In Situ Monitoring of Palladium-Catalyzed Chemical Reactions by Nanogap-Enhanced Raman Scattering using Single Pd Cube Dimers.

The central dilemma in label-free in situ surface-enhanced Raman scattering (SERS) for monitoring of heterogeneously catalyzed reactions is the need of plasmonically active nanostructures for signal enhancement. Here, we show that the assembly of catalytically active transition-metal nanoparticles into dimers boosts their intrinsically insufficient plasmonic activity at the monomer level by several orders of magnitude, thereby enabling the in situ SERS monitoring of various important heterogeneously catalyzed reactions at the single-dimer level. Specifically, we demonstrate that Pd nanocubes (NCs), which alone are not sufficiently plasmonically active as monomers, can act as a monometallic yet bifunctional platform with both catalytic and satisfactory plasmonic activity via controlled assembly into single dimers with an ∼1 nm gap. Computer simulations reveal that the highest enhancement factors (EFs) occur at the corners of the gap, which has important implications for the SERS-based detection of catalytic conversions: it is sufficient for molecules to come in contact with the "hot spot corners", and it is not required that they diffuse deeply into the gap. For the widely employed Pd-catalyzed Suzuki-Miyaura cross-coupling reaction, we demonstrate that such Pd NC dimers can be employed for in situ kinetic SERS monitoring, using a whole series of aryl halides as educts. Our generic approach based on the controlled assembly into dimers can easily be extended to other transition-metal nanostructures.

Synthesis of a Gold-Metal Oxide Core-Satellite Nanostructure for In†Situ SERS Study of CuO-Catalyzed Photooxidation.

This work reports on an assembling-calcining method for preparing gold-metal oxide core-satellite nanostructures, which enable surface-enhanced Raman spectroscopic detection of chemical reactions on metal oxide nanoparticles. By using the nanostructure, we study the photooxidation of Si-H catalyzed by CuO nanoparticles. As evidenced by the in situ spectroscopic results, oxygen vacancies of CuO are found to be very active sites for oxygen activation, and hydroxide radicals (*OH) adsorbed at the catalytic sites are likely to be the reactive intermediates that trigger the conversion from silanes into the corresponding silanols. According to our finding, oxygen vacancy-rich CuO catalysts are confirmed to be of both high activity and selectivity in photooxidation of various silanes.

C-H Arylation on Nickel Nanoparticles Monitored by In†Situ Surface-Enhanced Raman Spectroscopy.

Bifunctional Au@Ni core-satellite nanostructures synthesized by a one-step assembly method were employed for in situ surface-enhanced Raman spectroscopic (SERS) monitoring of Ni-catalyzed C-C bond-forming reactions. Surprisingly, the reaction that was thought to be an Ullmann-type self-coupling reaction, was found to be a cross-coupling reaction proceeding by photoinduced aromatic C-H bond arylation. In situ SERS monitoring enabled the discovery, and a series of biphenyl compounds were synthesized photocatalytically, and at room temperature, using cheap Ni nanoparticle catalysts.