and demonstrates instructive strategies to regulate layered structures for ZIBs.

Lattice oxygen activation and local electric field enhancement by co-doping Fe and F in CoO nanoneedle arrays for industrial electrocatalytic water oxidation.

Oxygen evolution reaction (OER) is critical to renewable energy conversion technologies, but the structure-activity relationships and underlying catalytic mechanisms in catalysts are not fully understood. We herein demonstrate a strategy to promote OER with simultaneously achieved lattice oxygen activation and enhanced local electric field by dual doping of cations and anions. Rough arrays of Fe and F co-doped CoO nanoneedles are constructed, and a low overpotential of 277 mV at 500 mA cm-2 is achieved. The dually doped Fe and F could cooperatively tailor the electronic properties of CoO, leading to improved metal-oxygen covalency and stimulated lattice oxygen activation. Particularly, Fe doping induces a synergetic effect of tip enhancement and proximity effect, which effectively concentrates OH- ions, optimizes reaction energy barrier and promotes O2 desorption. This work demonstrates a conceptual strategy to couple lattice oxygen and local electric field for effective electrocatalytic water oxidation.

High Q-Factor Single-Mode Lasing in Inorganic Perovskite Microcavities with Microfocusing Field Confinement.

The realization of high-Q single-mode lasing on the microscale is significant for the advancement of on-chip integrated light sources. It remains a challenging trade-off between Q-factor enhancement and light-field localization to raise the lasing emission rate. Here, we fabricated a zero-dimensional perovskite microcavity integrated with a nondamage pressed microlens to three-dimensionally tailor the intracavity light field and demonstrated linearly and nonlinearly (two-photon) pumped lasing by this microfocusing configuration. Notably, the microlensing microcavity experimentally achieves a high Q-factor (16700), high polarization (99.6%), and high Purcell factor (11.40) single-mode lasing under high-repetition pulse pumping. Three-dimensional light-field confinement formed by the microlens and plate microcavity simultaneously reduces the mode volume (∼3.66 µm3) and suppresses diffraction and transverse walk-off loss, which induces discretization on energy-momentum dispersions and spatial electromagnetic-field distributions. The Q factor and Purcell factor of our lasing come out on top among most of the reported perovskite microcavities, paving a promising avenue toward further studying electrically driven on-chip microlasers.

Effects of the excitation wavelength and temperature on the zero-phonon emission line of Cr:YAG.

In this work, a detailed study was conducted of the temperature and excitation wavelength-dependent photoluminescence (PL) spectra of the chromium-doped yttrium aluminum garnet (Cr:YAG) transparent ceramic. Focusing on the two sets of zero-phonon lines (ZPLs) of the 2 E→4 A 2 transition in this material, the PL spectra are discovered to evolve significantly with respect to temperature and be highly dependent on the excitation wavelength. Compared to the continuous variation behavior with temperature, an increase in the excitation wavelength leads to a blueshift of the peak position within the regions of 450 nm to 465 nm, 465 nm to 490 nm, and 490 nm to 500 nm, and a sharp change in the PL position at the excitation wavelengths of 465 nm and 490 nm. The electron-phonon coupling (EPC) effect is believed to be more sensitive to the excitation wavelength. Different excitation wavelengths involve different electronic levels participating in the light emission processes, which explains the evolution behavior of the PL peak position with respect to the excitation wavelength. Moreover, the emergence of weak peaks next to the ZPLs at particular temperatures and excitation wavelengths is also observed. This work compares the influence of the temperature and excitation wavelength to the PL properties of the Cr:YAG transparent ceramic, which promotes an advanced understanding of the luminescence behavior of the Cr:YAG transparent ceramics.

Manipulation of Temperature-Dependent Luminescence Behaviors of Mn4+-Activated Fluoride Phosphors.

