Polyoxometalate (POM)-layered double hydroxides (LDH) composite materials: design and catalytic applications

Layered double hydroxides (LDHs) are an important large class of two-dimensional (2D) anionic lamellar materials that possess flexible modular structure, facile exchangeability of inter-lamellar guest anions and uniform distribution of metal cations in the layer. Owing to the modular accessible gallery and unique inter-lamellar chemical environment, polyoxometalates (POMs) intercalated with LDHs has shown a vast array of physical properties with applications in environment, energy, catalysis, etc. Here we describe how polyoxometalate clusters can be used as building components for the construction of systems with important catalytic properties. This review article mainly focuses on the discussion of new synthetic approaches developed recently that allow the incorporation of the element of design in the construction of a fundamentally new class of materials with pre-defined functionalities in catalytic applications. Introducing the element of design and taking control over the finally observed functionality we demonstrate the unique opportunity for engineering materials with modular properties for specific catalytic applications

Self-assembly in polyoxometalate and metal coordination-based systems: synthetic approaches and developments

Utilizing new experimental approaches and gradual understanding of the underlying chemical processes has led to advances in the self-assembly of inorganic and metal–organic compounds at a very fast pace over the last decades. Exploitation of unveiled information originating from initial experimental observations has sparked the development of new families of compounds with unique structural characteristics and functionalities. The main source of inspiration for numerous research groups originated from the implementation of the design element along with the discovery of new chemical components which can self-assemble into complex structures with wide range of sizes, topologies and functionalities. Not only do self-assembled inorganic and metal–organic chemical systems belong to families of compounds with configurable structures, but also have a vast array of physical properties which reflect the chemical information stored in the various “modular” molecular subunits. The purpose of this short review article is not the exhaustive discussion of the broad field of inorganic and metal–organic chemical systems, but the discussion of some representative examples from each category which demonstrate the implementation of new synthetic approaches and design principles

From Micro to Macro: Uncovering and Predicting Information Cascading Process with Behavioral Dynamics

Cascades are ubiquitous in various network environments. How to predict these cascades is highly nontrivial in several vital applications, such as viral marketing, epidemic prevention and traffic management. Most previous works mainly focus on predicting the final cascade sizes. As cascades are typical dynamic processes, it is always interesting and important to predict the cascade size at any time, or predict the time when a cascade will reach a certain size (e.g. an threshold for outbreak). In this paper, we unify all these tasks into a fundamental problem: cascading process prediction. That is, given the early stage of a cascade, how to predict its cumulative cascade size of any later time? For such a challenging problem, how to understand the micro mechanism that drives and generates the macro phenomenons (i.e. cascading proceese) is essential. Here we introduce behavioral dynamics as the micro mechanism to describe the dynamic process of a node's neighbors get infected by a cascade after this node get infected (i.e. one-hop subcascades). Through data-driven analysis, we find out the common principles and patterns lying in behavioral dynamics and propose a novel Networked Weibull Regression model for behavioral dynamics modeling. After that we propose a novel method for predicting cascading processes by effectively aggregating behavioral dynamics, and propose a scalable solution to approximate the cascading process with a theoretical guarantee. We extensively evaluate the proposed method on a large scale social network dataset. The results demonstrate that the proposed method can significantly outperform other state-of-the-art baselines in multiple tasks including cascade size prediction, outbreak time prediction and cascading process prediction.Comment: 10 pages, 11 figure

Modular polyoxometalate-layered double hydroxide composites as efficient oxidative catalysts

The exploitation of intercalation techniques in the field of two-dimensional layered materials offers unique opportunities for controlling chemical reactions in confined spaces and developing nanocomposites with desired functionality. In this paper, we demonstrate the exploitation of the novel and facile ‘one-pot’ anion-exchange method for the functionalization of layered double hydroxides (LDHs). As a proof of concept, we demonstrate the intercalation of a series of polyoxometalate (POM) clusters, Na3[PW12O40]•15H2O (Na3PW12), K6[P2W18O62]•14H2O (K6P2W18), and Na9LaW10O36•32H2O (Na9LaW10) into tris(hydroxymethyl)amino-methane (Tris) modified layered double hydroxides (LDHs) under ambient conditions without the necessity of degassing CO2. Investigation of the resultant intercalated materials of Tris-LDHs-PW12 (1), Tris-LDH-P2W18 (2), and Tris-LDH-LaW10 (3) for the degradation of methylene blue (MB), rhodamine B (RB) and crystal violet (CV) has been carried out, where Tris-LDH-PW12 reveals the best performance in the presence of H2O2. Additionally, degradation of a mixture of RB, MB and CV by Tris-LDH-PW12 follows the order of CV > MB > RB, which is directly related to the designed accessible area of the interlayer space. Also, the composite can be readily recycled and reused at least ten cycles without measurable decrease of activity

