Deconvoluting Energy Transport Mechanisms in Metal Halide Perovskites Using CsPbBr3 Nanowires as a Model System

Understanding energy transport in metal halide perovskites is essential to effectively guide further optimization of materials and device designs. However, difficulties to disentangle charge carrier diffusion, photon recycling, and photon transport have led to contradicting reports and uncertainty regarding which mechanism dominates. In this study, monocrystalline CsPbBr₃ nanowires serve as 1D model systems to help unravel the respective contribution of energy transport processes in metal-halide perovskites. Spatially, temporally, and spectrally resolved photoluminescence (PL) microscopy reveals characteristic signatures of each transport mechanism from which a robust model describing the PL signal accounting for carrier diffusion, photon propagation, and photon recycling is developed. For the investigated CsPbBr₃ nanowires, an ambipolar carrier mobility of μ = 35 cm² V⁻¹ s⁻¹ is determined, and is found that charge carrier diffusion dominates the energy transport process over photon recycling. Moreover, the general applicability of the developed model is demonstrated on different perovskite compounds by applying it to data provided in previous related reports, from which clarity is gained as to why conflicting reports exist. These findings, therefore, serve as a useful tool to assist future studies aimed at characterizing energy transport mechanisms in semiconductor nanowires using PL.     

Bifunctional nanoporous ruthenium-nickel alloy nanowire electrocatalysts towards oxygen/hydrogen evolution reaction

A class of ruthenium-nickel alloy catalysts featured with nanoporous nanowires (NPNWs) were synthesized by a strategy combining rapid solidification with two-step dealloying. RuNi NPNWs exhibit excellent electrocatalytic activity and stability for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in which the RuNi-2500 NPNWs catalyst shows an OER overpotential of 327 mV to deliver a current density of 10 mA cm^?2 and the RuNi-0 NPNWs catalyst requires the overpotential of 69 mV at 10 mA cm^?2 showing the best HER activity in alkaline media. Moreover, the RuNi-1500 NPNWs catalyst was used as the bifunctional electrocatalyst in a two-electrode alkaline electrolyzer for water splitting, which exhibits a low cell voltage of 1.553 V and a long-term stability of 24 h at 10 mA cm^?2, demonstrating that the RuNi NPNWs catalysts can be considered as promising bifunctional alkaline electrocatalysts.     

1D sub 10 nm nanofabrication of ultrahydrophobic Ag@TiO2 nanowires and their photocatalytic,UV shielding and antibacterial properties

Here we report the synthesis of 1D TiO₂ sub 10 nm nanowires through one pot hydrothermal method in an alkaline NaOH medium at 95 °C for 36 h. Further, these TiO₂ nanowires were embellished with silver (Ag) using polyvinylpyrrolidone (PVP) and ethylene glycol (EG) based solvothermal route at 160 °C for 4 h. With Ag decoration the photocatalytic activity was enhanced and the complete photooxidation of Methylene Blue (MB) was achieved in 35 min under optimized conditions. Super- and ultra-hydrophobic coating on cotton fabric exhibited a consistent antibacterial activity with enhanced UV-blocking property. Enhanced multifunctional properties observed were primarily attributed to the formation of Ag decorated 1D sub 10 nm TiO₂ nanowires heterojunctions achieved using facile chemical route. Hence, such multiple functionalities make the 1D sub 10 nm TiO₂ nanowires good candidate for industrial and domestic wastewater treatment.     

Plasma-assisted CO2 reforming of methane over Ni-based catalysts: Promoting role of Ag and Sn secondary metals

