Mechanistic Understanding of Oxygen Activation on Bulk Au(111) Surface Using Tip-Enhanced Raman Spectroscopy.

Gaining mechanistic understanding of oxygen activation on metal surfaces is a topical area of research in surface science. However, direct investigation of on-surface oxidation processes at the nanoscale and the empirical validation of oxygen activation pathways remain challenging for the conventional analytical tools. In this study, we applied tip-enhanced Raman spectroscopy (TERS) to gain mechanistic insights into oxygen activation on bulk Au(111) surface. Specifically, oxidation of 4-aminothiophenol (4-ATP) to 4-nitrothiophenol (4-NTP) on Au(111) surface was investigated using hyperspectral TERS imaging. Nanoscale TERS images revealed a markedly higher oxidation efficiency in disordered 4-ATP adlayers compared to the ordered adlayers signifying that the oxidation of 4-ATP molecules proceeds via interaction with the on-surface oxidative species. These results were further validated via direct oxidation of the 4-ATP adlayers with H2O2 solution. Finally, TERS measurements of oxidized 4-ATP adlayers in the presence of H2O18 provided the first empirical evidence for the generation of oxidative species on bulk Au(111) surface via water-mediated activation of molecular oxygen. This study expands our mechanistic understanding of oxidation chemistry on bulk Au surface by elucidating the oxygen activation pathway.

Insights into the Polymerization Reactions on Solid Surfaces Provided by Scanning Tunneling Microscopy.

Understanding the polymerization process at the molecular level is essential for the rational design and synthesis of polymers with controllable structures and properties. Scanning tunneling microscopy (STM) is one of the most important techniques to investigate the structures and reactions on conductive solid surfaces, and it has successfully been used to reveal the polymerization process on the surface at the molecular level in recent years. In this Perspective, after a brief introduction of on-surface polymerization reactions and STM, we focus on the applications of STM in the study of the processes and mechanism of on-surface polymerization, from one-dimensional to two-dimensional polymerization reactions. We conclude by a discussion of the challenges and perspectives on this topic.

Nanoscale chemical analysis of 2D molecular materials using tip-enhanced Raman spectroscopy.

Two-dimensional (2D) molecular materials have attracted immense attention due to their unique properties, promising a wide range of exciting applications. To understand the structure-property relationship of these low-dimensional materials, sensitive analytical tools capable of providing structural and chemical characterisation at the nanoscale are required. However, most conventional analytical techniques fail to meet this challenge, especially in a label-free and non-destructive manner under ambient conditions. In the last two decades, tip-enhanced Raman spectroscopy (TERS) has emerged as a powerful analytical technique for nanoscale chemical characterisation by combining the high spatial resolution of scanning probe microscopy and the chemical sensitivity and specificity of surface-enhanced Raman spectroscopy. In this review article, we provide an overview of the application of TERS for nanoscale chemical analysis of 2D molecular materials, including 2D polymers, biomimetic lipid membranes, biological cell membranes, and 2D reactive systems. The progress in the structural and chemical characterisation of these 2D materials is demonstrated with key examples from our as well as other laboratories. We highlight the unique information that TERS can provide as well as point out the common pitfalls in experimental work and data interpretation and the possible ways of averting them.

Defect-engineered surfaces to investigate the formation of self-assembled molecular networks.

Herein we report the impact of covalent modification (grafting), inducing lateral nanoconfinement conditions, on the self-assembly of a quinonoid zwitterion derivative into self-assembled molecular networks at the liquid/solid interface. At low concentrations where the compound does not show self-assembly behaviour on bare highly oriented pyrolytic graphite (HOPG), close-packed self-assembled structures are visualized by scanning tunneling microscopy on covalently modified HOPG. The size of the self-assembled domains decreases with increasing the density of grafted molecules, i.e. the molecules covalently bound to the surface. The dynamics of domains are captured with molecular resolution, revealing not only time-dependent growth and shrinkage processes but also the orientation conversion of assembled domains. Grafted pins play a key role in initiating the formation of on-surface molecular self-assembly and their stabilization, providing an elegant route to study various aspects of nucleation and growth processes of self-assembled molecular networks.

