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.

N-Heterocyclic Carbene Monolayers on Metal-Oxide Films: Correlations between Adsorption Mode and Surface Functionality.

N-Heterocyclic carbene (NHC) ligands have been self-assembled on various metal and semimetal surfaces, creating a covalent bond with surface metal atoms that led to high thermal and chemical stability of the self-assembled monolayer. This study explores the self-assembly of NHCs on metal-oxide films (CuOx, FeOx, and TiOx) and reveals that the properties of these metal-oxide substrates play a pivotal role in dictating the adsorption behavior of NHCs, influencing the decomposition route of the monolayer and its impact on work function values. While the attachment of NHCs onto CuOx is via coordination with surface oxygen atoms, NHCs interact with TiOx through coordination with surface metal atoms and with FeOx via coordination with both metal and oxygen surface atoms. These distinct binding modes arise due to variances in the electronic properties of the metal atoms within the investigated metal-oxide films. Contact angle and ultraviolet photoelectron spectroscopy measurements have shown a significantly higher impact of F-NHC adsorption on CuOx than on TiOx and FeOx , correlated to a preferred, averaged upright orientation of F-NHC on CuOx.

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.

Influence of Charged Self-Assembled Monolayers on Single Nanoparticle Collision.

Studying nanoparticle (NP)-electrode interactions in single nanoparticle collision events is critical to understanding dynamic processes such as nanoparticle motion, adsorption, oxidation, and catalytic activity, which are abundant on electrode surfaces. Herein, NP-electrode electrostatic interactions are studied by tracking the oxidation of AgNPs at Au microelectrodes functionalized with charged self-assembled monolayers (SAMs). Tuning the charge of short alkanethiol-based monolayers and selecting AgNPs that can be partially or fully oxidized upon impact enabled probing the influence of attractive and repulsive NP-electrode electrostatic interactions on collision frequency, electron transfer, and nanoparticle sizing. We find that repulsive electrostatic interactions lead to a significant decrease in collision frequency and erroneous nanoparticle sizing. In stark difference, attractive electrostatic interactions dramatically increase the collision frequency and extend the sizing capability to larger nanoparticle sizes. Thus, these findings demonstrate how NP-monolayer interactions can be studied and manipulated by combining nanoimpact electrochemistry and functionalized SAMs.

High-spatial-resolution mapping of catalytic reactions on single particles.

The critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established. But despite the growing availability of tools that enable detailed in situ characterization, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has been used to image and characterize single turnover sites at catalytic surfaces, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. These observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles-which contain metal atoms with low coordination numbers-are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.

Self-Assembled Monolayers of N-Heterocyclic Olefins on Au(111).

Self-assembled monolayers (SAMs) of N-heterocyclic olefins (NHOs) have been prepared on Au(111) and their thermal stability, adsorption geometry, and molecular order were characterized by X-ray photoelectron spectroscopy, polarized X-ray absorption spectroscopy, scanning tunneling microscopy (STM), and density functional theory (DFT) calculations. The strong σ-bond character of NHO anchoring to Au induced high geometrical flexibility that enabled a flat-lying adsorption geometry via coordination to a gold adatom. The flat-lying adsorption geometry was utilized to further increase the surface interaction of the NHO monolayer by backbone functionalization with methyl groups that induced high thermal stability and a large impact on work-function values, which outperformed that of N-heterocyclic carbenes. STM measurements, supported by DFT modeling, identified that the NHOs were self-assembled in dimers, trimers, and tetramers constructed of two, three, and four complexes of NHO-Au-adatom. This self-assembly pattern was correlated to strong NHO-Au interactions and steric hindrance between adsorbates, demonstrating the crucial influence of the carbon-metal σ-bond on monolayer properties.

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.

The influence of adsorption geometry on the reduction affinity of nitroaromatics on Au(111).

