Identifying the active sites and intermediates on copper surfaces for electrochemical nitrate reduction to ammonia.

Copper (Cu) is a widely used catalyst for the nitrate reduction reaction (NO3RR), but its susceptibility to surface oxidation and complex electrochemical conditions hinders the identification of active sites. Here, we employed electropolished metallic Cu with a predominant (100) surface and compared it to native oxide-covered Cu. The electropolished Cu surface rapidly oxidized after exposure to either air or electrolyte solutions. However, this oxide was reduced below 0.1 V vs. RHE, thus returning to the metallic Cu before NO3RR. It was distinguished from the native oxide on Cu, which remained during NO3RR. Fast NO3- and NO reduction on the metallic Cu delivered 91.5 ± 3.7% faradaic efficiency for NH3 at -0.4 V vs. RHE. In contrast, the native oxide on Cu formed undesired products and low NH3 yield. Operando shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) analysis revealed the adsorbed NO3-, NO2, and NO species on the electropolished Cu as the intermediates of NH3. Low overpotential NO3- and NO adsorptions and favorable NO reduction are key to increased NH3 productivity over Cu samples, which was consistent with the DFT calculation on Cu(100).

Role of Local Conductivities in the Plasmon Reflections at the Edges and Stacking Domain Boundaries of Trilayer Graphene.

We employed infrared scattering-type scanning near-field optical microscopy (IR-sSNOM) to study surface plasmon polaritons (SPPs) in trilayer graphene (TLG). Our study reveals systematic differences in near-field IR spectra and SPP wavelengths between Bernal (ABA) and rhombohedral (ABC) TLG domains on SiO2, which can be explained by stacking-dependent intraband conductivities. We also observed that the SPP reflection profiles at ABA-ABC boundaries could be mostly accounted for by an idealized domain boundary defined by the conductivity discontinuity. However, we identified distinct shapes in the SPP profiles at the edges of the ABA and ABC TLG, which cannot be solely attributed to idealized edges with stacking-dependent conductivities. Instead, this can be explained by the presence of various edge structures with local conductivities differing from those of bulk TLGs. Our findings unveil a new structural element that can control SPP, and provide insights into the structures and electronic states of the edges of few-layer graphene.

Vibrationally Hot Reactants in a Plasmon-Assisted Chemical Reaction.

Recent studies on plasmon-assisted chemical reactions postulate that the hot electrons of plasmon-excited nanostructures may induce a non-thermal vibrational activation of metal-bound reactants. However, the postulate has not been fully validated at the level of molecular quantum states. We directly and quantitatively prove that such activation occurs on plasmon-excited nanostructures: The anti-Stokes Raman spectra of reactants undergoing a plasmon-assisted reaction reveal that a particular vibrational mode of the reactant is selectively excited, such that the reactants possess >10 times more energy in the mode than is expected from the fully thermalized molecules at the given local temperature. Furthermore, a significant portion (∼20%) of the excited reactant is in vibrational overtone states with energies exceeding 0.5 eV. Such mode-selective multi-quantum excitation could be fully modeled by the resonant electron-molecule scattering theory. Such observations suggest that the vibrationally hot reactants are created by non-thermal hot electrons, not by thermally heated electrons or phonons of metals. The result validates the mechanism of plasmon-assisted chemical reactions and further offers a new method to explore the vibrational reaction control on metal surfaces.

Characterization of the Interfacial Structures of Core/Shell CdSe/ZnS QDs.

Core/shell quantum dots (QDs) have been extensively studied, yet their optical properties widely vary among studies. Such variation may arise from the variation in interfacial structures induced by the subtle difference in each synthetic procedure. Here, we studied the interfacial structures of CdSe/ZnS QDs using the time-of-flight medium energy ion-scattering spectroscopy (TOF-MEIS), which offers the radial elemental distributions as well as the overall elemental compositions of QDs. The TOF-MEIS spectra provided strong evidence for the existence of an alloyed layer at the interface between CdSe and ZnS in typical CdSe/ZnS QDs. On the basis of the emission and absorption spectra of QDs sampled during the synthesis, we conclude that such interfacial alloying is caused by the dissolution of CdSe seeds during the synthesis steps. Such a dissolution mechanism is further corroborated by the observation that the ligand environment of solvent (X or L type) leads to different shapes of interfaces.

Molecular vibrational imaging at nanoscale.