Visualizing On-Surface Decomposition Chemistry at the Nanoscale Using Tip-Enhanced Raman Spectroscopy.

Chemical imaging of molecular decomposition processes at solid-liquid interfaces is a long-standing problem in achieving mechanistic understanding. Conventional analytical tools fail to meet this challenge due to the lack of required chemical sensitivity and specificity at the nanometer scale. In this work, we demonstrate that high-resolution hyperspectral tip-enhanced Raman spectroscopy (TERS) imaging can be a powerful analytical tool for studying on-surface decomposition chemistry at the nanoscale. Specifically, we present a TERS-based hyperspectral approach to visualize the on-surface decomposition process of a pyridine-4-thiol self-assembled monolayer on atomically flat Au(111) surfaces under ambient conditions. Reactive intermediates involved in the degradation process are spectroscopically detected with 5 nm spatial resolution. With supporting density functional theory simulations, a key species could be assigned to the disulfide reaction intermediate. This work opens a new application area for studying on-surface decomposition chemistry and related dynamics quantitatively at solid-liquid interfaces with nanometer spatial resolution.

Observing polymerization in 2D dynamic covalent polymers.

The quality of crystalline two-dimensional (2D) polymers1-6 is intimately related to the elusive polymerization and crystallization processes. Understanding the mechanism of such processes at the (sub)molecular level is crucial to improve predictive synthesis and to tailor material properties for applications in catalysis7-10 and (opto)electronics11,12, among others13-18. We characterize a model boroxine 2D dynamic covalent polymer, by using in situ scanning tunnelling microscopy, to unveil both qualitative and quantitative details of the nucleation-elongation processes in real time and under ambient conditions. Sequential data analysis enables observation of the amorphous-to-crystalline transition, the time-dependent evolution of nuclei, the existence of 'non-classical' crystallization pathways and, importantly, the experimental determination of essential crystallization parameters with excellent accuracy, including critical nucleus size, nucleation rate and growth rate. The experimental data have been further rationalized by atomistic computer models, which, taken together, provide a detailed picture of the dynamic on-surface polymerization process. Furthermore, we show how 2D crystal growth can be affected by abnormal grain growth. This finding provides support for the use of abnormal grain growth (a typical phenomenon in metallic and ceramic systems) to convert a polycrystalline structure into a single crystal in organic and 2D material systems.

Molecular-Level Insights on Reactive Arrangement in On-Surface Photocatalytic Coupling Reactions Using Tip-Enhanced Raman Spectroscopy.

Plasmon-enhanced photocatalytic coupling reactions have been used as model systems in surface-enhanced Raman spectroscopy and tip-enhanced Raman spectroscopy (TERS) research for decades. However, the role of reactive arrangement on efficiency of these model reactions has remained largely unknown to date often leading to conflicting interpretations of experimental results. Herein, we use an interdisciplinary toolbox of nanoscale TERS imaging in combination with molecular-resolution ambient scanning tunnelling microscopy (STM) and density functional theory (DFT) modeling to investigate the role of reactive arrangement in photocatalytic coupling of 4-nitrobenzenethiol (4-NTP) to p,p'-dimercaptoazobisbenzene on single-crystal and polycrystalline Au surfaces for the first time. TERS imaging with 3 nm resolution clearly revealed a significantly higher catalytic efficiency inside a kinetically driven disordered phase of the 4-NTP adlayer on Au compared to the thermodynamically stable ordered phase. Furthermore, molecular level details of the self-assembled structures in the disordered and ordered phases obtained using ambient high-resolution STM enabled an unambiguous structure-reactivity correlation of photocatalytic coupling. Finally, quantitative mechanistic insights obtained from DFT modeling based on the accurate parameters determined from STM imaging emphatically confirmed that a combination of steric hindrance effect and energetic barrier leads to a lower reaction efficiency in the ordered phase of the 4-NTP adlayer. This fundamental study establishes the first direct structure-reactivity correlation in photocatalytic coupling and highlights the critical role of reactive arrangement in the efficiency of on-surface coupling reactions in heterogeneous catalysis at large.