Electroweak radiative corrections to triple photon production at the ILC

In this paper, we present the precision predictions for three photon production in the standard model (SM) at the ILC including the full next-to-leading (NLO) electroweak (EW) corrections, high order initial state radiation (h.o.ISR) contributions and beamstrahlung effects. We present the LO and the NLO EW+h.o.ISR+beamstrahlung corrected total cross sections for various colliding energy when $\sqrt s \ge 200 {\rm GeV}$ and the kinematic distributions of final photons with $\sqrt s = 500 {\rm GeV}$ at ILC, and find that the NLO EW corrections, the h.o.ISR contributions and the beamstrahlung effects are important in exploring the process $e^+e^- \to \gamma\gamma\gamma$.Comment: 6 pages, 8 figures, accepted for publication in Physics Letters

Rational design of a polyoxometalate intercalated layered double hydroxide: highly efficient catalytic epoxidation of allylic alcohols under mild and solvent-free conditions

Intercalation catalysts, owing to their modular and accessible gallery and unique interlamellar chemical environment, have shown wide application in various catalytic reactions. However, the poor mass transfer between the active components of the intercalated catalysts and organic substrates is one of the challenges that limit their further application. Herein, we have developed a novel heterogeneous catalyst by intercalating the polyoxometalate (POM) of Na9LaW10O36⋅32 H2O (LaW10) into layered double hydroxides (LDHs), which have been covalently modified with ionic liquids (ILs). The intercalation catalyst demonstrates high activity and selectivity for the epoxidation of various allylic alcohols in the presence of H2O2. For example, trans-2-hexen-1-ol undergoes up to 96 % conversion and 99 % epoxide selectivity at 25 °C in 2.5 h. To the best of our knowledge, the Mg3Al−ILs−C8−LaW10 composite material constitutes one of the most efficient heterogeneous catalysts for the epoxidation of allylic alcohols (including the hydrophobic allylic alcohols with long alkyl chains) reported so far

Classical Keggin intercalated into layered double hydroxides: facile preparation and catalytic efficiency in Knoevenagel condensation reaction

The family of polyoxometalate (POM) intercalated layered double hydroxides (LDHs) composite materials has shown great promise for the design of functional materials with numerous applications. It is known that intercalation of the classical Keggin polyoxometalate (POM) of [PW12O40]3- (PW12) into layered double hydroxides (LDHs) is very unlikely to take place by conventional ion exchange methods due to spatial and geometrical restrictions. In this paper, such intercalated compound of Mg0.73Al0.22(OH)2 [PW12O40]0.04•0.98H2O (Mg3Al-PW12) has been successfully obtained by adopting a spontaneous flocculation method. The Mg3Al-PW12 has been fully characterized using a wide range of methods (XRD, SEM, TEM, XPS, EDX, XPS, FT-IR, NMR, BET). XRD patterns of Mg3Al-PW12 exhibit no impurity phase usually observed next to the (003) diffraction peak. Subsequent application of the Mg3Al-PW12 as catalyst in Knoevenagel condensation reactions of various aldehydes and ketones with Z–CH2-Z‘ type substrates (ethyl-cyanoacetate and malononitrile) at 60 oC in mixed solvents (Vi-propanol:Vwater = 2 : 1) demonstrated highly efficient catalytic activity. The synergistic effect between the acidic and basic sites of the Mg3Al-PW12 composite proved to be crucial for the efficiency of the condensation reactions. Additionally, the Mg3Al-PW12 catalysed Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate demonstrated the highest turnover number (TON) of 47980 reported so far