Crystal Structure Dependent Dissolution of Non-Cubic Au Crystallites in Aqua Regia.

Properties of metal crystallites are governed by their morphologies and inherent crystal structures. In this work, bipyramidal Au microcrystallites hosting non-cubic lattices, body-centered orthorhombic and tetragonal (together termed as bc(o,t)), are investigated for their stability in aqua regia. Specifically, microcrystallites comprising 92 % of bc(o,t) have been subjected to aqua regia of different concentrations and the changes in morphology and lattice phases have been monitored using scanning electron microscopy and X-ray diffraction techniques. The dissolution process was found to be crystal structure dependent and begin at the bipyramidal tips enriched with fcc lattice while retaining the bc(o,t) rich body. Interestingly, with increasing the reaction times, the remaining core was found to be highly reluctant to dissolution and instead, transformed to tetragonal lattices which with increasing treatment, exhibited lattice parameters closer to that of fcc. The study reveals the presence of a bc(o,t)-fcc core-shell structure with the tips enriched with fcc.

Unraveling the Spatial Distribution of Catalytic Non-Cubic Au Phases in a Bipyramidal Microcrystallite by X-ray Diffraction Microscopy.

Tuning of crystal structures and shapes of submicrometer-sized noble metals have revealed fascinating catalytic, optical, electrical, and magnetic properties that enable developments of environmentally friendly and durable nanotechnological applications. Several attempts have been made to stabilize Au, knowing its extraordinary stability in its conventional face-centered cubic (fcc) lattice, into different lattices, particularly to develop Au-based catalysis for industry. Here, we report the results from scanning X-ray diffraction microscopy (SXDM) measurements on an ambient-stable penta-twinned bipyramidal Au microcrystallite (about 1.36 µm in length and 230 nm in diameter) stabilized in noncubic lattice, exhibiting catalytic properties. With more than 82% of the crystal volume, the majority crystallite structure is identified as body-centered orthorhombic (bco), while the remainder is the standard fcc. A careful analysis of the diffraction maps reveals that the tips are made up of fcc, while the body contains mainly bco with very high strain. The reported structural imaging technique of representative single crystallite will be useful to investigate the growth mechanism of similar multiphase nano- and micrometer-sized crystals.

Nobler than the Noblest: Noncubic Gold Microcrystallites.

Conventional gold comprising the cubic lattice is universally known for its stability. However, well known to chemists and metallurgists, this nobility is challenged by reagents such as aqua regia, which dissolve gold to form a salt solution. Among metals, mercury blends with gold to form amalgam, otherwise transition metals such as copper tend to interact with gold surfaces in electrochemical media. Herein, we report a combined experimental and theoretical investigation of the stability of Au microcrystallites bearing unconventional crystal lattices that exhibit enhanced stability towards Hg and aqua regia and practically no interaction with Cu during electroless plating. The unconventional gold is undoubtedly nobler.

Transparent and Flexible Supercapacitors with Networked Electrodes.

Transparent and flexible energy storage devices have received immense attention due to their suitability for innovative electronics and displays. However, it remains a great challenge to fabricate devices with high storage capacity and high degree of transmittance. This study describes a simple process for fabrication of supercapacitors with ≈75% of visible transparency and areal capacitance of ≈3 mF cm-2 with high stability tested over 5000 cycles of charging and discharging. The electrodes consist of Au wire networks obtained by a simple crackle template method which are coated with MnO2 nanostructures by electrodeposition process. Importantly, the membrane separator itself is employed as substrate to bring in the desired transparency and light weight while additionally exploiting its porous nature in enhancing the interaction of electrolyte with the active material from both sides of the substrate, thereby enhancing the storage capacity. The method opens up new ways for fabricating transparent devices.