Dehydration for a solid coordination network based on CuII-(py)2C(OH)2 trimers

Abstract de congreso: Póster presentado en 12th International Conference on Materials Chemistry (MC12), 20 - 23 July 2015, York, United Kingdom

Metalloporphyrin-based MOFs: First Cobalt Based TPPS-bipy Coordination Network

Poster presentado en el congreso: Third International Conference on Multifunctional, Hybrid and Nanomaterials (3-7 March 2013, Sorrento, Italy)

Heterogeneous catalytic activity on Mn, Fe and Co-based metalloporphyrinic Solid Coordination Frameworks (SCFs)

Comunicación al congreso 1st European Conference on Metal Organic Frameworks and Porous Polymers, celebrado en Postdam del 11 al 14 de octubre de 2015

A coordination-based approach to elasticity of floppy and stiff random networks

We study the role of connectivity on the linear and nonlinear elastic behavior of amorphous systems using a two-dimensional random network of harmonic springs as a model system. A natural characterization of these systems arises in terms of the network coordination relative to that of an isostatic network $\delta z$; a floppy network has $\delta z<0$, while a stiff network has $\delta z>0$. Under the influence of an externally applied load we observe that the response of both floppy and rigid network are controlled by the same critical point, corresponding to the onset of rigidity. We use numerical simulations to compute the exponents which characterize the shear modulus, the amplitude of non-affine displacements, and the network stiffening as a function of $\delta z$, derive these theoretically and make predictions for the mechanical response of glasses and fibrous networks.

Construction of coordination networks with high connectivity: a new 8-connected self-penetrating network based on tetranuclear metal clusters

Two highly connected cobalt(II) and zinc(II) coordination polymers with tetranuclear metal clusters as the nodes of network have been prepared, being the first example of an 8-connected self-penetrating net based on a cross-linked alpha-Po subnet.

Design of silicone rubber according to requirements based on the multi-objective optimization of chemical reactions

The explicit expression between composition and mechanical properties of silicone rubber was derived from the physics of polymer elasticity, the implicit expression among material composition, reaction conditions and reaction efficiency was obtained from chemical thermodynamics and kinetics, and then an implicit multi-objective optimization model was constructed. Genetic algorithm was applied to optimize material composition and reaction conditions, and the finite element method of cross-linking reaction processes was used to solve multi-objective functions, on the basis of which a new optimization methodology of crosslinking reaction processes was established. Using this methodology, rubber materials can be designed according to pre-specified requirements.

Detour-Based Mobility Coordination in DTNs

Commonly, research work in routing for delay tolerant networks (DTN) assumes that node encounters are predestined, in the sense that they are the result of unknown, exogenous processes that control the mobility of these nodes. In this paper, we argue that for many applications such an assumption is too restrictive: while the spatio-temporal coordinates of the start and end points of a node's journey are determined by exogenous processes, the specific path that a node may take in space-time, and hence the set of nodes it may encounter could be controlled in such a way so as to improve the performance of DTN routing. To that end, we consider a setting in which each mobile node is governed by a schedule consisting of a ist of locations that the node must visit at particular times. Typically, such schedules exhibit some level of slack, which could be leveraged for DTN message delivery purposes. We define the Mobility Coordination Problem (MCP) for DTNs as follows: Given a set of nodes, each with its own schedule, and a set of messages to be exchanged between these nodes, devise a set of node encounters that minimize message delivery delays while satisfying all node schedules. The MCP for DTNs is general enough that it allows us to model and evaluate some of the existing DTN schemes, including data mules and message ferries. In this paper, we show that MCP for DTNs is NP-hard and propose two detour-based approaches to solve the problem. The first (DMD) is a centralized heuristic that leverages knowledge of the message workload to suggest specific detours to optimize message delivery. The second (DNE) is a distributed heuristic that is oblivious to the message workload, and which selects detours so as to maximize node encounters. We evaluate the performance of these detour-based approaches using extensive simulations based on synthetic workloads as well as real schedules obtained from taxi logs in a major metropolitan area. Our evaluation shows that our centralized, workload-aware DMD approach yields the best performance, in terms of message delay and delivery success ratio, and that our distributed, workload-oblivious DNE approach yields favorable performance when compared to approaches that require the use of data mules and message ferries.

