Selective Chemical Substitution of Cu in the Structure of TiAl₃ Type InPd₃: Experimental and Theoretical Studies

Abstract

InPd 3-x Cu x (x = 0-1) were prepared by high temperature synthesis starting from the highly pure constituent elements. The crystal structures were determined by X-ray diffraction. In the structure of InPd 3-x Cu x (x = 0-1), Cu stabilizes the TiAl 3 -type InPd 3 and selectively substitutes one of the two Pd positions and at the limiting composition ordered InPd 2 Cu is formed where Cu completely occupies that position. The intriguing selective substitution was investigated by first-principles total energy calculations followed by electronic structure and chemical bonding analysis.

Enhanced Electrocatalytic Conversion of Nitrates to Ammonia: Fuel from Waste

“…This change in d‐spacing after In inclusion suggests that the metal ions are incorporated into the matrix of Pd. This is substantiated by a match with the d‐spacing of plane (2 0 0) of titanium‐aluminide‐(Al 3 Ti)‐type InPd 3 (2.07 Å) [23–25] . In addition to SEM, EDS analysis shown in Figure S1 confirms the presence of In and Pd in the In−Pd‐ACC samples, showing 78.9 atomic % and 21.1 atomic % of Pd and In, respectively.…”

“…This is substantiated by a match with the dspacing of plane (2 0 0) of titanium-aluminide-(Al 3 Ti)-type InPd 3 (2.07 Å). [23][24][25] In addition to SEM, EDS analysis shown in Figure S1 confirms the presence of In and Pd in the InÀ Pd-ACC samples, showing 78.9 atomic % and 21.1 atomic % of Pd and In, respectively. 15.0 mg/g of Pd and 6.2 mg/g of In was found to be loaded as analyzed from the inductively coupled plasma optical emission spectroscopy (ICP-OES).…”

Understanding Formation of the InPd3 Polymorphs: A DFT Study

“…An interesting order-disorder phase transformation was established in sputter deposited InPd3, by Huang and Chang; a disordered face-centered cubic phase adopts an ordered tetragonal structure after annealing up to 550°C [15]. Selective chemical substitution of Cu in TiAl3-type InPd3 was explored by combinations of X-ray diffraction and DFT calculations, where Cu substitutes one of the two crystallographically different Pd-positions due to electronic reasons [16,17].…”

Selective Chemical Substitution in Intermetallic Compounds: DFT Study of Two Representative Cases: Cu5Zn3Sb2 and InPd2Cu

“…The formation of perfectly ordered InPd2Cu is particularly noteworthy, as it suggests that the ordering may be driven by a combination of size, electronegativity, and valence electron concentration effects, as well as the crystal symmetry and bonding interactions. [15,16].…”