The Aryne Phosphate Reaction.

Condensed phosphates are a critically important class of molecules in biochemistry. Non-natural analogues are important for various applications, such as single-molecule real-time DNA sequencing. Often, such analogues contain more than three phosphate units in their oligophosphate chain. Consequently, investigations into phosphate reactivity enabling new ways of phosphate functionalization and oligophosphorylation are essential. Here, we scrutinize the potential of phosphates to act as arynophiles, paving the way for follow-up oligophosphorylation reactions. The aryne phosphate reaction is a powerful tool to-depending on the perspective-(oligo)phosphorylate arenes or arylate (oligo-cyclo)phosphates. Based on Kobayashi-type o-silylaryltriflates, the aryne phosphate reaction enables rapid entry into a broad spectrum of arylated products, like monophosphates, diphosphates, phosphodiesters and polyphosphates. The synthetic potential of these new transformations is demonstrated by efficient syntheses of nucleotide analogues and an unprecedented one-flask octaphosphorylation.

Noble Metal Phosphides Supported on CoNi Metaphosphate for Efficient Overall Water Splitting.

Transition metal metaphosphates and noble metal phosphides prepared under similar conditions are potential hybrid catalysts for electrocatalytic water splitting, which is of great significance for H2 production. Herein, the structure and electrocatalytic activity of different noble metal species (i.e., Rh, Pd, Ir) on CoNiP4O12 nanoarrays have been systematically studied. Due to the different formation energies of noble metal phosphides, the phosphides of Rh (RhPx) and Pd (PdPx) as well as the noble metal Ir are obtained under the same phosphorylation conditions perspectively. RhPx/CoNiP4O12 and PdPx/CoNiP4O12 exhibit much better HER activity than Ir/CoNiP4O12 due to the advantages of phosphides. Density functional theory (DFT) calculations reveal that the extraordinary activity of RhPx/CoNiP4O12 originated from the strong affinity to H2O and optimal adsorption for H*. The best RhPx/CoNiP4O12 only requires a low overpotential of 30 and 234 mV to deliver 10 mA cm-2 for HER and OER, respectively, and therefore is effective for overall water splitting (requiring 1.57 V to achieve a current density of 10 mA cm-2). This work not only develops a novel RhPx/CoNiP4O12 electrocatalyst for overall water splitting but also provides deep insight into the formation mechanism of noble metal phosphides.

Mushroom-like cobalt nickle metaphosphate@nickel diselenide core-shell nanorods for asymmetric supercapacitors.

Although transition metal metaphosphates (TMPOs) display special physical/chemical features and high theoretical capacities, their applications for supercapacitors (SCs) are still restricted by their low energy densities and inferior cycling stability. Herein, a novel strategy has been proposed to address these issues through in situ construction of cobalt nickle metaphosphate (Co0.2Ni0.8(PO3)2)@nickel diselenide (NiSe2) core-shell heterostructure on carbon paper (CP) as a self-supporting flexible electrode for SCs. Particularly, this unique mushroom-like porous nanoarchitecture assembled by one-dimensional (1D) Co0.2Ni0.8(PO3)2 nanorods and zero-dimensional (0D) NiSe2 nanospheres can expose abundant active sites and afford multi-dimensional channels, which favors rapid electron ions/electron transfer, accelerates the reaction kinetics, and alleviates volume changes during charging/discharging processes. Profiting from its well-aligned 1D/0D nanostructure and strong synergistic effect between Co0.2Ni0.8(PO3)2 and NiSe2, the Co0.2Ni0.8(PO3)2@NiSe2/CP electrode delivers a specific capacity of 219.4 mAh/g/0.414 mAh cm-2 at 1 A/g and good cycling stability with capacity retention of 90.7% after 5000 cycles, outperforming many previously reported TMPO-based electrodes in literature. Impressively, an asymmetric supercapacitor (ASC) device assembled with Co0.2Ni0.8(PO3)2@NiSe2 as cathode and porous carbon as anode achieves an energy density of 69.2 Wh kg-1 at 736.0 W kg-1 and maintains a capacity retention of 97.6% after 20,000 charge-discharge cycles. This work provides an efficient approach to design multi-dimensional hybrid nanomaterials for high-performance SCs.

Interaction of Aluminum Metaphosphates in the Setting of Potassium Silicate Solutions in Terms of the Crystalline Phase Composition.

Aluminum phosphates are known as inorganic hardening agents for the setting of alkali silicate solutions, but only few studies have been published on the setting mechanism of potassium water glass. The solution behavior of two aluminum metaphosphates in alkaline environments were investigated photometrically determining the dissolved aluminum content. The crystalline phase composition of the hardened potassium silicate systems was determined by X-ray diffraction. New insights into the setting mechanism were obtained concerning the structure of the aluminum metaphosphate and the SiO2/K2O ratio of three different potassium silicate solutions. With increasing pH value aluminum tetrametaphosphate reacts rapidly and forms crystalline potassium tetrametaphosphate dihydrate by an ion-exchange-reaction. In parallel, a depolymerization of the cyclic metaphosphate structure occurs leading to potassium dihydrogen phosphate as final fragmentation product. With aluminum hexametaphosphate no ion-exchange reaction product was observed. Only potassium dihydrogen phosphate could be found in higher quantities compared to the reaction with aluminum tetrametaphosphate.