Tailoring the stoichiometry of C3N4 nanosheets under electron beam irradiation

Two-dimensional polymeric graphitic carbon nitride (g-C3N4) is a low-cost material with versatile properties that can be enhanced by the introduction of dopant atoms and by changing the degree of polymerization/stoichiometry, which offers significant benefits for numerous applications. Herein, we investigate the stability of g-C3N4 under electron beam irradiation inside a transmission electron microscope operating at different electron acceleration voltages. Our findings indicate that the degradation of g-C3N4 occurs with N species preferentially removed over C species. However, the precise nitrogen group from which N is removed from g-C3N4 (C–N–C, [double bond, length as m-dash]NH or –NH2) is unclear. Moreover, the rate of degradation increases with decreasing electron acceleration voltage, suggesting that inelastic scattering events (radiolysis) dominate over elastic events (knock-on damage). The rate of degradation by removing N atoms is also sensitive to the current density. Hence, we demonstrate that both the electron acceleration voltage and the current density are parameters with which one can use to control the stoichiometry. Moreover, as N species were preferentially removed, the d-spacing of the carbon nitride structure increased. These findings provide a deeper understanding of g-C3N4

The chemistry of ZnWO₄ nanoparticle formation

The need for a change away from classical nucleation and growth models for the description of nanoparticle formation is highlighted. By the use of in situ total X-ray scattering experiments the transformation of an aqueous polyoxometalate precursor mixture to crystalline ZnWO$_{4}$ nanoparticles under hydrothermal conditions was followed. The precursor solution is shown to consist of specific Tourné-type sandwich complexes. The formation of pristine ZnWO$_{4}$ within seconds is understood on the basis of local restructuring and three-dimensional reordering preceding the emergence of long range order in ZnWO$_{4}$ nanoparticles. An observed temperature dependent trend in defect concentration can be rationalized based on the proposed formation mechanism. Following nucleation the individual crystallites were found to grow into prolate morphology with elongation along the unit cell c-direction. Extensive electron microscopy characterization provided evidence for particle growth by oriented attachment; a notion supported by sudden particle size increases observed in the in situ total scattering experiments. A simple continuous hydrothermal flow method was devised to synthesize highly crystalline monoclinic zinc tungstate (ZnWO$_{4}$) nanoparticles in large scale in less than one minute. The present results highlight the profound influence of structural similarities in local structure between reactants and final materials in determining the specific nucleation of nanostructures and thus explains the potential success of a given synthesis procedure in producing nanocrystals. It demonstrates the need for abolishing outdated nucleation models, which ignore subtle yet highly important system dependent differences in the chemistry of the forming nanocrystals

Tailoring the stoichiometry of C3N4 nanosheets under electron beam irradiation

Two-dimensional polymeric graphitic carbon nitride (g-C3N4) is a low-cost material with versatile properties that can be enhanced by the introduction of dopant atoms and by changing the degree of polymerization/stoichiometry, which offers significant benefits for numerous applications. Herein, we investigate the stability of g-C3N4 under electron beam irradiation inside a transmission electron microscope operating at different electron acceleration voltages. Our findings indicate that the degradation of g-C3N4 occurs with N species preferentially removed over C species. However, the precise nitrogen group from which N is removed from g-C3N4 (C–N–C, [double bond, length as m-dash]NH or –NH2) is unclear. Moreover, the rate of degradation increases with decreasing electron acceleration voltage, suggesting that inelastic scattering events (radiolysis) dominate over elastic events (knock-on damage). The rate of degradation by removing N atoms is also sensitive to the current density. Hence, we demonstrate that both the electron acceleration voltage and the current density are parameters with which one can use to control the stoichiometry. Moreover, as N species were preferentially removed, the d-spacing of the carbon nitride structure increased. These findings provide a deeper understanding of g-C3N4

