Incorporation Of Metal Atoms Research Articles

Ammonia-regulated dynamic evolution of Ti precursor incorporating into dealuminized beta for efficient 1-Hexene epoxidation

Demetalation-metalation method has gained prominence for its higher metal loading, efficiency and shortened synthetic period, particularly in the incorporation of metal atoms with large radii into zeolite framework in recent years. An ammonia-regulated approach has been developed for selectively evolved deep-substituted Ti precursors in dealuminized beta zeolites, which enables a controlled promotion of metalation of Ti atoms. Additionally, this ammonia-regulated approach could also enhance 1-hexene kinetic adsorption by constructing mesopores, which is demonstrated by the lower reaction order of 1-hexene. The synthesized ammonia-regulated N-Ti-beta exhibits rich framework Ti species and a high specific surface area, leading to significantly improved 1-hexene epoxidation performance (conversion of 61%, selectivity of 98%, and a high H2O2 utilization efficiency of 93%). This study not only provides a new strategy to dynamically regulate evolution of Ti precursors by ammonia but also holds promise for advancing related industrial processes in demetalation-metalation methods.

Promoting oxygen reduction via coordination environment modulation through secondary metal-atom incorporation

The incorporation of Cu single atoms into Fe-based single-atom catalysts (Fe-SACs) can regulate the coordination environment of Fe active sites and significantly enhance the oxygen reduction reaction (ORR) performance.

Flash Bottom‐Up Arc Synthesis of Nanocarbons as a Universal Route for Fabricating Single‐Atom Electrocatalysts (Small Methods 8/2021)

Inside Back Cover In the article number 2100239, Yoo, Kim, and co-workers report a universal strategy for fabricating single-atom catalysts (SACs) using a flash bottom-up arc discharge. It allows simultaneous incorporation of metal atoms into a carbon lattice during formation of nanocarbons. It is applicable to various metals and nanocarbons.

Potential of Cyanine Derived Dyes in Photodynamic Therapy.

Photodynamic therapy (PDT) is a method of cancer treatment that leads to the disintegration of cancer cells and has developed significantly in recent years. The clinically used photosensitizers are primarily porphyrin, which absorbs light in the red spectrum and their absorbance maxima are relatively short. This review presents group of compounds and their derivatives that are considered to be potential photosensitizers in PDT. Cyanine dyes are compounds that typically absorb light in the visible to near-infrared-I (NIR-I) spectrum range (750–900 nm). This meta-analysis comprises the current studies on cyanine dye derivatives, such as indocyanine green (so far used solely as a diagnostic agent), heptamethine and pentamethine dyes, squaraine dyes, merocyanines and phthalocyanines. The wide array of the cyanine derivatives arises from their structural modifications (e.g., halogenation, incorporation of metal atoms or organic structures, or synthesis of lactosomes, emulsions or conjugation). All the following modifications aim to increase solubility in aqueous media, enhance phototoxicity, and decrease photobleaching. In addition, the changes introduce new features like pH-sensitivity. The cyanine dyes involved in photodynamic reactions could be incorporated into sets of PDT agents.

Impact of metals on (star)dust chemistry: a laboratory astrophysics approach.

Laboratory experiments are essential in exploring the mechanisms involved in stardust formation. One key question is how a metal is incorporated into dust for an environment rich in elements involved in stardust formation (C, H, O, Si). To address experimentally this question we have used a radiofrequency cold plasma reactor in which cyclic organosilicon dust formation is observed. Metallic (silver) atoms were injected in the plasma during the dust nucleation phase to study their incorporation in the dust. The experiments show formation of silver nanoparticles (~15 nm) under conditions in which organosilicon dust of size 200 nm or less is grown. The presence of AgSiO bonds, revealed by infrared spectroscopy, suggests the presence of junctions between the metallic nanoparticles and the organosilicon dust. Even after annealing we could not conclude on the formation of silver silicates, emphasizing that most of silver is included in the metallic nanoparticles. The molecular analysis performed by laser mass spectrometry exhibits a complex chemistry leading to a variety of molecules including large hydrocarbons and organometallic species. In order to gain insights into the involved chemical molecular pathways, the reactivity of silver atoms/ions with acetylene was studied in a laser vaporization source. Key organometallic species, Ag n C2H m (n=1-3; m=0-2), were identified and their structures and energetic data computed using density functional theory. This allows us to propose that molecular Ag-C seeds promote the formation of Ag clusters but also catalyze hydrocarbon growth. Throughout the article, we show how the developed methodology can be used to characterize the incorporation of metal atoms both in the molecular and dust phases. The presence of silver species in the plasma was motivated by objectives finding their application in other research fields than astrochemistry. Still, the reported methodology is a demonstration laying down the ground for future studies on metals of astrophysical interest such as iron.