Chemoselective reduction of nitro groups in multifunctional nitroaromatics is a challenging catalytic process with high interest due to the importance of the resulting anilines for the chemical industry. Molecular-level understanding of the ways by which adsorption geometry of nitroaromatics influence their affinity toward nitro reduction will enable the development of highly selective reactions. Herein, taking advantage of the well-ordered self-assembly of para- and ortho-nitrothiophenol (p-NTP and o-NTP, respectively) monolayers on Au(111), we examined the correlation between adsorption geometry and nitro reduction affinity. The anchoring geometry of NTPs and their nitro reduction affinity were determined by conducting polarized X-ray absorption spectroscopy while the influence of NTPs' adsorption geometry on the interaction with the Au surface was analyzed by density functional theory (DFT) calculations. Exposure of surface anchored p-NTPs to reducing conditions led to their reorientation from a tilt angle of 52° to 25°, which enabled strong interactions between the π system of the molecules and the Au surface. Direct correlation was identified between the surface proximity of the nitro group, its parallel position to the surface and the resulting reduction yield. The asymmetric structure of o-NTP led to a tilted adsorption geometry in which the nitro group was rotated away from the plane of the aromatic ring and therefore was positioned parallel and in high proximity to the Au surface. This positioning led to surface-bonding that involved the oxygen atoms of o-NTP. The higher surface proximity and stronger surface interactions of the nitro group in o-NTP enabled nitro reduction already at 180 °C, while in p-NTP nitro reduction was achieved only at 230 °C, due to the longer distance between the NO2 group and the Au surface that led to weaker adsorbate-surface interactions. Thus, parallel positioning of the nitro group and high surface proximity were found as essential descriptors for nitro reduction affinity in both p-NTP and o-NTP on the Au surface. These findings provide explicit guidelines for tuning the reactant and surface properties in order to control the reactant's adsorption geometry for selective nitro reduction in multifunctional nitroaromatics.

N-Heterocyclic Carbene Based Nanolayer for Copper Film Oxidation Mitigation.

The wide use of copper is limited by its rapid oxidation. Main oxidation mitigation approaches involve alloying or surface passivation technologies. However, surface alloying often modifies the physical properties of copper, while surface passivation is characterized by limited thermal and chemical stability. Herein, we demonstrate an electrochemical approach for surface-anchoring of an N-heterocyclic carbene (NHC) nanolayer on a copper electrode by electro-deposition of alkyne-functionalized imidazolium cations. Water reduction reaction generated a high concentration of hydroxide ions that induced deprotonation of imidazolium cations and self-assembly of NHCs on the copper electrode. In addition, alkyne group deprotonation enabled on-surface polymerization by coupling surface-anchored and solvated NHCs, which resulted in a 2 nm thick NHC-nanolayer. Copper film coated with a NHC-nanolayer demonstrated high oxidation resistance at elevated temperatures and under alkaline conditions.

Influence of N-Substituents on the Adsorption Geometry of OH-Functionalized Chiral N-Heterocyclic Carbenes.

Adsorption of chiral molecules on heterogeneous catalysts is a simple approach for inducing an asymmetric environment to enable enantioselective reactivity. Although the concept of chiral induction is straightforward, its practical utilization is far from simple, and only a few examples toward the successful chiral induction by surface anchoring of asymmetric modifiers have been demonstrated so far. Elucidating the factors that lead to successful chiral induction is therefore a crucial step for understanding the mechanism by which chirality is transferred. Herein, we identify the adsorption geometry of OH-functionalized N-heterocyclic carbenes (NHCs), which are chemical analogues to chiral modifiers that successfully promoted α-arylation reactions once anchored on Pd nanoparticles. Polarized near-edge X-ray absorption fine structure (NEXAFS) measurements on Pd(111) revealed that NHCs that were associated with low enantioselectivity were characterized with a well-ordered structure, in which the imidazole ring was vertically positioned and the OH-functionalized side arms were flat-lying. OH-functionalized NHCs that were associated with high enantioselectivity revealed a disordered/flexible adsorption geometry, which potentially enabled better interaction between the OH group and the prochiral reactant.

AFM-IR and s-SNOM-IR measurements of chemically addressable monolayers on Au nanoparticles.