High coercivity SmCo5_5 synthesized with assistance of colloidal SiO2_2

SmCo$_5$ is one of the most promising candidates for achieving a hard magnet with a high coercivity. Usually, composition, morphology, and size determine the coercivity of a magnet, however, it is challenging to synthesize phase pure SmCo$_5$ with optimal size and high coercivity. In this paper, we report on the successful synthesis of phase pure SmCo$_5$ with spherical/prolate spheroids shape. Size control is obtained by utilizing colloidal SiO$_2$ as a template preventing aggregation and growth of the precursor. The amount of SiO$_2$ nanoparticles (NPs) in the precursor tunes the average particle size (APS) of the synthesized SmCo$_5$ with particle dimension from 740 to 504 nm. As-prepared pure SmCo$_5$ fine powder obtained from using 2 ml SiO$_2$ suspension possesses an APS of 625 nm and exhibits an excellent coercivity of 2986 kA m$^{−1}$ (37.5 kOe) without alignment of the particles prior to magnetisation measurements. Comparing with a reference sample prepared without adding any SiO$_2$ NPs, an enhancement of 35% of the coercivity was achieved. The improvement is due to phase purity, stable single-domain (SSD) size, and shape anisotropy originating from the prolate spheroid particles

Enhancement of magnetic properties through morphology control of SrFe12O19 nanocrystallites

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In Situ PDF Study of the Nucleation and Growth of Intermetallic PtPb Nanocrystals

The mechanism of Pt and PtPb nanocrystal formation under supercritical ethanol conditions has been investigated by means of in situ X-ray total scattering and pair distribution function (PDF) analysis. The metal complex structures of two different platinum precursor solutions, chloroplatinic acid and Pt(acac)$_2$ (acac=acetylacetonate) provide atomic-scale detail about the nucleation mechanisms after initiation of the reaction with Pb(acac)$_2$ by heating. The stronger Pt−O chemical bonding in the Pt(acac)$_2$ precursor complex compared with the Pt−Cl bonding in the chloroplatinic acid precursor complex leads to a much slower reduction of the Pt center, and this allows more optimal co-reduction conditions providing a pathway for formation of phase-pure intermetallic PtPb product. The matching chemistry of the Pt(acac)$_2$ and Pb(acac)$_2$ precursors allow development of a facile continuous flow supercritical ethanol process for obtaining phase-pure hexagonal PtPb nanocrystals. The study thus highlights the importance of in situ studies in revealing atomic-scale information about nucleation mechanisms, which can be used in design of specific synthesis pathways, and the new continuous-flow process to obtain PtPb nanocrystals holds potential for large-scale production

High-Performance Low-Cost n-Type Se-Doped Mg3Sb2-Based Zintl Compounds for Thermoelectric Application

Thermoelectric materials, capable of converting heat directly into electricity without moving parts, provide a promising solid-state solution for waste heat harvesting. However, currently available commercial thermoelectric materials PbTe and Bi2Te3 are based on tellurium, an extremely scarce and expensive element, which prohibits large scale applications. Herein, we present a systematic study on a new low-cost Te-free material, n-type Se-doped Mg3Sb1.5Bi0.5, by combining the structure and property characterization with electronic structure and electrical transport modeling. Compared with pure Mg3Sb2, Se-doped Mg3Sb1.5Bi0.5 shows the considerably enhanced power factor as well as much lower thermal conductivity. The excellent electrical transport originates from a nontrivial near-edge conduction band with six conducting carrier pockets and a light conductivity effective mass as well as the weak contribution from a secondary conduction band with a valley degeneracy of 2. The accurate location of the conduction band minimum is revealed from the Fermi surface, which appears to be crucial for the understanding of the electronic transport properties. In addition, the total thermal conductivity is found to be reasonably low (∼0.62 W m-1 K-1 at 725 K). As a result, an optimal zT of 1.23 at 725 K is obtained in Mg3.07Sb1.5Bi0.48Se0.02. The high zT, as well as the earth-abundant constituent elements, makes the low-cost Se-doped Mg3Sb1.5Bi0.5 a promising candidate for the intermediate-temperature thermoelectric application. Moreover, the systematic electronic structure and transport modeling provide an insightful guidance for the further optimization of this material and other related Zintl compounds