The demand to visualize the spatial distribution of chemical species based on vibrational spectra is rapidly increasing. Driven by such a need, various Raman and infrared spectro-microscopies with a nanometric spatial resolution have been developed over the last two decades. Despite rapid progress, a large gap still exists between the general needs and what these techniques can achieve. This Perspective highlights the key challenges and recent breakthroughs of the two vibrational nano-imaging techniques, scattering-type scanning near-field optical microscopy and tip-enhanced Raman scattering.

Radical-Mediated C-C Coupling of Alcohols Induced by Plasmonic Hot Carriers.

The C-C coupling reactions of aliphatic alcohols to aromatics and larger-mass compounds have large endothermicities and activation energies, calling for catalysts operating at high temperatures. Here, we demonstrate that plasmon-excited nanoparticles catalyze the C-C coupling of aliphatic alcohols at room temperature to produce polyaromatic hydrocarbons and graphene oxide. The conversion is quenched by radical and electron scavengers and by the surface passivation of metals, suggesting that the reaction proceeds through alkoxy, peroxyl, hydroxyalkyl, and alkyl radical intermediates created by the metal to molecule transfer of plasmonic hot carriers. Besides being the first realization of C-C coupling of aliphatic alcohols at room temperature, the result constitutes a rare example of an endothermic plasmon-induced reaction producing new bonds and a new method for photogenerating graphene derivatives. More importantly, the result demonstrates the facile generation of organic radicals directly from alcohols, which may be used as precursors for radical-based organic reactions.

Spatially Controlled Fabrication of Surface-Enhanced Raman Scattering Hot Spots through Photoinduced Dewetting of Silver Thin Films.

A well-designed narrow gap between noble metal nanostructures plays a prominent role in surface-enhanced Raman scattering (SERS) to concentrate electromagnetic fields at the local point, called a "hot spot". However, SERS-active substrate fabrication remains a substantial hurdle due to the high process cost and the difficulty of engineering efficient plasmonic hot spots at the target area. In this study, we demonstrate a simple photolithographic method for generating ultrasensitive SERS hot spots at desired positions. The solid-state dewetting of a Ag thin film (thickness of ∼10 nm) using a continuous-wave laser (∼1 MW/cm2) generates a closely packed assembly of hemispherical Ag nanoislands. Some of these nanoislands provide substantial plasmonic-field enhancement that is sufficient for single-molecule detection and plasmon-catalyzed chemical reaction. Such hot spot structures can be patterned on the substrate with a spatial resolution of better than 1 µm. In integrated analytical devices, the patterned SERS hot spots can be used as position-specific chemical-sensing elements.

EIN3-Mediated Ethylene Signaling Attenuates Auxin Response during Hypocotyl Thermomorphogenesis.

The gaseous phytohormone ethylene plays vital roles in diverse developmental and environmental adaptation processes, such as fruit ripening, seedling establishment, mechanical stress tolerance and submergence escape. It is also known that in the light, ethylene promotes hypocotyl growth by stimulating the expression of PHYTOCHROME INTERACTING FACTOR3 (PIF3) transcription factor, which triggers microtubule reorganization during hypocotyl cell elongation. In particular, ethylene has been implicated in plant responses to warm temperatures in recent years. However, it is currently unclear how ethylene signals are functionally associated with hypocotyl thermomorphogenesis at the molecular level. Here, we show that ETHYLENE-INSENSITIVE3 (EIN3)-mediated ethylene signals attenuate hypocotyl thermomorphogenesis by suppressing auxin response. At warm temperatures, when the activity of the PIF4 thermomorphogenesis promoter is prominently high, the ethylene-activated EIN3 transcription factor directly induces the transcription of ARABIDOPSIS PP2C CLADE D7 (APD7) gene encoding a protein phosphatase that inactivates the plasma membrane (PM) H+-ATPase proton pumps. In conjunction with the promotive role of the PM H+-ATPases in hypocotyl cell elongation, our observations strongly support that the EIN3-directed induction of APD7 gene is linked with the suppression of auxin-induced cell expansion, leading to the reduction in thermomorphogenic hypocotyl growth. Our data demonstrate that APD7 acts as a molecular hub that integrates ethylene and auxin signals into hypocotyl thermomorphogenesis. We propose that the ethylene-auxin signaling crosstalks via the EIN3-APD7 module facilitate the fine-tuning of hypocotyl thermomorphogenesis under natural environments, which often fluctuate in a complex manner.

