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Abstract Synthetic thorite and huttonite, two polymorphs of ThSiO4, were investigated by a combination of in situ high-pressure synchrotron X-ray powder diffraction and in situ high pressure Raman spectroscopy. The average onset pressure of the thorite-to-huttonite transition was determined to be 6.6 ± 0.2 GPa, using both techniques. The bulk moduli of thorite and huttonite were determined to be 139(9) and 246(11) GPa, respectively, by fitting their unit-cell volume data to a second order Birch-Murnaghan equation of state (EOS). Based on its bulk modulus, thorite is the most compressible zircon-structured orthosilicate, as it has the largest unit cell volume among tetravalent metal orthosilicates. The pressure derivatives of the vibrational modes of thorite were found to be consistent with those previously reported for other orthosilicates (e.g., zircon, hafnon, stetindite, and coffinite), while having the smallest Grüneisen parameter. A new P-T phase diagram for ThSiO4 is proposed, where the boundary of the thorite → huttonite transition is: P(T) = (7.8 ± 0.9 GPa) − (0.006 ± 0.002 GPa/K)T. Based on the new P-T phase diagram, we further estimated the enthalpy of formation of huttonite, ΔHf,ox, to be 0.6 ± 6.0 kJ/mol, suggesting its metastability and rare locality in nature. 

Iron oxides are frequently found in natural and industrial glass compositions and can affect various physical and chemical properties of the glasses and their melts. Thus, a fundamental understanding of iron-bearing silicate melts and glasses is of both scientific and technological importance. This study investigates the structures of sodium iron silicate glasses with compositions of NaFeSiO4, NaFeSi2O6, NaFeSi3O8, and Na5FeSi4O12 using molecular dynamics simulations in combination with Extended X-ray Absorption Fine Structure (EXAFS) characterizations. Short and medium range structural features of these glasses support that ferrous (Fe2+) and ferric (Fe3+) ions play the roles of network modifier and network former, respectively, with the Fe oxidation states playing an important role in the polymerization of the glass network. These simulation results agree well with newly measured room temperature EXAFS spectra. The simulated glass structures were also compared to the melts structures with the same composition but different redox ratios. The average coordination numbers of the cations were found to be affected both by the melt temperature and iron redox ratio. 

Fe2O3 is an appealing anode material due to its high specific capacity (1007 mAh g− 1), low cost, natural abundance, and nontoxicity. However, its unstable structure during cycling processes has hindered its potential. In this study, we present a “green” synthesis method to fabricate stable porous Fe2O3 encapsulated in a buffering hollow structure (p-Fe2O3@h-TiO2) as an effective anode material for Li-ion batteries. The synthesis process only involves glucose as an “etching” agent, without the need for organic solvents or difficult-to-control environments. Characterizations of the nanostructures, chemical compositions, crystallizations, and thermal behaviors for the intermediate/final products confirm the formation of p-Fe2O3@h-TiO2. The synthesized Fe2O3 anode material effectively accommodates volume change, decreases pulverization, and alleviates agglomeration, leading to a high capacity that is over eleven times greater than that of the as-received commercial Fe2O3 after a long cycling process. This work provides an attractive, “green” and efficient method to convert commercially abundant resources like Fe2O3 into effective electrode materials for energy storage systems. 

With plenty of charges and rich functional groups, bovine serum albumin (BSA) protein provides effective transport for multiple metallic ions inside blood vessels. Inspired by the unique ionic transport function, we develop a BSA protein coating to stabilize Li anode, regulate Li+ transport, and resolve the Li dendrite growth for Li metal batteries (LMBs). The experimental and simulation studies demonstrate that the coating has strong interactions with Li metal, increases the wetting with electrolyte, reduces the electrolyte/Li side reactions, and significantly suppresses the Li dendrite formation. As a result, the BSA coating exhibits excellent stability in the electrolyte and improves the performance of Li|Cu and Li|Li cells as well as the LiFePO4|Li batteries. This work reveals that LMBs can benefit from the biological function of BSA, i.e., special transport capability of metallic ions, and lays an important foundation in design of protein-based materials for effectively enhancing the electrochemical performance of energy storage systems.