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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 2 ). Given these recognized environmental concerns, it is imperative to develop clean technologies for converting captured CO 2 to high-valued chemicals, one of which is value-added hydrocarbons. In this article, environmental effects due to CO 2 emission are discussed and various routes for CO 2 hydrogenation to hydrocarbons including light olefins, fuel oils (gasoline and jet fuel), and aromatics are comprehensively elaborated. Our emphasis is on catalyst development. In addition, we present an outlook that summarizes the research challenges and opportunities associated with the hydrogenation of CO 2 to hydrocarbon products., (Copyright © 2022 Cui, Liu, Yao, Edwards, Xiao and Cao.)

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. In this regard, the optimal particle size of a Fe metal catalyst for highly effective microwave-initiated dehydrogenation reactions is approximately 80-120 nm, and the catalytic performance is strongly dependent on the ratio of the mean radius of Fe particles to the microwave skin depth ( r /δ) at the operating frequency. Importantly, the particle size of selected Fe catalysts will ultimately affect the basic heating properties of the catalysts and decisively influence their catalytic performance under microwave initiation. In addition, we have found that when two or more materials-present as a mechanical mixture-are simultaneously exposed to microwave irradiation, each constituent material will respond to the microwaves independently. Thus, the interaction between the two materials has been found to have synergistic effects, subsequently contributing to heating and improving the overall catalytic performance., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

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-Fe 2 O 3 with glycine as a fuel, and a subsequent reduction step to produce iron-containing catalysts (i.e., Fe 3 O 4 , Fe-Fe 3 O 4 , and Fe 0 ). The synthesized iron-based nanoparticles were investigated for methyl orange (MO) degradation through Microwave (MW) energy under continuous flow conditions. Fe-Fe 3 O 4 showed higher MO degradation efficiency than α-Fe 2 O 3 , Fe 3 O 4 and Fe 0 at low absorbed MW power (i.e. 5-80 W). The enhanced degradation efficiency is associated to the combination of higher availability of electron density and higher heating effect under MW energy. Investigation of dielectric properties showed relative dielectric loss of Fe 3 O 4 , Fe-Fe 3 O 4 , and Fe 0 as 3847, 2010, and 1952, respectively. The calculated average local temperature by the comparative analysis of MW treatment with conventional thermal (CT) treatment showed a marked thermal effect of MW-initiated MO degradation. This work highlights the potential of microwave-driven water depollution under continuous-flow processing conditions and demonstrates the positive impact that earth-abundant Fe catalyst synthesized by green SCS method can have over the treatment of wastewater., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

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. Despite the excellent microwave absorption properties observed among these various carbons, only activated carbons and graphene nanoplatelets were found to be highly effective for the microwave-initiated dehydrogenation of hexadecane. During the dehydrogenation of hexadecane on a Fe/SiC catalyst, active carbon species were formed at the early stage of the reactions but were subsequently transformed into filamentous but catalytically inert carbons that ultimately deactivated the operating catalyst., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

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. Our temperature dependent alkali metal NMR measurements reveal that the dynamics of the alkalide species is both reversible and thermally activated suggesting a complicated exchange process for the ion paired species. The results of this study go beyond a picture of alkalides being a "gaslike" anion in solution and highlight the significance of the interaction of the alkalide with its complex countercation (superalkali).

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. We report here a synthetic protocol to the fixation of carbon dioxide by converting it directly into aviation jet fuel using novel, inexpensive iron-based catalysts. We prepare the Fe-Mn-K catalyst by the so-called Organic Combustion Method, and the catalyst shows a carbon dioxide conversion through hydrogenation to hydrocarbons in the aviation jet fuel range of 38.2%, with a yield of 17.2%, and a selectivity of 47.8%, and with an attendant low carbon monoxide (5.6%) and methane selectivity (10.4%). The conversion reaction also produces light olefins ethylene, propylene, and butenes, totalling a yield of 8.7%, which are important raw materials for the petrochemical industry and are presently also only obtained from fossil crude oil. As this carbon dioxide is extracted from air, and re-emitted from jet fuels when combusted in flight, the overall effect is a carbon-neutral fuel. This contrasts with jet fuels produced from hydrocarbon fossil sources where the combustion process unlocks the fossil carbon and places it into the atmosphere, in longevity, as aerial carbon - carbon dioxide.

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 2 at its point of use. Hitherto, despite numerous efforts to exploit the obvious attractions of hydrogen technologies and hydrogen fuel cells, various challenges have been encountered, some of which are reviewed here. Now, however, given the exigent need to urgently seek low-carbon paths for humankind's energy future, numerous countries are advancing the deployment of hydrogen technologies and hydrogen fuel cells not only for transport, but also as a means of the storage of excess renewable energy from, for example, wind and solar farms. Furthermore, hydrogen is also being blended into the natural gas supplies used in domestic heating and targeted in the decarbonisation of critical, large-scale industrial processes such as steel making. We briefly review specific examples in countries such as Japan, South Korea and the People's Republic of China, as well as selected examples from Europe and North America in the utilization of hydrogen technologies and hydrogen fuel cells., (© 2020 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.)

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 '… then youthful Russian Chemical Society… ', 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. This was, and still is, the centrepiece of a historical journey for chemistry to today's position as a pre-eminent science. This article is part of the theme issue 'Mendeleev and 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. 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'.