Molecular-Scale Chemical Imaging of the Orientation of an On-Surface Coordination Complex by Tip-Enhanced Raman Spectroscopy.

Metal-organic coordination structures at interfaces play an essential role in many biological and chemical systems. Understanding the molecular specificity, orientation, and spatial distribution of the coordination complexes at the nanometer scale is of great importance for effective molecular engineering of nanostructures and fabrication of functional devices with controllable properties. However, fundamental properties of such coordination systems are still rarely studied directly. In this work, we present a spectroscopic approach on the basis of tip-enhanced Raman spectroscopy (TERS) to investigate cobalt(II) tetraphenyl-porphyrine coordination species on the scale of a single molecule under ambient conditions. Coordination species anchored on gold surfaces modified with pyridine thiol self-assembled monolayers can be spectroscopically distinguished and mapped with ca. 2 nm resolution. In addition, in combination with density functional theory simulations, the adsorption configuration and molecular orientation of the coordination complexes are also revealed using TERS imaging.

In†Situ Scanning Tunneling Microscopy of Cobalt-Phthalocyanine-Catalyzed CO2 Reduction Reaction.

We report a molecular investigation of a cobalt phthalocyanine (CoPc)-catalyzed CO2 reduction reaction by electrochemical scanning tunneling microscopy (ECSTM). An ordered adlayer of CoPc was prepared on Au(111). Approximately 14 % of the adsorbed species appeared with high contrast in a CO2 -purged electrolyte environment. The ECSTM experiments indicate the proportion of high-contrast species correlated with the reduction of CoII Pc (-0.2 V vs. saturated calomel electrode (SCE)). The high-contrast species is ascribed to the CoPc-CO2 complex, which is further confirmed by theoretical simulation. The sharp contrast change from CoPc-CO2 to CoPc is revealed by in situ ECSTM characterization of the reaction. Potential step experiments provide dynamic information for the initial stage of the reaction, which include the reduction of CoPc and the binding of CO2 , and the latter is the rate-limiting step. The rate constant of the formation and dissociation of CoPc-CO2 is estimated on the basis of the in situ ECSTM experiment.

Real-Time Molecular-Scale Imaging of Dynamic Network Switching between Covalent Organic Frameworks.

The in situ on-surface conversion process from boroxine-linked covalent organic frameworks (COFs) to boronate ester-linked COFs is triggered and catalyzed at room temperature by an electric field and monitored with scanning tunneling microscopy (STM). The adaptive behavior within the generated dynamic covalent libraries (DCLs) was revealed, providing in-depth understanding of the dynamic network switching process.

Electric-Field-Mediated Reversible Transformation between Supramolecular Networks and Covalent Organic Frameworks.

By using an oriented electric field in a scanning tunneling microscope, one can locally control the condensation of boronic acids at the liquid/solid interface. The phase transition between self-assembled molecular networks and covalent organic frameworks is controlled by changing the polarity of the applied bias. The electric-field-induced phase transformation is reversible under ambient conditions.

Molecular Evidence for the Catalytic Process of Cobalt Porphyrin Catalyzed Oxygen Evolution Reaction in Alkaline Solution.

We report an electrochemical scanning tunneling microscopy (ECSTM) study of the 5,10,15,20-tetraphenyl-21 H,23 H-porphyrin cobalt(II) (CoTPP) catalyzed oxygen evolution reaction (OER). A highly ordered self-assembled monolayer of CoTPP is formed on the Au(111) electrode. Cyclic voltammetry results show the OER activity of the electrode is enhanced with the increasing alkalinity of the electrolytes. The CoTPP molecules appear as two symmetric bright spots in STM images in alkaline solution, which is in sharp contrast to that in acidic solution. The molecular contour changes are attributed to the formation of the CoTPP-OH- species before OER, which is further confirmed by UV-vis absorption spectroscopy. In situ ECSTM results reveal the evolution from the CoTPP-OH- species to CoTPP molecules during OER.

