Five Hypotheses on the Origins of Temperature Dependence of 77Se NMR Shifts in Diselenides.

Notable thermal shifts in diselenides have been documented in 77Se NMR for more than 50 years, but no satisfactory explanation has been found. Here, five hypotheses are considered as possible explanations for the large temperature dependence of the 77Se chemical shifts of diaryl and dialkyl diselenides compared to monoselenides and selenols. Density functional theory calculations are provided to bolster hypotheses and better understand the effects of barrier height and dipole energies. It is proposed that the temperature dependence of diselenide 77Se NMR chemical shifts is due to rotation around the Se-Se bond and sampling of twisted conformers at higher temperatures. The molecular twisting is solvent dependent; here, DMSO-d6 and toluene-d8 were evaluated. No correlation was established between para-substituents on diaryl diselenides and the magnitude of the change in the 77Se NMR shift (Δδ) with temperature.

Harmonic Generation up to Fifth Order from Al/Au/CuS Nanoparticle Films.

Dual heterostructures integrating noble-metal and copper chalcogenide nanoparticles have attracted a great deal of attention in nonlinear optics, because coupling of their localized surface plasmon resonances (LSPRs) substantially enhances light-matter interactions through local-field effects. Previously, enhanced cascaded third-harmonic generation was demonstrated in Au/CuS heterostructures mediated by harmonically coupled surface plasmon resonances. This suggests a promising approach for extending nonlinear enhancement to higher harmonics by adding an additional nanoparticulate material with higher-frequency harmonic resonances to the hybrid films. Here we report the first observation of enhanced cascaded fourth- and fifth-harmonic generation in Al/Au/CuS driven by coupled LSPRs at the fundamental (1050 nm), second harmonic (525 nm), and third harmonic (350 nm) of the pump frequency. An analytical model based on incoherent dipole-dipole interactions among plasmonic nanoparticles accounts for the observed enhancements. The results suggest a novel design for efficiently generating higher harmonics in resonant plasmonic structures by means of multiple sum-frequency cascades.

Celebrating the 150th anniversary of Vanderbilt University.

An introduction to the Nanoscale Horizons, Nanoscale and Nanoscale Advances themed collection celebrating the 150th anniversary of Vanderbilt University, featuring work from researchers currently affiliated with Vanderbilt University, esteemed alumni, and researchers with strong connections and extensive collaborations with the university.

Phase Control in the Synthesis of Iron Sulfides.

The identity and repeating arrangement of atoms determine the properties of all solids. Even combinations of two atoms can have multiple crystal structures of varying stoichiometries and symmetries with vastly different electronic and chemical behaviors. The conditions of existing bottom-up routes for achieving one phase over another are serendipitous, and the links among precursor reactivity, decomposition mechanism, temperature, and time are elusive. Our studies take a systematic approach to understanding the role that the precursor kinetic decomposition has in the synthesis of iron sulfides, isolating it from other mechanistic factors. The data suggest that phase determination in binary solids can be logically predicted through the consideration of the anion stacking and thermodynamic relationships between phases. Mapping these relationships allows for the rational synthetic targeting of metastable crystalline phases.

Role of carboxylates in the phase determination of metal sulfide nanoparticles.

Techniques are well established for the control of nanoparticle shape and size in colloidal synthesis, but very little is understood about precursor interactions and their effects on the resultant crystalline phase. Here we show that oleate, a surface stabilizing ligand that is ubiquitous in nanocrystal synthesis, plays a large role in the mechanism of phase selection of various metal sulfide nanoparticles when thiourea is used as the sulfur source. Gas and solid-phase FTIR, 13C, and 1H NMR studies revealed that oleate and thiourea interact to produce oleamide which promotes the isomeric shift of thiourea into ammonium thiocyanate, a less reactive sulfur reagent. Because of these sulfur sequestering reactions, sulfur deficient and metastable nanoparticles are produced, a trend seen across four different metals: copper, iron, nickel, and cobalt. At low carboxylate concentrations, powder XRD indicated that the following phases formed: covellite (CuS); vaesite (NiS2); smythite (FeS1.3), greigite (FeS1.3), marcasite (FeS2) and pyrite (FeS2); and cattierite (CoS2). At high sodium oleate concentration, these phases formed: digenite (CuS0.55), nickel sulfide (NiS), pyrrhotite (FeS1.1), and jaipurite (CoS).

Determining the impact of gold nanoparticles on amyloid aggregation with 2D IR spectroscopy.

