In Situ Electron Microscopy of Transformations of Copper Nanoparticles under Plasmonic Excitation.

Metal nanoparticles are attracting interest for their light-absorption properties, but such materials are known to dynamically evolve under the action of chemical and physical perturbations, resulting in changes in their structure and composition. Using a transmission electron microscope equipped for optical excitation of the specimen, the structural evolution of Cu-based nanoparticles under simultaneous electron beam irradiation and plasmonic excitation was investigated with high spatiotemporal resolution. These nanoparticles initially have a Cu core-Cu2O oxide shell structure, but over the course of imaging, they undergo hollowing via the nanoscale Kirkendall effect. We captured the nucleation of a void within the core, which then rapidly grows along specific crystallographic directions until the core is hollowed out. Hollowing is triggered by electron-beam irradiation; plasmonic excitation enhances the kinetics of the transformation likely by the effect of photothermal heating.

Time-resolved transmission electron microscopy for nanoscale chemical dynamics.

The ability of transmission electron microscopy (TEM) to image a structure ranging from millimetres to Ångströms has made it an indispensable component of the toolkit of modern chemists. TEM has enabled unprecedented understanding of the atomic structures of materials and how structure relates to properties and functions. Recent developments in TEM have advanced the technique beyond static material characterization to probing structural evolution on the nanoscale in real time. Accompanying advances in data collection have pushed the temporal resolution into the microsecond regime with the use of direct-electron detectors and down to the femtosecond regime with pump-probe microscopy. Consequently, studies have deftly applied TEM for understanding nanoscale dynamics, often in operando. In this Review, time-resolved in situ TEM techniques and their applications for probing chemical and physical processes are discussed, along with emerging directions in the TEM field.

Hot Carrier Lifetimes and Electrochemical Water Dissociation Enhanced by Nickel Doping of a Plasmonic Electrocatalyst.

Hot carriers generated by localized surface plasmon resonance (LSPR) excitation of plasmonic metal nanoparticles are known to enhance electrocatalytic reactions. However, the participation of plasmonically generated carriers in interfacial electrochemical reactions is often limited by fast relaxation of these carriers. Herein, we address this challenge by tuning the electronic structure of a plasmonic electrocatalyst. Specifically, we design an electrocatalyst for alkaline hydrogen evolution reaction (HER) that consists of nanoparticles of a ternary Cu-Pt-Ni ternary alloy. The CuPt alloy has both plasmonic attributes and electrocatalytic HER activity. Ni doping contributes an electron-deficient 3d band and fully filled 4s band, which promotes water adsorption and prolongs the lifetimes of excited carriers generated by plasmonic excitation. As an outcome, the Cu-Pt-Ni nanoparticles exhibit boosted activity for electrochemical water dissociation and HER under LSPR excitation.

Superionic Conduction in One-Dimensional Nanostructures.

Nanostructuring has become a powerful tool for tuning the electronic properties of materials and enhancing transport. As an example of relevance to next-generation battery technologies, nanocrystals have shown promise for realizing fast-ion conduction in solids; however, dissipationless ion transport over extended length scales is hindered by lossy interfaces formed between nanocrystals in a solid. Here we address this challenge by exploiting one-dimensional nanostructures for ion transport. Superionic conduction, with a record-high ionic conductivity of ∼4 S/cm at 150 °C, is demonstrated in solid electrolytes fabricated from nanowires of the earth-abundant solid copper selenide. This quasi-one-dimensional ionic conductivity is ∼5× higher than that in bulk cuprous selenide. Nanoscale dimensions in the radial direction lower ion-hopping barriers, while mesoscopically long, interface-free transport paths are available for ion transport in the axial direction. One-dimensional nanostructures can exceptionally boost solid-state devices that rely on ion transport.

Plasmon-Assisted Ammonia Electrosynthesis.

Ammonia is a promising liquid-phase carrier for the storage, transport, and deployment of carbon-free energy. However, the realization of an ammonia economy is predicated on the availability of green methods for the production of ammonia powered by electricity from renewable sources or by solar energy. Here, we demonstrate the synthesis of ammonium from nitrate powered by a synergistic combination of electricity and light. We use an electrocatalyst composed of gold nanoparticles, which have dual attributes of electrochemical nitrate reduction activity and visible-light-harvesting ability due to their localized surface plasmon resonances. Plasmonic excitation of the electrocatalyst induces ammonium synthesis with up to a 15× boost in activity relative to conventional electrocatalysis. We devise a strategy to account for the effect of photothermal heating of the electrode surface, which allows the observed enhancement to be attributed to non-thermal effects such as energetic carriers and charged interfaces induced by plasmonic excitation. The synergy between electrochemical activation and plasmonic activation is the most optimal at a potential close to the onset of nitrate reduction. Plasmon-assisted electrochemistry presents an opportunity for conventional limits of electrocatalytic conversion to be surpassed due to non-equilibrium conditions generated by plasmonic excitation.