In this paper, the giant tunability of thermal behaviors, i.e., from thermal deterioration to substantial growth, is firmly demonstrated for the vibronic luminescence of Mn4+ ions in fluoride phosphors. Such peculiar behavior is uncovered to be associated with the thermal excitation of a low-frequency phonon bath, and a theoretical model involving the excitation-wavelength-dependent populations of vibronic levels and the temperature-dependent nonradiative recombination processes is successfully constructed. Two main governing parameters, namely, the thermal activation energy Ea and the involved average phonon energy ΔE, are thus determined for the distinct thermal behaviors of Mn4+-ion luminescence. This demonstration may pave the way for manipulating the thermal behaviors of vibronic luminescence in solids to some extent.

Phosphorus-Mediated Local Charge Distribution of N-Configuration Adsorption Sites with Enhanced Zincophilicity and Hydrophilicity for High-Energy-Density Zn-Ion Hybrid Supercapacitors.

Tailor-made carbonaceous-based cathodes with zincophilicity and hydrophilicity are highly desirable for Zn-ion storage applications, but it remains a great challenge to achieve both advantages in the synthesis. In this work, a template electrospinning strategy is developed to synthesize nitrogen and phosphorous co-doped hollow porous carbon nanofibers (N, P-HPCNFs), which deliver a high capacity of 230.7 mAh g-1 at 0.2 A g-1 , superior rate capability of 131.0 mAh g-1 at 20 A g-1 , and a maximum energy density of 196.10 Wh kg-1 at the power density of 155.53 W kg-1 . Density functional theory calculations (DFT) reveal that the introduced P dopants regulate the distribution of local charge density of carbon materials and therefore facilitate the adsorption of Zn ions due to the increased electronegativity of pyridinic-N. Ab initio molecular dynamics (AIMD) simulations indicate that the doped P species induce a series of polar sites and create a hydrophilic microenvironment, which decreases the impedance between the electrode and the electrolyte and therefore accelerates the reaction kinetics. The marriage of ex situ/in situ experimental analyses and theoretical simulations uncovers the origin of the enhanced zincophilicity and hydrophilicity of N, P-HPCNFs for energy storage, which accounts for the faster ion migration and electrochemical processes.

Strain evolution and confinement effect in InAs/AlAs short-period superlattices studied by Raman spectroscopy.

Raman spectra of two series of InAs/AlAs short-period superlattices were measured at room temperature to investigate the impact of strain on the phonon modes taking into consideration the confinement effect and interface mode. The evolution of strain in the InAs layer and the AlAs layer was studied in (InAs)2/(AlAs)2 superlattices grown at various temperatures (400-550 °C). While the strain existed in the AlAs layer remained almost constant, the strain in the InAs layer varied significantly as the growth temperature increased from 500 to 550 °C. The confinement effect on the optical phonons was analyzed based on results from (InAs)n/(AlAs)n grown at 450 °C (n = 2, 3, 4, and 5). Additionally, the confinement effect was found to be stronger in shorter periods with higher interface quality. The interface phonon modes were resolved between the longitudinal optical and transverse optical phonon modes, which assist in the rough estimation of the thickness of the layers. The disorder-activated acoustic phonon modes at the low-frequency side were also addressed.

Tuning pyridinic-N and graphitic-N doping with 4,4'-bipyridine in honeycomb-like porous carbon and distinct electrochemical roles in aqueous and ionic liquid gel electrolytes for symmetric supercapacitors.

Doping engineering in nanostructured carbon materials is an effective approach to modify heteroatom species and surface electronic structures. Herein, an advanced electrode material based on a honeycomb-like porous carbon matrix with tunable N-doped configurations is prepared via 4,4'-bipyridine (4,4'-bpy)-assisted pyrolysis of SiO2@ZIF-8 templates and subsequent etching treatment. Interestingly, the amounts of pyridinic-N and graphitic-N can be controlled by rationally varying the content of 4,4'-bpy which acts as the N source in the pyrolysis process. Both experimental results and density functional theory calculations have revealed that synergistically with 3D interconnected porous architecture, pyridinic-N and graphitic-N have different effects on the electrochemical performances in aqueous and ionic liquid gel electrolytes for symmetric supercapacitors. Highly exposed pyridinic-N endows the carbon electrode with a strengthened pseudocapacitance contribution manifested as a high specific capacitance of 436.1 F g-1 and exceptional stability of almost 100% capacitance retention after 5000 cycles at 10 A g-1 in the KOH/polyvinyl alcohol (PVA) electrolyte. By contrast, graphitic-N is propitious for reinforced electrical double-layer capacitance contribution, reflected by a maximum energy density of 125.4 Wh kg-1 in the 1-ethyl-3-methylimidazolium tetrafluoroborate/poly(vinylidene fluoride-co-hexafluoropropylene) (EMIMBF4/PVDF-HFP) electrolyte. This work offers an in-depth insight into the understanding of the energy storage mechanism of N-rich carbon electrodes in different electrolyte media.