Direct Visualization of Gap-Plasmon Propagation on a Near-Touching Nanowire Dimer.

Dimers of metallic nanowires (NWs) with nanometric gaps could be an alternative to overcome the limitations of existing plasmonic waveguides. The gap-surface plasmon polaritons (gap-SPPs) of the dimers may propagate along the NW without crosstalk and greatly enhance the coupling efficiency with an emitter, enabling ultracompact optical circuits. Such a possibility has not been realized, and we experimentally show its possibility. The gap-SPPs of the AgNW-molecule-AgNW structure, with a gap of 3-5 nm defined by the molecules, are visualized using the surface-enhanced Raman scattering (SERS) of the molecules. The SERS images, representing the gap-field intensity distribution, reveal the decay and beating of the monopole-monopole and dipole-dipole gap modes. The propagation lengths of the two (l1 = 0.5-2 µm and l2 = 5-8 µm) closely follow the model prediction with a uniform gap, confirming that the scattering loss induced by the gap irregularities is surprisingly low.

Single-Molecule Surface-Enhanced Raman Scattering as a Probe of Single-Molecule Surface Reactions: Promises and Current Challenges.

The initial observations of surface-enhanced Raman scattering (SERS) from individual molecules (single-molecule SERS, SMSERS) have triggered ever more detailed mechanistic studies on the SERS process. The studies not only reveal the existence of extremely enhanced and confined fields at the gaps of Ag or Au nanoparticles but also reveal that the spatial, spectral, and temporal behaviors of the SMSERS signal critically depend on many factors, including plasmon resonances of nanostructures, diffusion (lateral and orientational) of molecules, molecular electronic resonances, and metal-molecule charge transfers. SMSERS spectra, with their molecular vibrational fingerprints, should in principle provide molecule-specific information on individual molecules in a way that any other existing single-molecule detection method (such as the ones based on fluorescence, mechanical forces, or electrical currents) cannot. Therefore, by following the spectro-temporal evolution of SMSERS signals of reacting molecules, one should be able to follow chemical reaction events of individual molecules without any additional labels. Despite such potential, however, real applications of SMSERS for single-molecule chemistry and analytical chemistry are scarce. In this Account, we discuss whether and how we can use SMSERS to monitor single-molecule chemical kinetics. The central problem lies in the experimental challenges of separately characterizing and controlling various sources of fluctuations and spatial variations in such a way that we can extract only the chemically relevant information from time-varying SMSERS signals. This Account is organized as follows. First, we outline the standard theory of SMSERS, providing an essential guide for identifying sources of spatial heterogeneity and temporal fluctuations in SMSERS signals. Second, we show how single-molecule reaction events of surface-immobilized reactants manifest themselves in experimental SMSERS trajectories. Comparison of the reactive SMSERS data (magnitudes and frequencies of discrete transitions) and the predictions of SMSERS models also allow us to assess how faithfully the SMSERS models represent reality. Third, we show how SMSERS spectral features can be used to discover new reaction intermediates and to interrogate metal-molecule electronic interactions. Finally, we propose possible improvements in experimental design (including nanogap structures and molecular systems) to make SMSERS applicable to a broader range of chemical reactions occurring under ambient conditions. The specific examples discussed in this Account are centered around the single-molecule photochemistry of 4-nitrobenzenethiol on metals, but the conclusions drawn from each example are generally applicable to any reaction system involving small organic molecules.

Electric Field Effect on Condensed-Phase Molecular Systems. VI. Field-Driven Orientation of Hydrogen Chloride in an Argon Matrix.

The orientation state of hydrogen chloride (HCl) molecules in a solid argon matrix was reversibly controlled by applying an external electric field of up to 4 × 108 V·m-1 using the ice film capacitor method. The rovibrational transitions of the field-oriented HCl were measured by reflection absorption infrared spectroscopy with p-polarized light. Upon application of the external field, free rotation of HCl inside the matrix gradually changed to perturbed rotation and then to a pendular state harmonically bound in the Stark potential well. Further increase in the field strength increased the degree of dipole alignment along the field direction, approaching an asymptotically perfect orientation of the molecules with an average tilt angle of <30° at a field strength above 1 × 108 V·m-1.