On comprehensive analysis of root canal shaping ability of three endodontic files of different kinematics.

Infection of the tooth's root canal requires what is called root canal treatment (RTC). The most important part of endodontic treatment is to shape the root canal and remove its infected portion using endodontic files of various protocols, kinematics and designs that suit the particular geometry. Cleaning and Shaping the canal efficiently remove the root canal bacterial biofilms or tissue remnants while keeping its natural geometry. The result is determined by shaping the ability of the relevant endodontic file. In the available literature, no norm has been established for the measurement of various endodontic files' ability to do effective shaping. We present in this study a method to analyse and measure the shaping ability of endodontic files of three different kinematics.

A rich catalog of C-C bonded species formed in CO2 reduction on a plasmonic photocatalyst.

The understanding and rational design of heterogeneous catalysts for complex reactions, such as CO2 reduction, requires knowledge of elementary steps and chemical species prevalent on the catalyst surface under operating conditions. Using in situ nanoscale surface-enhanced Raman scattering, we probe the surface of a Ag nanoparticle during plasmon-excitation-driven CO2 reduction in water. Enabled by the high spatiotemporal resolution and surface sensitivity of our method, we detect a rich array of C1-C4 species formed on the photocatalytically active surface. The abundance of multi-carbon compounds, such as butanol, suggests the favorability of kinetically challenging C-C coupling on the photoexcited Ag surface. Another advance of this work is the use of isotope labeling in nanoscale probing, which allows confirmation that detected species are the intermediates and products of the catalytic reaction rather than spurious contaminants. The surface chemical knowledge made accessible by our approach will inform the modeling and engineering of catalysts.

Roadmap on quantum nanotechnologies.

Quantum phenomena are typically observable at length and time scales smaller than those of our everyday experience, often involving individual particles or excitations. The past few decades have seen a revolution in the ability to structure matter at the nanoscale, and experiments at the single particle level have become commonplace. This has opened wide new avenues for exploring and harnessing quantum mechanical effects in condensed matter. These quantum phenomena, in turn, have the potential to revolutionize the way we communicate, compute and probe the nanoscale world. Here, we review developments in key areas of quantum research in light of the nanotechnologies that enable them, with a view to what the future holds. Materials and devices with nanoscale features are used for quantum metrology and sensing, as building blocks for quantum computing, and as sources and detectors for quantum communication. They enable explorations of quantum behaviour and unconventional states in nano- and opto-mechanical systems, low-dimensional systems, molecular devices, nano-plasmonics, quantum electrodynamics, scanning tunnelling microscopy, and more. This rapidly expanding intersection of nanotechnology and quantum science/technology is mutually beneficial to both fields, laying claim to some of the most exciting scientific leaps of the last decade, with more on the horizon.

Control of Chemical Reaction Pathways by Light-Matter Coupling.

Because plasmonic metal nanostructures combine strong light absorption with catalytically active surfaces, they have become platforms for the light-assisted catalysis of chemical reactions. The enhancement of reaction rates by plasmonic excitation has been extensively discussed. This review focuses on a less discussed aspect: the induction of new reaction pathways by light excitation. Through commentary on seminal reports, we describe the principles behind the optical modulation of chemical reactivity and selectivity on plasmonic metal nanostructures. Central to these phenomena are excited charge carriers generated by plasmonic excitation, which modify the energy landscape available to surface reactive species and unlock pathways not conventionally available in thermal catalysis. Photogenerated carriers can trigger bond dissociation or desorption in an adsorbate-selective manner, drive charge transfer and multielectron redox reactions, and generate radical intermediates. Through one or more of these mechanisms, a specific pathway becomes favored under light. By improved control over these mechanisms, light-assisted catalysis can be transformational for chemical synthesis and energy conversion.

Effect of volumetric shrinkage of restorative materials on tooth structure: A finite element analysis.

Post-treatment coronal hermetic seal of the root canal opening prevents the food or saliva which assist to achieve successful endodontic treatment. Gutta-percha is filled in the inner canal, that is, from cervical third to apical third. Gutta-percha does not provide the hermetic seal because it does not bound with dentine walls. Various new restorative materials have been developed in the last 6-7 decade but drawback related to the polymerization shrinkage of the composite resin remains a clinical problem. In general, dental composites having volumetric shrinkage of the material depends on its formulation and curing conditions. In this article, the effect of this polymerization shrinkage on the tooth structure has been studied.

Motion of Defects in Ion-Conducting Nanowires.

