The Ligand Shell as an Energy Barrier in Surface Reactions on Transition Metal Nanoparticles.

Transition metal nanoparticles, including those employed in catalytic, electrocatalytic, and photocatalytic conversions, have surfaces that are typically coated with a layer of short or long-chain ligands. There is little systematic understanding of how much this ligand layer affects the reactivity of the underlying surface. We show for Ag nanoparticles that a surface-adsorbed thiol layer greatly impedes the kinetics of an ionic chemical reaction taking place on the Ag surface. The model reaction studied is the galvanic exchange of Ag with Au(3+) ions, the kinetics of which is measured on individual thiol-coated nanoparticles using in situ optical scattering spectroscopy. We observe a systematic lowering of the reactivity of the nanoparticle as the chain length of the thiol is increased, from which we deduce that the ligand layer serves as an energy barrier to the transport of incoming/outgoing reactive ions. This barrier effect can be decreased by light irradiation, resulting from weakened binding of the thiol layer to the metal surface. We find that the influence of the surface ligand layer on reactivity is much stronger than factors such as nanoparticle size, shape, or crystallinity. These findings provide improved understanding of the role of ligand or adsorbates in colloidal catalysis and photocatalysis and have important implications for the transport of reactants and ions to surfaces and for engineering the reactivity of nanoparticles using surface passivation.

Kinetics of self-assembled monolayer formation on individual nanoparticles.

Self-assembled monolayer (SAM) formation of alkanethiols on nanoparticle surfaces is an extensively studied surface reaction. But the nanoscale aspects of the rich microscopic kinetics of this reaction may remain hidden due to ensemble-averaging in colloidal samples, which is why we investigated in real-time how alkanethiol SAMs form on a single Ag nanoparticle. From single-nanoparticle trajectories obtained using in situ optical spectroscopy, the kinetics of SAM formation appears to be limited by the growth of the layer across the nanoparticle surface. A significant spread in the growth kinetics is seen between nanoparticles. The single-nanoparticle rate distributions suggest two distinct modes for SAM growth: spillover of adsorbed thiols from the initial binding sites on the nanoparticle and direct adsorption of thiol from solution. At low concentrations, wherein direct adsorption from solution is not prevalent and growth takes place primarily by adsorbate migration, the SAM formation rate was less variable from one nanoparticle to another. On the other hand, at higher thiol concentrations, when both modes of growth were operative, the population of nanoparticles with inherent variations in surface conditions and/or morphology exhibited a heterogeneous distribution of rates. These new insights into the complex dynamics of SAM formation may inform synthetic strategies for ligand passivation and functionalization of nanoparticles and models of reactive adsorption and catalysis on nanoparticles.

In Situ Single-Nanoparticle Spectroscopy Study of Bimetallic Nanostructure Formation.

Bimetallic nanostructures (NSs), with utility in catalysis, are typically prepared using galvanic exchange (GE), but the final catalyst morphology is dictated by the dynamics of the process. In situ single nanoparticle (NP) optical scattering spectroscopy, coupled with ex situ electron microscopy, is used to capture the dynamic structural evolution of a bimetallic NS formed in a GE reaction between Ag and [PtCl6 ](2-) . We identify an early stage involving anisotropic oxidation of Ag to AgCl concomitant with reductive deposition of small Pt clusters on the NS surface. At later stages of GE, unreacted Ag inclusions phase segregate from the overcoated AgCl as a result of lattice strain between Ag and AgCl. The nature of the structural evolution elucidates why multi-domain Ag/AgCl/Pt NSs result from the GE process. The complex structural dynamics, determined from single-NP trajectories, would be masked in ensemble studies due to heterogeneity in the response of different NPs.

Identification of a critical intermediate in galvanic exchange reactions by single-nanoparticle-resolved kinetics.

The realization of common materials transformations in nanocrystalline systems is fostering the development of novel nanostructures and allowing a deep look into the atomistic mechanisms involved. Galvanic corrosion is one such transformation. We studied galvanic replacement within individual metal nanoparticles by using a combination of plasmonic spectroscopy and scanning transmission electron microscopy. Single-nanoparticle reaction trajectories showed that a Ag nanoparticle exposed to Au³âº makes an abrupt transition into a nanocage structure. The transition is limited by a critical structural event, which we identified by electron microscopy to comprise the formation of a nanosized void. Trajectories also revealed a surprisingly strong nonlinearity of the reaction kinetics, which we explain by a model involving the critical coalescence of vacancies into a growing void. The critical void size for galvanic exchange to spontaneously proceed was found to be 20 atomic vacancies.

Harvesting multiple electron-hole pairs generated through plasmonic excitation of Au nanoparticles.

Multi-electron redox reactions, although central to artificial photosynthesis, are kinetically sluggish. Amidst the search for synthetic catalysts for such processes, plasmonic nanoparticles have been found to catalyse multi-electron reduction of CO2 under visible light. This example motivates the need for a general, insight-driven framework for plasmonic catalysis of such multi-electron chemistry. Here, we elucidate the principles underlying the extraction of multiple redox equivalents from a plasmonic photocatalyst. We measure the kinetics of electron harvesting from a gold nanoparticle photocatalyst as a function of photon flux. Our measurements, supported by theoretical modelling, reveal a regime where two-electron transfer from the excited gold nanoparticle becomes prevalent. Multiple electron harvesting becomes possible under continuous-wave, visible-light excitation of moderate intensity due to strong interband transitions in gold and electron-hole separation accomplished using a hole scavenger. These insights will help expand the utility of plasmonic photocatalysis beyond CO2 reduction to other challenging multi-electron, multi-proton transformations such as N2 fixation.

Co-operativity in a nanocrystalline solid-state transition.

Co-operativity is a remarkable phenomenon mostly seen in biology, where initial reaction events significantly alter the propensity of subsequent reaction events, giving rise to a nonlinear tightly regulated synergistic response. Here we have found unique evidence of atomic level co-operativity in an inorganic material. A thousand-atom nanocrystal (NC) of the inorganic solid cadmium selenide exhibits strong positive co-operativity in its reaction with copper ions. A NC doped with a few copper impurities becomes highly prone to be doped even further, driving an abrupt transition of the entire NC to the copper selenide phase, as manifested by a strongly sigmoidal response in optical spectroscopy and electron diffraction measurements. The examples presented here suggest that cooperative phenomena may have an important role in the solid state, especially in the nucleation of new chemical phases, crystal growth, and other materials' transformations.