As nanomaterials become more prevalent in both industry and medicine, it is crucial to fully understand their health risks. One area of concern is the interaction of nanoparticles with proteins, including their ability to modulate the uncontrolled aggregation of amyloid proteins associated with diseases, such as Alzheimer's disease and type II diabetes, and potentially extend the lifetime of cytotoxic soluble oligomers. This work demonstrates that two-dimensional infrared spectroscopy and 13C18O isotope labeling can be used to follow the aggregation of human islet amyloid polypeptide (hIAPP) in the presence of gold nanoparticles (AuNPs) with single-residue structural resolution. 60 nm AuNPs were found to inhibit hIAPP, tripling the aggregation time. Furthermore, calculating the actual transition dipole strength of the backbone amide I' mode reveals that hIAPP forms a more ordered aggregate structure in the presence of AuNPs. Ultimately, such studies can provide insight into how mechanisms of amyloid aggregation are altered in the presence of nanoparticles, furthering our understanding of protein-nanoparticle interactions.

Dependence of Transition-Metal Telluride Phases on Metal Precursor Reactivity and Mechanistic Implications.

Modern bottom-up synthesis to nanocrystalline solid-state materials often lacks the reasoned product control that molecular chemistry boasts from having over a century of research and development. In this study, six transition metals including iron, cobalt, nickel, ruthenium, palladium, and platinum were reacted with the mild reagent didodecyl ditelluride in their acetylacetonate, chloride, bromide, iodide, and triflate salts. This systematic analysis demonstrates how rationally matching the reactivity of metal salts to the telluride precursor is necessary for the successful production of metal tellurides. The trends in reactivity suggest that radical stability is the better predictor of metal salt reactivity than hard-soft acid-base theory. Of the six transition-metal tellurides, the first colloidal syntheses of iron and ruthenium tellurides (FeTe2 and RuTe2) are reported.

Molecular Decomposition Routes of Diaryl Diselenide Precursors in Relation to the Phase Determination of Copper Selenides.

1H nuclear magnetic resonance (NMR), 77Se NMR, and powder X-ray diffraction (XRD) were used to monitor the thermal decomposition of diphenyl and dibenzyl diselenide precursors toward the synthesis of copper selenides. Copper was found to promote the decomposition of both precursors. The inorganic nanocrystals and organic byproducts were sensitive to the specific diaryl diselenides and the presence of oleylamine and copper. Molecular mechanistic routes are proposed. Berzelianite (Cu1.8Se), klockmannite (CuSe), umangite (Cu3Se2), and both petrícekite (m-CuSe2) and krutaite (p-CuSe2) were identified as products. Multistep transformations between phases were discovered through reactions with the organoselenium precursors, and organic decomposition products are proposed.

Minimizing the Reorganization Energy of Cobalt Redox Mediators Maximizes Charge Transfer Rates from Quantum Dots.

Light-induced charge separation is at the very heart of many solar harvesting technologies. The reduction of energetic barriers to charge separation and transfer increases the rate of separation and the overall efficiency of these technologies. Here we report that the internal reorganization energy of the redox acceptor, the movement of the atoms with changing charge, has a profound effect on the charge transfer rates from donor quantum dots. We experimentally studied and modelled with Marcus Theory charge transfer to cobalt complexes that have similar redox potentials covering 350 mV, but vastly different reorganization energies spanning 2 eV. While the driving force does influence the electron transfer rates, the reorganization energies had a far more profound effect, increasing charge transfer rates by several orders of magnitude. Our studies suggest that careful design of redox mediators to minimize reorganization energy is an untapped route to drastically increase the efficiency of quantum dot applications that feature charge transfer.

Alkyl selenol reactivity with common solvents and ligands: influences on phase control in nanocrystal synthesis.

This study develops mechanistic understanding of the factors which control the phase in syntheses of copper selenide nanocrystals by investigating how the chemistry of the dodecylselenol reactant is altered by the ligand and solvent environment. 1H NMR and 77Se NMR were used to study how commonly used solvents (octadecene and dioctylether) and ligands (oleylamine, oleic acid, stearylamine, stearic acid and trioctyl phosphine) change the nature of the dodecylselenol reactant at 25 °C, 155 °C and 220 °C. Unsaturations were prone to selenol additons, carboxylates underwent selenoesterification, amines caused the release of H2Se gas, and the phosphine formed phosphine selenide. Adventitious water caused oxidation to didodecyldiselenide. NMR studies were correlated with the phases that resulted in syntheses of nanocrystalline copper selenides, in which berzalianite, umangite or a metastable hexagonal phase were produced as identified by X-ray diffraction, depending on the ligand and solvent environemnts. Formation of the rare hexagonal Cu2-xSe phase could be assigned to cases that included DD2Se2 as a reactive intermediate, or strong L-type ligation of amines which was dependant on alkyl chain length.

Polycrystalline texture causes magnetic instability in greigite.