One-pot solvothermal synthesis of flower-like Fe-doped In2S3/Fe3S4 S-scheme hetero-microspheres with enhanced interfacial electric field and boosted visible-light-driven CO2 reduction.

S-scheme heterojunctions hold great potential for CO2 photoreduction into solar fuels, but their activities are severely limited by the low efficiency of interfacial charge transfer. In this work, a facile one-pot solvothermal reaction has been developed to dope Fe into flower-like In2S3/Fe3S4 hetero-microspheres (Fe-In2S3/Fe3S4 HMSs), which are demonstrated as an efficient S-scheme photocatalyst for visible-light-driven CO2 photoreduction. The doping of Fe not only reduces the bandgap of In2S3 and thus extends the optical response to the visible-light region, but also increases the densities of donors and sulfur vacancies, which leads to an elevated Fermi level (Ef). The difference of Ef between In2S3 and Fe3S4 is enlarged and their band bending at the interface is therefore enhanced, which results in promoted carriers transfer in the S-scheme pathway due to the reinforced interfacial electric field. Moreover, Fe-doped In2S3 reduces the formation energy of the *CO intermediate, which thermodynamically favors the CO evolution at the surface. As a result, the Fe-In2S3/Fe3S4 HMSs exhibit a significantly boosted CO2 photoreduction activity in comparison with bare In2S3 and Fe-In2S3 samples. This work demonstrates the great potential of heteroatom-engineered S-scheme photocatalysts for CO2 photoreduction.

Luminescence performance and vibronic behavior of Mn4+-activated Ca14-xKxAl10Zn6O35 deep-red phosphor.

In this study, a significant improvement of deep-red luminescence was successfully achieved via the substitution approach in the Mn4+-activated Ca14-xKxAl10Zn6O35 phosphor. The optimal Mn4+ doping level x was determined by studying luminescence concentration quenching behavior. The measured photoluminescence (PL) spectrum showed five distinct vibronic structures with the main peak centered at 712 nm. A theoretical simulation work was conducted for comparison, and the predominant phonon mode involving in the vibronic transition process was revealed. From the temperature-dependent PL spectra, an abnormal luminescence enhancement was observed at the temperature rising from T=100 to 340 K, and the underlying phonon-assisted luminescence mechanism was theoretically disclosed. Finally, we studied the temperature-dependent luminescence lifetime, and the primary phonon energy in the vibronic behavior was identified from the fitting work.

Coexistence of Photoelectric Conversion and Storage in van der Waals Heterojunctions.

Van der Waals (vdW) heterojunctions, based on two-dimensional (2D) materials, have great potential for the development of ecofriendly and high-efficiency nanodevices, which shows valuable applications as photovoltaic cells, photodetectors, etc. However, the coexistence of photoelectric conversion and storage in a single device has not been achieved until now. Here, we demonstrate a simple strategy to construct a vdW p-n junction between a WSe_{2} layer and quasi-2D electron gas. After an optical illumination, the device stores the light-generated carriers for up to seven days, and then releases a very large photocurrent of 2.9 mA with bias voltage applied in darkness; this is referred to as chargeable photoconductivity (CPC), which completely differs from any previously observed photoelectric phenomenon. In normal photoconductivity, the recombination of electron-hole pairs occurs at the end of their lifetime; in contrast, infinite-lifetime photocarriers can be generated and stored in CPC devices without recombination. The photoelectric conversion and storage are completely self-excited during the charging process. The ratio between currents in full- and empty-photocarrier states below the critical temperature reaches as high as 10^{9}, with an external quantum efficiency of 93.8% during optical charging. A theoretical model developed to explain the mechanism of this effect is in good agreement with the experimental data. This work paves a path toward the high-efficiency devices for photoelectric conversion and storage.

