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At least 1,783 records · Page 99

Strong-field Driven Sub-cycle Band Structure Modulation and Dephasing Control

In this work, we present measurements of ultrafast electric-field observables in magnesium oxide using a non-resonant nonlinear optical interaction. Using field observables, we show that strong laser fields modulate the band structure on sub-cycle timescales, thereby altering the material’s nonlinear optical response. We perform time-dependent perturbation theory calculations using a field-dependent dispersion relation and semiconductor Bloch equation calculations, both of which agree with experimental observations. Furthermore, we extract pulse decay times from the real-time signal electric field envelope and show sub-cycle control of dephasing times. Our work offers a new perspective on strong-field-driven electron dynamics in solids through electric-field observables. The demonstrated attosecond modulation of the nonlinear response could have important implications for quantum light generation and quantum spectroscopy using nonlinear optical processes.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Visualizing interfacial collective reaction behaviour of Li–S batteries

Benefiting from high energy density (2,600 Wh kg -1 )) and low cost, lithium-sulfur (Li-S) batteries are considered promising candidates for advanced energy-storage systems. Despite tremendous efforts in suppressing the long-standing shuttle effect of lithium polysulfides, understanding of the interfacial reactions of lithium polysulfides at the nanoscale remains elusive. This is mainly because of the limitations of in situ characterization tools in tracing the liquid-solid conversion of unstable lithium polysulfides at high temporal-spatial resolution. There is an urgent need to understand the coupled phenomena inside Li-S batteries, specifically, the dynamic distribution, aggregation, deposition and dissolution of lithium polysulfides. Here, by using in situ liquid-cell electrochemical transmission electron microscopy, we directly visualized the transformation of lithium polysulfides over electrode surfaces at the atomic scale. Notably, an unexpected gathering-induced collective charge transfer of lithium polysulfides was captured on the nanocluster active-centre-immobilized surface. It further induced an instantaneous deposition of nonequilibrium Li2S nanocrystals from the dense liquid phase of lithium polysulfides. Without mediation of active centres, the reactions followed a classical single-molecule pathway, lithium polysulfides transforming into Li 2 S 2 and Li 2 S step by step. Molecular dynamics simulations indicated that the long-range electrostatic interaction between active centres and lithium polysulfides promoted the formation of a dense phase consisting of Li + and S n 2- (2 < n ≤ 6), and the collective charge transfer in the dense phase was further verified by ab initio molecular dynamics simulations. Finally, the collective interfacial reaction pathway unveils a new transformation mechanism and deepens the fundamental understanding of Li-S batteries.

25 ENERGY STORAGE↗

Density Functional Tight-Binding Simulations Reveal the Presence of Surface Defects on the Quartz (101)–Water Interface

Understanding the structure and reactivity of quartz–water interfaces is critical for numerous applications in the geological, environmental, and biological sciences. However, disagreements on the atomic-level structure of the interfaces between experiments and simulations are hampering our ability to predict the surface reactivity. Here, we used density functional tight-binding (DFTB)-based molecular dynamics to simulate a series of quartz (101) surfaces having different types and densities of surface defects in water and compared them with the structures determined by X-ray reflectivity measurements. The DFTB simulations are able to reproduce previous classical and quantum mechanical predictions of the pristine quartz (101)–water interface that disagree with experimental observations. To remedy this situation, a set of defective quartz surfaces having various surface silicon (Si) vacancies were built as indicated by recent experimental studies. We found that the rotation of surface [SiO 4 ] tetrahedra near Si vacancies can lead to outward displacements of Si atoms similar to those observed in the experiments. The presence of additional surface Si vacancies caused inward relaxations of terminal oxygens through the formation of hydrogen bonds. Finally, the overall results indicate that the quartz (101)–water interface may include a mixture of geminal (≡Si–(OH) 2 )- and vicinal (≡Si–OH)-type silanol groups together with the presence of surface Si vacancies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charging and ion ejection dynamics of large helium nanodroplets exposed to intense femtosecond soft xray pulses

