Advancing MXene Electrocatalysts for Energy Conversion Reactions: Surface,Stoichiometry, and Stability

MXenes, due to their tailorable chemistry and favourable physical properties, have great promise in electrocatalytic energy conversion reactions. To exploit fully their enormous potential, further advances specific to electrocatalysis revolving around their performance, stability, compositional discovery and synthesis are required. The most recent advances in these aspects are discussed in detail: surface functional and stoichiometric modifications which can improve performance, Pourbaix stability related to their electrocatalytic operating conditions, density functional theory and advances in machine learning for their discovery, and prospects in large scale synthesis and solution processing techniques to produce membrane electrode assemblies and integrated electrodes. This Review provides a perspective that is complemented by new density functional theory calculations which show how these recent advances in MXene material design are paving the way for effective electrocatalysts required for the transition to integrated renewable energy systems.     

Three‐dimensional finite element modelling of coupled free/porous flows: applications to industrial and environmental flows

Conjunctive modelling of free/porous flows provides a powerful and cost‐effective tool for designing industrial filters used in the process industry and also for quantifying surface–subsurface flow interactions, which play a significant role in urban flooding mechanisms resulting from sea‐level rise and climate changes. A number of well‐established schemes are available in the literature for simulation of such regimes; however, three‐dimensional (3D) modelling of such flow systems still presents numerical and practical challenges. This paper presents the development of a fully 3D, transient finite element model for the prediction and quantitative analyses of the hydrodynamic behaviour encountered in industrial filtrations and environmental flows represented by coupled flows. The weak‐variational formulation in this model is based on the use of C⁰ continuous equal‐order Lagrange polynomial functions for velocity and pressure fields represented by 3D hexahedral finite elements. A mixed UVWP finite element scheme based on the standard Galerkin technique satisfying the Ladyzhenskaya–Babuska–Brezzi stability criterion through incorporation of an artificial compressibility term in the continuity equation has been employed for the solution of coupled partial differential equations. We prove that the discretization generates unified stabilization for both the Navier–Stokes and Darcy equations and preserves the geometrical flexibility of the computational grids. A direct node‐linking procedure involving the rearrangement of the global stiffness matrix for the interface elements has been developed by the authors, which is utilized to couple the governing equations in a single model. A variety of numerical tests are conducted, indicating that the model is capable of yielding theoretically expected and accurate results for free, porous and coupled free/porous problems encountered in industrial and environmental engineering problems representing complex filtration (dead‐end and cross‐flow) and interacting surface–subsurface flows. The model is computationally cost‐effective, robust, reliable and easily implementable for practical design of filtration equipments, investigation of land use for water resource availability and assessment of the impacts of climatic variations on environmental catastrophes (i.e. coastal and urban floods). The model developed in this work results from the extension of a multi‐disciplinary project (AEROFIL) primarily sponsored by the European aerospace industries for development of a computer simulation package (Aircraft Cartridge Filter Analysis Modelling Program), which was successfully utilized and deployed for designing hydraulic dead‐end filters used in Airbus A380.Copyright © 2012 John Wiley & Sons, Ltd.     

Dopant-site occupancies and superconducting properties of the Fe-substituted La2.5Nd0.5CaBa3(Cu1−xFex)7Oz perovskite

The structural and superconducting properties of single-phase Fe-substituted La_2.5Nd_0.5CaBa₃(Cu_1−xFe_x)₇O_z (LNCBCuFe) with 0.0x0.06 compounds having triple-perovskite structure are investigated using X-ray diffraction, a.c. susceptibility, d.c. magnetization, oxygen content and Mössbauer effect measurements. Mössbauer spectral analysis of x=0.03 sample displays unusual Fe-dopant site occupancies and the Cu(2) plane to Cu(1) chain site ratio in the LNCBCuFe are quite different from those of the usual Fe-doped YBa₂Cu₃O_7−δ. Specifically, we observe substantial occupation of a new chain-associated quasi-octahedral site, E, at 300 K which transforms into the well-known distorted tetrahedron chain site, A, on lowering the temperature to 78 K. The observed reduction of T_c with increasing x in LNCBCuFe supports the view that the hole filling mechanism contributes predominantly to the suppression of superconductivity by Fe.     

