Low to near-zero CO production of hydrogen from fossil fuels: critical role of microwave-initiated catalysis.

Presently, there is no single, clear route for the near-term production of the huge volumes of CO-free hydrogen necessary for the global transition to any type of hydrogen economy. All conventional routes to produce hydrogen from hydrocarbon fossil fuels (notably natural gas) involve the production-and hence the emission-of CO, most notably in the steam methane reforming (SMR) process. Our recent studies have highlighted another route; namely, the critical role played by the microwave-initiated catalytic pyrolysis, decomposition or deconstruction of fossil hydrocarbon fuels to produce hydrogen with low to near-zero CO emissions together with high-value solid nanoscale carbonaceous materials.

Highly selective upcycling of plastic mixture waste by microwave-assisted catalysis over Zn/b-ZnO.

7 billion of 9.2 billion tons of plastic produced becomes waste while conventional catalytic plastic recycling methods are vulnerable with degraded performance and intensive energy input. Here, a hybrid Zn/b-ZnO catalyst, together with the specially-designed microwave reaction system, has achieved fast plastic waste upgrading under atmospheric pressure without using H.

A review of catalytic hydrogenation of carbon dioxide: From waste to hydrocarbons.

With the rapid development of industrial society and humankind's prosperity, the growing demands of global energy, mainly based on the combustion of hydrocarbon fossil fuels, has become one of the most severe challenges all over the world. It is estimated that fossil fuel consumption continues to grow with an annual increase rate of 1.3%, which has seriously affected the natural environment through the emission of greenhouse gases, most notably carbon dioxide (CO).

Size-Dependent Microwave Heating and Catalytic Activity of Fine Iron Particles in the Deep Dehydrogenation of Hexadecane.

Knowledge of the electromagnetic microwave radiation-solid matter interaction and ensuing mechanisms at active catalytic sites will enable a deeper understanding of microwave-initiated chemical interactions and processes, and will lead to further optimization of this class of heterogeneous catalysis. Here, we study the fundamental mechanism of the interaction between microwave radiation and solid Fe catalysts and the deep dehydrogenation of a model hydrocarbon, hexadecane. We find that the size-dependent electronic transition of particulate Fe metal from a microwave "reflector" to a microwave "absorber" lies at the heart of efficient metal catalysis in these heterogeneous processes.

Catalytic Activity of Various Carbons during the Microwave-Initiated Deep Dehydrogenation of Hexadecane.

Carbon materials have been widely used as microwave susceptors in many chemical processes because they are highly effective at transforming incoming electromagnetic energy for local (hot spot) heating. This property raises the intriguing possibility of using the all-pervasive carbonaceous deposits in operating heterogeneous catalytic processes to augment the catalytic performance of microwave-initiated reactions. Here, the catalytic activities of a range of carbon materials, together with carbon residues produced from a "test" reaction-the dehydrogenation of hexadecane under microwave-initiated heterogeneous catalytic processes, have been investigated.

Decarbonising energy: The developing international activity in hydrogen technologies and fuel cells.

Hydrogen technologies and fuel cells offer an alternative and improved solution for a decarbonised energy future. Fuel cells are electrochemical converters; transforming hydrogen (or energy sources containing hydrogen) and oxygen directly into electricity. The hydrogen fuel cell, invented in 1839, permits the generation of electrical energy with high efficiency through a non-combustion, electrochemical process and, importantly, without the emission of CO at its point of use.

Sustainable chemical processing of flowing wastewater through microwave energy.

Iron oxide nanostructured catalysts have emerged as potential candidates for efficient energy conversion and electrochemical energy storage devices. However, synthesis and design of nanomaterial plays a key role in its performance and efficiency. Herein, we describe a one-pot solution combustion synthesis (SCS) of α-FeO with glycine as a fuel, and a subsequent reduction step to produce iron-containing catalysts (i.

Superalkali-Alkalide Interactions and Ion Pairing in Low-Polarity Solvents.

The nature of anionic alkali metals in solution is traditionally thought to be "gaslike" and unperturbed. In contrast to this noninteracting picture, we present experimental and computational data herein that support ion pairing in alkalide solutions. Concentration dependent ionic conductivity, dielectric spectroscopy, and neutron scattering results are consistent with the presence of superalkali-alkalide ion pairs in solution, whose stability and properties have been further investigated by DFT calculations.

Transforming carbon dioxide into jet fuel using an organic combustion-synthesized Fe-Mn-K catalyst.

With mounting concerns over climate change, the utilisation or conversion of carbon dioxide into sustainable, synthetic hydrocarbons fuels, most notably for transportation purposes, continues to attract worldwide interest. This is particularly true in the search for sustainable or renewable aviation fuels. These offer considerable potential since, instead of consuming fossil crude oil, the fuels are produced from carbon dioxide using sustainable renewable hydrogen and energy.

Metals and non-metals in the periodic table.

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.

The periodic law of the chemical elements: '' [1].

The historical roots, the discovery and the modern relevance of Dmitri Mendeleev's remarkable advance have been the subject of numerous scholarly works. Here, with a brief overview, we hope to provide a link into the contents of this special issue honouring the great scientist. Mendeleev's advance, announced in March 1869, as he put it in 1889, to the '…', first set out the very basis of the periodic law of the chemical elements, the natural relation between the properties of the elements and their atomic weights.