IR and UV/VIS Spectroscopic Characterization of the Higher Fullerene C76-D2 for Its Quantitative and Qualitative Determination

The only stable isomer of the higher fullerene C76 of D2 symmetry was isolated from carbon soot by the new and advanced extraction and chromatographic methods and processes. Characterization of the isolated C76-D2 was performed by the IR(KBr) and UV/VIS method in the absorption mode. All of the experimentally observed infrared and electronic absorption bands are in excellent agreement with the theoretical calculations for this fullerene. The molar absorptivity ε and the integrated molar absorptivity Ψ of the observed entire new series of various characteristic, both deconvoluted and convoluted IR absorption bands of the C76-D2 isomer, in different integration ranges were determined. In addition, the molar extinction coefficients of its UV/VIS absorption bands were determined. The obtained novel IR and UV/VIS spectroscopic parameters are significant for the quantitative assessment of C76-D2. All the presented data are important both for its qualitative and quantitative determination, either in natural resources on Earth and in space or in artificially synthesized materials, electronic and optical devices, optical limiters, sensors, polymers, solar cells, nanophotonic lenses, diagnostic and therapeutic agents, pharmaceutical substances, for targeted drug delivery, incorporation of metal atoms, in biomedical engineering, industry, applied optical science, batteries, catalysts and so forth.

Microwave-Assisted Rapid Synthesis of Graphene-Supported Single Atomic Metals.

Graphene-supported single atomic metals (G-SAMs) have recently attracted considerable research interest for their intriguing catalytic, electronic, and magnetic properties. The development of effective synthetic methodologies toward G-SAMs with monodispersed metal atoms is vital for exploring their fundamental properties and potential applications. A convenient, rapid, and general strategy to synthesize a series of monodispersed atomic transition metals (for example, Co, Ni, Cu) embedded in nitrogen-doped graphene by two-second microwave (MW) heating the mixture of amine-functionalized graphene oxide and metal salts is reported here. The MW heating is able to simultaneously induce the reduction of graphene oxide, the doping of nitrogen, and the incorporation of metal atoms into the graphene lattices in one simple step. The rapid MW process minimizes metal diffusion and aggregation to ensure exclusive single metal atom dispersion in graphene lattices. Electrochemical studies demonstrate that graphene-supported Co atoms can function as highly active electrocatalysts toward the hydrogen evolution reaction. This MW-assisted method provides a rapid and efficient avenue to supported metal atoms for wide ranges of applications.

Post-Synthesis Modifications of Two-Dimensional MoSe2 or MoTe2 by Incorporation of Excess Metal Atoms into the Crystal Structure.

Phase engineering has extensively been used to achieve metallization of two-dimensional (2D) semiconducting materials, as it should boost their catalytic properties or improve electrical contacts. In contrast, here we demonstrate compositional phase change by incorporation of excess metals into the crystal structure. We demonstrate post-synthesis restructuring of the semiconducting MoTe2 or MoSe2 host material by unexpected easy incorporation of excess Mo into their crystal planes, which causes local metallization. The amount of excess Mo can reach values as high as 10% in MoTe2 thus creating a significantly altered material compared to its parent structure. The incorporation mechanism is explained by density functional theory in terms of the energy difference of Mo atoms incorporated in the line phases as compared to Mo ad-clusters. Angle resolved photoemission spectroscopy reveals that the incorporated excess Mo induces band gap states up to the Fermi level causing its pinning at these electronic states. The incorporation of excess transition metals in MoTe2 and MoSe2 is not limited to molybdenum, but other transition metals can also diffuse into the lattice, as demonstrated experimentally by Ti deposition. The mechanism of incorporation of transition metals in MoSe2 and MoTe2 is revealed, which should help to address the challenges in synthesizing defect-free single layer materials by, for example, molecular beam epitaxy. The easy incorporation of metal atoms into the crystal also indicates that the previously assumed picture of a sharp metal/2D-material interface may not be correct, and at least for MoSe2 and MoTe2, in-diffusion of metals from metal-contacts into the 2D material has to be considered. Most importantly though, the process of incorporation of transition metals with high concentrations into pristine 2D transition-metal dichalcogenides enables a pathway for their post-synthesis modifications and adding functionalities.

