Investigating Spillover Energy as a Descriptor for Single-Atom Alloy Catalyst Design.

The identification of thermodynamic descriptors of catalytic performance is essential for the rational design of heterogeneous catalysts. Here, we investigate how spillover energy, a descriptor quantifying whether intermediates are more stable at the dopant or host metal sites, can be used to design single-atom alloys (SAAs) for formic acid dehydrogenation. Using theoretical calculations, we identify NiCu as a SAA with favorable spillover energy and demonstrate that formate intermediates produced after the initial O-H activation are more stable at Ni sites where rate-determining C-H activation occurs. Surface science experiments demonstrated that NiCu(111) SAAs are more reactive than Cu(111) while they still follow the formate reaction pathway. However, reactor studies of silica-supported NiCu SAA nanoparticles showed only a modest improvement over Cu resulting from surface coverage effects. Overall, this study demonstrates the potential of engineering SAAs using spillover energy as a design parameter and highlights the importance of adsorbate-adsorbate interactions under steady-state operation.

Tg Confinement Effect of Random Copolymers of 4-tert-Butylstyrene and 4-Acetoxystyrene with Different Compositions.

We observe that the Tg confinement effect of polymer films can saturate with polymer-substrate interaction. Thickness dependences of the glass transition temperature, Tg(h0), of random copolymer films of 4-tert-butylstyrene (TBS) and 4-acetoxystyrene (AS) supported by silica (SiOx) were measured for different TBS concentrations, XTBS. For 0 ≤ XTBS ≤ 0.47, Tg(h0) displays identical enhancements, independent of XTBS. For XTBS > ∼0.66; however, Tg(h0) decreases steadily with XTBS. The XTBS > 0.66 result is in keeping with expectations that TBS interacts less strongly with SiOx than AS does, and weaker polymer-substrate interaction renders greater dominance of the air surface over substrate surface on Tg, and thereby Tg reduction. We propose that saturation in Tg(h0) found for XTBS ≤ 0.47 is caused by the maximization in polymer-substrate-specific bond formation. Further experiments and a calculation support this proposition.