Ion ejection from charged helium nanodroplets exposed to intense femtosecond soft X-ray pulses is studied by single-pulse ion time-of-flight (TOF) spectroscopy in coincidence with small-angle X-ray scattering. Scattering images encode the droplet size and absolute photon flux incident on each droplet, while ion TOF spectra are used to determine the maximum ion kinetic energy, Ekin, of He+ j fragments (j = 1-4). Measurements span HeN droplet sizes between N similar to 10(7) and similar to 10(10) (radii R-0 = 78-578 nm), and droplet charges between similar to 9x10(-5) and similar to 3x10(-3) e/atom. Conditions encompass a wide range of ionization and expansion regimes, from departure of all photoelectrons from the droplet, leading to pure Coulomb explosion, to substantial electron trapping by the electrostatic potential of the charged droplet, indicating the onset of hydrodynamic expansion. The unique combination of absolute Xray intensities, droplet sizes, and ion Ekin on an event-by-event basis reveals a detailed picture of the correlations between the ionization conditions and the ejection dynamics of the ionic fragments. The maximum E-kin of He+ is found to be governed by Coulomb repulsion from unscreened cations across all expansion regimes. The impact of ion-atom interactions resulting from the relatively low charge densities is increasingly relevant with less electron trapping. The findings are consistent with the emergence of a charged spherical shell around a quasineutral plasma core as the degree of ionization increases. The results demonstrate a complex relationship between measured ion E-kin and droplet ionization conditions that can only be disentangled through the use of coincident single-pulse TOF and scattering data.

Helium↗

Interleaved dual-species arrays of single atoms using a passive optical element and one trapping laser

We demonstrate trapping of individual rubidium (Rb) and cesium (Cs) atoms in an interleaved array of bright tweezers and dark bottle-beam traps, using a microfabricated optical element illuminated by a single-laser beam and a 4f system with spatial filtering. Our approach exploits the opposite-sign dynamic polarizabilities of Rb and Cs, ensuring that each species is exclusively trapped in either bright or dark sites. The passive optical mask creates optimal trap depths for both species using three transmittance levels while minimizing the optical phase difference, implemented using a variable-thickness absorbing layer of amorphous germanium. This trapping architecture achieves atom loading rates close to 50% while reducing system complexity compared to conventional methods using active optoelectronic components and/or multiple-laser wavelengths.

Fang, Chengyu [Univ. of Wisconsin, Madison, WI (Un↗

Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li 2 OHCl

Li 2 OHCl is an exemplar of the antiperovskite family of ionic conductors, for which high ionic conductivities have been reported, but in which the atomic-level mechanism of ion migration is unclear. The stable phase is both crystallographically defective and disordered, having similar to 1/3 of the Li sites vacant, while the presence of the OH(- )anion introduces the possibility of rotational disorder that may be coupled to cation migration. In this work, complementary experimental and computational methods are applied to understand the relationship between the crystal chemistry and ionic conductivity in Li 2 OHCl , which undergoes an orthorhombic to cubic phase transition near 311 K (approximate to 38 degrees C) and coincides with the more than a factor of 10 change in ionic conductivity (from 1.2 x 10 -5 mS/cm at 37 degrees C to 1.4 x 10 -3 mS/cm at 39 degrees C). X ray and neutron experiments conducted over the temperature range 20-200 degrees C, including diffraction, quasi-elastic neutron scattering (QENS), the maximum entropy method (MEM) analysis, and ab initio molecular dynamics (AIMD) simulations, together show conclusively that the high lithium ion conductivity of cubic Li2OHCl is correlated to "paddlewheel" rotation of the dynamic OH - anion. The present results suggest that in antiperovskites and derivative structures a high cation vacancy concentration combined with the presence of disordered molecular anions can lead to high cation mobility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solar Wind Ion Sputtering of Sodium from Silicates Using Molecular Dynamics Calculations of Surface Binding Energies

For nearly 40 yr, studies of exosphere formation on airless bodies have been hindered by uncertainties in our understanding of the underlying ion collisional sputtering by the solar wind (SW). These ion impacts on airless bodies play an important role in altering their surface properties and surrounding environment. Much of the collisional sputtering data needed for exosphere studies come from binary collision approximation (BCA) sputtering models. These depend on the surface binding energy (SBE) for the atoms sputtered from the impacted material. However, the SBE is not reliably known for many materials important for planetary science, such as plagioclase feldspars and sodium pyroxenes. BCA models typically approximate the SBE using the cohesive energy for a monoelemental solid. We use molecular dynamics (MD) to provide the first accurate SBE data we are aware of for Na sputtered from the above silicate minerals, which are expected to be important for exospheric formation at Mercury and the Moon. The MD SBE values are ∼8 times larger than the Na monoelemental cohesive energy. This has a significant effect on the predicted SW ion sputtering yield and energy distribution of Na and the formation of the corresponding Na exosphere. We also find that the SBE is correlated with the coordination number of the Na atoms within the substrate and with the cohesive energy of the Na-bearing silicate. Our MD SBE results will enable more accurate BCA predictions for the SW ion sputtering contribution to the Na exosphere of Mercury and the Moon.