The insatiable-and ever-growing-demand of both the developed and the developing countries for power continues to be met largely by the carbonaceous fuels comprising coal, and the hydrocarbons natural gas and liquid petroleum. We review the properties of the chemical elements, overlaid with trends in the periodic table, which can help explain the historical-and present-dominance of hydrocarbons as fuels for power generation. However, the continued use of hydrocarbons as fuel/power sources to meet our economic and social needs is now recognized as a major driver of dangerous global environmental changes, including climate change, acid deposition, urban smog and the release of many toxic materials. This has resulted in an unprecedented interest in and focus on alternative, renewable or sustainable energy sources. A major area of interest to emerge is in hydrogen energy as a sustainable vector for our future energy needs. In that vision, the issue of hydrogen storage is now a key challenge in support of hydrogen-fuelled transportation using fuel cells. The chemistry of hydrogen is itself beautifully diverse through a variety of different types of chemical interactions and bonds forming compounds with most other elements in the periodic table. In terms of their hydrogen storage and production properties, we outline various relationships among hydride compounds and materials of the chemical elements to provide some qualitative and quantitative insights. These encompass thermodynamic and polarizing strength properties to provide such background information. We provide an overview of the fundamental nature of hydrides particularly in relation to the key operating parameters of hydrogen gravimetric storage density and the desorption/operating temperature at which the requisite amount of hydrogen is released for use in the fuel cell. While we await the global transition to a completely renewable and sustainable future, it is also necessary to seek CO 2 mitigation technologies applied to the use of fossil fuels. We review recent advances in the strategy of using hydrocarbon fossil fuels themselves as compounds for the high capacity storage and production of hydrogen without any CO 2 emissions. Based on these advances, the world may end up with a hydrogen economy completely different from the one it had expected to develop; remarkably, with 'Green hydrogen' being derived directly from the hydrogen-stripping of fossil fuels. This article is part of the theme issue 'Mendeleev and the periodic table'.

A new strategy is reported here to synthesize both nitrogen deficient and protonated graphitic carbon nitride (g-C 3 N 4 ) nanosheets by the conjoint use of NH 4 Cl as a dynamic gas template together with hypophosphorous acid (H 3 PO 2 ) as a doping agent. The NH 4 Cl treatment allows for the scalable production of protonated g-C 3 N 4 nanosheets. With the corresponding co-addition of H 3 PO 2 , nitrogen vacancies, accompanied by both additional protons and interstitially-doped phosphorus, are introduced into the g-C 3 N 4 framework, and the electronic bandgap of g-C 3 N 4 nanosheets as well as their optical properties and hydrogen-production performance can be precisely tuned by careful adjustment of the H 3 PO 2 treatment. This conjoint approach thereby results in improved visible-light absorption, enhanced charge-carrier separation and a high H 2 evolution rate of 881.7 μmol h -1 achieved over the H 3 PO 2 doped g-C 3 N 4 nanosheets with a corresponding apparent quantum yield (AQY) of 40.4% (at 420 nm). We illustrate that the synergistic H 3 PO 2 doping modifies the layered g-C 3 N 4 materials by introducing nitrogen vacancies as well as protonating them, leading to significant photocatalytic H 2 evolution enhancements, while the g-C 3 N 4 materials doped with phosphoric acid (H 3 PO 4 ) are simply protonated further, revealing the varied doping effects of phosphorus having different (but accessible) valence states., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

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 2 . Both local coordination modes and the intermediate range liquid structure are determined, which demonstrate that distinct structural correlations between cation and anion in the liquid phase extend beyond 8.6 ?. Indeed, the local solvation around Na ? is surprisingly well defined with strong solvent orientational order, in contrast to the classical description of alkalide anions not interacting with their environment. The ion-paired Li(MeNH 2 ) 4 + ?Na ? species appears to be the dominant alkali?alkalide environment in these liquids, whereby Li + and Na ? share a MeNH 2 molecule through the amine group in their primary solvation spheres.

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. This technique has great potential for industrial applications to examine the sedimentation, creaming and hence the stability of emulsions.

The flexibility window in zeolites was originally identified using geometric simulation as a hypothetical property of SiO 2 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. We here extend the concept to ordered aluminosilicate systems using softer 'bar' constraints that permit additional flexibility around aluminium centres. Our experimental investigation of pressure-induced amorphization in sodalites is consistent with the results of our modelling. The softer constraints allow us to identify a flexibility window in the anomalous case of goosecreekite., Competing Interests: The authors declare no competing interests.

Coking leads to the deactivation of solid acid catalyst. This phenomenon is a ubiquitous problem in the modern petrochemical and energy transformation industries. Here, we show a method based on microwave cavity perturbation analysis for an effective examination of both the amount and the chemical composition of cokes formed over acid zeolite catalysts. The employed microwave cavity can rapidly and non-intrusively measure the catalytically coked zeolites with sample full body penetration. The overall coke amount is reflected by the obtained dielectric loss (ε″) value, where different coke compositions lead to dramatically different absorption efficiencies (ε″/cokes' wt%). The deeper-dehydrogenated coke compounds (e.g., polyaromatics) lead to an apparently higher ε″/wt% value thus can be effectively separated from lightly coked compounds. The measurement is based on the nature of coke formation during catalytic reactions, from saturated status (e.g., aliphatic) to graphitized status (e.g., polyaromatics), with more delocalized electrons obtained for enhanced Maxwell-Wagner polarization.Catalyst deactivation by coke deposition is a major drawback in industrial processes. Here, the authors show a non-intrusive microwave cavity perturbation technique as a powerful tool to determine the nature and extent of coke accumulation in industrially-relevant zeolite catalysts.

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.)