Plasmon-Induced Hot Electrons in Nanostructured Materials: Generation, Collection, and Application to Photochemistry.

Plasmon refers to the coherent oscillation of all conduction-band electrons in a nanostructure made of a metal or a heavily doped semiconductor. Upon excitation, the plasmon can decay through different channels, including nonradiative Landau damping for the generation of plasmon-induced energetic carriers, the so-called hot electrons and holes. The energetic carriers can be collected by transferring to a functional material situated next to the plasmonic component in a hybrid configuration to facilitate a range of photochemical processes for energy or chemical conversion. This article centers on the recent advancement in generating and utilizing plasmon-induced hot electrons in a rich variety of hybrid nanostructures. After a brief introduction to the fundamentals of hot-electron generation and decay in plasmonic nanocrystals, we extensively discuss how to collect the hot electrons with various types of functional materials. With a focus on plasmonic nanocrystals made of metals, we also briefly examine those based upon heavily doped semiconductors. Finally, we illustrate how site-selected growth can be leveraged for the rational fabrication of different types of hybrid nanostructures, with an emphasis on the parameters that can be experimentally controlled to tailor the properties for various applications.

Colloidal Synthesis of Metal Nanocrystals: From Asymmetrical Growth to Symmetry Breaking.

Nanocrystals offer a unique platform for tailoring the physicochemical properties of solid materials to enhance their performances in various applications. While most work on controlling their shapes revolves around symmetrical growth, the introduction of asymmetrical growth and thus symmetry breaking has also emerged as a powerful route to enrich metal nanocrystals with new shapes and complex morphologies as well as unprecedented properties and functionalities. The success of this route critically relies on our ability to lift the confinement on symmetry by the underlying unit cell of the crystal structure and/or the initial seed in a systematic manner. This Review aims to provide an account of recent progress in understanding and controlling asymmetrical growth and symmetry breaking in a colloidal synthesis of noble-metal nanocrystals. With a touch on both the nucleation and growth steps, we discuss a number of methods capable of generating seeds with diverse symmetry while achieving asymmetrical growth for mono-, bi-, and multimetallic systems. We then showcase a variety of symmetry-broken nanocrystals that have been reported, together with insights into their growth mechanisms. We also highlight their properties and applications and conclude with perspectives on future directions in developing this class of nanomaterials. It is hoped that the concepts and existing challenges outlined in this Review will drive further research into understanding and controlling the symmetry breaking process.

Extraordinary Thermal Stability and Sinter Resistance of Sub-2 nm Platinum Nanoparticles Anchored to a Carbon Support by Selenium.

Nanoparticle sintering has long been a major challenge in developing catalytic systems for use at elevated temperatures. Here we report an in situ electron microscopy study of the extraordinary sinter resistance of a catalytic system comprised of sub-2 nm Pt nanoparticles on a Se-decorated carbon support. When heated to 700 °C, the average size of the Pt nanoparticles only increased from 1.6 to 2.2 nm, while the crystal structure, together with the {111} and {100} facets, of the Pt nanoparticles was well retained. Our electron microscopy analyses suggested that the superior resistance against sintering originated from the Pt-Se interaction. Confirmed by energy-dispersive X-ray elemental mapping and electron energy loss spectra, the Se atoms surrounding the Pt nanoparticles could survive the heating. This work not only offers an understanding of the physics behind the thermal behavior of this catalytic material but also sheds light on the future development of sinter-resistant catalytic systems.

Thermal Stability of Au Rhombic Dodecahedral Nanocrystals Can Be Greatly Enhanced by Coating Their Surface with an Ultrathin Shell of Pt.

Rhombic dodecahedral nanocrystals have been considered particularly difficult to synthesize because they are enclosed by {110}, a low-index facet with the greatest surface energy. Recently, we demonstrated the use of seed-mediated growth for the facile and robust synthesis of Au rhombic dodecahedral nanocrystals (AuRD). While the unique shape and surface structure of AuRD are desirable for potential applications in plasmonics and catalysis, respectively, their high surface energy makes them highly susceptible to thermal degradation. Here we demonstrate that it is feasible to greatly improve the thermal stability with some sacrifice to the plasmonic properties of the original AuRD by coating their surface with an ultrathin shell made of Pt. Our in situ electron microscopy analysis indicates that the ultrathin Pt coating can increase the thermal stability from 60 up to 450 °C, a trend that is also supported by the results from a computational study.

