Metal oxide, Mixed oxide, and hybrid metal@oxide nanocrystals : size-and shape-controlled synthesis and catalytic applications

Le contrôle de la taille et de la morphologie de nanocristaux d’oxydes métalliques simples, d’oxydes mixtes et d’oxydes métalliques hybrides est un sujet de grand intérêt. La dépendance de leur propriétés physio-chimiques avec leurs taille et morphologies, génèrent une variété de leur applications dans plusieurs domaines. Cependant, le dévellopement des nanocristaux en controllant la taille, la forme, l’assemblage et l’homogénéité de la composition chimique pour l’optimisation de propriété spécifiques demandent la combinaison de nombreux parametres de synthèse. Les trois différentes approches ont été développées dans le cadre de la thèse pour la synthèse d’une variété de nouveaux nanomatériaux d’oxydes simples, d’oxydes mixtes et d’oxydes métalliques hybrides dont la taille et la forme ont été bien controllées. Ces méthodes ont été nommées comme des méthodes solvo-hydrothermiques assistées par des molécules structurantes à l’état monophasique (eau ou eau/éthanol) et à l’état biphasique (eau-toluène). Nos approches de synthèse ont permi de préparer des nanocristaux des oxydes de métaux de transition (V, Cr, Mn, Co, Ni, In), et des terres rares (Sm, Ce, La, Gd, Er, Ti, Y, Zr), ainsi que des oxydes métalliques mixtes (tungstate, orthovanadate, molybdate). Ces nanomatériaux sont sous forme colloïdale mono-dispersée qui présente une cristallinité élevée. La taille et la forme de tels nanocristaux peuvent facilement être contrôlées par une simple variation des paramètres de synthèse telle que la concentration de précurseurs, la nature de la molécule structurante, la température et le temps de réaction. A large variété de techniques a été utilisée pour la caracterisation de ces nanomatériaux telles que TEM/HRTEM, SEM, SAED, EDS, XRD, XPS, FTIR, TGA-DTA, UV-vis, photoluminescence, BET. Les propriétés catalytiques de ces matériaux ont aussi été étudiées. Dans ce travail, le contrôle de la cinétique de croissance des nucléides ainsi que le mécanisme gouvernant la forme qui conduit à la taille et la morphologie finale du nanocrystal ont été proposé. L’effet de la taille et de la forme des nanoparticules d’oxyde métallique hybrides sur les propriétés catalytiques pour la réaction d’oxydation du CO et la photo-dégradation du bleue de méthylène a été aussi étudié. Car les catalyseurs existant actuellement à base de métaux nobles sont très couteux et en plus très sensibles à l’empoisonnement par le gas H2S ou les émissions polluantes de SOx. L’activité catalytique des nanocristaux d’oxydes métallique hybrides Cu@CeO2 de formes cubiques dans l’oxydation de CO et de Ag@TiO2 de formes de ceinture dans la photo dégradation du bleue de méthylène ont montré la dépendance de la taille et la forme des nanocristaux avec leur propriétés catalytiques.The ability to finely control the size and shape of metal oxide, mixed metal oxide, hybrid metal/oxide nanocrystals has become an area of great interest, as many of their physical and chemical properties are highly dependent on morphology, and the more technological applications will be possible for their use. Large-scale synthesis of such high-quality nanocrystals is the first and key step to this area of science. A tremendous effort has recently been spent in attempt to control these novel properties through manipulation of size, shape, structure, and composition. Flexibly nanocrystal size/shape control for both monodisperse single and multiple-oxide nanomaterial systems, however, remains largely empirical and still presents a great challenge. In this dissertation, new synthetic approaches have been developed and described for the synthetic design of a series of colloidal monodisperse metal oxide, mixed metal oxide, hybrid metal-oxide nanocrystals with controlled size and shape. These materials were generally characterized using TEM/HRTEM, SEM, SAED, EDS, XRD, XPS, FTIR, TGA-DTA, UV-vis, photoluminescence, BET techniques. Effect of the size and shape of these obtained hybrid metal-oxide nanocrystals on the catalytic properties is illustrated. We have developed three different new surfactant-assistant pathways for the large-scale synthesis of three types of nanomaterials including metal oxide, mixed metal oxide, hybrid noble-metal-oxide colloidal monodisperse nanocrystals. Namely, the solvo-hydrothermal surfactant-assisted methods in one-phase (water or water/ethanol) and two-phase (water-toluene) systems were used for the synthesis of metal oxide (transition metal-V, Cr, Mn, Co, Ni, In and rare earth-Sm, Ce, La, Gd, Er, Ti, Y, Zr) and mixed metal oxide (tungstate, orthovanadate, molybdate). The seed-media growth with the assistant of bifunctional surfactant was used for the synthesis of hybrid noble metal@oxide (Ag@TiO2, (Cu or Ag)@CeO2, Au/tungstate, Ag/molybdate, etc.) nanocrystals. A significant feature of our synthetic approaches was pointed out that most resulting nanocrystal products are monodisperse, high crystallinity, uniform shape, and narrow distribution. The size and shape of such nanocrystals can be controlled easily by simple tuning the reaction parameters such as the concentration of precursors and surfactants, the nature of surfactant, the temperature and time of synthetic reaction. The prepared nanocrystals with the functional surface were used as the building blocks for the self-assembly into hierarchical mesocrystal microspheres. The effective ways how to control the growth kinetics of the nuclei and the shape-guiding mechanisms leading to the manipulation of morphology of final products were proposed. Our current approaches have several conveniences including used nontoxic and inexpensive reagents (most using inorganic metal salts as starting precursors instead of expensive and toxic metallic alkoxides or organometallics), relatively mild conditions, high-yield, and large-scale production; in some causes, water or ethanol was used as environmentally benign reaction solvent. Catalytic activity and selectivity are governed by the nature of the catalyst surface, making shaped nanocrystals ideal substrates for understanding the influence of surface structure on heterogeneous catalysis at the nanoscale. Finally, this work was concentrated on demonstration of heterogeneous catalytic activity of hybrid metal-oxide nanomaterials (Cu@CeO2, Ag@TiO2) as a typical example. We synthesized the high-crystalline titanium oxide and cerium oxide nanocrystals with control over their shape and surface chemistry in high yield via the aqueous surfactant-assist method. The novel hybrid metal-oxide nanocrystals were produced by the depositing noble metal ion (Cu, Ag, Au) precursors on the pre-synthesized oxide seeds via seed-mediated growth. The catalytic activity of these metal-oxide nanohybrids of Cu@CeO2 nanocubes for CO oxidation conversion and Ag@TiO2 nanobelts for Methylene Blue photodegradation with size/shape-dependent properties were verified