Accelerating Triple Transport in Zinc-Air Batteries and Water Electrolysis by Spatially Confining Co Nanoparticles in Breathable Honeycomb-Like Macroporous N-Doped Carbon.

Rational engineering electrode structure to achieve an efficient triple-phase contact line is vital for applications such as in zinc-air batteries and water electrolysis. Herein, a facile "MOF-in situ-leaching and confined-growth-MOF" strategy is developed to construct a breathable trifunctional electrocatalyst based on N-doped graphitic carbon with Co nanoparticles spatially confined in an inherited honeycomb-like macroporous structure (denoted as Co@HMNC). The unique orderly arranged macroporous channels and the "ships in a bottle" confinement effect jointly expedite the triple transport, endowing the catalysts with fast reaction kinetics. As a result, the obtained Co@HMNC catalyst presents superb trifunctional performance with a positive half-wave potential (E1/2 ) of 0.90 V for oxygen reduction reaction (ORR), and low overpotentials of 318 and 51 mV for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) at 10 mA cm-2 , respectively. The Co@HMNC-based liquid Zn-air battery reaches a large specific capacity of 859 mA h gZn -1 , a high-power density of 198 mW cm-2 , and long-term stability for 375 h, suggesting its promise for actual applications.

pH-induced hydrothermal synthesis of Bi2WO6 nanoplates with controlled crystal facets for switching bifunctional photocatalytic water oxidation/reduction activity.

Bifunctional photocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) have attracted growing interest to understand the mechanisms governing different evolution reactions, and the bifunctional activity of a single type of crystalline photocatalyst has gained especial attention. We herein report the high photocatalytic OER and HER activities of Bi2WO6 nanoplates (BWO NPs) which are synthesized by a simple hydrothermal method, and the switchable OER and HER performances controlled by the pH value of the precursor solvent. In the pH range from 4 to 9, the thickness of BWO NPs along the [001] direction exhibits interesting dependence on the pH value, which decreases as the pH value increases. Correspondingly, the BWO NPs obtained at the pH value of 7 (BWO-7) show the highest photocatalytic OER activity, while the BWO NPs synthesized at the pH value of 9 (BWO-9) exhibit the highest photoactivity towards HER. The electronic band structure analysis indicates that the highest photocatalytic OER activity is related to the band alignment of the valence band maximum of Bi2WO6, which determines the efficient separation of photogenerated electrons and holes as well as the fast charge transfer kinetics. The crystal facet evolution resulting from thickness reduction promotes the exposure of {001} facets for HER and decreases the exposure of {100} and {010} facets for OER. This work provides new insights into the combined effects of crystal facets and electronic band structures on photocatalysis.

One-step phosphorization preparation of gradient-P-doped CdS/CoP hybrid nanorods having multiple channel charge separation for photocatalytic reduction of water.