The performance of catalysts depends on their nanoscale properties, and local variations in structure and composition can have a dramatic impact on the catalytic reactivity. Therefore, probing the localized reactivity of catalytic surfaces using high spatial resolution vibrational spectroscopy, such as infrared (IR) nanospectroscopy and tip-enhanced Raman spectroscopy, is essential for mapping their reactivity pattern. Two fundamentally different scanning probe IR nanospectroscopy techniques, namely, scattering-type scanning near-field optical microscopy (s-SNOM) and atomic force microscopy-infrared spectroscopy (AFM-IR), provide the capabilities for mapping the reactivity pattern of catalytic surfaces with a spatial resolution of ∼20 nm. Herein, we compare these two techniques with regard to their applicability for probing the vibrational signature of reactive molecules on catalytic nanoparticles. For this purpose, we use chemically addressable self-assembled molecules on Au nanoparticles as model systems. We identified significant spectral differences depending on the measurement technique, which originate from the fundamentally different working principles of the applied methods. While AFM-IR spectra provided information from all the molecules that were positioned underneath the tip, the s-SNOM spectra were more orientation-sensitive. Due to its field-enhancement factor, the s-SNOM spectra showed higher vibrational signals for dipoles that were perpendicularly oriented to the surface. The s-SNOM sensitivity to the molecular orientation influenced the amplitude, position, and signal-to-noise ratio of the collected spectra. Ensemble-based IR measurements verified that differences in the localized IR spectra stem from the enhanced sensitivity of s-SNOM measurements to the adsorption geometry of the probed molecules.

Self-Assembled Monolayers of Nitron: Self-Activated and Chemically Addressable N-Heterocyclic Carbene Monolayers with Triazolone Structural Motif.

N-heterocyclic carbenes (NHCs) have emerged as a unique molecular platform for the formation of self-assembled monolayers (SAMs) on various surfaces. However, active carbene formation requires deprotonation of imidazolium salt precursors, which is mostly facilitated by exposure of the salt to exogenous base. Base residues were found to be adsorbed on the metal surface and hindered the formation of well-ordered carbene-based monolayers. Herein, we show that nitron, a triazolone-based compound that freely tautomerizes to a carbene, can spontaneously self-assemble into monolayers on Pt and Au surfaces, which obviates the necessity for base-induced deprotonation for active carbene formation. SAMs of nitron were found to be thermally stable and could not be displaced by thiols, and thus their high chemical stability was demonstrated. The amino group in surface-anchored nitron was shown to be chemically available for SN 2 reactions, and makes surface-anchored nitron a chemically addressable cross-linking reagent for surface modifications.

Strong Metal-Adsorbate Interactions Increase the Reactivity and Decrease the Orientational Order of OH-Functionalized N-Heterocyclic Carbene Monolayers.

Fundamental understanding of the correlation between the structure and reactivity of chemically addressable N-heterocyclic carbene (NHC) molecules on various surfaces is essential for the design of functional NHC-based self-assembled monolayers. In this work, we identified the ways by which the deposition of chemically addressable OH-NHCs on Au(111) or Pt(111) surfaces modified the anchoring geometry and chemical reactivity of surface-anchored NHCs. The properties of surface-anchored NHCs were probed by conducting X-ray photoelectron spectroscopy and polarized near-edge X-ray absorption fine structure measurements. While no preferred orientation was identified for OH-NHCs on Pt(111), the anchored molecules adopted a preferred flat-lying position on Au(111). Dehydrogenation and aromatization of the imidazoline ring along with partial hydroxyl oxidation were detected in OH-NHCs that were anchored on Au(111). The dehydrogenation and aromatization reactions were facilitated, along with partial decomposition, for OH-NHCs that were anchored on Pt(111). The spectroscopic results reveal that stronger metal-adsorbate interactions increase the reactivity of surface-anchored OH-NHCs while decreasing their molecular orientational order.

Site-dependent selectivity in oxidation reactions on single Pt nanoparticles.

Site-dependent selectivity in oxidation reactions on Pt nanoparticles was identified by conducting IR nanospectroscopy measurements while using allyl-functionalized N-heterocyclic carbenes (allyl-NHCs) as probe molecules. Following exposure to oxidizing conditions the allyl groups in NHCs that were located on the center of Pt nanoparticles were oxidized to hydroxyl while those located on the nanoparticle's periphery were oxidized into carboxylic acid. The superior reactivity on the periphery of the nanoparticles was correlated to higher density of low coordinated atoms on these surface sites.

[A MULTIFACETED APPROACH FOR TRAUMATIC AURICULAR AVULSION WITH VENOUS CONGESTION].