Lunar surface↗

Interplay of structural fluctuations and charge carrier dynamics is key for high performance of hybrid lead halide perovskites

The ability of methylammonium lead triiodide (MAPbI 3 ) to achieve photoelectric conversion efficiency that is on par with crystalline silicon has led to a surge of interest in perovskite photovoltaics. However, an in-depth understanding of how the ubiquitous coupling between the fast rovibrational movements of the organic cations and the phonon vibrations of the inorganic framework affects the relaxation and recombination of hot carriers remains largely elusive. Access to such knowledge is critical to guide design and increase efficiency of new classes of perovskite solar cells. In this report, we report a time-domain ab initio investigation of temperature dependent excited state dynamics in MAPbI 3 , with particular emphasis on nuclear anharmonic effects. The observed strong anharmonicity is attributed to softness of the material and unusual dynamical coupling between the organic and inorganic components. At an elevated temperature, the hydrogen bonding between MA and iodines is weakened, enhancing rotation of MA cations, which become more dynamically disordered. As a result, thermal vibrations of the inorganic Pb–I sublattice are suppressed, and the lattice anharmonicity is decreased. Thermal fluctuations of the electronic energy levels are found to follow the trend of anharmonic motions of Pb and I atoms, with holes relaxing faster to the band edges than electrons, due to higher density of the hole states. While elevated temperature accelerates intraband carrier cooling, it slows nonradiative carrier recombination. The latter result is important for performance, since solar cells and other devices heat up during operation. The reported signatures of coupled structural dynamics of the organic cations and inorganic framework unravel the interplay between anomalous structural fluctuations and charge carrier dynamics, which is of particular importance for fundamental understanding of the structure–property relationships in hybrid metal halide perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Metal–support interactions in metal oxide-supported atomic, cluster, and nanoparticle catalysis

Supported metal catalysts are essential to a plethora of processes in the chemical industry. The overall performance of these catalysts depends strongly on the interaction of adsorbates at the atomic level, which can be manipulated and controlled by the different constituents of the active material (i.e., support and active metal). The description of catalyst activity and the relationship between active constituent and the support, or metal–support interactions (MSI), in heterogeneous (thermo)catalysts is a complex phenomenon with multivariate (dependent and independent) contributions that are difficult to disentangle, both experimentally and theoretically. So-called “strong metal–support interactions” have been reported for several decades and summarized in excellent review articles. However, in recent years, there has been a proliferation of new findings related to atomically dispersed metal sites, metal oxide defects, and, for example, the generation and evolution of MSI under reaction conditions, which has led to the designation of (sub)classifications of MSI deserving to be critically and systematically evaluated. These include dynamic restructuring under alternating redox and reaction conditions, adsorbate-induced MSI, and evidence of strong interactions in oxide-supported metal oxide catalysts. Here, we review recent literature on MSI in oxide-supported metal particles to provide an up-to-date understanding of the underlying physicochemical principles that dominate the observed effects in supported metal atomic, cluster, and nanoparticle catalysts. Critical evaluation of different subclassifications of MSI is provided, along with discussions on the formation mechanisms, theoretical and characterization advances, and tuning strategies to manipulate catalytic reaction performance. We also provide a perspective on the future of the field, and we discuss the analysis of different MSI effects on catalysis quantitatively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid-state NMR of unlabeled plant cell walls: high-resolution structural analysis without isotopic enrichment