Elucidating the Role of Reduction Kinetics in the Phase-Controlled Growth on Preformed Nanocrystal Seeds: A Case Study of Ru.

This study demonstrates the crucial role of reduction kinetics in phase-controlled synthesis of noble-metal nanocrystals using Ru nanocrystals as a case study. We found that the reduction kinetics played a more important role than the templating effect from the preformed seed in dictating the crystal structure of the deposited overlayers despite their intertwined effects on successful epitaxial growth. By employing two different polyols, a series of Ru nanocrystals with tunable sizes of 3-7 nm and distinct patterns of crystal phase were synthesized by incorporating different types of Ru seeds. Notably, the use of ethylene glycol and triethylene glycol consistently resulted in the formation of Ru shell in natural hexagonal close-packed (hcp) and metastable face-centered cubic (fcc) phases, respectively, regardless of the size and phase of the seed. Quantitative measurements and theoretical calculations suggested that this trend was a manifestation of the different reduction kinetics associated with the precursor and the chosen polyol, which, in turn, affected the reduction pathway (solution versus surface) and packing sequence of the deposited Ru atoms. This work not only underscores the essential role of reduction kinetics in controlling the packing of atoms and thus the phase taken by Ru nanocrystals but also suggests a potential extension to other noble-metal systems.

Nanomaterial-Enabled Photothermal Heating and Its Use for Cancer Therapy via Localized Hyperthermia.

Photothermal therapy (PTT), which employs nanoscale transducers delivered into a tumor to locally generate heat upon irradiation with near-infrared light, shows great potential in killing cancer cells through hyperthermia. The efficacy of such a treatment is determined by a number of factors, including the amount, distribution, and dissipation of the generated heat, as well as the type of cancer cell involved. The amount of heat generated is largely controlled by the number of transducers accumulated inside the tumor, the absorption coefficient and photothermal conversion efficiency of the transducer, and the irradiance of the light. The efficacy of treatment depends on the distribution of the transducers in the tumor and the penetration depth of the light. The vascularity and tissue thermal conduction both affect the dissipation of heat and thereby the distribution of temperature. The successful implementation of PTT in the clinic setting critically depends on techniques for real-time monitoring and management of temperature.

Galvanic Replacement Synthesis of Metal Nanostructures: Bridging the Gap between Chemical and Electrochemical Approaches.

ConspectusGalvanic replacement synthesis involves oxidation and dissolution of atoms from a substrate while the salt precursor to another material with a higher reduction potential is reduced and deposited on the substrate. The driving force or spontaneity of such a synthesis comes from the difference in reduction potential between the redox pairs involved. Both bulk and micro/nanostructured materials have been explored as substrates for galvanic replacement synthesis. The use of micro/nanostructured materials can significantly increase the surface area, offering immediate advantages over the conventional electrosynthesis. The micro/nanostructured materials can also be intimately mixed with the salt precursor in a solution phase, resembling the setting of a typical chemical synthesis. The reduced material tends to be directly deposited on the surface of the substrate, just like the situation in an electrosynthesis. Different from an electrosynthesis where the two electrodes are spatially separated by an electrolyte solution, the cathodes and anodes are situated on the same surface, albeit at different sites, even for a micro/nanostructured substrate. Since the oxidation and dissolution reactions occur at sites different from those for reduction and deposition reactions, one can control the growth pattern of the newly deposited atoms on the same surface of a substrate to access nanostructured materials with diverse and controllable compositions, shapes, and morphologies in a single step. Galvanic replacement synthesis has been successfully applied to different types of substrates, including those made of crystalline and amorphous materials, as well as metallic and nonmetallic materials. Depending on the substrate involved, the deposited material can take different nucleation and growth patterns, resulting in diverse but well-controlled nanomaterials sought for a variety of studies and applications.In this Account, we recapitulate our efforts over the past two decades in fabricating metal nanostructures for a broad range of applications by leveraging the unique capability of galvanic replacement synthesis. We begin with a brief introduction to the fundamentals of galvanic replacement between metal nanocrystals and salt precursors, followed by a discussion of the roles played by surface capping agents in achieving site-selected carving and deposition for the fabrication of various bimetallic nanostructures. Two examples based on the Ag-Au and Pd-Pt systems are selected to illustrate the concept and mechanism. We then highlight our recent work on the galvanic replacement synthesis involving nonmetallic substrates, with a focus on the protocol, mechanistic understanding, and experimental control for the fabrication of Au- and Pt-based nanostructures with tunable morphologies. Finally, we showcase the unique properties and applications of nanostructured materials derived from galvanic replacement reactions for biomedicine and catalysis. We also offer some perspectives on the challenges and opportunities in this emerging field of research.