Preferential Field Coverage Through Detour-Based Mobility Coordination

Controlling the mobility pattern of mobile nodes (e.g., robots) to monitor a given field is a well-studied problem in sensor networks. In this setup, absolute control over the nodes’ mobility is assumed. Apart from the physical ones, no other constraints are imposed on planning mobility of these nodes. In this paper, we address a more general version of the problem. Specifically, we consider a setting in which mobility of each node is externally constrained by a schedule consisting of a list of locations that the node must visit at particular times. Typically, such schedules exhibit some level of slack, which could be leveraged to achieve a specific coverage distribution of a field. Such a distribution defines the relative importance of different field locations. We define the Constrained Mobility Coordination problem for Preferential Coverage (CMC-PC) as follows: given a field with a desired monitoring distribution, and a number of nodes n, each with its own schedule, we need to coordinate the mobility of the nodes in order to achieve the following two goals: 1) satisfy the schedules of all nodes, and 2) attain the required coverage of the given field. We show that the CMC-PC problem is NP-complete (by reduction to the Hamiltonian Cycle problem). Then we propose TFM, a distributed heuristic to achieve field coverage that is as close as possible to the required coverage distribution. We verify the premise of TFM using extensive simulations, as well as taxi logs from a major metropolitan area. We compare TFM to the random mobility strategy—the latter provides a lower bound on performance. Our results show that TFM is very successful in matching the required field coverage distribution, and that it provides, at least, two-fold query success ratio for queries that follow the target coverage distribution of the field.

Multi-Objective Reactive Power Support from Wind farms for Network Performance Enhancement

This paper examines the ability of the doubly fed induction generator (DFIG) to deliver multiple reactive power objectives during variable wind conditions. The reactive power requirement is decomposed based on various control objectives (e.g. power factor control, voltage control, loss minimisation, and flicker mitigation) defined around different time frames (i.e. seconds, minutes, and hourly), and the control reference is generated by aggregating the individual reactive power requirement for each control strategy. A novel coordinated controller is implemented for the rotor-side converter and the grid-side converter considering their capability curves and illustrating that it can effectively utilise the aggregated DFIG reactive power capability for system performance enhancement. The performance of the multi-objective strategy is examined for a range of wind and network conditions, and it is shown that for the majority of the scenarios, more than 92% of the main control objective can be achieved while introducing the integrated flicker control scheme with the main reactive power control scheme. Therefore, optimal control coordination across the different control strategies can maximise the availability of ancillary services from DFIG-based wind farms without additional dynamic reactive power devices being installed in power networks.

A Coordination and Ligand Replacement Based Three-Input Colorimetric Logic Gate Sensing Platform for Melamine, Mercury Ions, and Cysteine

Discrimination of different species in various target scopes within a single sensing platform can provide many advantages such as simplicity, rapidness, and cost effectiveness. Here we design a three-input colorimetric logic gate based on the aggregation and anti-aggregation of gold nanoparticles (Au NPs) for the sensing of melamine, cysteine, and Hg2+. The concept takes advantages of the highly specific coordination and ligand replacement reactions between melamine, cysteine, Hg2+, and Au NPs. Different outputs are obtained with the combinational inputs in the logic gates, which can serve as a reference to discriminate different analytes within a single sensing platform. Furthermore, besides the intrinsic sensitivity and selectivity of Au NPs to melamine-like compounds, the “INH” gates of melamine/cysteine and melamine/Hg2+ in this logic system can be employed for sensitive and selective detections of cysteine and Hg2+, respectively.