Abstract Background Multidimensional solid-state nuclear magnetic resonance (ssNMR) spectroscopy has emerged as an indispensable technique for resolving polymer structure and intermolecular packing in primary and secondary plant cell walls. Isotope ( 13 C) enrichment provides feasible sensitivity for measuring 2D/3D correlation spectra, but this time-consuming procedure and its associated expenses have restricted the application of ssNMR in lignocellulose analysis. Results Here, we present a method that relies on the sensitivity-enhancing technique Dynamic Nuclear Polarization (DNP) to eliminate the need for 13 C-labeling. With a 26-fold sensitivity enhancement, a series of 2D 13 C– 13 C correlation spectra were successfully collected using the unlabeled stems of wild-type Oryza sativa (rice). The atomic resolution allows us to observe a large number of intramolecular cross peaks for fully revealing the polymorphic structure of cellulose and xylan. NMR relaxation and dipolar order parameters further suggest a sophisticated change of molecular motions in a ctl1 ctl2 double mutant: both cellulose and xylan have become more dynamic on the nanosecond and microsecond timescale, but the motional amplitudes are uniformly small for both polysaccharides. Conclusions By skipping isotopic labeling, the DNP strategy demonstrated here is universally extendable to all lignocellulose materials. This time-efficient method has landed the technical foundation for understanding polysaccharide structure and cell wall assembly in a large variety of plant tissues and species.

09 BIOMASS FUELS↗

Verification of stability and unraveling the electronic and physical properties of bulk and (001)-surfaces of newly synthesized Ti 2 ZnX (X = C, N) MAX phases

MAX phase family has been extended by the addition of late transition metals at the A-site with the expectation of diverse functional properties. Here, we present our systematic density functional investigation on the thermodynamic and phonon stabilities, elastic properties, including elastic constants, elastic moduli and elastic anisotropy of newly synthesized Ti 2 ZnX (X = C, N) phases in comparison with conventional Ti 2 AlX (X = C, N). Due to the smaller size of N as compared to C, the unit cell dimension is reduced when C atoms are replaced by N atoms at the X-site. Furthermore, the Ti 2 ZnC and Ti 2 ZnN are stable at the equilibrium volume of 110.84 Å 3 and 105.70 Å 3 . The thermodynamic, mechanical and dynamical stabilities are validated by estimating the formation energies, elastic constants and phonon dispersions, respectively. The elastic properties of Ti 2 ZnN are less anisotropic as compared to those of Ti 2 ZnC. To understand the thin-film characteristics in Ti 2 ZnX, the surface properties with (001)-terminated slabs are investigated. Both Ti 2 ZnX bulk and (001)-surfaces exhibit metal-like electronic structures. There is a strong covalent bonding between Ti-X and Ti-Zn atoms confirmed by the charge density map and Mulliken population analysis. Additional states are generated at the Fermi level (EF) due to the unusual d-p states hybridization between Ti and Zn atoms. The anisotropy in chemical bonding is confirmed by the cleavage energy difference between Ti-X and Ti-Zn. Here, Ti(X)-001 and Zn-001 terminations are stable surfaces; however, in terms of chemical potentials, Zn-001 termination is the most favourable in Ti 2 ZnX.