Facile reductive synthesis of both nitrogen deficient and protonated g-CN nanosheets for the synergistic enhancement of visible-light H evolution.

A new strategy is reported here to synthesize both nitrogen deficient and protonated graphitic carbon nitride (g-CN) nanosheets by the conjoint use of NHCl as a dynamic gas template together with hypophosphorous acid (HPO) as a doping agent. The NHCl treatment allows for the scalable production of protonated g-CN nanosheets. With the corresponding co-addition of HPO, nitrogen vacancies, accompanied by both additional protons and interstitially-doped phosphorus, are introduced into the g-CN framework, and the electronic bandgap of g-CN nanosheets as well as their optical properties and hydrogen-production performance can be precisely tuned by careful adjustment of the HPO treatment.

Solvation of Na in the Sodide Solution, LiNa?10MeNH.

Alkalides, the alkali metals in their ?1 oxidation state, represent some of the largest and most polarizable atomic species in condensed phases. This study determines the solvation environment around the sodide anion, Na, in a system of co-solvated Li. We present isotopically varied total neutron scattering experiments alongside empirical potential structure refinement and ab initio molecular dynamics simulations for the alkali?alkalide system, LiNa?10MeNH.

Rapid, non-invasive characterization of the dispersity of emulsions microwaves.

A rapid and non-invasive method to determine the dispersity of emulsions is developed based on the interrelationship between the droplet size distribution and the dielectric properties of emulsions. A range of water-in-oil emulsions with different water contents and droplet size distributions were analysed using a microwave cavity perturbation technique together with dynamic light scattering. The results demonstrate that the dielectric properties, as measured by non-invasive microwave cavity analysis, can be used to characterise the dispersity of emulsions, and is also capable of characterizing heavy oil emulsions.

Defining the flexibility window in ordered aluminosilicate zeolites.

The flexibility window in zeolites was originally identified using geometric simulation as a hypothetical property of SiO systems. The existence of the flexibility window in hypothetical structures may help us to identify those we might be able to synthesize in the future. We have previously found that the flexibility window in silicates is connected to phase transitions under pressure, structure amorphization and other physical behaviours and phenomena.

Rapid Production of High-Purity Hydrogen Fuel through Microwave-Promoted Deep Catalytic Dehydrogenation of Liquid Alkanes with Abundant Metals.

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 production. The high intrinsic hydrogen content of liquid-range alkane hydrocarbons (including diesel) offers a potential route to CO -free hydrogen production through their catalytic deep dehydrogenation.

Hydrogen bonds between methanol and the light liquid olefins 1-pentene and 1-hexene: from application to fundamental science.

We have recently developed a new extraction process for significantly reducing the olefin content in commercial FCC gasoline. To gain insights into the origins of this process, we have investigated the dissolution of the light liquid olefins 1-pentene and 1-hexene in methanol through computer modelling together with NMR spectroscopy. We find two important hydrogen bonding modes for methanol olefin interactions - namely, O-Hπ and C-HO.

Electron Solvation and the Unique Liquid Structure of a Mixed-Amine Expanded Metal: The Saturated Li-NH -MeNH System.

Metal-amine solutions provide a unique arena in which to study electrons in solution, and to tune the electron density from the extremes of electrolytic through to true metallic behavior. The existence and structure of a new class of concentrated metal-amine liquid, Li-NH -MeNH , is presented in which the mixed solvent produces a novel type of electron solvation and delocalization that is fundamentally different from either of the constituent systems. NMR, ESR, and neutron diffraction allow the environment of the solvated electron and liquid structure to be precisely interrogated.

Intrinsic flexibility of porous materials; theory, modelling and the flexibility window of the EMT zeolite framework.

Framework materials have structures containing strongly bonded polyhedral groups of atoms connected through their vertices. Typically the energy cost for variations of the inter-polyhedral geometry is much less than the cost of distortions of the polyhedra themselves - as in the case of silicates, where the geometry of the SiO4 tetrahedral group is much more strongly constrained than the Si-O-Si bridging angle. As a result, framework materials frequently display intrinsic flexibility, and their dynamic and static properties are strongly influenced by low-energy collective motions of the polyhedra.

Methanol-to-hydrocarbons conversion over MoO/H-ZSM-5 catalysts prepared lower temperature calcination: a route to tailor the distribution and evolution of promoter Mo species, and their corresponding catalytic properties.

A series of MoO/H-ZSM-5 (Si/Al = 25) catalysts were prepared calcination at a lower-than-usual temperature (400 °C) and subsequently evaluated in the methanol-to-hydrocarbon reaction at that same temperature. The catalytic properties of those catalysts were compared with the sample prepared at the more conventional, higher temperature of 500 °C. For the lower temperature preparations, molybdenum oxide was preferentially dispersed over the zeolite external surface, while only the higher loading level of MoO (7.

Origins of conductivity improvement in fluoride-enhanced silicon doping of ZnO films.

Fluoride in spray pyrolysis precursor solutions for silicon-doped zinc oxide (SiZO) transparent conductor thin films significantly improves their electrical conductivity by enhancing silicon doping efficiency and not, as previously assumed, by fluoride doping. Containing only earth-abundant elements, SiZO thus prepared rivals the best solution-processed indium-doped ZnO in performance.

Superconductivity in transition metals.

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.

On the occurrence of metallic character in the periodic table of the chemical elements.

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.