Constructing Fe-N4 Sites through Anion Exchange-mediated Transformation of Fe Coordination Environments in Hierarchical Carbon Support for Efficient Oxygen Reduction.

Metal single atoms (SAs) anchored in carbon support via coordinating with N atoms are efficient active sites to oxygen reduction reaction (ORR). However, rational design of single atom catalysts with highly exposed active sites is challenging and urgently desirable. Herein, an anion exchange strategy is presented to fabricate Fe-N4 moieties anchored in hierarchical carbon nanoplates composed of hollow carbon spheres (Fe-SA/N-HCS). With the coordinating O atoms are substituted by N atoms, Fe SAs with Fe-O4 configuration are transformed into the ones with Fe-N4 configuration during the thermal activation process. Insights into the evolution of central atoms demonstrate that the SAs with specific coordination environment can be obtained by modulating in situ anion exchange process. The strategy produces a large quantity of electrochemical accessible site and high utilization rate of Fe-N4 . Fe-SA/N-HCS shows excellent ORR electrocatalytic performance with half-wave potential of 0.91 V (vs. RHE) in 0.1 M KOH, and outstanding performance when used in rechargeable aqueous and flexible Zn-air batteries. The evolution pathway for SAs demonstrated in this work offers a novel strategy to design SACs with various coordination environment and enhanced electrocatalytic activity.

Reversible Halide Exchange Reaction of Organometal Trihalide Perovskite Colloidal Nanocrystals for Full-Range Band Gap Tuning.

In recent years, methylammonium lead halide (MAPbX3, where X = Cl, Br, and I) perovskites have attracted tremendous interest caused by their outstanding photovoltaic performance. Mixed halides have been frequently used as the active layer of solar cells, as a result of their superior physical properties as compared to those of traditionally used pure iodide. Herein, we report a remarkable finding of reversible halide-exchange reactions of MAPbX3, which facilitates the synthesis of a series of mixed halide perovskites. We synthesized MAPbBr3 plate-type nanocrystals (NCs) as a starting material by a novel solution reaction using octylamine as the capping ligand. The synthesis of MAPbBr(3-x)Clx and MAPbBr(3-x)Ix NCs was achieved by the halide exchange reaction of MAPbBr3 with MACl and MAI, respectively, in an isopropyl alcohol solution, demonstrating full-range band gap tuning over a wide range (1.6-3 eV). Moreover, photodetectors were fabricated using these composition-tuned NCs; a strong correlation was observed between the photocurrent and photoluminescence decay time. Among the two mixed halide perovskite series, those with I-rich composition (x = 2), where a sole tetragonal phase exists without the incorporation of a cubic phase, exhibited the highest photoconversion efficiency. To understand the composition-dependent photoconversion efficiency, first-principles density-functional theory calculations were carried out, which predicted many plausible configurations for cubic and tetragonal phase mixed halides.

Toward Highly Luminescent and Stabilized Silica-Coated Perovskite Quantum Dots through Simply Mixing and Stirring under Room Temperature in Air.

Methylammonium (MA) lead halide (MAPbX3, X = Cl, Br, I) perovskite quantum dots (PQDs) are very sensitive to environment (moisture, oxygen, and temperature), suffering from poor stability. To improve the stability, we synthesized silica-coated PQDs (SPQDs) by an improved ligand-assisted reprecipitation method through simply mixing and stirring under room temperature in air without adding water and catalyst, the whole process took only a few seconds. The photoluminescence (PL) spectra of the SPQDs can be tuned continuously from 460 to 662 nm via adjusting the composition proportion of precursors. The highest PL quantum yields (PLQYs) of blue-, green-, and red-emissive SPQDs are 56, 95, and 70%, respectively. The SPQDs show remarkably improved environmental and thermal stability compared to the naked PQDs because of effective barrier created by the coated silica between the core materials and the ambience. Furthermore, it is found that different light-emitting SPQDs can maintain their original PL properties after mixing of them and anion-exchange reactions have not happened. These attributes were then used to mix green- and yellow-emissive SPQDs with polystyrene (PS) to form color-converting layers for the fabrication of white light-emitting devices (WLEDs). The WLEDs exhibit excellent white light characteristics with CIE 1931 color coordinates of (0.31, 0.34) and color rendering index (CRI) of 85, demonstrating promising applications of SPQDs in lighting and displays.