36 MATERIALS SCIENCE↗

Atomistic Method Applied to Computational Modeling of Surface Alloys

The formation of surface alloys is a growing research field that, in terms of the surface structure of multicomponent systems, defines the frontier both for experimental and theoretical techniques. Because of the impact that the formation of surface alloys has on surface properties, researchers need reliable methods to predict new surface alloys and to help interpret unknown structures. The structure of surface alloys and when, and even if, they form are largely unpredictable from the known properties of the participating elements. No unified theory or model to date can infer surface alloy structures from the constituents properties or their bulk alloy characteristics. In spite of these severe limitations, a growing catalogue of such systems has been developed during the last decade, and only recently are global theories being advanced to fully understand the phenomenon. None of the methods used in other areas of surface science can properly model even the already known cases. Aware of these limitations, the Computational Materials Group at the NASA Glenn Research Center at Lewis Field has developed a useful, computationally economical, and physically sound methodology to enable the systematic study of surface alloy formation in metals. This tool has been tested successfully on several known systems for which hard experimental evidence exists and has been used to predict ternary surface alloy formation (results to be published: Garces, J.E.; Bozzolo, G.; and Mosca, H.: Atomistic Modeling of Pd/Cu(100) Surface Alloy Formation. Surf. Sci., 2000 (in press); Mosca, H.; Garces J.E.; and Bozzolo, G.: Surface Ternary Alloys of (Cu,Au)/Ni(110). (Accepted for publication in Surf. Sci., 2000.); and Garces, J.E.; Bozzolo, G.; Mosca, H.; and Abel, P.: A New Approach for Atomistic Modeling of Pd/Cu(110) Surface Alloy Formation. (Submitted to Appl. Surf. Sci.)). Ternary alloy formation is a field yet to be fully explored experimentally. The computational tool, which is based on the BFS (Bozzolo, Ferrante, and Smith) method for the calculation of the energetics, consists of a small number of simple PCbased computer codes that deal with the different aspects of surface alloy formation. Two analysis modes are available within this package. The first mode provides an atom-by-atom description of real and virtual stages 1. during the process of surface alloying, based on the construction of catalogues of configurations where each configuration describes one possible atomic distribution. BFS analysis of this catalogue provides information on accessible states, possible ordering patterns, and details of island formation or film growth. More importantly, it provides insight into the evolution of the system. Software developed by the Computational Materials Group allows for the study of an arbitrary number of elements forming surface alloys, including an arbitrary number of surface atomic layers. The second mode involves large-scale temperature-dependent computer 2. simulations that use the BFS method for the energetics and provide information on the dynamic processes during surface alloying. These simulations require the implementation of Monte-Carlo-based codes with high efficiency within current workstation environments. This methodology capitalizes on the advantages of the BFS method: there are no restrictions on the number or type of elements or on the type of crystallographic structure considered. This removes any restrictions in the definition of the configuration catalogues used in the analytical calculations, thus allowing for the study of arbitrary ordering patterns, ultimately leading to the actual surface alloy structure. Moreover, the Monte Carlo numerical technique used for the large-scale simulations allows for a detailed visualization of the simulated process, the main advantage of this type of analysis being the ability to understand the underlying features that drive these processes. Because of the simplicity of the BFS method for e energetics used in these calculations, a detailed atom-by-atom analysis can be performed at any point in the simulation, providing necessary insight on the details of the process. The main objective of this research program is to develop a tool to guide experimenters in understanding and interpreting often unexpected results in alloy formation experiments. By reducing the computational effort without losing physical accuracy, we expect that powerful simulation tools will be developed in the immediate future, which will allow material scientists to easily visualize and analyze processes at a level not achievable experimentally.

Bozzolo, Guillermo H.↗

Structural Studies of Alloyed and Nanoparticle Transition Metal Dichalcogenides by Selenium-77 Solid-State Nuclear Magnetic Resonance Spectroscopy

Layered transition metal dichalcogenides (TMDCs) such as MoS 2 , MoSe 2 , and WSe 2 are under intense investigation because they are atomically thin semiconductors with photophysical properties that can be tuned by changing their composition or morphology. Mechanochemical processing has been proposed as a method to obtain alloyed TMDCs in the series Mo 1–x W x S y Se 2–y (x = 0–1; y = 0–2). However, elucidating the chemical transformations occurring at the atomic scale following mechanochemical processing can be challenging because the products are often amorphous or microcrystalline. To address this challenge, we probe TMDC mixing and alloying by using a combination of powder X-ray diffraction, Raman spectroscopy, diffuse reflectance spectroscopy, 77 Se solid-state nuclear magnetic resonance (SSNMR) spectroscopy, and planewave density functional theory (DFT) calculations. The nature of the milling material and reaction atmosphere are shown to be essential factors in limiting the formation of undesired oxide byproducts. We demonstrate acquisition of 77 Se SSNMR spectra using different combinations of Carr-Purcell Meiboom-Gill acquisition (CPMG) pulse sequences, magic angle spinning (MAS), and MAS dynamic nuclear polarization. Further, the combination of SSNMR with the other characterization methods clearly demonstrates that high energy impact ball milling induces molecular level alloying of Mo, W and chalcogen atoms in the family Mo 1–x W x S y Se 2–y . Gauge including projector augmented wave DFT calculations yield accurate 77 Se chemical shift (CS) tensor components. 77 Se SSNMR spectroscopy was also applied to study the structure of WSe 2 nanocrystals intercalated with ethylenediamine. The intercalated WSe 2 nanocrystals exhibit a more positive isotropic 77 Se CS as compared to bulk WSe 2 , however, the 77 Se CS anisotropy is the same, confirming the WSe 2 layers have a similar structure as in their bulk counterparts.

