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Metal-organic frameworks (MOFs) hold great promise for diverse applications when combined with polymers. However, a persistent challenge lies in the susceptibility of exposed MOF pores to molecule and polymer penetration, compromising the porosity and overall performance. Here, we design a molecular-caged MOF (MC-MOF) to achieve contracted window without sacrificing the MOF porosity by torsional conjugated ligands. These molecular cages effectively shield against the undesired molecule penetration during polymerization, thereby preserving the pristine porosity of MC-MOF and providing outstanding light and thermal management to the composites. The polymer containing 0.5 wt % MC-MOF achieves an 83% transmittance and an exceptional haze of 93% at 550 nanometers, coupled with remarkable thermal insulation. These MC-MOF/polymer composites offer the potential for more uniform daylighting and reduced energy consumption in sustainable buildings when compared to traditional glass materials. This work delivers a general method to uphold MOF porosity in polymers through molecular cage design, advancing MOF-polymer applications in energy and sustainability.

Phonon-assisted photon upconversion holds great potential for numerous applications, e.g., optical refrigeration. However, traditional semiconductors face energy gain limitations due to thermal energy, typically achieving only ~25 milli-electron volts at room temperature. Here, we demonstrate that quasi-two-dimensional perovskites, with a soft hybrid organic-inorganic lattice, can efficiently upconvert photons with an anti-Stokes shift exceeding 200 milli-electron volts. By using microscopic transient absorption measurements and density functional theory calculations, we explicate that the giant energy gain stems from strong lattice fluctuation leading to a picosecond timescale transient band energy renormalization with a large energy variation of around ±180 milli-electron volts at room temperature. The motion of organic molecules drives the deformation of inorganic framework, providing energy and local states necessary for efficient upconversion within a time constant of around 1 ps. These results establish a deep understanding of perovskite-based photon upconversion and offer previously unknown insights into the development of various upconversion applications.

Bismuth-based double perovskite Cs 2 AgBiBr 6 is regarded as a potential candidate for low-toxicity, high-stability perovskite solar cells. However, its performance is far from satisfactory. Albeit being an indirect bandgap semiconductor, we observe bright emission with large bimolecular recombination coefficient (reaching 4.5 ± 0.1 × 10 -11 cm 3 s -1 ) and low charge carrier mobility (around 0.05 cm 2 s -1 V -1 ). Besides intermediate Fröhlich couplings present in both Pb-based perovskites and Cs 2 AgBiBr 6 , we uncover evidence of strong deformation potential by acoustic phonons in the latter through transient reflection, time-resolved terahertz measurements, and density functional theory calculations. The Fröhlich and deformation potentials synergistically lead to ultrafast self-trapping of free carriers forming polarons highly localized on a few units of the lattice within a few picoseconds, which also breaks down the electronic band picture, leading to efficient radiative recombination. The strong self-trapping in Cs 2 AgBiBr 6 could impose intrinsic limitations for its application in photovoltaics., (Copyright © 2021 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works. Distributed under a Creative Commons Attribution NonCommercial License 4.0 (CC BY-NC).)

Broad spectral range reflectance imaging spectroscopy (BR-RIS) from the near UV through the mid-infrared (IR) (350 to 25,000 nm or 28,571 to 400 cm -1 ) was investigated as an imaging modality to provide maps of organic and inorganic artists' materials in paintings. While visible-to-near-IR (NIR) reflectance and elemental x-ray fluorescence (XRF) imaging spectroscopies have been used for in situ mapping, each method alone is insufficient for robust identification. Combining the two improves results but requires complex data processing. To test BR-RIS, image cubes from early Italian Renaissance illuminated manuscripts were acquired using two spectrometers. Maps of pigments, including trace minerals associated with mined azurite, and their associated binding media were made. BR-RIS has a more straightforward analysis approach as implemented here than visible-to-NIR, mid-IR, or XRF imaging spectroscopy alone and offers the largest amount of macroscale information for mapping artists' materials by comparison.

Striking morphological similarities found between superstructures of a wide variety of seemingly unrelated crystalline membrane systems hint at the existence of a common formation mechanism. Resembling systems such as multiwalled carbon nanotubes, bacterial protein shells, or peptide nanotubes, the self-assembly of SDS/β-cyclodextrin complexes leads to monodisperse multilamellar microtubes. We uncover the mechanism of this hierarchical self-assembly process by time-resolved small- and ultrasmall-angle x-ray scattering. In particular, we show that symmetric crystalline bilayers bend into hollow cylinders as a consequence of membrane line tension and an anisotropic elastic modulus. Starting from single-walled microtubes, successive nucleation of new cylinders inside preexisting ones drives an inward growth. As both the driving forces that underlie the self-assembly behavior and the resulting morphologies are common to systems of ordered membranes, we believe that this formation mechanism has a similarly general applicability.

We report the discovery of the hydrotropic properties of a recyclable aromatic acid, p -toluenesulfonic acid ( p -TsOH), for potentially low-cost and efficient fractionation of wood through rapid and near-complete dissolution of lignin. Approximately 90% of poplar wood (NE222) lignin can be dissolved at 80°C in 20 min. Equivalent delignification using known hydrotropes, such as aromatic salts, can be achieved only at 150°C or higher for more than 10 hours or at 150°C for 2 hours with alkaline pulping. p -TsOH fractionated wood into two fractions: (i) a primarily cellulose-rich water-insoluble solid fraction that can be used for the production of high-value building blocks, such as dissolving pulp fibers, lignocellulosic nanomaterials, and/or sugars through subsequent enzymatic hydrolysis; and (ii) a spent acid liquor stream containing mainly dissolved lignin that can be easily precipitated as lignin nanoparticles by diluting the spent acid liquor to below the minimal hydrotrope concentration. Our nuclear magnetic resonance analyses of the dissolved lignin revealed that p -TsOH can depolymerize lignin via ether bond cleavage and can separate carbohydrate-free lignin from the wood. p -TsOH has a relatively low water solubility, which can facilitate efficient recovery using commercially proven crystallization technology by cooling the concentrated spent acid solution to ambient temperatures to achieve environmental sustainability through recycling of p -TsOH.