Quantitative Analysis of the Incorporation Behaviors of Sr and Ti Atoms During the Atomic Layer Deposition of SrTiO3 Thin Films.

The atomic layer deposition (ALD) of multication oxide films is complicated because the deposition behaviors of the component oxides are not independent of one another. In this study, the Ti and Sr atom incorporation behaviors during the ALD of SrTiO3 films were quantitatively examined via the carefully designed ALD process sequences. H2O and O3 were adopted as the oxygen sources of the SrO subcycles, whereas only O3 was used for the TiO2 ALD subcycles. Apart from the general conjecture on the roles of the different types of oxygen sources, the oxygen source that was adopted for the subcycles of the other component oxide had almost complete control of the metal atom incorporation behaviors. This means that the first half-cycle of ALD played a dominant role in determining the metal incorporation rate, which revealed the critical role of the steric hindrance effect during the metal precursor injection for the ALD rate. O3 had almost doubled its reactivity toward the Ti and Sr precursors compared with H2O. Although these are the expected results from the common knowledge on ALD, the quantitative analysis of the incorporation behaviors of each metal atom provided insightful viewpoints for the ALD process of this technically important oxide material. Furthermore, the SrTiO3 films with a bulk dielectric constant as high as 236 were obtained by the Ru-SrTiO3-RuO2 capacitor structure.

Incorporation and redistribution of impurities into silicon nanowires during metal-particle-assisted growth.

The incorporation of metal atoms into silicon nanowires during metal-particle-assisted growth is a critical issue for various nanowire-based applications. Here we have been able to access directly the incorporation and redistribution of metal atoms into silicon nanowires produced by two different processes at growth rates ranging from 3 to 40 nm s(-1), by using laser-assisted atom probe tomography and scanning transmission electron microscopy. We find that the concentration of metal impurities in crystalline silicon nanowires increases with the growth rate and can reach a level of two orders of magnitude higher than that in their equilibrium solubility. Moreover, we demonstrate that the impurities are first incorporated into nanowire volume and then segregate at defects such as the twin planes. A dimer-atom-insertion kinetic model is proposed to account for the impurity incorporation into nanowires.

Functionalization of Open Two-Dimensional Metal–Organic Templates through the Selective Incorporation of Metal Atoms

Surface-confined molecular networks can serve as templates to steer the adsorption and organization of secondary ligands, metal atoms, and clusters. Here, the incorporation of Ni atoms and clusters into open two-dimensional robust metal–organic templates self-assembled from butadiyne dibenzoic acid molecules and Fe atoms on Au(111) and Ag(100) surfaces is investigated by scanning tunneling microscopy. The metal substrate plays a crucial role in the interaction of Ni atoms with the metal–organic host networks. On Ag(100) the metal–organic template steers the growth of Ni clusters underneath the network pattern near the central butadiyne moiety. In contrast, on Au(111) Ni interacts preferentially with the benzene rings forming size-limited clusters inside the network cavities. Thereby, on both surfaces Ni clusters consisting of a few atoms with both high areal density and thermal stability up to 450 K are realized. The Ni-functionalized networks enable the coordination of additional molecules into the open structures demonstrating the utilization of selective interactions for the assembly of multicomponent architectures at different organizational stages.

