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  1. There are now many examples of single molecule rotors, motors, and switches in the literature that, when driven by photons, electrons, or chemical reactions, exhibit well-defined motions. As a step toward using these single molecule devices to perform useful functions, one must understand how they interact with their environment and quantify their ability to perform work on it. Using a single molecule rotary switch, we examine the transfer of electrical energy, delivered via electron tunneling, to mechanical motion and measure the forces the switch experiences with a noncontact q-plus atomic force microscope. Action spectra reveal that the molecular switch has two stable states and can be excited resonantly between them at a bias of 100 mV via a one-electron inelastic tunneling process which corresponds to an energy input of 16 zJ. While the electrically induced switching events are stochastic and no net work is done on the cantilever, by measuring the forces between the molecular switch and the AFM cantilever, we can derive the maximum hypothetical work the switch could perform during a single switching event, which is ∼55 meV, equal to 8.9 zJ, which translates to a hypothetical efficiency of ∼55% per individual inelastic tunneling electron-induced switching event. When considering the total electrical energy input, this drops to 1 × 10–7% due to elastic tunneling events that dominate the tunneling current. However, this approach constitutes a general method for quantifying and comparing the energy input and output of molecular-mechanical devices. 
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  2. The migration of species across interfaces can crucially affect the performance of heterogeneous catalysts. A key concept in using bimetallic catalysts for hydrogenation is that the active metal supplies hydrogen atoms to the host metal, where selective hydrogenation can then occur. Herein, we demonstrate that, following dihydrogen dissociation on palladium islands, hydrogen atoms migrate from palladium to silver, to which they are generally less strongly bound. This migration is driven by the population of weakly bound states on the palladium at high hydrogen atom coverages which are nearly isoenergetic with binding sites on the silver. The rate of hydrogen atom migration depends on the palladium−silver interface length, with smaller palladium islands more efficiently supplying hydrogen atoms to the silver. This study demonstrates that hydrogen atoms can migrate from a more strongly binding metal to a more weakly binding surface under special conditions, such as high dihydrogen pressure.

     
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  3. Abstract

    A challenge in the synthesis of single‐wall carbon nanotubes (SWCNTs) is the lack of control over the formation and evolution of catalyst nanoparticles and the lack of control over their size or chirality. Here, zeolite MFI nanosheets (MFI‐Ns) are used to keep cobalt (Co) nanoparticles stable during prolonged annealing conditions. Environmental transmission electron microscopy (ETEM) shows that the MFI‐Ns can influence the size and shape of nanoparticles via particle/support registry, which leads to the preferential docking of nanoparticles to four or fewer pores and to the regulation of the SWCNT synthesis products. The resulting SWCNT population exhibits a narrow diameter distribution and SWCNTs of nearly all chiral angles, including sub‐nm zigzag (ZZ) and near‐ZZ tubes. Theoretical simulations reveal that the growth of these unfavorable tubes from unsupported catalysts leads to the rapid encapsulation of catalyst nanoparticles bearing them; their presence in the growth products suggests that the MFI‐Ns prevent nanoparticle encapsulation and prologue ZZ and near‐ZZ SWCNT growth. These results thus present a path forward for controlling nanoparticle formation and evolution, for achieving size‐ and shape‐selectivity at high temperature, and for controlling SWCNT synthesis.

     
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