Friedel–Crafts alkylation catalysed by GaCl3-based liquid coordination complexes

Friedel–Crafts alkylation of benzene with 1-decene was catalysed by a new family of liquid Lewis acids: liquid coordination complexes (LCCs). LCCs are prepared by mixing a metal halide (e.g. GaCl3) and a donor molecule (e.g. N,N-dimethylacetamide, urea, or trioctylphosphine oxide), with the metal halide typically used in excess. This leads to the formation of a eutectic mixture comprised of charged and neutral species in a dynamic equilibrium. GaCl3-based LCCs were used in catalytic amounts, giving high reaction rates under ambient conditions, with selectivities to 2-phenyldecane superior to those previously reported in the literature. The influence of reaction conditions and catalyst composition on the reaction rate and selectivity was investigated. Optimised reaction conditions were suggested. This exploratory study offers promise with regard to the development of safer, LCC-based alternatives to HF in industrial alkylations.

Clinopyroxene based glasses and glass-ceramics for functional applications

As piroxenas são um vasto grupo de silicatos minerais encontrados em muitas rochas ígneas e metamórficas. Na sua forma mais simples, estes silicatos são constituídas por cadeias de SiO3 ligando grupos tetrahédricos de SiO4. A fórmula química geral das piroxenas é M2M1T2O6, onde M2 se refere a catiões geralmente em uma coordenação octaédrica distorcida (Mg2+, Fe2+, Mn2+, Li+, Ca2+, Na+), M1 refere-se a catiões numa coordenação octaédrica regular (Al3+, Fe3+, Ti4+, Cr3+, V3+, Ti3+, Zr4+, Sc3+, Zn2+, Mg2+, Fe2+, Mn2+), e T a catiões em coordenação tetrahédrica (Si4+, Al3+, Fe3+). As piroxenas com estrutura monoclínica são designadas de clinopiroxenes. A estabilidade das clinopyroxenes num espectro de composições químicas amplo, em conjugação com a possibilidade de ajustar as suas propriedades físicas e químicas e a durabilidade química, têm gerado um interesse mundial devido a suas aplicações em ciência e tecnologia de materiais. Este trabalho trata do desenvolvimento de vidros e de vitro-cerâmicos baseadas de clinopiroxenas para aplicações funcionais. O estudo teve objectivos científicos e tecnológicos; nomeadamente, adquirir conhecimentos fundamentais sobre a formação de fases cristalinas e soluções sólidas em determinados sistemas vitro-cerâmicos, e avaliar a viabilidade de aplicação dos novos materiais em diferentes áreas tecnológicas, com especial ênfase sobre a selagem em células de combustível de óxido sólido (SOFC). Com este intuito, prepararam-se vários vidros e materiais vitro-cerâmicos ao longo das juntas Enstatite (MgSiO3) - diopsídio (CaMgSi2O6) e diopsídio (CaMgSi2O6) - Ca - Tschermak (CaAlSi2O6), os quais foram caracterizados através de um vasto leque de técnicas. Todos os vidros foram preparados por fusão-arrefecimento enquanto os vitro-cerâmicos foram obtidos quer por sinterização e cristalização de fritas, quer por nucleação e cristalização de vidros monolíticos. Estudaram-se ainda os efeitos de várias substituições iónicas em composições de diopsídio contendo Al na estrutura, sinterização e no comportamento durante a cristalização de vidros e nas propriedades dos materiais vitro-cerâmicos, com relevância para a sua aplicação como selantes em SOFC. Verificou-se que Foi observado que os vidros/vitro-cerâmicos à base de enstatite não apresentavam as características necessárias para serem usados como materiais selantes em SOFC, enquanto as melhores propriedades apresentadas pelos vitro-cerâmicos à base de diopsídio qualificaram-nos para futuros estudos neste tipo de aplicações. Para além de investigar a adequação dos vitro-cerâmicos à base de clinopyroxene como selantes, esta tese tem também como objetivo estudar a influência dos agentes de nucleação na nucleação em volume dos vitro-cerâmicos resultantes á base de diopsídio, de modo a qualificá-los como potenciais materiais hopedeiros de resíduos nucleares radioactivos.