Templating of arrays of Ru nanoclusters by monolayer graphene/Ru Moirés with different periodicities

We have studied the formation of Ru nanocluster arrays on several monolayer graphene/Ru Moiré structures with different relative orientations of the graphene and Ru lattices. Experiments and ab initio calculations clearly show that the presence of a graphene/Ru Moiré does not guarantee the ordered adsorption of Ru nanoclusters. The simultaneous deposition of Ru onto coexisting Moirés demonstrates that a structure with aligned graphene and Ru lattices templates the formation of arrays of small Ru clusters with narrow size spread and adsorption exclusively in a single site (the ‘low fcc’ site). The other Moirés considered here gave rise to substantially larger clusters with broader size distribution and without detectable site selectivity. Calculations explain these findings via the density of states (DOS) at different sites of the graphene/Ru Moiré. The ordered nucleation of many small clusters instead of incorporation of metal atoms into larger ones requires one Moiré site with a large DOS at the Fermi level, so that the binding of metal adatoms to this site is stronger than to competing sites in the Moiré and to existing metal clusters.

MeV Au2+ ions induced surface patterning in silica

This paper reports the formation of self-organised surface morphological features on silica irradiated with MeV energy gold ions. Amorphous silica substrates were irradiated with 1.8MeV gold ions at normal incidence at room temperature to various doses in the range of 5×1016ions/cm2 to 2×1017ions/cm2. The formation of a periodic surface pattern with a wavelength of 1.35μm was observed at an irradiation dose of 1×1017ions/cm2. The observation of surface segregation of gold at around the same dose suggests possible role of surface stresses caused by the incorporation of metal atoms in the formation of the observed periodic surface morphology.

Diameter-Controlled Solid-Phase Seeding of Germanium Nanowires: Structural Characterization and Electrical Transport Properties

Despite the huge progress recently made in understanding the phenomena of metal-promoted growth of one-dimensional (1D) semiconductors, the controlled formation of small diameter semiconductor nanowires is still challenging. Liquid growth promoters, such as the low melting Au/Ge eutectic, allow control of the aspect ratio, diameter, and structure of 1D crystals via external parameters, such as precursor feedstock, temperature, and operating pressure. However, the incorporation of metal atoms during the growth process, size variations of the nanowires due to agglomeration of the nucleating metal seeds, and surface diffusion of Au via the vapor–liquid–solid route have been reported. Here, we detail the influence of solid growth seeds, such as NiGe2 formed from Ni nanoparticles, on the lateral dimensions of Ge nanowires grown using a supercritical fluid growth process. Beneficial control over the mean nanowire diameter, in the sub-20 nm regime, with a predominantly ⟨110⟩ growth direction and low structural d...

The effect of noble metal atom incorporation on DNA spectral properties and its stability under irradiation

The optical absorption, fluorescence, phosphorescence and effect of irradiation on spectral properties of polyplatillenum (DNA–Pt complex) were studied. Two important features were fixed: the increase of the phosphorescence intensity of DNA caused by Pt binding to DNA macromolecules; and the increase of DNA photodegradation rate when Pt is incorporated in DNA.

Stabilization of surface reaction intermediates by added metal atoms on metal surfaces of low free energy

Dynamic restructuring of the Ag(111) surface occurs during the reaction of sulfur dioxide with Ag(111)-p(4 x 4)-O at 300 K, resulting in the incorporation of added silver atoms into the unit cells of both adsorbed sulfite and sulfate. This result clearly demonstrates that incorporation of metal atoms into the structures of adsorbates and reaction intermediates is not restricted to more open, higher free energy single crystal planes. These observations indicate that the participation of added metal atoms must be considered in the theoretical treatment of metal catalyzed reactions.

Synthesis, Self‐Assembly, and Applications of Polyferrocenylsilane Block Copolymers

The incorporation of metal atoms into synthetic polymer chains leads to desirable properties and generates a new and versatile class of functional materials with enhanced processability. New creative approaches have led to macromolecular structures in which metals are not only incorporated via the use of traditional covalent bonds but also by potentially reversible coordination interactions. Metallopolymers with precisely controlled chain length are therefore attracting rapidly expanding attention as a result of their properties and potential applications. This article focuses on polyferrocenylsilanes and polyferrocenylsilane block copolymers where iron and silicon are present in the main chain of the organometallic segment. These materials also represent an area of rapidly growing interest as a result of their self‐assembly. The resulting nanostructured materials have a wealth of potential applications and recent breakthroughs in this area are discussed. The subject matter of the article is divided up into subsections covering polyferrocenylsilane homopolymer and block copolymer synthesis, solution and solid state self‐assembly, and applications.