Wireless Powered Cooperative Relaying using NOMA with Imperfect CSI

The impact of imperfect channel state (CSI) information in an energy harvesting (EH) cooperative non-orthogonal multiple access (NOMA) network, consisting of a source, two users, and an EH relay is investigated in this paper. The relay is not equipped with a fixed power source and acts as a wireless powered node to help signal transmission to the users. Closed-form expressions for the outage probability of both users are derived under imperfect CSI for two different power allocation strategies namely fixed and dynamic power allocation. Monte Carlo simulations are used to numerically evaluate the effect of imperfect CSI. These results confirm the theoretical outage analysis and show that NOMA can outperform orthogonal multiple access even with imperfect CSI.Comment: 6 pages, 6 figures, accepted in IEEE GLOBECOM 2018 NOMA Worksho

RELATIONSHIP BETWEEN EROSION AND ACCUMULATION OF SEDIMENTS IN COASTAL ZONE OF BINH THUAN PROVINCE-SOUTH CENTRAL OF VIETNAM

Joint Research on Environmental Science and Technology for the Eart

Enabling non-linear energy harvesting in power domain based multiple access in relaying networks: Outage and ergodic capacity performance analysis

The Power Domain-based Multiple Access (PDMA) scheme is considered as one kind of Non-Orthogonal Multiple Access (NOMA) in green communications and can support energy-limited devices by employing wireless power transfer. Such a technique is known as a lifetime-expanding solution for operations in future access policy, especially in the deployment of power-constrained relays for a three-node dual-hop system. In particular, PDMA and energy harvesting are considered as two communication concepts, which are jointly investigated in this paper. However, the dual-hop relaying network system is a popular model assuming an ideal linear energy harvesting circuit, as in recent works, while the practical system situation motivates us to concentrate on another protocol, namely non-linear energy harvesting. As important results, a closed-form formula of outage probability and ergodic capacity is studied under a practical non-linear energy harvesting model. To explore the optimal system performance in terms of outage probability and ergodic capacity, several main parameters including the energy harvesting coefficients, position allocation of each node, power allocation factors, and transmit signal-to-noise ratio (SNR) are jointly considered. To provide insights into the performance, the approximate expressions for the ergodic capacity are given. By matching analytical and Monte Carlo simulations, the correctness of this framework can be examined. With the observation of the simulation results, the figures also show that the performance of energy harvesting-aware PDMA systems under the proposed model can satisfy the requirements in real PDMA applications.Web of Science87art. no. 81

Existence and Decay of Solutions of a Nonlinear Viscoelastic Problem with a Mixed Nonhomogeneous Condition

We study the initial-boundary value problem for a nonlinear wave equation given by u_{tt}-u_{xx}+\int_{0}^{t}k(t-s)u_{xx}(s)ds+ u_{t}^{q-2}u_{t}=f(x,t,u) , 0 < x < 1, 0 < t < T, u_{x}(0,t)=u(0,t), u_{x}(1,t)+\eta u(1,t)=g(t), u(x,0)=\^u_{0}(x), u_{t}(x,0)={\^u}_{1}(x), where \eta \geq 0, q\geq 2 are given constants {\^u}_{0}, {\^u}_{1}, g, k, f are given functions. In part I under a certain local Lipschitzian condition on f, a global existence and uniqueness theorem is proved. The proof is based on the paper [10] associated to a contraction mapping theorem and standard arguments of density. In Part} 2, under more restrictive conditions it is proved that the solution u(t) and its derivative u_{x}(t) decay exponentially to 0 as t tends to infinity.Comment: 26 page