Obtaining functional form for chaotic time series evolution using genetic algorithm

A genetic algorithm (GA) based strategy is presented for deducing an exact or near-exact functional form from a time series. The GA formalism proposed here utilizes (i) the "postfix" representation with a view to reduce the procedural complexities and (ii) the "elitist mating" scheme to produce fitter offspring strings. The GA procedure is exemplified by considering chaotic time series of the well-known logistic, Henon and universal maps. The GA correctly recovers the underlying functional forms for the respective time series. Measurements from a number of finite-dimensional physical, biological, and other systems often give rise to complex time series and the presented methodology should prove useful in obtaining functional forms describing accurately the evolution of the time series. (c) 1999 American Institute of Physics.     

A fluctuation theory for Markov chains

A fluctuation theory for Markov chains on an ordered countable state space is developed, using ladder processes. These are shown to be Markov renewal processes. Results are given for the joint distribution of the extremum (maximum or minimum) and the first time the extremum is achieved. Also a new classification of the states of a Markov chain is suggested. Two examples are given.     

Photoluminescence of SrS: Cu phosphors

Results of the investigation on the spectral characteristics of PL of SrS:Cu phosphors are presented. Probable emitters for the three observed bands, viz. 4710 Å, 5200 Å and 5480 Å, have been suggested.     

Integer programming formulations of vehicle routing problems

Various mathematical formulations are available for situations represented by vehicle routing problems. The assignment-based integer programming formulations of these problems are more common and easy to understand. Such formulations are discussed in this paper and a much simpler formulation for the vechicle routing problem is presented for the case, when all the vehicles have the same load capacity and maximum allowable cost per route.     

Tests of a “free-volume” model of gas permeation through polymer membranes. I. Pure CO2, CH4, C2H4, and C3H8 in polyethylene

Permeability coefficients have been measured for CO₂, CH₄, C₂H₄, and C₃H₈ in polyethylene membranes at temperatures of 5, 20, and 35°C and at applied gas pressures of up to 30 atm. The temperature and pressure dependence of the permeability coefficients was represented satisfactorily by an extension of Fujita's free-volume model of diffusion of small molecules in polymers. The results of the present steady-state permeability measurements provide further support for the conclusion reached from previous unsteady-state diffusivity measurements that Fujita's model is applicable to the transport of small molecules, such as CO₂, CH₄, C₂H₄, and C₃H₈, in polyethylene. It was previously thought that this model is applicable only to the transport of larger molecules, such as of organic vapors, in polymers.     

Positron annihilation in annealed and quenched teflon and in sulphur

The value (τ₂) and the intensity (I₂) of the delayed component in the lifetime spectra of positrons annihilating in annealed and quenched teflon and in sulphur and crystex (polymer sulphur), at room temperature and at 77° K are reported. These data and the X-ray diffraction patterns for these materials are discussed in terms of the free volume model for the formation and quenching of positronium atoms in molecular materials.     

Analytical application of DHOA for the determination of trace metallic constituents in U based fuel materials by ICP-AES

DHOA (Di-n-hexyl-octanamide) is one of the alternative extractants to TBP (tri-n-butyl phosphate) known for the extraction of uranium from moderate nitric acid medium without significant extraction of the fission products. Analytical application of DHOA was explored to develop a methodology for determination of trace metallic constituents in uranium based nuclear materials. This involved the separation of uranium matrix by 1.1 M DHOA-dodecane followed by the analysis of the raffinate for trace constituents by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). A systematic study showed that four contacts of 1.1 M DHOA-dodecane were required for quantitative extraction of U from 4 M HNO₃ feed for the sample size of 1 g in 10 mL. The feasibility of using DHOA for extraction of U from trace metallic constituents in U based fuel materials without losing trace quantities of analytes of interest was studied by using synthetic samples after appropriate spiking of common impurities and critical elements at their required specification limits (common elements—5 ppm, critical elements—1 ppm). A systematic study was carried out to compare the analytical performance of DHOA with TBP, which revealed that DHOA could successfully be employed for the determination of 19 trace constituents with lower estimation limits of 5 ppm for common impurities and 1 ppm for critical elements.