Frequency-Domain Proof of the Existence of Atomic-Scale SERS Hot-Spots.

The existence of sub-nanometer plasmonic hot-spots and their relevance in spectroscopy and microscopy applications remain elusive despite a few recent theoretical and experimental evidence supporting this possibility. In this Letter, we present new spectroscopic evidence suggesting that Angstrom-sized hot-spots exist on the surfaces of plasmon-excited nanostructures. Surface-enhanced Raman scattering (SERS) spectra of 4,4'-biphenyl dithiols placed in metallic junctions show simultaneously blinking Stokes and anti-Stokes spectra, some of which exhibit only one prominent vibrational peak. The activated vibrational modes were found to vary widely between junction sites. Such site-specific, single-peak spectra could be successfully modeled using single-molecule SERS induced by a hot-spot with a diameter no larger than 3.5 Å, located at the specific molecular sites. Furthermore, the model, which assumes the stochastic creation of hot-spots on locally flat metallic surfaces, consistently reproduces the intensity distributions and occurrence statistics of the blinking SERS peaks, further confirming that the sources of the hot-spots are located on the metallic surfaces. This result not only provides compelling evidence for the existence of Angstrom-sized hot-spots but also opens up the new possibilities for the vibrational and electronic control of single-molecule photochemistry and real-space visualization of molecular vibration modes.

Mapping of Bernal and non-Bernal stacking domains in bilayer graphene using infrared nanoscopy.

Bilayer graphene (BLG) shows great potential as a new material for opto-electronic devices because its bandgap can be controlled by varying the stacking orders, as well as by applying an external electric field. An imaging technique that can visualize and characterize various stacking domains in BLG may greatly help in fully utilizing such properties of BLG. Here we demonstrate that infrared (IR) scattering-type scanning near-field optical microscopy (sSNOM) can visualize Bernal and non-Bernal stacking domains of BLG, based on the stacking-specific inter- and intra-band optical conductivities. The method enables nanometric mapping of stacking domains in BLG on dielectric substrates, augmenting current limitations of Raman spectroscopy and electron microscopy techniques for the structural characterization of BLG.

Stem-piped light activates phytochrome B to trigger light responses in Arabidopsis thaliana roots.

The roles of photoreceptors and their associated signaling mechanisms have been extensively studied in plant photomorphogenesis with a major focus on the photoresponses of the shoot system. Accumulating evidence indicates that light also influences root growth and development through the light-induced release of signaling molecules that travel from the shoot to the root. We explored whether aboveground light directly influences the root system of Arabidopsis thaliana Light was efficiently conducted through the stems to the roots, where photoactivated phytochrome B (phyB) triggered expression of ELONGATED HYPOCOTYL 5 (HY5) and accumulation of HY5 protein, a transcription factor that promotes root growth in response to light. Stimulation of HY5 in response to illumination of only the shoot was reduced when root tissues carried a loss-of-function mutation in PHYB, and HY5 mutant roots exhibited alterations in root growth and gravitropism in response to shoot illumination. These findings demonstrate that the underground roots directly sense stem-piped light to monitor the aboveground light environment during plant environmental adaptation.

Identification of the First Elementary Step in the Photocatalytic Reduction of Nitrobenzenethiols on a Metallic Surface.

Reduction of nitrobenzene is widely used for the assessment of the catalytic activities of nanoparticles, yet its mechanism is still largely unverified. Here, using the surface-enhanced Raman scattering (SERS), we have identified an intermediate of the first step in the photocatalytic reduction of nitrobenzenethiols (NBTs) on a metallic surface. The formation of the intermediate is identified by a fast red-shift of the NO2 symmetric-stretching peak of the SERS spectra of reacting NBTs, prior to the slow intensity decay. On the basis of the laser power dependences of the rates of spectral changes, electrochemical SERS, and quantum chemical calculations, we conclude that the intermediate is the anion radical of nitrobenzenethiol that is formed by the metal-to-molecule single-electron transfer reaction. The subsequent intensity decay of the peak, which is the rate-determining step of the whole reduction reaction, corresponds to another single-electron reduction of the anion radical into dihydroxyaminobenzenethiol or dianion of NBT.

Metal-Catalyzed Chemical Reaction of Single Molecules Directly Probed by Vibrational Spectroscopy.