Quantification, Exchange, and Removal of Surface Ligands on Noble-Metal Nanocrystals.

ConspectusSurface ligands are vital to the colloidal synthesis of noble-metal nanocrystals with well-controlled sizes and shapes for various applications. The surface ligands not only dictate the formation of nanocrystals with diverse shapes but also serve as a colloidal stabilizer to prevent the suspended nanocrystals from aggregation during their synthesis or storage. By leveraging the facet selectivity of some surface ligands, one can further control the sites for growth or galvanic replacement to transform presynthesized nanocrystals into complex structures that are otherwise difficult to fabricate using conventional methods. Furthermore, the presence of surface ligands on nanocrystals also facilitates their applications in areas such as sensing, imaging, nanomedicine, and self-assembly. Despite their popular use in enhancing the properties of nanocrystals and thus optimizing their performance in a wide variety of applications, it remains a major challenge to quantitatively determine the coverage density of ligand molecules, not to mention the difficulty of substituting or removing them without compromising the surface structure and aggregation state of the nanocrystals.In this Account, we recapitulate our efforts in developing methods capable of qualitatively or quantitatively measuring, exchanging, and removing the surface ligands adsorbed on noble-metal nanocrystals. We begin with an introduction to the typical interactions between ligand molecules and surface atoms, followed by a discussion of the Langmuir model that can be used to describe the adsorption of surface ligands. It is also emphasized that the adsorption process may become very complex in the case of a polymeric ligand due to the variations in binding configuration and chain conformation. We then highlight the capabilities of various spectroscopy methods to analyze the adsorbed ligands qualitatively or quantitatively. Specifically, surface-enhanced Raman scattering, Fourier transform infrared, and X-ray photoelectron spectroscopy are three examples of qualitative methods that can be used to confirm the absence or presence of a surface ligand. On the other hand, ultraviolet-visible spectroscopy and inductively coupled plasma mass spectrometry can be used for quantitative measurements. Additionally, the coverage density of a ligand can be derived by analyzing the morphological changes during nanocrystal growth. We then discuss how the ligands present on the surface of metal nanocrystals can be exchanged directly or indirectly to meet the requirements of different applications. The former can be done using a ligand with stronger binding, whereas the latter is achieved by introducing a sacrificial shell to the surface of the nanocrystals. Furthermore, we highlight three additional strategies besides simple washing to remove the surface ligands, including calcination, heating in a solution, and UV-ozone treatment. Finally, we showcase three applications of metal nanocrystals in nanomedicine, tumor targeting, and self-assembly by taking advantage of the diversity of surface ligands bearing different functional groups. We also offer perspectives on the challenges and opportunities in realizing the full potential of surface ligands.

Facile Synthesis and Characterization of Uniform Au Nanospheres Capped by Citrate for Biomedical Applications.

We report a simple and versatile method for effectively replacing the toxic ligands, such as cetyltrimethylammonium bromide (CTAB) and cetyltrimethylammonium chloride (CTAC), on the surface of Au nanospheres with different sizes by citrate. The method involves the deposition of an ultrathin shell of fresh Au in the presence of sodium citrate at an adequate concentration. After the ligand exchange process, multiple techniques are used to confirm that the surface of the resultant Au nanospheres is covered by citrate while there is no sign of aggregation. We also demonstrate the mitigation of cell toxicity after exchanging the surface-bound CTAB/CTAC with citrate, opening the door to a range of biomedical applications.

Robust, Reproducible, and Scalable Synthesis of Silver Nanocubes.