Low-Barrier Hydrogen Bonds in Negative Thermal Expansion Material H 3 [Co(CN) 6 ]

The covalent nature of the low-barrier N−H−N hydrogen bonds in the negative thermal expansion material H 3 [Co(CN) 6 ] has been established by using a combination of X-ray and neutron diffraction electron density analysis and theoretical calculations. This finding explains why negative thermal expansion can occur in a material not commonly considered to be built from rigid linkers. The pertinent hydrogen atom is located symmetrically between two nitrogen atoms in a double-well potential with hydrogen above the barrier for proton transfer, thus forming a low-barrier hydrogen bond. Hydrogen is covalently bonded to the two nitrogen atoms, which is the first experimentally confirmed covalent hydrogen bond in a network structure. Source function calculations established that the present N−H−N hydrogen bond follows the trends observed for negatively charge-assisted hydrogen bonds and low-barrier hydrogen bonds previously established for O−H−O hydrogen bonds. The bonding between the cobalt and cyanide ligands was found to be a typical donor–acceptor bond involving a high-field ligand and a transition metal in a low-spin configuration

Supercritical flow synthesis of Pt1-xRux nanoparticles: comparative phase diagram study of nanostructure versus bulk

The thermodynamic stability of nanocrystals is different from that of bulk systems, and nanoscale phase diagrams are to a large degree unknown. Here we present a systematic investigation of the Pt1–xRux phase diagram through supercritical flow synthesis of Pt1–xRux nanoparticles across the entire compositional range. The synthesis was done in stoichiometric steps of 0.1 using an ethanol–toluene mixture as solvent at 450 °C and 200 bar. The products were characterized by high-resolution synchrotron powder X-ray diffraction, transmission electron microscopy, and elemental mapping of individual particles using energy-dispersive X-ray spectroscopy. The diffraction data revealed a single-phase face-centered cubic (fcc) alloy for x ≤ 0.2, while an additional hexagonal close-packed (hcp) phase emerges as x approaches 1. This behavior deviates significantly from the bulk phase diagram, where a biphasic region is only observed for 0.62 < x < 0.8. Thus, compositional design of Pt–Ru alloys is more flexible on the nanoscale, opening up significant possibilities for catalyst optimization. Rietveld refinements and microstructural line profile analysis show that the fcc unit cell dimensions follow Vegard’s law within a good approximation. On the other hand, crystallite size, microstrain, phase content, and hcp c/a ratio depend nonlinearly on x but show some correlation to the bulk phase diagram. Elemental mapping shows the nanoparticles to be homogeneous, but in some cases, fcc–hcp phase boundaries and modulations in the elemental distribution were observed. All samples below x < 0.3 exhibit a spherical morphology. At higher ruthenium content, x ≥ 0.3, another morphology emerges with elongated particles together with the dominating spherical mophology. The TEM average particle sizes range from 5.0(8) to 10.4(7) nm

Copper doped TiO2 nanoparticles characterized by X-ray absorption spectroscopy, total scattering, and powder diffraction - a benchmark structure-property study

Metal functionalized nanoparticles potentially have improved properties e. g. in catalytic applications, but their precise structures are often very challenging to determine. Here we report a structural benchmark study based on tetragonal anatase TiO2 nanoparticles containing 0-2 wt% copper. The particles were synthesized by continuous flow synthesis under supercritical water-isopropanol conditions. Size determination using synchrotron PXRD, TEM, and X-ray total scattering reveals 5-7 nm monodisperse particles. The precise dopant structure and thermal stability of the highly crystalline powders were characterized by X-ray absorption spectroscopy and multi-temperature synchrotron PXRD (300-1000 K). The combined evidence reveals that copper is present as a dopant on the particle surfaces, most likely in an amorphous oxide or hydroxide shell. UV-VIS spectroscopy shows that copper presence at concentrations higher than 0.3 wt% lowers the band gap energy. The particles are unaffected by heating to 600 K, while growth and partial transformation to rutile TiO2 occur at higher temperatures. Anisotropic unit cell behavior of anatase is observed as a consequence of the particle growth (a decreases and c increases)