The separation and transfer of photogenerated charge carriers are the crucial process in photocatalysis, and the realization of multiple charge separation and transfer routes in a single catalyst structure is very promising to achieve high-efficiency catalytic performance. We herein report a simple strategy to synthesize CdS/CoP hybrid nanorods (HNRs) via a one-step phosphorization treatment of the CdS/Co(OH)2 precursors, in which the gradient-P-doped-CdS NRs and CoP cocatalyst can be synchronously obtained (denoted as gP-CdS/CoP HNRs). The gradient P doping gradually reduced the band gap of CdS as well as elevated Fermi level with doping concentration up, resulting in the formation of a built-in electric field in the CdS NRs. The built-in electric field points from the surface towards the interior of the CdS NRs, which facilities the separation of photogenerated charge carriers in CdS and the transfer of electrons to the CdS/CoP interface. The transferred electrons are then captured by the CoP cocatalysts, leading to further separation of the charge carriers. Owing to the coupling of gradient-P-doped CdS nanorods with the CoP cocatalysts, the optimized gP-CdS/CoP HNRs exhibit remarkably enhanced photocatalytic water reduction performance, with a H2 production rate of 22.95 mmol g-1 h-1 which is 28.7 and 3.2 times higher than that of pristine CdS and gP-CdS, respectively. This work demonstrates the synergetic effects of charge carrier separation in the coupled nanostructure of the gradient-P-doped CdS NRs with the CoP cocatalyst, which provides a new platform for developing heterostructures with multiple charge separation and transfer routes for photocatalysis.

Synergistic effects of Fe and Mn dual-doping in Co3S4 ultrathin nanosheets for high-performance hybrid supercapacitors.

Dopant engineering in nanostructured materials is an effective strategy to enhance electrochemical performances via regulating the electronic structures and achieving more active sites. In this work, a robust electrode based on Fe and Mn co-doped Co3S4 (FM-Co3S4) ultrathin nanosheet arrays (NSAs) on the Ni foam substrate is prepared through a facile hydrothermal method followed by a subsequent sulfurization reaction. It has been found that the incorporation of Fe ions is beneficial to higher specific capacity of the final electrode and Mn ions contribute to the excellent rate capability in the reversible redox processes. Density functional theory (DFT) calculations further verify that the Mn doping in the Co3S4 obviously shorten the energy gap of Co3S4, which favors the electrochemical performances. Due to the synergetic effects of different transition metal ions, the as-prepared FM-Co3S4 ultrathin NSAs exhibit a high specific capacity of 390 mAh g-1 at 5 A g-1, as well as superior rate capability and excellent cycling stability. Moreover, the corresponding quasi-solid-state hybrid supercapacitors constructed with the FM-Co3S4 ultrathin NSAs and active carbon exhibit a high energy density of 55 Wh kg-1 at the power density of 752 W kg-1. These findings demonstrate a new platform for developing high-performance electrodes for energy storage applications.

Approach of fermi level and electron-trap level in cadmium sulfide nanorods via molybdenum doping with enhanced carrier separation for boosted photocatalytic hydrogen production.

Doping semiconductor with non-noble metal is a promising strategy to modulate the electronic structures and therefore develop efficient photocatalysts. In this study, we report a facile one-pot solvothermal strategy to synthesize Mo-doped CdS nanorods (NRs) using ammonium tetrathiomolybdate as the sources for both of S and Mo, cadmium acetate as the Cd source, and ethanediamine as the solvent heated at 180 °C for 24 h. The experimental characterizations and theoretical calculations reveal that Mo in the form of Mo4+ is incorporated into the CdS lattice to substitute Cd2+ ions and the Mo-S-Cd bonds are formed accordingly. The Mo doping not only introduces localized electron-trapping states at the bottom of conduction band minimum, but also elevates the Fermi level towards the defect level, which endows the doped system with enhanced n-type characteristic and the defect state with strong electron-trapping ability. Moreover, a nonuniform distribution of charge density is formed for the Mo-doped CdS NRs, facilitating the separation of photoexcited charge carriers. Therefore, the Mo-doped CdS NRs exhibit remarkably enhanced photocatalytic activity, with an average H2 production rate of 14.62 mmol·g-1·h-1 without using Pt as the co-catalyst, about 5.8 times higher than that of bare CdS. This work provides new insight into the facile synthesis of visible-light-driven photocatalysts as well as the effect of metal ion doping on the modulation of electronic structures.

Steady-state and time-resolved upconversion photoluminescence in Yb3+-Er3+ co-doped transparent ceramics of YAG.