Magnetic stability of iron mineral phases is a key for their use as paleomagnetic information carrier and their applications in nanotechnology, and it critically depends on the size of the particles and their texture. Ferrimagnetic greigite (Fe3S4) in nature and synthesized in the laboratory forms almost exclusively polycrystalline particles. Textural effects of inter-grown, nano-sized crystallites on the macroscopic magnetization remain unresolved because their experimental detection is challenging. Here, we use ferromagnetic resonance (FMR) spectroscopy and static magnetization measurements in concert with micromagnetic simulations to detect and explain textural effects on the magnetic stability in synthetic, polycrystalline greigite flakes. We demonstrate that these effects stem from inter-grown crystallites with mean coherence length (MCL) of about 20 nm in single-domain magnetic state, which generate modifiable coherent magnetization volume (CMV) configurations in the flakes. At room temperature, the instability of the CVM configuration is exhibited by the angular dependence of the FMR spectra in fields of less than 100 mT and its reset by stronger fields. This finding highlights the magnetic manipulation of polycrystalline greigite, which is a novel trait to detect this mineral phase in Earth systems and to assess its fidelity as paleomagnetic information carrier. Additionally, our magneto-spectroscopic approach to analyse instable CMV opens the door for a new more rigorous magnetic assessment and interpretation of polycrystalline nano-materials.

Synthesis of vulcanite (CuTe) and metastable Cu1.5Te nanocrystals using a dialkyl ditelluride precursor.

This study demonstrates that a dialkyl ditelluride reagent can produce metastable and difficult-to-achieve metal telluride phases in nanocrystal syntheses. Using didodecyl ditelluride and without the need for phosphine precursors, nanocubes of the pseudo-cubic phase (Cu1.5Te) were synthesized at the moderate temperature of 135 °C. At the higher temperature of 155 °C, 2-D nanosheets of vulcanite (CuTe) resulted, a nanomaterial in a phase that has not been previously achieved through thermal decomposition methods. Materials were characterized with TEM, powder XRD and UV-Vis-NIR absorbance spectroscopy.

Tolman's Electronic Parameter of the Ligand Predicts Phase in the Cation Exchange to CuFeS2Nanoparticles.

The metastable and thermodynamically favored phases of CuFeS2 are shown to be alternatively synthesized during partial cation exchange of hexagonal Cu2S using various phosphorus-containing ligands. Transmission electron microscopy and energy dispersive spectroscopy mapping confirm the retention of the particle morphology and the approximate CuFeS2 stoichiometry. Powder X-ray diffraction patterns and refinements indicate that the resulting phase mixtures of metastable wurtzite-like CuFeS2 versus tetragonal chalcopyrite are correlated with the Tolman electronic parameter of the tertiary phosphorus-based ligand used during the cation exchange. Strong L-type donors lead to the chalcopyrite phase and weak donors to the wurtzite-like phase. To our knowledge, this is the first demonstration of phase control in nanoparticle synthesis using solely L-type donors.

Ligand cleavage enables formation of 1,2-ethanedithiol capped colloidal quantum dot solids.

Colloidal quantum dots have garnered significant interest in optoelectronics, particularly in quantum dot solar cells (QDSCs). Here we report QDSCs fabricated using a ligand that is modified, following film formation, such that it becomes an efficient hole transport layer. The ligand, O-((9H-fluoren-9-yl)methyl) S-(2-mercaptoethyl) carbonothioate (FMT), contains the surface ligand 1,2-ethanedithiol (EDT) protected at one end using fluorenylmethyloxycarbonyl (Fmoc). The strategy enables deprotection following colloidal deposition, producing films containing quantum dots whose surfaces are more thoroughly covered with the remaining EDT molecules. To compare fabrication methods, we deposited CQDs onto the active layer: in one case, the traditional EDT-PbS/EDT-PbS is used, while in the other EDT-PbS/FMT-PbS is used. The devices based on the new EDT/FMT match the PCE values of EDT/EDT controls, and maintain a higher PCE over an 18 day storage interval, a finding we attribute to an increased thiol coverage using the FMT protocol.

Role of Surface Morphology on Exciton Recombination in Single Quantum Dot-in-Rods Revealed by Optical and Atomic Structure Correlation.

The physical structure of colloidal quantum dot (QD) nanostructures strongly influences their optical and electronic behavior. A fundamental understanding of this interplay between structure and function is crucial to fully tailor the performance of QDs and their assemblies. Here, by directly correlating the atomic and chemical structure of single CdSe-CdS quantum dot-in-rods with time-resolved fluorescence measurements on the same structures, we identify morphological irregularities at their surfaces that moderate photoluminescence efficiencies. We find that two nonradiative exciton recombination mechanisms are triggered by these imperfections: charging and trap-assisted nonradiative processes. Furthermore, we show that the proximity of the surface defects to the CdSe core of the core-shell structures influences whether the charging or trap-assisted nonradiative channel dominates exciton recombination. Our results extend to other QD nanostructures and emphasize surface roughness as a crucial parameter when designing colloidal QDs with specific excitonic fates.

Design of a Hole Trapping Ligand.