One-Step Synthesis of FA-Directing FAPbBr3 Perovskite Nanocrystals toward High-Performance Display.

Hybrid organic-inorganic and all-inorganic metal halide perovskite nanocrystals (PNCs) have aroused extensive attention from both academic and industrial researchers, considering their excellent performance in optoelectronic applications. Herein, we develop a facile and time-saving strategy to synthesize NH2CH═NH2PbBr3 (NH2CH═NH+, FA) PNCs at room temperature. Benefiting from this facile method, high-quality FAPbBr3 PNCs with photoluminescence quantum yield up to 76% and narrow full width at half-maxima of 20 nm can be produced on a large scale. Moreover, anion-exchange reactions run by using FAPbBr3 as a template, producing various PNCs with different anion constituents. By manipulating the ratios of two different anions, a series PNCs with various bright photoluminescence ranging from 452 to 646 nm could be done. On account of superior and adjustable photoluminescence over the visible spectral region, FAPbBr3 PNCs can be applied as a promising color-converting material in liquid-crystal display (LCD) backlight, white light-emitting diode (WLED), and inkjet printing pattern. As a proof of concept, FAPbBr3 PNCs with green emission were integrated in WLED and LCD backlight, accomplishing a color rendering index of 87.5 and a wide color gamut of 116%, respectively.

CoSe2 nanowires array as a 3D electrode for highly efficient electrochemical hydrogen evolution.

In this Letter, we describe the development of a CoSe2 nanowires array on carbon cloth (CoSe2 NW/CC) through a facile two-step hydrothermal preparative strategy. As a novel 3D nanoarray electrode for electrochemical hydrogen evolution, CoSe2 NW/CC exhibits excellent catalytic activity and durability in acidic media. It needs overpotentials of 130 and 164 mV to approach 10 and 100 mA cm(-2), respectively, and its activity is maintained for at least 48 h. This work would open up new avenues for the rational design of a variety of arrayed transition-metal chalcogenide cathodes for technological application toward large-scale hydrogen generation from water.

CoNi(2)S(4) nanosheet arrays supported on nickel foams with ultrahigh capacitance for aqueous asymmetric supercapacitor applications.

We report that CoNi2S4 nanosheet arrays exhibit ultrahigh specific capacitance of 2906 F g(-1) and areal capacitance of 6.39 F cm(-2) at a current density of 5 mA cm(-2), as well as good rate capability and cycling stability, and superior electrochemical performances with an energy density of 33.9 Wh kg(-1) at a power density of 409 W kg(-1) have been achieved in an assembled aqueous asymmetric supercapacitor. The CoNi2S4 nanosheet arrays were in situ grown on nickel foams by a facile two-step hydrothermal method. The formation mechanism of the CoNi2S4 nanosheet arrays was based on an anion-exchange reaction involving the pseudo Kirkendall effect. The two aqueous asymmetric supercapacitors in series using the CoNi2S4 nanosheet arrays as the positive electrodes can power four 3-mm-diameter red-light-emitting diodes. The outstanding supercapacitive performance of CoNi2S4 nanosheet arrays can be attributed to ravine-like nanosheet architectures with good mechanical and electrical contact, low crystallinity and good wettability without an annealing process, rich redox reactions, as well as high conductivity and transport rate for both electrolyte ions and electrons. Our results demonstrate that CoNi2S4 nanosheet arrays are promising electrode materials for supercapacitor applications.