Transparent ceramics (TCs) represent a new family of functional hard materials. In this Letter, steady-state and time-resolved upconversion photoluminescence in Yb3+-Er3+ co-doped TC of yttrium aluminum garnet (TC-YAG) are reported for the first time, to the best of our knowledge. Under the excitation of near-infrared 940 nm laser at room temperature, the Yb3+-Er3+ co-doped TC-YAG emits intense multi-color luminescence consisting of cyan, green, and red groups of sharp lines. More excitingly, the green group of luminescence due to the transitions from 4S3/2 to 4I15/2 states of Er3+ are the prominent components with the average lifetime of ∼0.3ms. The internal quantum efficiency of the green luminescence is estimated to be 32.8%. A unique dual-resonance energy transfer from Yb3+ to Er3+ via the excited-state vibronic transitions is proposed as the principal mechanism of the strongest green luminescence of Er3+ ions in TC-YAG.

AlGaN-based Schottky barrier deep ultraviolet photodetector grown on Si substrate.

This letter reports the influence of material quality and device processing on the performance of AlGaN-based Schottky barrier deep ultraviolet photodetectors grown on Si substrates. The thermal annealing can significantly improve Schottky barrier height and wet chemical etching can effectively remove etching damage. Meanwhile, the decrease of threading dislocation density and the pit size, especially the later, can substantially suppress reverse leakage. As a result, the reverse leakage current density of the as-fabricated deep UV photodetector was reduced down to 3×10-8 A/cm2. Furthermore, the responsivity of the deep UV photodetectors was greatly improved by reducing the point defect concentration.

5 nm Nanogap Electrodes and Arrays by Super-resolution Laser Lithography.

The development of reliable, mass-produced, and cost-effective sub-10 nm nanofabrication technology leads to an unprecedented level of integration of photonic devices. In this work, we describe the development of a laser direct writing (LDW) lithography technique with ∼5 nm feature size, which is about 1/55 of the optical diffraction limit of the LDW system (405 nm laser and 0.9 NA objective), and the realization of 5 nm nanogap electrodes. This LDW lithography exhibits an attractive capability of well-site control and mass production of ∼5 × 105 nanogap electrodes per hour, breaking the trade-off between resolution and throughput in a nanofabrication technique. Nanosensing chips have been demonstrated with the as-obtained nanogap electrodes, where controllable surface enhancement Raman scattering of rhodamine 6G has been realized via adjusting the gap width and, especially, the applied bias voltages. Our results establish that such a low-cost and high-efficient lithography technology has great potential to fabricate compact integrated circuits and biochips.

A one-pot "shielding-to-etching" strategy to synthesize amorphous MoS2 modified CoS/Co0.85Se heterostructured nanotube arrays for boosted energy-saving H2 generation.

In this study, a facile one-pot "shielding-to-etching" strategy has been designed for the synthesis of amorphous MoS2 modified CoS/Co0.85Se heterostructured nanotube arrays (a-MoS2/CoS/Co0.85Se HNTs) as a highly efficient electrocatalyst for boosted energy-saving H2 production, using Co(OH)x(CO3)y nanorods as the template. Interestingly, these multi-composition and hollow structured products were achieved in a controllable manner via only a one-pot synthesis, in which the nanorods with shielding layers were firstly obtained and then converted into nanotubes through further etching reaction. Benefiting from the combined nature of multiple-component hollow nanostructures, the electronic structure of the electrocatalyst is efficiently modulated, the electron transfer and ion diffusion pathways are effectively shortened and abundant active sites are created, which leads to excellent activity for urea oxidation and hydrogen evolution reactions with the as-prepared a-MoS2/CoS/Co0.85Se HNTs being employed as the electrodes. As a result, the whole urea electrolysis cell exhibits a driven voltage of only 1.42 V to achieve a current density of 10 mA cm-2, surpassing most reported transition-metal-based electrocatalysts. Moreover, a battery-assisted urea electrolyzer was assembled as well to demonstrate the feasibility of practical less-energy-intensive H2 generation. The method developed in this work is expected to broaden the way of designing and synthesizing multiple-component hollow nanostructures for various applications.