Density functional theory (DFT) and coupled cluster theory (CCSD(T)) were used to study the addition of CO to group 4 (MO) and group 6 (MO) (n = 1, 2, 3) nanoclusters. The structures and energetics arising from Lewis acid-base addition (physisorption) and formation of CO (chemisorption) of CO to these clusters were predicted. Physisorption and chemisorption of CO are predicted to be thermodynamically allowed for group 4 (MO) clusters, with chemisorption being more favored energetically. Correlations of the ligand binding energies (LBEs) for the group 4 clusters are made with the fluoride affinities and M-O and M═O bond strengths of the clusters. The LBEs for chemisorption on the Zr and Ti clusters are consistent with published experimental and computational studies of bulk solids. Physisorption LBEs for the Ti and Zr clusters are more exothermic than the bulk values, as the cluster models allow for better relaxation at the metal sites. Chemisorption is not predicted to occur with group 6 (MO) clusters, as the larger chemisorbed structures were all found to be metastable. CO is predicted to weakly physisorb to (WO) with physisorption correlating with the Lewis acidity of the metal site.
A series
of multistage (pressure-sensitive/hot melt) adhesives
utilizing dynamic thia-Michael bonding motifs are reported. The benzalcyanoacetate
Michael acceptors used in this work undergo bond exchange under ambient
conditions without external catalysis, facilitating pressure-sensitive
adhesion. A key feature of this system is the dynamic reaction-induced
phase separation that lends reinforcement to the otherwise weakly
bonded materials, enabling weak, repeatable pressure-sensitive adhesion
under ambient conditions and strong adhesion when processed as a hot
melt adhesive. By using different pairs of benzalcyanoacetate cross-linking
units, the phase separation characteristics of the adhesives can be
directly manipulated, allowing for a tailored adhesive response.
The structure, chemistry, and charge of interfaces between materials and aqueous fluids play a central role in determining properties and performance of numerous water systems. Sensors, membranes, sorbents, and heterogeneous catalysts almost uniformly rely on specific interactions between their surfaces and components dissolved or suspended in the waterand often the water molecules themselvesto detect and mitigate contaminants. Deleterious processes in these systems such as fouling, scaling (inorganic deposits), and corrosion are also governed by interfacial phenomena. Despite the importance of these interfaces, much remains to be learned about their multiscale interactions. Developing a deeper understanding of the molecular-and mesoscale phenomena at water/solid interfaces will be essential to driving innovation to address grand challenges in supplying sufficient fit-for-purpose water in the future. In this Review, we examine the current state of knowledge surrounding adsorption, reactivity, and transport in several key classes of water/solid interfaces, drawing on a synergistic combination of theory, simulation, and experiments, and provide an outlook for prioritizing strategic research directions.
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