It remains a challenge to accomplish colloidal synthesis of noble-metal nanocrystals marked by high quality, large quantity, and batch-to-batch consistency. Here we report a self-airtight setup for achieving robust, reproducible, and scalable production of Ag nanocubes with uniform and controlled sizes from 18 to 60 nm. Different from the conventional open-to-air setup, the self-airtight system makes it practical to stabilize the reaction condition by minimizing the loss of volatile reagents. The new setup also allows us to easily optimize the amount of O2 (from air) trapped in the system, ensuring burst nucleation of single-crystal seeds, followed by their slow growth into nanocubes. Most significantly, the new setup allows for the production of Ag nanocubes at gram quantities without sacrificing uniformity, corner/edge sharpness, controlled size, and high purity across different batches. The availability of high-quality Ag nanocubes in such a large quantity is anticipated to substantially boost their use in applications related to plasmonics, catalysis, and biomedicine.

Putting Hybrid Nanomaterials to Work for Biomedical Applications.

Hybrid nanomaterials have found use in many biomedical applications. This article provides a comprehensive review of the principles, techniques, and recent advancements in the design and fabrication of hybrid nanomaterials for biomedicine. We begin with an introduction to the general concept of material hybridization, followed by a discussion of how this approach leads to materials with additional functionality and enhanced performance. We then highlight hybrid nanomaterials in the forms of nanostructures, nanocomposites, metal-organic frameworks, and biohybrids, including their fabrication methods. We also showcase the use of hybrid nanomaterials to advance biomedical engineering in the context of nanomedicine, regenerative medicine, diagnostics, theranostics, and biomanufacturing. Finally, we offer perspectives on challenges and opportunities.

Controlling the Nucleation and Growth of Au on a-Se Nanospheres to Enhance Their Cellular Uptake and Cytotoxicity.

We report a method to experimentally control the heterogeneous nucleation and growth of Au nanoparticles on the surface of amorphous Se (a-Se) nanospheres. When a AuIII precursor is added into a colloidal suspension of a-Se nanospheres, galvanic replacement occurs between them and the resultant Au0 atoms then heterogeneously nucleate and grow from the surface of the a-Se nanospheres. As a unique feature of this system, the Au0 atoms can only be produced on the surface of the a-Se nanospheres in the nucleation stage. Once Au nuclei are formed on the surface at the very beginning of a synthesis, they will serve as the preferential sites for further deposition of Au0 atoms, making it possible to control the number of Au nanoparticles on each nanosphere and the morphology of the final product. The dependence of the initial reduction rate on the pH can be used to obtain Se-Au hybrid nanoparticles containing one, two, three, and multiple Au nanoparticles on the surface of each a-Se nanosphere. The presence of Au patches on the hybrid nanoparticles offers an experimental handle to optimize the ligand distribution for the achievement of enhanced cellular uptake and cytotoxicity for the a-Se nanospheres.

Facet-Controlled Synthesis of Platinum-Group-Metal Quaternary Alloys: The Case of Nanocubes and {100} Facets.

We report a robust method for the facet-controlled synthesis of nanocrystals with an ultrathin shell made of a nearly equimolar RuRhPdPt quaternary alloy. Our strategy involves the use of well-defined Rh cubic seeds, halide-free precursors, and a method for precisely controlling the reaction kinetics of different precursors. In the setting of dropwise addition, the precursors with different reactivities can be reduced at about the same pace for the generation of an alloy with a uniform and well-controlled composition. The core-shell nanocubes show greatly enhanced activity toward ethanol oxidation when benchmarked against Pd and Pt counterparts. Combining in situ and ex situ electron microscopy studies, we also demonstrate that the core-shell nanocubes possess good thermal and electrochemical stability in terms of both geometrical shape and elemental composition, with their cubic shape and alloy composition retained when annealing at 500 °C or after long-term electrochemical cycling. It is expected that the synthetic approach can be further extended to fabricate multimetallic catalysts with enhanced activities toward a variety of thermal and electrochemical reactions.

Twin Proliferation and Prolongation under Kinetic Control: Pd-Au Janus Icosahedra versus Pd@Au Core-Shell Starfishes.