INTRODUCTION: Choice of operative technique is often a major factor in the success of replantation of traumatic avulsions of the auricle. While microsurgery is considered to produce the best aesthetic results, this approach may not be an option due to vascular damage. We present the case of a 66-year-old Caucasian male with a subtotal traumatic left auricle avulsion. Microsurgical repair was not attempted as vessels amenable to anastomosis could not be found. Instead, the auricle was replanted in a non-microsurgical manner as a composite graft using Monocryl sutures. As a preventative measure for clot formation heparin was injected intradermally throughout the anterior auricular surface and helix. Twenty-four hours postoperatively, as signs of venous congestion were noted, a multimodal therapy was initiated combining mechanical, chemical and biological therapies. Medicinal leech therapy (hirudotherapy) was used to enhance venous drainage and prevent clot formation. Hirudotherapy is an effective and safe treatment modality for venous outflow obstruction in avulsed auricle injuries. However, one must consider the possible complications of leech therapy and the need for close monitoring. An examination conducted two months following the initial injury revealed optimal patient outcomes with excellent aesthetic results and full auricular sensation. Good vascular outflow is integral to the successful salvage of replanted tissues. Venous stasis must be identified and addressed early for good patient outcomes. The current report highlights the importance of a multifaceted approach in cases of traumatic auricular avulsions followed by venous congestion.

Flexible NO2 -Functionalized N-Heterocyclic Carbene Monolayers on Au(111) Surface.

Invited for the cover of this issue are Elad Gross, F. Dean Toste, and co-workers at The Hebrew University and UC Berkeley. The image depicts the flexible anchoring geometry of addressable carbene molecules on Au surface, which upon exposure to reducing conditions changed their orientation from a standing into a flat-lying position. Read the full text of the article at 10.1002/chem.201903434.

Flexible NO2 -Functionalized N-Heterocyclic Carbene Monolayers on Au (111) Surface.

The formation of flexible self-assembled monolayers (SAMs) in which an external trigger modifies the geometry of surface-anchored molecules is essential for the development of functional materials with tunable properties. In this work, it is demonstrated that NO2 -functionalized N-heterocyclic carbene molecules (NHCs), which were anchored on Au (111) surface, change their orientation from tilted into flat-lying position following trigger-induced reduction of their nitro groups. DFT calculations identified that the energetic driving force for reorientation was the lower steric hindrance and stronger interactions between the chemically reduced NHCs and the Au surface. The trigger-induced changes in the NHCs' anchoring geometry and chemical functionality modified the work function and the hydrophobicity of the NHC-decorated Au surface, demonstrating the impact of a chemically tunable NHC-based SAM on the properties of the metal surface.

Integration of chemical catalysis with extractive fermentation to produce fuels.

Nearly one hundred years ago, the fermentative production of acetone by Clostridium acetobutylicum provided a crucial alternative source of this solvent for manufacture of the explosive cordite. Today there is a resurgence of interest in solventogenic Clostridium species to produce n-butanol and ethanol for use as renewable alternative transportation fuels. Acetone, a product of acetone-n-butanol-ethanol (ABE) fermentation, harbours a nucleophilic α-carbon, which is amenable to C-C bond formation with the electrophilic alcohols produced in ABE fermentation. This functionality can be used to form higher-molecular-mass hydrocarbons similar to those found in current jet and diesel fuels. Here we describe the integration of biological and chemocatalytic routes to convert ABE fermentation products efficiently into ketones by a palladium-catalysed alkylation. Tuning of the reaction conditions permits the production of either petrol or jet and diesel precursors. Glyceryl tributyrate was used for the in situ selective extraction of both acetone and alcohols to enable the simple integration of ABE fermentation and chemical catalysis, while reducing the energy demand of the overall process. This process provides a means to selectively produce petrol, jet and diesel blend stocks from lignocellulosic and cane sugars at yields near their theoretical maxima.

The Synergy between Metal Facet and Oxide Support Facet for Enhanced Catalytic Performance: The Case of Pd-TiO2.

The demand for catalyst with higher activity and higher selectivity is still a central issue in current material science community. On the basis of first-principles calculations, we demonstrate that the catalytic performance of the Pd-TiO2 hybrid nanostructures can be selectively promoted or depressed by choosing the suitable shaped Pd and TiO2 nanocrystals. To be more specific, the catalytic activities of Pd nanoparticles enclosed by (100) or (111) facets can be promoted more significantly when dosed on the TiO2(001) than on TiO2(101) under irradiation. Such theoretical prediction has then been further verified by the experimental observations in which the Pd(100)-TiO2(001) composites exhibit the highest catalytic performance toward the activation of oxygen among all the other shaped hybrid nanostructures. As a result, the selection of facets of support materials can provide an extra tuning parameter to control the catalytic activities of metal nanoparticles. This research opened up a new direction for designing and preparing catalysts with enhanced catalytic performance.