36 MATERIALS SCIENCE↗

Molecular dynamics simulations of reflection and sputtering behavior of boron under deuterium ion irradiation

Boronization is a commonly used method of wall conditioning in fusion reactors. The application of boron films to the plasma-facing materials results in enhanced plasma performance due to the reduction of intrinsic impurities. This is primarily driven by a reduction in oxygen content that is chemically trapped in the boron film. The reactive nature of these boron films also raises questions concerning interactions with hydrogen isotopes. In this work, boron-deuterium interactions were studied using molecular dynamics (MD). Reactive force field potentials were used to model the chemical interactions between B and D. An amorphous boron substrate was irradiated by D atoms at varying incident energies, 10 eV < E i < 150 eV and angles, 0° < α < 85°. The reflection probability was calculated and compared to results from the commonly-used binary collision approximation (BCA) method. This comparison found that the BCA underestimated the reflection probability at E i < 35 eV and α > 45 ∘ . The source of this discrepancy was found to be the surface binding energy model. The BCA calculation with an isotropic surface binding energy model was more closely aligned to the MD result. This, in combination with a correction function based on the MD results allows for corrections to the reflection probability of deuterium impinging on boron surfaces. The sputtering of the substrate material was also studied. While this study did not contain sufficient events to quantitatively describe the sputtering behavior, some qualitative results emerged: namely, chemical sputtering of B and D-containing molecules (BD, BD 2 , BD 3 ) at low ( < 20 eV) incident deuterium energies. This result suggests that chemical sputtering could be a significant factor in limiting boron coating lifetime when exposed to lower ion energies, such as those in detached plasmas. The results show that chemical interactions should be taken into account when modeling the interactions between D ions and B surfaces.

Boron↗

Surface conversion techniques for low energy neutral atom imagers

This investigation has focused on development of key technology elements for low energy neutral atom imaging. More specifically, we have investigated the conversion of low energy neutral atoms to negatively charged ions upon reflection from specially prepared surfaces. This 'surface conversion' technique appears to offer a unique capability of detecting, and thus imaging, neutral atoms at energies of 0.01 - 1 keV with high enough efficiencies to make practical its application to low energy neutral atom imaging in space. Such imaging offers the opportunity to obtain the first instantaneous global maps of macroscopic plasma features and their temporal variation. Through previous in situ plasma measurements, we have a statistical picture of large scale morphology and local measurements of dynamic processes. However, with in situ techniques it is impossible to characterize or understand many of the global plasma transport and energization processes. A series of global plasma images would greatly advance our understanding of these processes and would provide the context for interpreting previous and future in situ measurements. Fast neutral atoms, created from ions that are neutralized in collisions with exospheric neutrals, offer the means for remotely imaging plasma populations. Energy and mass analysis of these neutrals provides critical information about the source plasma distribution. The flux of neutral atoms available for imaging depends upon a convolution of the ambient plasma distribution with the charge exchange cross section for the background neutral population. Some of the highest signals are at relatively low energies (well below 1 keV). This energy range also includes some of the most important plasma populations to be imaged, for example the base of the cleft ion fountain.

Quinn, J. M.↗

Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor

The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

Evaluation Studies↗

Photocatalytic Semiconductor–Metal Hybrid Nanoparticles: Single-Atom Catalyst Regime Surpasses Metal Tips

Semiconductor–metal hybrid nanoparticles (HNPs) are promising materials for photocatalytic applications, such as water splitting for green hydrogen generation. While most studies have focused on Cd containing HNPs, the realization of actual applications will require environmentally compatible systems. Using heavy-metal free ZnSe-Au HNPs as a model, we investigate the dependence of their functionality and efficiency on the cocatalyst metal domain characteristics ranging from the single-atom catalyst (SAC) regime to metal-tipped systems. The SAC regime was achieved via the deposition of individual atomic cocatalysts on the semiconductor nanocrystals in solution. Utilizing a combination of electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy, we established the presence of single Au atoms on the ZnSe nanorod surface. Upon increased Au concentration, this transitions to metal tip growth. Photocatalytic hydrogen generation measurements reveal a strong dependence on the cocatalyst loading with a sharp response maximum in the SAC regime. Ultrafast dynamics studies show similar electron decay kinetics for the pristine ZnSe nanorods and the ZnSe-Au HNPs in either SAC or tipped systems. This indicates that electron transfer is not the rate-limiting step for the photocatalytic process. Combined with the structural-chemical characterization, we conclude that the enhanced photocatalytic activity is due to the higher reactivity of the single-atom sites. This holistic view establishes the significance of SAC-HNPs, setting the stage for designing efficient and sustainable heavy-metal-free photocatalyst nanoparticles for numerous applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