Stable emission in glass Lead halide perovskites can exhibit bright, narrow band photoluminescence but have stability issues related to formation of inactive phases and the loss of lead ions. Hou et al . show that the black, photoactive phase of cesium lead iodide can be stabilized by forming a composite with a glassy phase of a metal-organic framework through liquid-phase sintering. The photoluminescence is at least two orders of magnitude greater than that of the pure perovskite. The glass stabilizes the perovskite under high laser excitation, and about 80% of the photoluminescence was maintained after 10,000 hours of water immersion. —PDS
Selective catalytic reduction of CO 2 to methanol has tremendous importance in the chemical industry. It mitigates two critical issues in the modern society, the overwhelming climate change and the dependence on fossil fuels. The most used catalysts are currently based on mixed copper and zinc phases, where the high surface of active copper species is a critical factor for the catalyst performance. Motivated by the recent breakthrough in the controllable synthesis of bimetallic MOF-74 materials by ball milling, we targeted to study the potential of ZnCu-MOF-74 for catalytic CO 2 reduction. Here, we tested whether the nanosized channels decorated with readily accessible and homogeneously distributed Zn and Cu metal sites would be advantageous for the catalytic CO 2 reduction. Unlike the inactive monometallic Cu-MOF-74, ZnCu-MOF-74 shows moderate catalytic activity and selectivity for the methanol synthesis. Interestingly, the postsynthetic mechanochemical treatment of desolvated ZnCu-MOF-74 resulted in amorphization and a significant increase in both the activity and selectivity of the catalyst despite the destruction of the well-ordered and porous MOF-74 architecture. The results emphasize the importance of defects for the MOF catalytic activity and the potential of amorphous MOFs to be considered as heterogeneous catalysts. Scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and 13 C magic angle-spinning nuclear magnetic resonance (MAS NMR) were applied to establish quantitative structure− reactivity relationships. The apparent activation energy of rate reaction kinetics has indicated different pathway mechanisms, primarily through reverse water−gas shift (RWGS). Prolonged time on stream productivity, stability and deactivation were assessed, analysing the robustness or degradation of metal−organic framework nanomaterials. Scalable MOF production processes are making the latter more appealing within emerging industrial decarbonisation, in particular for carbon capture and utilisation (CCU) or hydrogen carrier storage. Acknowledging scale, the costs of fabrication are paramount.
Two types of preformed alginate wet gels, one with a low (30−35%) and the other with a high (65−75%) content of glucuronic acid, were reacted with an aliphatic triisocyanate that was priorly allowed to diffuse in the pores. This reaction formed urethane groups on the surface of the alginate framework and also formed a polyurea (PUA) network connecting these urethane groups via respective reactions of the triisocyanate with alginate surface −OH groups or with gelation water remaining adsorbed on the inner surfaces of the wet gels. These processes formed a conformal nanothin film of PUA around the alginate network. After drying the wet gels with the supercritical fluid CO 2 , we obtained PUA/polyurethane-crosslinked alginate (X-alginate) aerogels. Although X-alginate aerogels are essentially copolymers, unlike all copolymers mentioned in previous literature reports, the relative topology of the alginate and the cross-linker is defined at the nanoscopic scale rather than at the molecular level. For the systematic study of X-alginate aerogels as a function of synthetic conditions, the experimental protocol was designed according to the central circumscribed rotatory design model using the alginate and the triisocyanate concentration as independent variables. Empirical models were derived for all relevant material properties by fitting experimental data to the two independent variables. The chemical identity of all samples was confirmed with attenuated total reflectance−Fourier transform infrared spectroscopy and solid-state 13 C and 15 N cross-polarization magic angle spinning NMR spectroscopy. The percentage of PUA uptake in X-alginate aerogels (58−98%) was calculated from skeletal density data. Scanning electron microscopy showed that all samples were nanofibrous, indicating that PUA coated conformally the skeletal network of both alginates, and the micromorphology remained the same as in the native (non-cross-linked) samples. X-alginate aerogels are mechanically strong materials, in contrast to their native counterparts, which are extremely weak mechanically. Compared to various organic aerogels from the literature, X-alginate aerogels can be as stiff as many other polymeric aerogels with 2 or 3 times higher densities. In addition, X-alginate aerogels are good candidates for sound insulation applications, as the speed of sound in most samples was estimated to be significantly lower than the speed of sound in dry air.
The melting behaviour of metal–organic frameworks (MOFs) has aroused significant research interest in the areas of materials science, condensed matter physics and chemical engineering. This work first introduces a novel method to fabricate a bimetallic MOF glass, through melt‐quenching of the cobalt‐based zeolitic imidazolate framework (ZIF) [ZIF‐62(Co)] with an adsorbed ferric coordination complex. The high‐temperature chemically reactive ZIF‐62(Co) liquid facilitates the formation of coordinative bonds between Fe and imidazolate ligands, incorporating Fe nodes into the framework after quenching. The resultant Co–Fe bimetallic MOF glass therefore shows a significantly enhanced oxygen evolution reaction performance. The novel bimetallic MOF glass, when combined with the facile and scalable mechanochemical synthesis technique for both discrete powders and surface coatings on flexible substrates, enables significant opportunities for catalytic device assembly.
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