Heterogeneous bimetallic nanocrystals featuring explicit spatial configurations and abundant twin defects can simultaneously enable geometric and ligand effects to enhance catalytic and photonic applications. Herein, we report two growth patterns of Au atoms on penta-twinned Pd decahedra, involving twin proliferation to generate asymmetric Pd-Au Janus icosahedra and twin elongation to produce anisotropic Pd@Au core-shell starfishes, respectively. Mechanistic analysis indicates that the injection rate determines the lower-limit number (nlow) of Au(III) ions in the steady state and thus controls the growth pattern. When nlow ≤ 5.5, the kinetic rate is slow enough to initiate asymmetrical one-side growth but fast enough to outpace surface diffusion; Au tetrahedral subunits are successively proliferated along the axial ⟨110⟩ direction of Pd decahedra to form Pd-Au Janus icosahedra. Composed of five Pd and 15 Au tetrahedral subunits, such a heterogeneous icosahedron supports high (2.2 GPa) tensile strain and high strain difference up to +21.9%. In contrast, when nlow > 5.5, the fast reduction kinetics promotes symmetric growth with inadequate surface diffusion. As such, Au atoms are laterally deposited along five high-indexed ⟨211⟩ ridges of Pd decahedra to generate concave Pd@Au core-shell starfishes with tunable sizes (28-40 nm), twin elongation ratios (33.82-162.08%), and lattice expansion ratios (8.82-20.10%).

Shape Transformation via Etching and Regrowth: A Systematic Study of Pd Nanocrystals with Different Shapes and Twin Structures.

This article describes a systematic study of the oxidative etching and regrowth behaviors of Pd nanocrystals, including single-crystal cubes bounded by {100} facets, single-crystal octahedra and tetrahedra enclosed by {111} facets; and multiple-twinned icosahedra covered by {111} facets and twin boundaries. During etching, Pd atoms are preferentially oxidized and removed from the corners regardless of the type of nanocrystal, and the resultant Pd2+ ions are then reduced back to elemental Pd. For cubes and icosahedra, the newly formed Pd atoms are deposited on the {100} facets and twin boundaries, respectively, due to their relatively higher energies. For octahedra and tetrahedra, the Pd atoms self-nucleate in the solution phase, followed by their growth into small particles. We can control the regrowth rate relative to etching rate by varying the concentration of HCl in the reaction solution. As the concentration of HCl is increased, 18-nm Pd cubes are transformed into octahedra of 23, 18, and 13 nm, respectively, in edge length. Due to the absence of regrowth, however, Pd octahedra are transformed into truncated octahedra, cuboctahedra, and spheres with decreasing sizes whereas Pd tetrahedra evolve into truncated tetrahedra and spheres. In contrast, Pd icosahedra with twin boundaries on the surface are converted to asymmetric icosahedra, flower-like icosahedra, and spheres. This work not only advances the understanding of etching and growth behaviors of metal nanocrystals with various shapes and twin structures but also offers an alternative method for controlling their shape and size.

Facile Synthesis of Ru Nanoboxes with a Hexagonal Close-Packed Structure by Templating with Ag Nanocubes and Their Catalytic Properties.

Noble-metal nanoboxes offer an attractive form of nanomaterials for catalytic applications owing to their open structure and highly efficient use of atoms. Herein, we report the facile synthesis of Ag-Ru core-shell nanocubes and then Ru nanoboxes with a hexagonal close-packed (hcp) structure, as well as evaluation of their catalytic activity toward a model hydrogenation reaction. By adding a solution of Ru(acac)3 in ethylene glycol (EG) dropwise to a suspension of silver nanocubes in EG at 170 °C, Ru atoms are generated and deposited onto the entire surface of a nanocube. As the volume of the RuIII precursor is increased, Ru atoms are also produced through a galvanic replacement reaction, generating Ag-Ru nanocubes with a hollow interior. The released Ag+ ions are then reduced by EG and deposited back onto the nanocubes. By selectively etching away the remaining Ag with aqueous HNO3 , the as-obtained Ag-Ru nanocubes are transformed into Ru nanoboxes, whose walls are characterized by an hcp structure and an ultrathin thickness of a few nanometers. Finally, we evaluated the catalytic properties of the Ru nanoboxes with two different wall thicknesses by using a model hydrogenation reaction; both samples showed excellent performance.

