ABSTRACT
Assembling well-defined MOF superstructures remains challenging as it requires easily removable hard templates or readily available immiscible solutions for an emulsion-based soft-template approach. In this work, a single-step emulsion-free soft templating approach is reported to spontaneously prepare hollow ZIF-8 and ZIF-67 colloidosomes with no further purification. These superstructures can load different enzymes regardless of the size and charge with a high encapsulation efficiency of 99%. We envisage that this work will expand the repertoires of MOF superstructures by the judicious selection of precursors and the reaction medium.
ABSTRACT
Porous materials with molecular-scale ordering have attracted major attention mainly because of the possibility to engineer their pores for selective applications. Periodic mesoporous organosilica is a class of hybrid materials where self-assembly of the organic linkers provides a crystal-like pore wall. However, unlike metal coordination, specific geometries cannot be predicted because of the competitive and dynamic nature of noncovalent interactions. Herein, we study the influence of competing noncovalent interactions in the pore walls on the biodegradation of organosilica frameworks for drug delivery application. These results support the importance of studying self-assembly patterns in hybrid frameworks to better engineer the next generation of dynamic or "soft" porous materials.
ABSTRACT
Unintentional self-doping in semiconductors through shallow defects is detrimental to optoelectronic device performance. It adversely affects junction properties and it introduces electronic noise. This is especially acute for solution-processed semiconductors, including hybrid perovskites, which are usually high in defects due to rapid crystallization. Here, we uncover extremely low self-doping concentrations in single crystals of the two-dimensional perovskites (C6H5C2H4NH3)2PbI4·(CH3NH3PbI3)n-1 (n = 1, 2, and 3), over three orders of magnitude lower than those of typical three-dimensional hybrid perovskites, by analyzing their conductivity behavior. We propose that crystallization of hybrid perovskites containing large organic cations suppresses defect formation and thus favors a low self-doping level. To exemplify the benefits of this effect, we demonstrate extraordinarily high light-detectivity (1013 Jones) in (C6H5C2H4NH3)2PbI4·(CH3NH3PbI3)n-1 photoconductors due to the reduced electronic noise, which makes them particularly attractive for the detection of weak light signals. Furthermore, the low self-doping concentration reduces the equilibrium charge carrier concentration in (C6H5C2H4NH3)2PbI4·(CH3NH3PbI3)n-1, advantageous in the design of p-i-n heterojunction solar cells by optimizing band alignment and promoting carrier depletion in the intrinsic perovskite layer, thereby enhancing charge extraction.
ABSTRACT
The impact of post-synthesis processing in reduced graphene oxide materials for supercapacitor electrodes has been analyzed. A comparative study of vacuum, freeze and critical point drying was carried out for hydrothermally reduced graphene oxide demonstrating that the optimization of the specific surface area and preservation of the porous network are critical to maximize its supercapacitance performance. As described below, using a supercritical fluid as the drying medium, unprecedented values of the specific surface area (364 m2 g-1) and supercapacitance (441 F g-1) for this class of materials have been achieved.
ABSTRACT
The number of studies on organic-inorganic hybrid perovskites has soared in recent years. However, the majority of hybrid perovskites under investigation are based on a limited number of organic cations of suitable sizes, such as methylammonium and formamidinium. These small cations easily fit into the perovskite's three-dimensional (3D) lead halide framework to produce semiconductors with excellent charge transport properties. Until now, larger cations, such as ethylammonium, have been found to form 2D crystals with lead halide. Here we show for the first time that ethylammonium can in fact be incorporated coordinately with methylammonium in the lattice of a 3D perovskite thanks to a balance of opposite lattice distortion strains. This inclusion results in higher crystal symmetry, improved material stability, and markedly enhanced charge carrier lifetime. This crystal engineering strategy of balancing opposite lattice distortion effects vastly increases the number of potential choices of organic cations for 3D perovskites, opening up new degrees of freedom to tailor their optoelectronic and environmental properties.
ABSTRACT
This paper describes the use of 4-carboxyphenyl-grafted screen-printed carbon electrodes (4-CP-SPEs) for trace lead analysis. These novel and simple use of electrodes were easily prepared by the electrochemical reduction of the corresponding diazonium salt. Pb detection was then performed by a three-steps method in order to avoid oxygen interference: (i) immersion of the grafted screen-printed electrode (SPE) in the sample and adsorption of Pb(II), (ii) reduction of adsorbed Pb(II) by chronoamperometry (CA), and (iii) oxidation of Pb by Anodic Square Wave Voltammetry (SWV). The reoxidation response was exploited for lead detection and quantification. In order to optimize the analytical responses, the influence of the adsorption medium pH and the adsorption time were investigated. Moreover, an interference study was carried out with Cu(II), Hg(II), Al(III), Mn(II), Zn(II), Cd(II) and no major interference can be expected to quantify Pb(II). The described method provided a limit of detection and a limit of quantification of 1.2 × 10(-9)M and 4.1 × 10(-9)M, respectively. These performances indicate that the 4-CP-SPE could be considered as an efficient tool for environmental analysis.