A series of novel aromatic compounds with a planar N 6 ring

A series of novel aromatic compounds ScN 6 - , VN 6 + , Ca 2N 6, and ScN 6Cu, including a previously reported TiN 6, are found to be local minima with C 6v, C 6v, D 6h, and C s symmetry, respectively, at the B3LYP/6-311+G ∗ level of theory. These compounds may be regarded as 10π-electron complexes containing one or two metal cations and a planar N 6 4 - ring. They are predicted to have aromatic character. The nucleus-independent chemical shifts (NICS), the molecular orbitals, and the HOMO–LUMO gap analysis confirm that the planar N 6 4 - ring indeed exhibits aromaticity, which is remarkably enhanced by the incorporation of metal atom in these metal–N 6 molecules.

Synthesis of MFe3S4Clusters Containing a Planar MIISite (M = Ni, Pd, Pt), a Structural Element in the C-Cluster of Carbon Monoxide Dehydrogenase

Synthesis of an analogue of the C-cluster of C. hydrogenoformans carbon monoxide dehydrogenase requires formation of a planar Ni(II) site and attachment of an exo iron atom in the core unit NiFe(4)S(5). The first objective has been achieved by two reactions: (i) displacement of Ph(3)P or Bu(t)()NC at tetrahedral Ni(II) sites of cubane-type [NiFe(3)S(4)](+) clusters with chelating diphosphines, and (ii) metal atom incorporation into a cuboidal [Fe(3)S(4)](0) cluster with a M(0) reactant in the presence of bis(1,2-dimethylphosphino)ethane (dmpe). The isolated product clusters [(dmpe)MFe(3)S(4)(LS(3))](2-) (M = Ni(II) (9), Pd(II) (12), Pt(II) (13); LS(3) = 1,3,5-tris((4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio)benzene(3-)) contain the cores [MFe(3)(mu(2)-S)(mu(3)-S)(3)](+) having planar M(II)P(2)S(2) sites and variable nonbonding M...S distances of 2.6-3.4 A. Reaction (i) involves a tetrahedral --> planar Ni(II) structural change between isomeric cubane and cubanoid [NiFe(3)S(4)](+) cores. Based on the magnetic properties of 12 and earlier considerations, the S = (5)/(2) ground state of the cubanoid cluster arises from the [Fe(3)S(4)](-) fragment, whereas the S = (3)/(2) ground state of the cubane cluster is a consequence of antiferromagnetic coupling between the spins of Ni(2+) (S = 1) and [Fe(3)S(4)](-). Other substitution reactions of [NiFe(3)S(4)](+) clusters and 1:3 site-differentiated [Fe(4)S(4)](2+) clusters are described, as are the structures of 12, 13, [(Me(3)P)NiFe(3)S(4)(LS(3))](2-), and [Fe(4)S(4)(LS(3))L'](2-) (L' = Me(2)NC(2)H(4)S(-), Ph(2)P(O)C(2)H(4)S(-)). This work significantly expands our initial report of cluster 9 (Panda et al. J. Am. Chem. Soc. 2004, 126, 6448-6459) and further demonstrates that a planar M(II) site can be stabilized within a cubanoid [NiFe(3)S(4)](+) core.

Metal incorporation into nanoporous carbon

AbstractNanoporous carbon films were deposited by 248 nm pulsed laser ablation of a graphite target in different background pressures of argon (PAr). The morphology changed from smooth, high-density amorphous carbon films at PAr = 20 mTorr to ultra-low density nanoporous material at PAr = 380 mTorr. Subsequently, the nanostructural, chemical and electrical properties of metal containing nanoporous carbon samples were investigated by ablating graphite targets containing known contents of Ni and Co. We demonstrate how the ablation plume dynamics affect both the nanostructure of the material and the incorporation of metal atoms. The suitability of these functionalised ultra-low density materials for gas sensing applications is discussed.