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The demarcation of the chemical elements into metals and non-metals dates back to the dawn of Dmitri Mendeleev's construction of the periodic table; it still represents the cornerstone of our view of modern chemistry. In this contribution, a particular emphasis will be attached to the question 'Why do the chemical elements of the periodic table exist either as metals or non-metals under ambient conditions?' This is perhaps most apparent in the p-block of the periodic table where one sees an almost-diagonal line separating metals and non-metals. The first searching, quantum-mechanical considerations of this question were put forward by Hund in 1934. Interestingly, the very first discussion of the problem--in fact, a prequantum- mechanical approach--was made earlier, by Goldhammer in 1913 and Herzfeld in 1927. Their simple rationalization, in terms of atomic properties which confer metallic or non-metallic status to elements across the periodic table, leads to what is commonly called the Goldhammer-Herzfeld criterion for metallization. For a variety of undoubtedly complex reasons, the Goldhammer-Herzfeld theory lay dormant for close to half a century. However, since that time the criterion has been repeatedly applied, with great success, to many systems and materials exhibiting non-metal to metal transitions in order to predict, and understand, the precise conditions for metallization. Here, we review the application of Goldhammer-Herzfeld theory to the question of the metallic versus non-metallic status of chemical elements within the periodic system. A link between that theory and the work of Sir Nevill Mott on the metal-non-metal transition is also highlighted. The application of the 'simple', but highly effective Goldhammer-Herzfeld and Mott criteria, reveal when a chemical element of the periodic table will behave as a metal, and when it will behave as a non-metal. The success of these different, but converging approaches, lends weight to the idea of a simple, universal criterion for rationalizing the instantly-recognizable structure of the periodic table where . . . the metals are here, the non-metals are there . . . The challenge of the metallic and non-metallic states of oxides is also briefly introduced. [ABSTRACT FROM AUTHOR]

We report a detailed investigation of the charge carrier transport in polycrystalline n-type impurity-doped zinc oxide (ZnO) thin films grown by spray pyrolysis over a wide range of carrier concentrations. Particular attention is devoted to a study of the composition-dependent metal-insulator transition (MIT) in this transparent conducting oxide (TCO). In order to describe the flow of electrons in these impurity-doped thin films over this full range of conditions, it is necessary to consider multiple electronic conduction processes. The first conduction process arises from current carriers thermally excited from impurity states into the (host) ZnO conduction band. The second involves thermally-activated, quantum-mechanical tunnelling within an impurity band located close to the host conduction band. The latter conduction process predominates at low temperatures whilst the former dominates at high temperatures. We find that a MIT occurs at a critical carrier concentration between 2 and 6 × 1019 cm-3. At higher concentrations in this metallic regime, the impurity band merges with the ZnO conduction band. The location of the MIT was determined from low temperature resistivity data and the results are discussed in terms of the Mott and Ioffe-Regel models. In addition, the overriding importance of grain boundaries is highlighted for these polycrystalline thin films; this is a key factor in determining and limiting electronic conduction in these samples, particularly at high temperatures. These results highlight the practical importance of understanding both the MIT and also grain boundary effects in determining the electrical performance of polycrystalline TCO films. [ABSTRACT FROM AUTHOR]

Microwave dielectric heating is an emerging technology in heterogeneous catalysis. However, catalyst design in this field is not as well developed as when conventional heating is used. In this study the selective oxidation of propene to acrolein has been used as a model reaction to understand the how the properties of bismuth mixed metal oxide catalysts can be tuned for use in microwave assisted catalysis. The role of the dielectric properties, that are crucial to enable the catalyst to be heated in the microwave electric field, were determined using cavity perturbation methods. Catalysts with a very high loss tangent reached high temperatures leading to combustion products, whereas materials with a low loss tangent could not be heated and were inactive. Bi2MoO6 and BiVO4 both showed promising performance during an initial screening and were investigated further. For Bi2MoO6, a partial substitution of molybdenum with vanadium resulted in the formation of Bi1−X/3V1−xMoxO4, with a decrease in particle size and dielectric loss tangent, and the highest rate of acrolein production was found when x=0.6 at 15 W microwave power. Higher microwave power resulted in thermal runaway which decreased the activity of the catalyst. [ABSTRACT FROM AUTHOR]