The study of heterogeneous catalytic reactions remains a major challenge because it involves a complex network of reaction steps with various intermediates. If the vibrational spectra of individual molecules could be monitored in real time, one could characterize the structures of the intermediates and the time scales of reaction steps without ensemble averaging. Surface-enhanced Raman scattering (SERS) spectroscopy does provide vibrational spectra with single-molecule sensitivity, but typical single-molecule SERS signals exhibit spatial heterogeneities and temporal fluctuations, making them difficult to be used in single-molecule kinetics studies. Here we show that SERS can monitor the single-molecule catalytic reactions in real time. The surface-immobilized reactants placed at the junctions of well-defined nanoparticle-thin film structures produce time-resolved SERS spectra with discrete, step-transitions of photoproducts. We interpret that such SERS-steps correspond to the reaction events of individual molecules occurring at the SERS hotspot. The analyses of the yield, dynamics, and the magnitude of such SERS steps, along with the associated spectral characteristics, fully support our claim. In addition, a model that is based on plasmonic field enhancement and surface photochemistry reproduces the key features of experimental observation. Overall, the result demonstrates that it is possible, under well-controlled conditions, to differentiate the chemical and physical processes contributing to the single-molecule SERS signals, and thus shows the use of single-molecule SERS as a tool for studying the metal-catalyzed organic reactions.

Nanostar probes for tip-enhanced spectroscopy.

To overcome the current limit of tip-enhanced spectroscopy that is based on metallic nano-probes, we developed a new scanning probe with a metallic nanostar, a nanoparticle with sharp spikes. A Au nanoparticle of 5 nm was first attached to the end of a tip through DNA-DNA hybridization and mechanical pick-up. The nanoparticle was converted to a nanostar with a core diameter of ∼70 nm and spike lengths between 50 nm and 80 nm through the reduction of Au(3+) with ascorbic acid in the presence of Ag(+). Fabrication yields of such tips exceeded 60%, and more than 80% of such tips showed a mechanical durability sufficient for use in scanning microscopy. Effectiveness of the new probes for tip-enhanced Raman scattering (TERS) and tip-enhanced fluorescence (TEF) was confirmed. The probes exhibited the necessary enhancement for TEF, and the tip-on and tip-off ratios varied between 5 and 100. This large tip-to-tip variability may arise from the uncontrolled orientation of the apexes of the spike with respect to the sample surface, which calls for further fabrication improvement. The result overall supports a new fabrication approach for the probe that is effective for tip-enhanced spectroscopy.

Stacking Structures of Few-Layer Graphene Revealed by Phase-Sensitive Infrared Nanoscopy.

The stacking orders in few-layer graphene (FLG) strongly influences the electronic properties of the material. To explore the stacking-specific properties of FLG in detail, one needs powerful microscopy techniques that visualize stacking domains with sufficient spatial resolution. We demonstrate that infrared (IR) scattering scanning near-field optical microscopy (sSNOM) directly maps out the stacking domains of FLG with a nanometric resolution, based on the stacking-specific IR conductivities of FLG. The intensity and phase contrasts of sSNOM are compared with the sSNOM contrast model, which is based on the dipolar tip-sample coupling and the theoretical conductivity spectra of FLG, allowing a clear assignment of each FLG domain as Bernal, rhombohedral, or intermediate stacks for tri-, tetra-, and pentalayer graphene. The method offers 10-100 times better spatial resolution than the far-field Raman and infrared spectroscopic methods, yet it allows far more experimental flexibility than the scanning tunneling microscopy and electron microscopy.

Plasmonic scissors for molecular design.

Heterogeneous catalysts play an important role in surface catalytic reactions, but selective bond breaking and control of reaction products in catalytic processes remain significant challenges. High-vacuum tip-enhanced Raman spectroscopy (HV-TERS) is one of the best candidates to realize surface catalytic reactions. Herein, HV-TERS was employed in a new method to control dissociation by using hot electrons, generated from plasmon decay, as plasmonic scissors. In this method, the N=N bond in 4,4'-dimercaptoazobenzene was selectively dissociated by plasmonic scissors, and the reaction products formed from the radical fragment (SC6H5N) were controlled by varying the pH value. Under acidic conditions, p-aminothiophenol was produced from the radical fragment by attachment of hydrogen ions, whereas under alkaline conditions, 4-nitrobenzenethiol was obtained by attachment of oxygen ions to the substrate.