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Macroscopic Co3O4 hexagonal tubes were successfully synthesized using hollow two-dimensional (2D) MOL (metal-organic layer) single crystals as sacrificial templates. The hollow 2D MOL single crystals were prepared under hydrothermal conditions with acetonitrile (MeCN) as an interference agent. The formation of hollow-structured 2D MOL single crystals was tracked by time-dependent experiments, and two simultaneous paths-namely, the crystal-to-crystal transformation in solution and the dissolution + migration (toward the external surface) of inner crystallites-were identified as playing a key role in the formation of the unique hollow structure. The calculated change in Gibbs free energy (ΔG = -1.18 eV) indicated that the crystal-to-crystal transformation was spontaneous at 393 K. Further addition of MeCN as an interference agent eventually leads to the formation of macroscopic hexagonal tubes. Among all of the as-synthesized Co3O4, Co-MeCN-O with a hexagonal tube morphology exhibited the best catalytic performse in catalytic performance was observed after 120 h at 220 °C and it is still stable after cycling tests, which indicates that it exhibits excellent stability for toluene oxidation. This study sheds lights on the controllable synthesis of macroporous-microporous materials in single-crystalline form without an external template, and, thus, it may serve as a reference for future design and synthesis of hollow porous materials with outstanding catalytic performance.The potential energy surface for opening and ring-enlargement reactions of 1,2-thiaphosphetane with different oxidation states and coordination at phosphorus has been computationally explored. The most favored [2 + 2] cycloreversions are the so-called normal Wittig-type reactions furnishing an alkene and a P═S-containing component. Somewhat unfavored are reactions involving the P-S bond cleavage and a C-to-P hydrogen shift as well as a ring enlargement to a 1,3,2-dithiaphospholane in the case of high coordinate derivatives. Apart from a two-step P-to-S oxygen transfer in 1,2σ4λ5-thiaphosphetane P-oxide, an interesting reaction is the P-S bond cleavage leading to a thiabetaine which, alternatively, can be formed by the C-attack of a phosphinidene oxide on a thiirane. A similar route, energetically more favored, was found for 1,2σ5λ5-thiaphosphetane starting from thiirane and the corresponding phosphane. For a wide set of P(III) reagents including HPR2 (R = Me, Ph), PR3 (R = Me, Ph, NMe2, OMe, F, Cl), and HP═O, the competitive direct S-attack was found to be the preferred pathway for the desulfurization of thiiranes, and the relative tendency for these P(III) reagents to act as an S-atom acceptor, the thermodynamic S-transfer potential (TSP) scale, was defined using the S8/S7 couple as a point of reference.Source separation of urine can enable nutrient recycling, facilitate wastewater management, and conserve water. Anisomycin Without stabilization of the urine, urea is quickly hydrolyzed into ammonia and (bi)carbonate, causing nutrient loss, clogging of collection systems, ammonia volatilization, and odor nuisance. In this study, electrochemically induced precipitation and stabilization of fresh urine was successfully demonstrated. By recirculating the urine over the cathodic compartment of an electrochemical cell, the pH was increased due to the production of hydroxyl ions at the cathode. The pH increased to 11-12, decreasing calcium and magnesium concentrations by >80%, and minimizing scaling and clogging during downstream processing. At pH 11, urine could be stabilized for one week, while an increase to pH 12 allowed urine storage without urea hydrolysis for >18 months. By a smart selection of membranes [anion exchange membrane (AEM) with a cation exchange membrane (CEM) or a bipolar membrane (BPM)], no chemical input was required in the electrochemical cell and an acidic stream was produced that can be used to periodically rinse the electrochemical cell and toilet. On-site electrochemical treatment, close to the toilet, is a promising new concept to minimize clogging in collection systems by forcing controlled precipitation and to inhibit urea hydrolysis during storage until further treatment in more centralized nutrient recovery plants.Thermoplastic “all-cellulose” composites were synthesized by covalent functionalization of cellulose acetate (CA) with oxidized carbonized cellulose (OCC). The OCC were manufactured via microwave-assisted hydrothermal carbonization (HTC) of cellulose followed by oxidation and dialysis. The OCC were of micrometer-size, had plane morphology and contained a variety of oxygen functionalities, enabling transformation into acyl chlorinated OCC under moderate reaction conditions. The synthesis of OCC-modified CA composites and neat CA were performed in the recyclable ionic liquid 1-allyl-3-methylimidazolium chloride. The degree of acetylation and amount of OCC were varied to establish their influence on thermal and physical properties of the composites. The OCC-modified CA composites displayed a notably enhanced film-forming ability, which led to improved optical and mechanical properties compared to neat CA. In addition, it was shown that OCC-modified CA composites can be synthesized from waste products, such as paper tissues. The OCC-modification was demonstrated to be a promising route to transparent and strong thermoplastic “all-cellulose” composites with moderate flexibility.An acentric borate family, Ag4B4O7X2 (X = Br, I), has been prepared by slow cooling stoichiometric melts in evacuated silica ampules. Their crystal structure is comprised of two porous interpenetrating frameworks and demonstrates a further development of the “salt-inclusion” architecture toward a “covalent-inclusion” structure. The (Ag2X)+ sublattice shows strong anharmonic vibrations. Thermal expansion is strongly anisotropic because of the presence of condensed rigid kernite boron-oxygen chains aligned perpendicular to the c axes.Organometallic uranium complexes that can activate small molecules are well-known. In contrast, there are no known organometallic trans-uranium species capable of small-molecule transformations. Using density functional theory, we previously showed that changing actinide-ligand bonds from U-O groups to Np-N- (amide/imido) bonds makes redox small-molecule activation more energetically favorable for Np species. Here, we determine how general this ligand-modulation strategy is for affecting small-molecule activation in Np species. We focus on two reactions, one involving redox transformation of the actinide(s) and the other involving no change in the oxidation state of the actinide(s). Specifically, we considered the hydrogen evolution reaction (HER) from H2O by actinide tris-aryloxide species. We also considered H2 capture and hydride transfer by actinide siloxide and silylamide complexes. For the HER, the barriers for Np(III) systems are much higher than those of U(III). The overall reaction energies are also much worse.