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Author ORCID ID is 0000000284782761
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  1. Here, the cyclability of silicon anodes in lithium ion batteries (LIBs) is affected by the reduction of the electrolyte on the anode surface to produce a coating layer termed the solid electrolyte interphase (SEI). One of the key steps for a major improvement of LIBs is unraveling the SEI’s structure-related diffusion properties as charge and discharge rates of LIBs are diffusion-limited. To this end, we have combined two surface sensitive techniques, sum frequency generation (SFG) vibrational spectroscopy, and X-ray reflectivity (XRR), to explore the first monolayer and to probe the first several layers of electrolyte, respectively, for solutions consisting ofmore » 1 M lithium perchlorate (LiClO 4) salt dissolved in ethylene carbonate (EC) or fluoroethylene carbonate (FEC) and their mixtures (EC/FEC 7:3 and 1:1 wt %) on silicon and sapphire surfaces. Our results suggest that the addition of FEC to EC solution causes the first monolayer to rearrange itself more perpendicular to the anode surface, while subsequent layers are less affected and tend to maintain their, on average, surface-parallel arrangements. This fundamental understanding of the near-surface orientation of the electrolyte molecules can aid operational strategies for designing high-performance LIBs.« less
  2. Catalytic activity and selectivity of n -hexane reforming are changed significantly by the surface acidic properties of the alumina support following halogen treatment.
  3. Recyclable catalysts, especially those that display selective reactivity, are vital for the development of sustainable chemical processes. Among available catalyst platforms, heterogeneous catalysts are particularly well-disposed toward separation from the reaction mixture via filtration methods, which renders them readily recyclable. Furthermore, heterogeneous catalysts offer numerous handles—some without homogeneous analogues—for performance and selectivity optimization. These handles include nanoparticle size, pore profile of porous supports, surface ligands and interface with oxide supports, and flow rate through a solid catalyst bed. Despite these available handles, however, conventional heterogeneous catalysts are themselves often structurally heterogeneous compared to homogeneous catalysts, which complicates efforts to optimizemore » and expand the scope of their reactivity and selectivity. Ongoing efforts in our laboratories are aimed to address the above challenge by heterogenizing homogeneous catalysts, which can be defined as the modification of homogeneous catalysts to render them in a separable (solid) phase from the starting materials and products. Specifically, we grow the small nanoclusters in dendrimers, a class of uniform polymers with the connectivity of fractal trees and generally radial symmetry. Thanks to their dense multivalency, shape persistence, and structural uniformity, dendrimers have proven to be versatile scaffolds for the synthesis and stabilization of small nanoclusters. Then these dendrimer-encapsulated metal clusters (DEMCs) are adsorbed onto mesoporous silica. Through this method, we have achieved selective transformations that had been challenging to accomplish in a heterogeneous setting, e.g., π-bond activation and aldol reactions. Extensive investigation into the catalytic systems under reaction conditions allowed us to correlate the structural features (e.g., oxidation states) of the catalysts and their activity. Moreover, we have demonstrated that supported DEMCs are also excellent catalysts for typical heterogeneous reactions, including hydrogenation and alkane isomerization. Critically, these investigations also confirmed that the supported DEMCs are heterogeneous and stable against leaching. Catalysts optimization is achieved through the modulation of various parameters. The clusters are oxidized (e.g., with PhICl 2) or reduced (e.g., with H 2) in situ. Changing the dendrimer properties (e.g., generation, terminal functional groups) is analogous to ligand modification in homogeneous catalysts, which affect both catalytic activity and selectivity. Similarly, pore size of the support is another factor in determining product distribution. In a flow reactor, the flow rate is adjusted to control the residence time of the starting material and intermediates, and thus the final product selectivity. Our approach to heterogeneous catalysis affords various advantages: (1) the catalyst system can tap into the reactivity typical to homogeneous catalysts, which conventional heterogeneous catalysts could not achieve; (2) unlike most homogeneous catalysts with comparable performance, the heterogenized homogeneous catalysts can be recycled; (3) improved activity or selectivity compared to conventional homogeneous catalysts is possible because of uniquely heterogeneous parameters for optimization. Here in this Account, we will briefly introduce metal clusters and describe the synthesis and characterizations of supported DEMCs. We will present the catalysis studies of supported DEMCs in both the batch and flow modes. Lastly, we will summarize the current state of heterogenizing homogeneous catalysis and provide future directions for this area of research.« less
  4. Light driven excitation of gold nanoparticles (GNPs) has emerged as a potential strategy to generate hot carriers for photocatalysis through excitation of localized surface plasmon resonance (LSPR). In contrast, carrier generation through excitation of interband transitions remains a less explored and underestimated pathway for photocatalytic activity. Photoinduced oxidative etching of GNPs with FeCl3 was investigated as a model reaction in order to elucidate the effects of both types of transitions. Our quantitative results show that interband transitions more efficiently generate hot carriers and that those carriers exhibit higher reactivity as compared to those generated solely by LSPR. Furthermore, by leveragingmore » the strong π-acidic character of the resulting photogenerated Au+ hole, an interband transition induced cyclization reaction of alkynylphenols was developed. One thing of note is that the, alkyne coordination to the Au+ hole intercepts the classic oxidation event and leads to the formation of the catalytically active gold clusters on subnanometer scale.« less

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