Peter P. Edwards

Energy in the microwave spectrum is increasingly applied in clean energy technologies. This review discusses recent innovations using microwave fields in hydrogen production and synthesis of new battery materials, highlighting the unique properties of microwave heating. Key innovations include microwave-assisted hydrogen generation from water, hydrocarbons and ammonia and the synthesis of high-performance anode and cathode materials. Microwave-assisted catalytic water splitting using Gd-doped ceria achieves efficient hydrogen production below 250°C. For hydrocarbons, advanced microwave-active catalysts Fe–Ni alloys and ruthenium nanoparticles enable high conversion rates and hydrogen yields. In ammonia synthesis, microwaves reduce the energy demands of the Haber–Bosch process and enhance hydrogen production efficiency using catalysts such as ruthenium and Co ₂ Mo ₃ N. In battery technology, microwave-assisted synthesis of cathode materials like LiFePO ₄ and LiNi _0.5 Mn _1.5 O ₄ yields high-purity materials with superior electrochemical performance. Developing nanostructured and composite materials, including graphene-based anodes, significantly improves battery capacities and cycling stability. The ability of microwave technology to provide rapid, selective heating and enhance reaction rates offers significant advancements in clean energy technologies. Ongoing research continues to bridge theoretical understanding and practical applications, driving further innovations in this field. This review aims to highlight recent advances in clean energy technologies based upon the novel use of microwave energy. The potential impact of these emerging applications is now being fully understood in areas that are critical to achieving net zero and can contribute to the decarbonization of key sectors. Notable in this landscape are the sectors of hydrogen fuel and battery technologies. This review examines the role of microwaves in these areas. This article is part of the discussion meeting issue ‘Microwave science in sustainability’.

Presently, there is no single, clear route for the near-term production of the huge volumes of CO ₂ -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 ₂ , 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 ₂ emissions together with high-value solid nanoscale carbonaceous materials. These innovations have been applied, firstly to wax, then methane, crude oil, diesel, then biomass and most recently Saudi Arabian light crude oil, as well as plastics waste. Microwave catalysis has therefore now emerged as a highly effective route for the rapid and effective production of hydrogen and high-value carbon nanomaterials co-products, in many cases accompanied by low to near-zero CO ₂ emissions. Underpinning all of these advances has been the important concept from solid state physics of the so-called Size-Induced-Metal-Insulator Transition (SIMIT) in mesoscale or mesoscopic particles of catalysts. The mesoscale refers to a range of physical scale in-between the micro- and the macro-scale of matter (Huang W, Li J and Edwards PP, 2018, Mesoscience: exploring the common principle at mesoscale, Natl. Sci. Rev . 5 , 321-326 (doi: 10.1093/nsr/nwx083 )). We highlight here that the actual physical size of the mesoscopic catalyst particles, located close to the SIMIT, is the primary cause of their enhanced microwave absorption and rapid heating of particles to initiate the catalytic—and highly selective—breaking of carbon–hydrogen bonds in fossil hydrocarbons and plastics to produce clean hydrogen and nanoscale carbonaceous materials. Importantly, also, since the surrounding ‘bath’ of hydrocarbons is cooler than the microwave-heated catalytic particles themselves, the produced neutral hydrogen molecule can quickly diffuse from the active sites. This important feature of microwave heating thereby minimizes undesirable side reactions, a common feature of conventional thermal heating in heterogeneous catalysis. The low to near-zero CO ₂ production of hydrogen via microwave-initiated decomposition or cracking of abundant hydrocarbon fossil fuels may be an interim, viable alternative to the conventional, widely-used SMR, that a highly efficient process, but unfortunately associated with the emission of vast quantities of CO ₂ . Microwave-initiated catalytic decomposition also opens up the intriguing possibility of using distributed methane in the current natural gas structure to produce hydrogen and high-value solid carbon at either central or distributed sites. That approach will lessen many of the safety and environmental concerns associated with transporting hydrogen using the existing natural gas infrastructure. When completely optimized, microwave-initiated catalytic decomposition of methane (and indeed all hydrocarbon sources) will produce no aerial carbon (CO ₂ ), and only solid carbon as a co-product. Furthermore, reaction conditions can surely be optimized to target the production of high-quality synthetic graphite as the major carbon-product; that material of considerable importance as the anode material for lithium-ion batteries. Even without aiming for such products derived from the solid carbon co-product, it is of course far easier to capture solid carbon rather than capturing gaseous CO ₂ at either the central or distributed sites. Through microwave-initiated catalytic pyrolysis, this decarbonization of fossil fuels can now become the potent source of sustainable hydrogen and high-value carbon nanomaterials. This article is part of the discussion meeting issue ‘Microwave science in sustainability’.

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 H₂. Bifunctional ZnO acts as a microwave absorber and substrate catalyst, and in-situ formed Zn clusters promote C-C bond cleavage and nearly 100% upcycle landfilled plastic mixtures into lubricant base oil precursors and monomers. Unprecedented turnover number (250 g_plastic g⁻¹_catalyst) of plastic depolymerisation and long-time stability over 50 successive cycles have been demonstrated, together with 8-time higher energy efficiency compared with conventional catalysis, indicating this strategy is an economical approach to efficient upcycling of plastics towards valuable products. Moreover, the catalyst can tolerate high contaminates, even the landfilled plastics can still be converted to lubricant base oil precursors, which has never been reported before.

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.

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.

This paper follows on from an earlier publication on high-blend-rate binary gasoline-alcohol mixtures and reports results for some equivalent ternary fuels from several investigation streams. In the present work, new findings are presented for high-load operation in a dedicated boosted multi-cylinder engine test facility, for operation in modified production engines, for knock performance in a single-cylinder test engine, and for exhaust particulate emissions at part load using both the prototype multi-cylinder engine and a separate single-cylinder engine. The wide variety of test engines employed have several differences, including their fuel delivery strategies. This range of engine specifications is considered beneficial with regard to the “drop-in fuel” conjecture, since the results presented here bear out the contention, already established in the literature, that when specified according to the known ternary blending rules, such fuels fundamentally perform identically to their binary equivalents in terms of engine performance, and outperform standard gasolines in terms of efficiency. However, in the present work, some differences in particulate emissions performance in direct-injection engines have been found at light load for the tested fuels, with a slight increase in particulate number observed with higher methanol contents than lower. A hypothesis is developed to explain this result but in general it was found that these fuels do not significantly affect PN emissions from such engines. As a result, this investigation supplies further evidence that renewable fuels can be introduced simply into the existing vehicle fleet, with the inherent backwards compatibility that this brings too.