The demarcation of the chemical elements into metals and non-metals dates back to the dawn of Dmitri Mendeleev's construction of the periodic table; it still represents the cornerstone of our view of modern chemistry. In this contribution, a particular emphasis will be attached to the question 'Why do the chemical elements of the periodic table exist either as metals or non-metals under ambient conditions?' This is perhaps most apparent in the p-block of the periodic table where one sees an almost-diagonal line separating metals and non-metals. The first searching, quantum-mechanical considerations of this question were put forward by Hund in 1934. Interestingly, the very first discussion of the problem-in fact, a pre-quantum-mechanical approach-was made earlier, by Goldhammer in 1913 and Herzfeld in 1927. Their simple rationalization, in terms of atomic properties which confer metallic or non-metallic status to elements across the periodic table, leads to what is commonly called the Goldhammer-Herzfeld criterion for metallization. For a variety of undoubtedly complex reasons, the Goldhammer-Herzfeld theory lay dormant for close to half a century. However, since that time the criterion has been repeatedly applied, with great success, to many systems and materials exhibiting non-metal to metal transitions in order to predict, and understand, the precise conditions for metallization. Here, we review the application of Goldhammer-Herzfeld theory to the question of the metallic versus non-metallic status of chemical elements within the periodic system. A link between that theory and the work of Sir Nevill Mott on the metal-non-metal transition is also highlighted. The application of the 'simple', but highly effective Goldhammer-Herzfeld and Mott criteria, reveal when a chemical element of the periodic table will behave as a metal, and when it will behave as a non-metal. The success of these different, but converging approaches, lends weight to the idea of a simple, universal criterion for rationalizing the instantly-recognizable structure of the periodic table where … the metals are here, the non-metals are there … The challenge of the metallic and non-metallic states of oxides is also briefly introduced. This article is part of the theme issue 'Mendeleev and the periodic table'.

Hydrogen as an energy carrier promises a sustainable energy revolution. However, one of the greatest challenges for any future hydrogen economy is the necessity for large scale hydrogen production not involving concurrent CO 2 production. The high intrinsic hydrogen content of liquid-range alkane hydrocarbons (including diesel) offers a potential route to CO 2 -free hydrogen production through their catalytic deep dehydrogenation. We report here a means of rapidly liberating high-purity hydrogen by microwave-promoted catalytic dehydrogenation of liquid alkanes using Fe and Ni particles supported on silicon carbide. A H 2 production selectivity from all evolved gases of some 98 %, is achieved with less than a fraction of a percent of adventitious CO and CO 2 . The major co-product is solid, elemental carbon., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A qualitative account of the occurrence and magnitude of superconductivity in the transition metals is presented, with a primary emphasis on elements of the first row. Correlations of the important parameters of the Bardeen-Cooper-Schrieffer theory of superconductivity are highlighted with respect to the number of d-shell electrons per atom of the transition elements. The relation between the systematics of superconductivity in the transition metals and the periodic table high-lights the importance of short-range or chemical bonding on the remarkable natural phenomenon of superconductivity in the chemical elements. A relationship between superconductivity and lattice instability appears naturally as a balance and competition between localized covalent bonding and so-called broken covalency, which favours d-electron delocalization and superconductivity. In this manner, the systematics of superconductivity and various other physical properties of the transition elements are related and unified., (© 2015 The Author(s) Published by the Royal Society. All rights reserved.)

The classification of a chemical element as either 'metal' or 'non-metal' continues to form the basis of an instantly recognizable, universal representation of the periodic table (Mendeleeff D. 1905 The principles of chemistry, vol. II, p. 23; Poliakoff M. & Tang S. 2015 Phil. Trans. R. Soc. A 373: , 20140211). Here, we review major, pre-quantum-mechanical innovations (Goldhammer DA. 1913 Dispersion und Absorption des Lichtes; Herzfeld KF. 1927 Phys. Rev. 29: , 701-705) that allow an understanding of the metallic or non-metallic status of the chemical elements under both ambient and extreme conditions. A special emphasis will be placed on recent experimental advances that investigate how the electronic properties of chemical elements vary with temperature and density, and how this invariably relates to a changing status of the chemical elements. Thus, the prototypical non-metals, hydrogen and helium, becomes metallic at high densities; and the acknowledged metals, mercury, rubidium and caesium, transform into their non-metallic forms at low elemental densities. This reflects the fundamental fact that, at temperatures above the absolute zero of temperature, there is therefore no clear dividing line between metals and non-metals. Our conventional demarcation of chemical elements as metals or non-metals within the periodic table is of course governed by our experience of the nature of the elements under ambient conditions. Examination of these other situations helps us to examine the exact divisions of the chemical elements into metals and non-metals (Mendeleeff D. 1905 The principles of chemistry, vol. II, p. 23)., (© 2015 The Author(s) Published by the Royal Society. All rights reserved.)