A new ligand that covalently attaches to the surface of colloidal CdSe/CdS nanorods and can simultaneously chelate a molecular metal center is described. The dithiocarbamate-bipyridine ligand system facilitates hole transfer through energetic overlap at the inorganic-organic interface and conjugation through the organic ligand to a chelated metal center. Density functional theory calculations show that the coordination of the free ligand to a CdS surface causes the formation of two hybridized molecular states that lie in the band gap of CdS. The further chelation of Fe(II) to the bipyridine moiety causes the presence of seven midgap states. Hole transfer from the CdS valence band to the midgap states is dipole allowed and occurs at a faster rate than what is experimentally known for the CdSe/CdS band-edge radiative recombination. In the case of the ligand bound with iron, a two-step process emerges that places the hole on the iron, again at rates much faster than band gap recombination. The system was experimentally assembled and characterized via UV-vis absorbance spectroscopy, fluorescence spectroscopy, time-resolved photoluminescence spectroscopy, and energy dispersive X-ray spectroscopy. Theoretically predicted red shifts in absorbance were observed experimentally, as well as the expected quench in photoluminescence and lifetimes in time-resolved photoluminescence.

Dual-mode crystal-bound and X-type passivation of quantum dots.

In this report, we present a new path to the control of quantum dot surface chemistry that can lead to a better understanding of nanoscale interfaces and the development of improved photocatalysts. Control of the synthetic methodology leads to QDs that are concomitantly ligated by crystal-bound organics at the surface anion sites and small X-type ligands on the surface cation sites.

Contact and Support Considerations in the Hydrogen Evolution Reaction Activity of Petaled MoS2 Electrodes.

Petaled MoS2 electrodes grown hydrothermally from Mo foils are found to have an 800 nm, intermediate, MoSxOy layer. Similar petaled MoS2 films without this intermediate layer are grown on Au. X-ray photoelectron and Raman spectroscopies and transmission electron microscopy indicate the resulting petaled multilayer MoS2 films are frayed and exhibit single-layer, 1T-MoS2 behavior at the edges. We compare the electrocatalytic hydrogen evolution reaction activity via linear sweep voltammetry with Tafel analysis as well as the impedance properties of the electrodes. We find that petaled MoS2/Au and petaled MoS2/Mo exhibit comparable overpotential to 10 mA cm(-2) at -279 vs -242 mV, respectively, and similar Tafel slopes of ∼68 mV/decade indicating a similar rate-determining step. The exchange current normalized to the geometric area of petaled MoS2/Au (0.000921 mA cm(-2)) is 3 times smaller than that of petaled MoS2/Mo (0.00290 mA cm(-2)), and is attributed to the lower petal density on the Au support. However, Au supports increase the turnover frequency per active site of petaled MoS2 to 0.48 H2 Mo(-1) s(-1) from 0.25 H2 Mo(-1) s(-1) on Mo supports. Both petaled MoS2 films have nearly ohmic contacts to their supports with uncompensated resistivity Ru of <2.5 Ω·cm(2).

Optoelectronic Properties of CuInS2 Nanocrystals and Their Origin.

The capacity of fluorescent colloidal semiconductor nanocrystals for commercial application has led to the development of nanocrystals with nontoxic constituent elements as replacements for the currently available Cd- and Pb-containing systems. CuInS2 is a good candidate material because of its direct band gap in the near-infrared spectral region and large optical absorption coefficient. The ternary nature, flexible stoichiometry, and different crystal structures of CuInS2 lead to a range of optoelectronic properties, which have been challenging to elucidate. In this Perspective, the optoelectronic properties of CuInS2 nanocrystals are described and what is known of their origin is discussed. We begin with an overview of their synthesis, structure, and mechanism of formation. A complete discussion of the tunable luminescence properties and the radiative decay mechanism of this system is then presented. Finally, progress toward application of these "green" nanocrystals is summarized.

Interlaced crystals having a perfect Bravais lattice and complex chemical order revealed by real-space crystallography.

The search for optimal thermoelectric materials aims for structures in which the crystalline order is disrupted to lower the thermal conductivity without degradation of the electron conductivity. Here we report the synthesis and characterisation of ternary nanoparticles (two cations and one anion) that exhibit a new form of crystalline order: an uninterrupted, perfect, global Bravais lattice, in which the two cations exhibit a wide array of distinct ordering patterns within the cation sublattice, forming interlaced domains and phases. Partitioning into domains and phases is not unique; the corresponding boundaries have no structural defects or strain and entail no energy cost. We call this form of crystalline order 'interlaced crystals' and present the example of hexagonal CuInS2. Interlacing is possible in multi-cation tetrahedrally bonded compound with an average of two electrons per bond. Interlacing has minimal effect on electronic properties, but should strongly reduce phonon transport, making interlaced crystals attractive for thermoelectric applications.