Superionic conductors are prime candidates for the electrolytes of all-solid-state batteries. Our understanding of the mechanism and performance of superionic conductors is largely based on their idealized lattice structures. But how do defects in the lattice affect ionic structure and transport in these materials? This is a question answered here by in situ transmission electron microscopy of copper selenide, a classic superionic conductor. Nanowires of copper selenide exhibit antiphase boundaries which are a form of a planar defect. We examine the lattice structure around an antiphase boundary and monitor with atomic resolution how this structure evolves in an ordered-to-superionic phase transition. Antiphase boundaries are found to act as barriers to the propagation of the superionic phase. Antiphase boundaries also undergo spatial diffusion and shape changes resulting from thermally activated fluctuations of the neighboring ionic structure. These spatiotemporal insights highlight the importance of collective ionic transport and the role of defects in superionic conduction.

Isotope Effects in Plasmonic Photosynthesis.

The photoexcitation of plasmonic nanoparticles has been shown to drive multistep, multicarrier transformations, such as the conversion of CO2 into hydrocarbons. But for such plasmon-driven chemistry to be precisely understood and modeled, the critical photoinitiation step in the reaction cascade must be identified. We meet this goal by measuring H/D and 12 C/13 C kinetic isotope effects (KIEs) in plasmonic photosynthesis. In particular, we found that the substitution of H2 O with D2 O slows hydrocarbon production by a factor of 5-8. This primary H/D KIE leads to the inference that hole-driven scission of the O-H bond in H2 O is a critical, limiting step in plasmonic photosynthesis. This study advances mechanistic understanding of light-driven chemical reactions on plasmonic nanoparticles.

Light-Induced Voltages in Catalysis by Plasmonic Nanostructures.

ConspectusPlasmonic nanostructures have garnered widescale scientific interest because of their strong light-matter interactions and the tunability of their absorption across the solar spectrum. At the heart of their superlative interaction with light is the resonant excitation of a collective oscillation of electrons in the nanostructure by the incident electromagnetic field. These resonant oscillations are known as localized surface plasmon resonances (LSPRs). In recent years, the community has uncovered intriguing photochemical attributes of noble metal nanostructures arising from their LSPRs. Chemical reactions that are otherwise unfavorable or sluggish in the dark are induced on the nanostructure surface upon photoexcitation of LSPRs. This phenomenon has led to the birth of plasmonic catalysis. The rates of a variety of kinetically challenging reactions are enhanced by plasmon-excited nanostructures. While the potential utility for solar energy harvesting and chemical production is clear, there is a natural curiosity about the precise origin(s) of plasmonic catalysis. One explanation is that the reactions are facilitated by the action of the intensely concentrated and confined electric fields generated on the nanostructure upon LSPR excitation. Another mechanism of activation involves hot carriers transiently produced in the metal nanostructure by damping of LSPRs.In this Account, we visit a phenomenon that has received less attention but has a key role to play in plasmonic catalysis and chemistry. Under common chemical scenarios, plasmonic excitation induces a potential or a voltage on a nanoparticle. This photopotential modifies the energetics of a chemical reaction on noble metal nanoparticles. In a range of cases studied by our laboratory and others, light-induced potentials underlie the plasmonic enhancement of reaction kinetics. The photopotential model does not replace other known mechanisms, but it complements them. There are multiple ways in which an electrostatic photopotential is produced by LSPR excitation, such as optical rectification, but one that is most relevant in chemical media is asymmetric charge transfer to solution-phase acceptors. Electrons and holes produced in a nanostructure by damping of LSPRs are not removed at the same rate. As a result, the slower carrier accumulates on the nanostructure, and a steady-state charge is built up on the nanostructure, leading to a photopotential. Potentials of up to a few hundred millivolts have been measured by our laboratory and others. A photocharged nanoparticle is a source of carriers of a higher potential than an uncharged one. As a result, redox chemical reactions on noble metal nanoparticles exhibit lower activation barriers under photoexcitation. In electrochemical reactions on noble metal nanoparticles, the photopotential supplements the applied potential. In a diverse set of reactions, the photopotential model explains the photoenhancement of rates as well as the trends as a function of light intensity and photon energy. With further gains, light-induced potentials may be used as a knob for controlling the activities and selectivities of noble metal nanoparticle catalysts.

Nanoscale optical imaging in chemistry.