Directed assembly of fullerene on modified Au(111) electrodes.

Here we show a conceptual approach to realize the scanning tunneling microscopy based induced-assembly of fullerene (C60) molecules on top of a buffer organic adlayer at room temperature in a solution environment. The realization of spatially-defined C60 assembly is attributed to the modulation of substrate-molecular interactions with the assistance of a buffer layer.

Potential- and concentration-dependent self-assembly structures at solid/liquid interfaces.

We report the potential and concentration controlled assembly of an alkyl-substituted benzo[1,2-b:4,5-b']dithiophene (DDBDT) on an Au(111) electrode by in situ electrochemical scanning tunneling microscopy (ECSTM). It is found that a lamellar structure is formed at low concentrations, while herringbone-like and rhombus structures are obtained at high concentrations. In situ STM results reveal that herringbone-like and rhombus structures could transform into lamellar structures when the electrode potential is tuned negatively. A phase diagram is obtained to illustrate the relationship and effects of concentration and substrate potential on the interfacial structures of DDBDT. Both the substrate potential and the solute concentration can modulate the self-assembly structure through changing the molecular surface density. The results provide important insights into the understanding and precise control of molecular self-assembly on solid surfaces through a combination of different approaches.

Chlorine levels and species in fine and size resolved atmospheric particles by X-ray absorption near-edge structure spectroscopy analysis in Beijing, China.

An understanding of the species of chlorine is crucial in the metropolis-Beijing, which is suffering serious haze pollution with high frequency. Particulate Matters (PMs) with five different sizes were collected in Beijing from July 2009 to March 2016, and characterized non-destructively by X-ray absorption near edge structure spectroscopy. PM<0.2, PM0.2-0.5 and PM>2.5 contributed for the major PMs mass in spring and summer, PM0.5-1.0 and PM1.0-2.5 contributed for the major PMs mass in autumn and winter. The concentrations of the three chlorine species were in the order of inorganic chlorine (Clinorg) > aliphatic chlorine (Clali) > aromatic chlorine (Claro), indicating that Clinorg constituted the primary chlorine fraction and less toxic Clali constituted the primary total organic chlorine (Clali + Claro, abbreviated as Clorg) in the PMs in Beijing. In addition, these three chlorine species exhibited identical seasonal variation in PM2.5: winter > autumn > spring > summer. Wet precipitation is an important factor to result in the lower mass concentrations of these three chlorine species in summer. The temporal variations of both size resolved PM mass concentrations and chlorine species concentrations suggested that the air pollution prevention and control in Beijing has just won initial success.

Ionic interaction-induced assemblies of bimolecular "chessboard" structures.

Here we applied ionic interactions as the driving force to fabricate well-ordered bicomponent assemblies by using two porphyrin ions equipped with oppositely-charged groups. Two kinds of bimolecular chessboard structures were successfully constructed on Au(111) and investigated by scanning tunneling microscopy (STM).

Single-Molecule Imaging of Iron-Phthalocyanine-Catalyzed Oxygen Reduction Reaction by in Situ Scanning Tunneling Microscopy.

We report herein an in situ electrochemical scanning tunneling microscopy (ECSTM) investigation of iron-phthalocyanine (FePc)-catalyzed oxygen reduction reaction (ORR). A highly ordered FePc adlayer is revealed on a Au(111) electrode. The center ions in the FePc adlayer show uniform high contrast in an oxygen-saturated electrolyte, which is attributed to the formation of an FePc-O2 complex. In situ STM results reveal the sharp contrast change upon shifting the electrode potential to trigger the ORR. Theoretical simulation has supplied further evidence for the contrast difference of the adsorbed FePc species.