Abundance of Low-Energy Oxygen Vacancy Pairs Dictates the Catalytic Performance of Cerium-Stabilized Zirconia.

Cerium-stabilized zirconia (Ce1-xZrxOy, CZO) is renowned for its superior oxygen storage capacity (OSC), a key property long believed to be beneficial to catalytic oxidation reactions. However, 50% Ce-containing CZO recorded with the highest OSC has disappointingly poor performance in catalytic oxidation reactions compared to those with higher Ce contents but lower OSC ability. Here, we employ global neural network (G-NN)-based potential energy surface exploration methods to establish the first ternary phase diagram for bulk structures of CZO, which identifies three critical compositions of CZO, namely, 50, 60, and 80% Ce-containing CZO that are thermodynamically stable under typical synthetic conditions. 50% Ce-containing CZO, although having the highest OSC, exhibits the lowest O vacancy (Ov) diffusion rate. By contrast, 60% Ce-containing CZO, despite lower OSC (33.3% OSC compared to that of 50% Ce-containing CZO), reaches the highest Ov diffusion ability and thus offers the highest CO oxidation catalytic performance. The physical origin of the high performance of 60% Ce-containing CZO is the abundance of energetically favorable Ov pairs along the ⟨110⟩ direction, which reduces the energy barrier of Ov diffusion in the bulk and promotes O2 activation on the surface. Our results clarify the long-standing puzzles on CZO and point out that 60% Ce-containing CZO is the most desirable composition for typical CZO applications.

Molecular Dynamics Simulations on the Behaviors of Hydrophilic/Hydrophobic Cyclic Peptide Nanotubes at the Water/Hexane Interface.

In this work, nine kinds of amino acid residues, i.e., alanine (A), leucine (L), valine (V), isoleucine (I), tryptophan (W), glutamine (Q), threonine (T), serine (S), and cysteine (C), were selected to construct seven cyclic peptide nanotubes (CPNTs) with diverse hydrophilic/hydrophobic external surfaces, which were further separately inserted at the water/hexane interface to investigate their microstructures and interfacial properties. Molecular dynamics (MD) simulations reveal that all the CPNTs except the QT- and VL-CPNTs have different degrees of tilt, fracture, and shedding at the interface. The end-CPs are more susceptible to the effect of the surroundings than the mid-CPs. The interactions of individual CP subunits with the neighborings disclose the firmness of the mid-CPs and the dissociation of the end-CPs. The results indicate that a hydrophobic CPNT is prone to stay at the interface, while a hydrophilic CPNT easily enters the water phase, resulting in many H-bonds with water. Results in this work enrich the dynamic properties of a hydrophilic/hydrophobic CPNT at the biphase interface at the atomic level.

Dynamic behavior and selective adsorption of a methanol/water mixture inside a cyclic peptide nanotube.

Present molecular dynamics simulations indicate that the methanol component in a methanol/water mixture is more likely to be trapped in a cyclic peptide nanotube (CPNT), while water molecules tend to be present at the channel mouths as transient guests. Channel water resides mainly between methanol and the CPNT wall, resulting in a distinct decrease in the H-bond number per channel methanol. Six designed CPNTs with different channel diameters and outer surface characteristics all possess distinct selectivity to methanol over water. Of these, the amphipathic 8 × (AQ)4-CPNT exhibits the best performance. Results in this study provide basic information for the application of a CPNT to enrich methanol from a methanol/water mixture. Graphical Abstract Typical overview of water and methanol molecular distribution in cyclic peptide nanotubes.