Carbon dioxide (CO₂) and methane (CH₄) are the primary greenhouse gases (GHGs) that drive global climate change. CO₂ reforming of CH₄ or dry reforming of CH₄ (DRM) is used for the simultaneous conversion of CO₂ and CH₄ into syngas and higher hydrocarbons. In this study, DRM was investigated using Ag–Ni/Al₂O₃ packing and Sn–Ni/Al₂O₃ packing in a parallel plate dielectric barrier discharge (DBD) reactor. The performance of the DBD reactor was significantly enhanced when applying Ag–Ni/Al₂O₃ and Sn–Ni/Al₂O₃ due to the relatively high electrical conductivity of Ag and Sn as well as their anti-coke performances. Using Ag–Ni/Al₂O₃ consisting of 1.5 wt% Ag and 5 wt% Ni/Al₂O₃ as the catalyst in the DBD reactor, 19% CH₄ conversion, 21% CO₂ conversion, 60% H₂ selectivity, 81% CO selectivity, energy efficiency of 7.9% and 0.74% (by mole) coke formation were achieved. In addition, using Sn–Ni/Al₂O₃, consisting of 0.5 wt% Sn and 5 wt% Ni/Al₂O₃, 15% CH₄ conversion, 19% CO₂ conversion, 64% H₂ selectivity, 70% CO selectivity, energy efficiency of 6.0%, and 2.1% (by mole) coke formation were achieved. Sn enhanced the reactant conversions and energy efficiency, and resulted in a reduction in coke formation; these results are comparable to that achieved when using the noble metal Ag. The decrease in the formation of coke could be correlated to the increase in the CO selectivity of the catalyst. Good dispersion of the secondary metals on Ni was found to be an important factor for the observed increases in the catalyst surface area and catalytic activities. Furthermore, the stability of the catalytic reactions was investigated for 1800 min over the 0.5 wt% Ag-5 wt% Ni/Al₂O₃ and 0.5 wt% Sn-5 wt% Ni/Al₂O₃ catalysts. The results showed an increase in the reactant conversions with an increase in the reaction time.     

Indirect charge transfer of holes via surface states in ZnO nanowires for photoelectrocatalytic applications

In this work, ZnO nanowires with high aspect ratio were obtained by fast and simple electrochemical anodization. Morphological, structural and photoelectrochemical characteristics of the synthesized ZnO nanowires were evaluated by using different techniques: field emission scanning electron microscopy, atomic force microscopy, high resolution transmission electron microscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV–VIS spectroscopy, Mott-Schottky analysis and photoelectrochemical impedance spectroscopy. The synthesized ZnO nanowires presented high roughness and high crystallinity. Besides, surface defects were identified in the sample. The value of the donor density (N_D) was in the order of 10¹⁹ cm^?3 in the dark and 10²⁰ cm^?3 under illumination. In addition, the ZnO nanowires presented good photosensibility, with a photocurrent density response 85 times higher than a ZnO compact layer, and lower resistance to charge transfer. The charge transfer processes taking place at the ZnO/electrolyte interface were studied, since these processes strongly influence the photoelectrocatalytic efficiency of the material. According to the results, the charge transfer of holes in the synthesized ZnO nanowires occurs indirectly via surface states. In this regard, surface states may be an important feature for photoelectrocatalytic applications since they could provide lower onset voltages and higher anodic current densities.     

Influence of the dispersion of Nanoclays on the cellular structure of foams based on polystyrene

In the present work blends of polystyrene (PS) with sepiolites have been produced using a melt extrusion process. The dispersion degree of the sepiolites in the PS has been analyzed by dynamic shear rheology and X-ray micro-computed tomography. Sepiolites treated with quaternary ammonium salts (O-QASEP) are better dispersed in the PS matrix than natural sepiolites (N-SEP) or sepiolites organo-modified with silane groups (O-SGSEP). A percolated network is obtained when using 6.0 wt% of O-QASEP, 8.0 wt% of N-SEP and 10.0 wt% of O-SGSEP. It has been shown that multiple extrusion processes have a negative effect on the polymer architecture. They produce a reduction in the length of the polymeric chains, and they do not lead to a better dispersion of the particles in the polymer matrix. Foams have been produced using a gas dissolution foaming process, where a strong effect of the dispersion degree on the cellular structure of the different foams was found. The effects on the cellular structure obtained by using different types of sepiolites, different contents of sepiolites and different extrusion conditions have been analyzed. The foams produced with the formulations containing O-QASEP present the lowest cell size and the most homogeneous cellular structures.     

Simultaneously enhancing mechanical and microwave absorption properties of Cf/SiC composites via SiC nanowires additions

C_f/SiC composite is an excellent structural and functional material, silicon carbide nanowires (SiCnws) are not only a toughening material but also a great application in the field of microwave absorption. In this study, SiCnws are grown on the surface of carbon fiber (C_f) by polymer impregnation and pyrolysis, and the SiC matrix was prepared by chemical vapor osmosis method. The SiCnws are introduced to enhance the mechanical and microwave absorption properties simultaneously. After 3 impregnations, the flexural strength of the composite was 107.35 ± 10 MPa. When the thickness is 1.86 mm, the minimum reflection loss value is ?41.08 dB, and the effective absorption bandwidth (RL ≤ ?10 dB) is 3.86 GHz. Furthermore, the microwave absorption mechanism of the material is discussed. This work provides a new method to prepare lightweight, stable and high-performance microwave absorption materials, and these materials are expected to be used in high temperature environments.     

