The product selectivity of many heterogeneous electrocatalytic processes is profoundly affected by the liquid side of the electrocatalytic interface. The electrocatalytic reduction of CO to hydrocarbons on Cu electrodes is a prototypical example of such a process. However, probing the interactions of surface-bound intermediates with their liquid reaction environment poses a formidable experimental challenge. As a result, the molecular origins of the dependence of the product selectivity on the characteristics of the electrolyte are still poorly understood. Herein, we examined the chemical and electrostatic interactions of surfaceadsorbed CO with its liquid reaction environment. Using a series of quaternary alkyl ammonium cations (methyl 4 N + , ethyl 4 N + , propyl 4 N + , and butyl 4 N + ), we systematically tuned the properties of this environment. With differential electrochemical mass spectrometry (DEMS), we show that ethylene is produced in the presence of methyl 4 N + and ethyl 4 N + cations, whereas this product is not synthesized in propyl 4 N + -and butyl 4 N + -containing electrolytes. Surface-enhanced infrared absorption spectroscopy (SEIRAS) reveals that the cations do not block CO adsorption sites and that the cation-dependent interfacial electric field is too small to account for the observed changes in selectivity. However, SEIRAS shows that an intermolecular interaction between surface-adsorbed CO and interfacial water is disrupted in the presence of the two larger cations. This observation suggests that this interaction promotes the hydrogenation of surface-bound CO to ethylene. Our study provides a critical molecular-level insight into how interactions of surface species with the liquid reaction environment control the selectivity of this complex electrocatalytic process.hydrogen bonding | cation effects | electrocatalysis | carbon dioxide reduction | catalytic selectivity T he reaction environment profoundly impacts the kinetics of many chemical processes. Examples include the influence of the solvating environment on the rates of electron transfer (1), isomerization (2), peptide folding (3), and organic reactions (4), as well as the sensitivity of enzymatic catalysis to changes in the molecular structure of the active site (5). For a chemical process that can lead to multiple reaction products, solvent effects can impact the relative rates of product formation and therefore the product selectivity (6, 7). These effects, which can have complex energetic and/or dynamical origins (1,8,9), are fundamentally rooted in intermolecular interactions between the reactants and their environment. In the context of heterogeneous electrocatalysis, the reaction environment is asymmetric; i.e., reactants at the electrochemical interface are interacting with the solid electrode and the liquid electrolyte. Understanding the interactions of intermediates with their interfacial environment is essential for controlling the reaction paths of electrocatalytic processes that exhibit poor product selectivity.The reduc...

A simple, yet robust route to prepare polymer nanoparticles with tunable internal structures through supramolecular assembly within emulsion droplets is presented. Nanoparticles with various internal morphologies, including dispersed spheres, dispersed spirals, stacked toroids, and concentric lamellae, are obtained due to the 3D confinement and variation of hydrogen-bonding agent. This method also allows us to form mesoporous particles through further disassembly of the supramoleclar assemblies by rupturing the hydrogen bonding.

The photodegradation of dye pollutants under visible light irradiation in TiO2 dispersions continues to draw considerable attention because of the greater effective utilization of solar energy and its potential application in treating wastewaters from textile and photographic industries. To get a better handle on the mechanistics details of this TiO2-assisted photodegradation of dyes with visible radiation, the process was examined by UV-visible spectroscopy, high-performance liquid chromatography, silica gel thin-layer chromatography, and matrix-assisted laser desorption ionization time-of-flight mass spectrometric techniques to separate and identify the N-de-ethylated intermediate products during the photodegradation of N,N,N,N-tetraethylsulforhodamine-B (SRB) in the absence and presence of iodide ions. Five intermediates, namely, N,N-diethyl-N'-ethyl-sulforhodamine, N,N-diethylsulforhodamine, N-ethyl-N'-ethylsulforhodamine, N-ethylsulforhodamine, and sulforhodamine were thus identified. They correspond to intermediate products having a different number of N-ethyl groups, which are removed sequentially from the SRB molecule. The reaction process was accompanied by the oxidation of I- to I3- in the presence of I- ions. Formation of radicals was assessed by spin-trap electron spin resonance spectrometry. The experimental results provided the basis for a more detailed description of the reaction mechanism(s).

Here we report the structural control of polystyrene-b-polyisoprene-b-poly(2-vinylpyridine) (PS-b-PI-b-P2VP) asymmetric ABC triblock copolymer particles under 3D confinement by tuning the interactions among blocks. The additives, including 3-n-pentadecylphenol, homopolystyrene, and solvents, which can modulate the interactions among polymer blocks, play significant roles in the particle morphology. Moreover, the structured particles can be disassembled into isolated micellar aggregates with novel morphologies or mesoporous particles with tunable pore shape. Interestingly, the formed pupa-like PS-b-PI-b-P2VP particles display interesting dynamic stretch-retraction behavior when the solvent property is changed after partial cross-linking of the P2VP block. We further prove that such dynamic behavior is closely related to the density of cross-linking. The strategies presented here are believed to be promising routes to rationally design and fabricate block copolymer particles with desirable shape and internal structure.

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Ullmann coupling of chiral 2-bromo[4]helicene has been performed on a Cu(100) surface. Only homochiral 2,2'-bis[4]helicene as the product is observed using STM. Such stereoselectivity is based on the fact that the surface will favour a configuration with the central part of the molecule on the surface, causing the outer ends to spiral away from the surface.

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