Anodized Nickel Foam for Oxygen Evolution Reaction in Fe-Free and Unpurified Alkaline Electrolytes at High Current Densities.

To achieve practically high electrocatalytic performance for the oxygen evolution reaction (OER), the active surface area should be maximized without severely compromising electron and mass transport throughout the catalyst electrode. Though the importance of electron and mass transport has been studied using low surface area catalysts under low current densities (∼tens of mA/cm2), the transport properties of large surface area catalysts under high operating current densities (∼500 mA/cm2) for practical OER catalysis have rarely been explored. Herein, three-dimensional (3D) hierarchically porous anodized nickel foams (ANFs) with large and variable surface areas were synthesized via electrochemical anodization of 3D nickel foam and applied as OER electrocatalysts in Fe-free and unpurified KOH electrolytes. Using Fe-free and in situ Fe-doped ANF that were prepared in Fe-free and unpurified electrolytes, respectively, we investigated the interdependent effects of active surface area and transport properties on OER activity under practically high current densities. While activity increased linearly with active surface area for Fe-free ANF, the activity of Fe-doped ANF showed a nonlinear increase with active surface area due to lower electrocatalytic activity enhancement. Detailed investigations on the possible factors (Fe incorporation, mass transport, and electron transport) identified that electron transport limitations played the major role in restricting the activity enhancement with increasing active surface area for Fe-doped ANF, although Fe-doped ANF has electron transport properties better than those of Fe-free ANF. This study exemplifies the growing significance of electron transport properties in large surface area catalysts, especially those with superb intrinsic catalytic activity and high operating current density.

Hexagonal Superalignment of Nano-Objects with Tunable Separation in a Dilute and Spacer-Free Solution.

Manipulating building-block nanomaterials to form an ordered superstructure in a dilute and spacer-free solution phase challenges the existing 5-nm node lithography and nanorobotics. The cooperative nature of nanocrystals, polymers, and cells can lead to superarrays or colloidal crystals. For known highly ordered systems, the characteristic length of materials, defined as the shortest dimension of objects, is generally larger than their separations. A spacer (small-molecule surfactant or polymer) is typically required to diminish short range van der Waals attraction, which results in a glassy or liquid state. Herein we propose a new concept of achieving highly ordered nano-objects in a dilute and spacer-free system via the synergistic effects of excellent solvation and appropriate constraints on rotational motion. As a proof of concept, this study demonstrates that aluminosilicate nanotubes (AlSiNTs) suspended in water under dilute conditions (e.g., 1.0 wt%) can spontaneously form hexagonal arrays with an intertubular distance as large as tens of nanometers. The separation distance of the ordered superstructure is also tunable via controlling the concentration and length of nanotubes. These superaligned structures are probed using small-angle x-ray scattering and cryo-TEM characterizations, with underlying mechanisms investigated at an atomic level using molecular dynamics simulations. The concept and discovery of this work can open up opportunities to a variety of applications including visible-UV photonics and nanolithography, and may be generalizable to other nano-object systems that fulfill similar requirements.

Scalable Wet Deposition of Zeolite AEI with a High Degree of Preferred Crystal Orientation.

Producing zeolite films with controlled preferred orientation on an industrial scale is a long-standing challenge. Herein we report on a scalable approach to the direct wet deposition of zeolite thin films and membranes while maintaining a high degree of control over the preferred crystal orientation. As a proof of concept, thin films comprising aluminophosphate zeolite AEI were cast on silicon wafer or porous alumina substrates. Electrical properties and separation performance of the zeolite thin films/membranes were engineered through controlling degree of preferred crystal orientation.

Solution-processed ultra-low-k thin films comprising single-walled aluminosilicate nanotubes.

Nanotube-based ultra-low-k thin films with high Young's modulus composed of single-walled aluminosilicate nanotubes (AlSiNTs) and a trace amount of poly(vinyl alcohol) (PVA) have been developed. The dehydrated AlSiNT film possesses a relative permittivity of 1.05, and a Young's modulus of 25 GPa, which exceed those of most existing ultra-low-k materials.