Single-molecule-level measurements are bringing about a revolution in our understanding of chemical and biochemical processes. Conventional measurements are performed on large ensembles of molecules. Such ensemble-averaged measurements mask molecular-level dynamics and static and dynamic fluctuations in reactivity, which are vital to a holistic understanding of chemical reactions. Watching reactions on the single-molecule level provides access to this otherwise hidden information. Sub-diffraction-limited spatial resolution fluorescence imaging methods, which have been successful in the field of biophysics, have been applied to study chemical processes on single-nanoparticle and single-molecule levels, bringing us new mechanistic insights into physiochemical processes. However, the scope of chemical processes that can be studied using fluorescence imaging is considerably limited; the chemical reaction has to be designed such that it involves fluorophores or fluorogenic probes. In this article, we review optical imaging modalities alternative to fluorescence imaging, which expand greatly the range of chemical processes that can be probed with nanoscale or even single-molecule resolution. First, we show that the luminosity, wavelength, and intermittency of solid-state photoluminescence (PL) can be used to probe chemical transformations on the single-nanoparticle-level. Next, we highlight case studies where localized surface plasmon resonance (LSPR) scattering is used for tracking solid-state, interfacial, and near-field-driven chemical reactions occurring in individual nanoscale locations. Third, we explore the utility of surface- and tip-enhanced Raman scattering to monitor individual bond-dissociation and bond-formation events occurring locally in chemical reactions on surfaces. Each example has yielded some new understanding about molecular mechanisms or location-to-location heterogeneity in chemical activity. The review finishes with new and complementary tools that are expected to further enhance the scope of knowledge attainable through nanometer-scale resolution chemical imaging.

Comment on "Thermal effects - an alternative mechanism for plasmon-assisted photocatalysis" by Y. Dubi, I. W. Un and Y. Sivan, Chem. Sci., 2020, 11, 5017.

A range of chemical reactions occurring on the surfaces of metal nanoparticles exhibit enhanced rates under plasmonic excitation. It is not straightforward to distinguish between photochemical and photothermal effect using Arrhenius fitting of the reaction rates alone.

The Chemical Potential of Plasmonic Excitations.

By the photoexcitation of localized surface plasmon resonances of metal nanoparticles, one can generate reaction equivalents for driving redox reactions. We show that, in such cases, there is a chemical potential contributed by the plasmonic excitation. This chemical potential is a function of the concentration of light, as we determine from the light-intensity-dependent activity in the plasmon-excitation-driven reduction of CO2 on Au nanoparticles. Our finding allows the treatment of plasmonic excitation as a reagent in chemical reactions; the chemical potential of this reagent is tunable by the light intensity.

Room-temperature superionic-phase nanocrystals synthesized with a twinned lattice.

The engineering of nanoscale features enables the properties of solid-state materials to be tuned. Here, we show the tunable preparation of cuprous sulfide nanocrystals ranging in internal structures from single-domain to multi-domain. The synthetic method utilizes in-situ oxidation to grow nanocrystals with a controlled degree of copper deficiency. Copper-deficient nanocrystals spontaneously undergo twinning to a multi-domain structure. Nanocrystals with twinned domains exhibit markedly altered crystallographic phase and phase transition characteristics as compared to single-domain nanocrystals. In the presence of twin boundaries, the temperature for transition from the ordered phase to the high-copper-mobility superionic phase is depressed. Whereas the superionic phase is stable in the bulk only above ca. 100 °C, cuprous sulfide nanocrystals of ca. 7 nm diameter and a twinned structure are stable in the superionic phase well below ambient temperature. These findings demonstrate twinning to be a structural handle for nanoscale materials design and enable applications for an earth-abundant mineral in solid electrolytes for Li-S batteries.

Force and vibration generated in apical direction by three endodontic files of different kinematics during simulated canal preparation: An in vitro analytical study.

During root canal shaping, pain could result from the high level of force or vibration generated. This could be related to file kinematics or geometry. In the present study, a comparison is made between forces and vibrations generated by endodontic files having three different kinematics. Square pillar resin blocks were used as simulated root canals to study forces and vibrations generated by the file having reciprocating motion (WaveOne Gold), transline motion (Self-Adjusting File), and rotary motion (2Shape). The forces and vibrations were measured using the dynamometer and accelerometer, respectively. Recorded time domain signals were processed in MATLAB to calculate the root mean square value. A one-way analysis of variance and Tukey's test for post hoc comparison at 95% confidence interval were applied over the root mean square data of different files. From a statistical analysis of the file systems, the null hypotheses could not be accepted (P < 0.05) as 95% of the confidence interval. Differences between the means were statistically significant. The root mean square values of force and vibration for WaveOne Gold significantly exceeded those of Self-Adjusting File, 2Shape1, and 2Shape2 while the root mean square values of vibration for 2Shape1 and 2Shape2 were significantly less than the Self-Adjusting File; however, the root mean square value of force for the 2Shape2 was significantly more than for the Self-Adjusting File. Under the present experimental conditions, significant differences in the root mean square values of force and vibration of the three endodontic files of different kinematics have been observed. The WaveOne Gold file system generated higher apical force and vibration than the transline and rotary file system.