Engineering topics
Chupas, P J
Publications and source records attributed to Chupas, P J.
Understanding fluxes as media for directed synthesis: in situ local structure of molten potassium polysulfides
Abstract not provided
Pair distribution function-derived mechanism of a single-crystal to disordered to single-crystal transformation in a hemilabile metal-organic framework
Flexible metal-organic frameworks (MOFs) are materials of great current interest. A small class of MOFs show flexibility driven by reversible bonding rearrangements that lead directly to unusual properties. Cu-SIP-3 is a MOF based on the 5-sulfoisophthalate ligand, where the strong copper-carboxylate bonds ensure that the three-dimensional integrity of the structure is retained while allowing bonding changes to occur at the more weakly bonding sulfonate group leading to unusual properties such as the ultra-selective adsorption of only certain gases. While the integrity of the framework remains intact during bonding changes, crystalline order is not retained at all times during the transformations. X-Ray diffraction reveals that highly crystalline single crystals lose order during the transformation before regaining crystallinity once it is complete. Here we show how X-ray pair distribution function analysis can be used to reveal the mechanism of the transformations in Cu-SIP-3, identifying the sequence of atomic displacements that occur in the disordered phase. A similar approach reveals the underlying mechanism of Cu-SIP-3's ultra-selective gas adsorption.
Combining pair distribution function and computational methods to understand lithium insertion in brookite (TiO{sub 2}).
X-ray pair distribution function (PDF) methods and first-principles calculations have been combined to probe the structure of electrochemically lithiated TiO{sub 2} Brookite. Traditional powder diffraction studies suggest that Brookite amorphizes upon lithium insertion, with the Bragg reflections disappearing. However, PDF analysis indicates that the TiO{sub 2} framework connectivity is maintained throughout lithium intercalation, with expansions along the a and b axes. The Li{sup +} ions within the framework are poorly observed in the X-ray PDF, which is dominated by contributions from the more strongly scattering Ti and O atoms. First-principles calculations were used to identify energetically favorable Li{sup +} sites within the Brookite lattice and to develop a complete structural model of the lithiated material. This model replicates the local structure and decreased intermediate range order observed in the PDF data. The analysis suggests that local structural distortions of the TiO{sub 2} lattice accommodate lithium in five-coordinate sites. This structural model is consistent with the observed electrochemical behavior.