Noble-Metal Nanocrystals with Controlled Shapes for Catalytic and Electrocatalytic Applications.

The successful synthesis of noble-metal nanocrystals with controlled shapes offers many opportunities to not only maneuver their physicochemical properties but also optimize their figures of merit in a wide variety of applications. In particular, heterogeneous catalysis and surface science have benefited enormously from the availability of this new class of nanomaterials as the atomic structure presented on the surface of a nanocrystal is ultimately determined by its geometric shape. The immediate advantages may include significant enhancement in catalytic activity and/or selectivity and substantial reduction in materials cost while providing a well-defined model system for mechanistic study. With a focus on the monometallic system, this review article provides a comprehensive account of recent progress in the development of noble-metal nanocrystals with controlled shapes, in addition to their remarkable performance in a large number of catalytic and electrocatalytic reactions. We hope that this review article offers the impetus and roadmap for the development of next-generation catalysts vital to a broad range of industrial applications.

Phase-Controlled Synthesis of Ru Nanocrystals via Template-Directed Growth: Surface Energy versus Bulk Energy.

Despite the successful control of crystal phase using template-directed growth, much remains unknown about the underlying mechanisms. Here, we demonstrate that the crystal phase taken by the deposited metal depends on the lateral size of face-centered cubic (fcc)-Pd nanoplate templates with 12 nm plates giving fcc-Ru while 18-26 nm plates result in hexagonal closed-packed (hcp)-Ru. Although Ru overlayers with a metastable fcc- (high in bulk energy) or stable hcp-phase (low in bulk energy) can be epitaxially deposited on the basal planes, the lattice mismatch will lead to jagged hcp- (high in surface energy) and smooth fcc-facets (low in surface energy), respectively, on the side faces. As the proportion of basal and side faces on the nanoplates varies with lateral size, the crystal phase will change depending on the relative contributions from the surface and bulk energies. The Pd@fcc-Ru outperforms the Pd@hcp-Ru nanoplates toward ethylene glycol and glycerol oxidation reactions.

Fast and Non-equilibrium Uptake of Hydrogen by Pd Icosahedral Nanocrystals.

We report for the first time that Pd nanocrystals can absorb H via a "single-phase pathway" when particles with a proper combination of shape and size are used. Specifically, when Pd icosahedral nanocrystals of 7- and 12-nm in size are exposed to H atoms, the H-saturated twin boundaries can divide each particle into 20 smaller single-crystal units in which the formation of phase boundaries is no longer favored. As such, absorption of H atoms is dominated by the single-phase pathway and one can readily obtain PdHx with anyx in the range of 0-0.7. When switched to Pd octahedral nanocrystals, the single-phase pathway is only observed for particles of 7 nm in size. We also establish that the H-absorption kinetics will be accelerated if there is a tensile strain in the nanocrystals due to the increase in lattice spacing. Besides the unique H-absorption behaviors, the PdHx (x=0-0.7) icosahedral nanocrystals show remarkable thermal and catalytic stability toward the formic acid oxidation due tothe decrease in chemical potential for H atoms in a Pd lattice under tensile strain.

Slowly Removing Surface Ligand by Aging Enhances the Stability of Pd Nanosheets toward Electron Beam Irradiation and Electrocatalysis.

Surface ligands play an important role in shape-controlled growth and stabilization of colloidal nanocrystals. Their quick removal tends to cause structural deformation and/or aggregation to the nanocrystals. Herein, we demonstrate that the surface ligand based on poly(vinylpyrrolidone) (PVP) can be slowly removed from Pd nanosheets (NSs, 0.93±0.17 nm in thickness) by simply aging the colloidal suspension. The aged Pd NSs show well-preserved morphology, together with significantly enhanced stability toward both e-beam irradiation and electrocatalysis (e.g., ethanol oxidation). It is revealed that the slow desorption of PVP during aging forces the re-exposed Pd atoms to reorganize, facilitating the surface to transform from being nearly perfect to defect-rich. The resultant Pd NSs with abundant defects no longer rely on surface ligand to stabilize the atomic arrangement and thus show excellent structural and electrochemical stability. This work provides a facile and effective method to maintain the integrity of colloidal nanocrystals by slowly removing the surface ligand.