Mechanistic Insights Gained by High Spatial Resolution Reactivity Mapping of Homogeneous and Heterogeneous (Electro)Catalysts.

The recent development of high spatial resolution microscopy and spectroscopy tools enabled reactivity analysis of homogeneous and heterogeneous (electro)catalysts at previously unattainable resolution and sensitivity. These techniques revealed that catalytic entities are more heterogeneous than expected and local variations in reaction mechanism due to divergences in the nature of active sites, such as their atomic properties, distribution, and accessibility, occur both in homogeneous and heterogeneous (electro)catalysts. In this review, we highlight recent insights in catalysis research that were attained by conducting high spatial resolution studies. The discussed case studies range from reactivity detection of single particles or single molecular catalysts, inter- and intraparticle communication analysis, and probing the influence of catalysts distribution and accessibility on the resulting reactivity. It is demonstrated that multiparticle and multisite reactivity analyses provide unique knowledge about reaction mechanism that could not have been attained by conducting ensemble-based, averaging, spectroscopy measurements. It is highlighted that the integration of spectroscopy and microscopy measurements under realistic reaction conditions will be essential to bridge the gap between model-system studies and real-world high spatial resolution reactivity analysis.

Selective Deposition of N-Heterocyclic Carbene Monolayers on Designated Au Microelectrodes within an Electrode Array.

The incorporation of organic self-assembled monolayers (SAMs) in microelectronic devices requires precise spatial control over the self-assembly process. In this work, selective deposition of N-heterocyclic carbenes (NHCs) on specific electrodes within a two-microelectrode array is achieved by using pulsed electrodeposition. Spectroscopic analysis of the NHC-coated electrode arrays reveals that each electrode is selectively coated with a designated NHC. The impact of NHC monolayers on the electrodes' work function is quantified using Kelvin probe force microscopy. These measurements demonstrate that the work function values of each electrode can be independently tuned by the adsorption of a specific NHC. The presented deposition method enables to selectively coat designated microelectrodes in an electrode array with chosen NHC monolayers for tuning their chemical and electronic functionality.

Nanoimaging of Facet-Dependent Adsorption, Diffusion, and Reactivity of Surface Ligands on Au Nanocrystals.

Analysis of the influence of dissimilar facets on the adsorption, stability, mobility, and reactivity of surface ligands is essential for designing ligand-coated nanocrystals with optimal functionality. Herein, para-nitrothiophenol and nitronaphthalene were chemisorbed and physisorbed, respectively, on Au nanocrystals, and the influence of different facets within a single Au nanocrystal on ligands properties were identified by IR nanospectroscopy measurements. Preferred adsorption was probed on (001) facets for both ligands, with a lower density on (111) facets. Exposure to reducing conditions led to nitro reduction and diffusion of both ligands toward the top (111) facet. Nitrothiophenol was characterized with a diffusivity higher than that of nitronaphthalene. Moreover, the strong thiol-Au interaction led to the diffusion of Au atoms and the formation of thiol-coated Au nanoparticles on the silicon surface. It is identified that the adsorption and reactivity of surface ligands were mainly influenced by the atomic properties of each facet, while diffusion was controlled by ligand-metal interactions.

Aqueous Photoelectrochemical CO2 Reduction to CO and Methanol over a Silicon Photocathode Functionalized with a Cobalt Phthalocyanine Molecular Catalyst.

We report a precious-metal-free molecular catalyst-based photocathode that is active for aqueous CO2 reduction to CO and methanol. The photoelectrode is composed of cobalt phthalocyanine molecules anchored on graphene oxide which is integrated via a (3-aminopropyl)triethoxysilane linker to p-type silicon protected by a thin film of titanium dioxide. The photocathode reduces CO2 to CO with high selectivity at potentials as mild as 0 V versus the reversible hydrogen electrode (vs RHE). Methanol production is observed at an onset potential of -0.36 V vs RHE, and reaches a peak turnover frequency of 0.18 s-1 . To date, this is the only molecular catalyst-based photoelectrode that is active for the six-electron reduction of CO2 to methanol. This work puts forth a strategy for interfacing molecular catalysts to p-type semiconductors and demonstrates state-of-the-art performance for photoelectrochemical CO2 reduction to CO and methanol.