Fabrication of 3D Ni nanosheet array on Crofer22APU interconnect and NiO-YSZ anode support to sinter with small-size Ag nanoparticles for low-temperature sealing SOFCs

A novel low-temperature sealing method was developed to seal solid oxide fuel cells. The 3D Ni nanosheet array was pre-fabricated on faying surfaces of Crofer22APU interconnect and NiO-YSZ anode-support. Then it was covered with Au film without changing its morphology. This special nanostructure improved sintering efficiency between Ag nanoparticles and substrates. A dense joint was obtained at the low-temperature between 250 °C–300 °C. This method effectively avoided the oxidation of interconnect during sealing. When joints were sealed at 300 °C, the shear strength reached 16 MPa. The fracture was mainly located in the central Ag layer, presenting a significant plastic deformation. Due to the effective protection of Ni layer, joints also possessed excellent oxidation resistance in oxidizing atmosphere at 800 °C for 400 h. After high-temperature oxidation, the shear strength was increased to 23 MPa, revealing an increasement of 43.8% compared with the as-sealed condition (16 MPa). This sealing method has great potential in sealing solid oxide fuel cells. It also can be extended to seal other energy-conversion devices.     

Layered-Perovskite Nanowires with Long-Range Orientational Order for Ultrasensitive Photodetectors

2D layered metal-halide perovskites combine efficient exciton radiative recombination in crystal interior with long-distance free-carrier conduction at layer edges, which are promising candidates for realizing high-performance photovoltaic, light-emission and photodetection devices. The anisotropic electrical conductivity in layered perovskites imposes an additional requirement of orientational control for enabling favorable charge transport. However, rational fabrication of single-crystalline nanostructures with pure crystallographic orientation is still elusive. Herein, large-scale pure (101)-orientated 2D-perovskite single-crystalline nanowire arrays are realized by combining solvent engineering with the capillary-bridge lithography technique. Ordered nucleation at liquid–air interface and unidirectional growth along the dewetting direction are demonstrated by fluorescence microscopy and grazing-incidence X-ray scattering in discrete capillary bridges. In consideration of crystal interior exhibiting high resistance arising from the serial insulating organic barriers and ultrafast dissociation of excitons to generate long-lived free carriers at layer edges, ultrasensitive photodetectors are demonstrated with average responsivity exceeding 1.1 × 10⁴ A W⁻¹ and detectivity exceeding 9.1 × 10¹⁵ Jones.     

Investigation of improved dielectric and thermal properties of ternary nanocomposite PMMA/MXene/ZnO fabricated by in-situ bulk polymerization

Electric power system applications demand for high-temperature dielectric materials. The improved performance of polymer nanocomposites requires improvement in their thermal conductivity & stability, dielectric stability and processing technique. However, they often lose their dielectric properties with a rise in temperature. Here, we offer a solution by incorporating electrically conducting material (MXene) and semiconducting inorganic nanoparticles (ZnO NPs) into an insulating PMMA polymer matrix to maintain high dielectric constant, both at the room and high temperature. Therefore, to achieve desirable thermal and dielectric properties is the main objective of the present study based on the homogeneous distribution of the nanofillers by in-situ bulk polymerization assisted by strong sonication in the corresponding polymer. The introduction of MXene and ZnO NPs into the PMMA not only acquires a substantial increment in the dielectric constant, to attain a value 437, with minimum energy loss of 0.36 at 25 Hz, but also improves the thermal conductivity of PMMA up to 14 times by causing the reduction of thermal resistance, which is actually responsible for the poor thermal conductivity of amorphous pure PMMA polymer. More importantly, hybrid PMMA/4:2 wt% MXene:ZnO nanocomposite leads to an excellent thermal stability. Moreover, further characterization of the synthesized nanocomposites by FTIR, SEM and XRD leads to the evaluation of strong interaction of ternary components with PMMA matrix.