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Nanocomposites of sulfur encapsulated in single-walled carbon nanotubes show increased hydrogen density in pores through enhanced electrostatic potential.

Adsorption and controlled release of agrochemicals has been studied widely using different nanomaterials and a variety of formulations. However, the potential for application of high surface-area metal–organic frameworks (MOFs) for the controlled release of agrochemicals has not been thoroughly explored. Herein, we report controlled and sustainable release of a widely used herbicide (2-methyl-4-chlorophenoxyacetic acid, MCPA) via incorporation in a range of zirconium-based MOFs and their biodegradable polymer composites. Three Zr-based MOFs, viz., UiO-66, UiO-66-NH2, and UiO-67 were loaded with MCPA either postsynthetically or in situ during synthesis of the MOFs. The MCPA-loaded MOFs were then incorporated into a biodegradable polycaprolactone (PCL) composite membrane. All three MOFs and their PCL composites were thoroughly characterized using FT-IR, TGA, SEM, PXRD, BET, and mass spectrometry. Release of MCPA from each of these MOFs and their PCL composites was then studied in both distilled water and in ethanol for up to 72 h using HPLC. The best performance for MCPA release was observed for the postsynthetically loaded MOFs, with PS-MCPA@UiO-66-NH2 showing the highest MCPA concentrations in ethanol and water of 0.056 and 0.037 mg/mL, respectively. Enhanced release of MCPA was observed in distilled water when the MOFs were incorporated in PCL. The concentrations of herbicides in the release studies provide us with a range of inhibitory concentrations that can be utilized depending on the crop, making this class of composite materials a promising new route for future agricultural applications.

Condensed phases of molecular hydrogen (H2) are highly desired for clean energy applications ranging from hydrogen storage to nuclear fusion and superconductive energy storage. However, in bulk hydrogen, such dense phases typically only form at exceedingly low temperatures or extremely high (typically hundreds of GPa) pressures. Here, confinement of H2 within nanoporous materials is shown to significantly manipulate the hydrogen phase diagram leading to preferential stabilization of unusual crystalline H2 phases. Using pressure and temperature-dependent neutron scattering at pressures between 200–2000 bar (0.02–0.2 GPa) and temperatures between 10–77 K to map out the phase diagram of H2 when confined inside both meso- and microporous carbons, we conclusively demonstrate the preferential stabilisation of face-centred cubic (FCC) solid ortho-H2 in microporous carbons, at temperatures five times higher than would be possible in bulk H2. Through examination of nanoconfined H2 rotational dynamics, preferential adsorption and spin trapping of ortho-H2, as well as the loss of rotational energy and severe restriction of rotational degrees of freedom caused by the unique micropore environments, are shown to result in changes to phase behaviour. This work provides a general strategy for further manipulation of the H2 phase diagram via nanoconfinement effects, and for tuning of anisotropic potential through control of confining material composition and pore size. This approach could potentially provide lower energy routes to the formation and study of more exotic non-equilibrium condensed phases of hydrogen that could be useful for a wide range of energy applications.

Nanostructured high-temperature superconductors YBa

Introducing heterostructure to graphitic carbon nitrides (g-C3N4) can improve the activity of visible-light-driven catalysts for efficient treatment of multiple toxic pollutants in water. Here we report for the first time that a complex material can be constructed from an oxygen-doped g-C3N4 and MIL-53(Fe) metal-organic framework using a facile hydrothermal synthesis and recycled polyethylene terephthalate from plastic waste. The novel multi-walled nanotube structure of the O-g-C3N4/MIL-53(Fe) composite which enables unique interfacial charge transfer at the heterojunction showed an obvious enhancement in separation efficiency of the photochemical electron-hole pairs. This resulted in narrow bandgap energy (2.30 eV compared to 2.55 eV in O-g-C3N4), high photocurrent intensity (0.17 mA cm-2 compared to 0.12 mA cm-2 and 0.09 mA cm-2 in MIL-53(Fe) and O-g-C3N4, respectively), and excellent catalytic performance in the photodegradation of anionic azo dyes (95% RR 195 and 99% RY 145 degraded after 4 h, and only a minor change in the efficiency observed after four consecutive tests). These results demonstrate the development of new catalysts made from waste feedstocks that show high stability, ease of fabrication and can operate in natural light for environmental remediation.

Over the past 150 years, our ability to produce and transform engineered materials has been responsible for our current high standards of living, especially in developed economies. However, we must carefully think of the effects our addiction to creating and using materials at this fast rate will have on the future generations. The way we currently make and use materials detrimentally affects the planet Earth, creating many severe environmental problems. It affects the next generations by putting in danger the future of the economy, energy, and climate. We are at the point where something must drastically change, and it must change now. We must create more sustainable materials alternatives using natural raw materials and inspiration from nature while making sure not to deplete important resources, i.e. in competition with the food chain supply. We must use less materials, eliminate the use of toxic materials and create a circular materials economy where reuse and recycle are priorities. We must develop sustainable methods for materials recycling and encourage design for disassembly. We must look across the whole materials life cycle from raw resources till end of life and apply thorough life cycle assessments (LCAs) based on reliable and relevant data to quantify sustainability. We need to seriously start thinking of where our future materials will come from and how could we track them, given that we are confronted with resource scarcity and geographical constrains. This is particularly important for the development of new and sustainable energy technologies, key to our transition to net zero. Currently ‘critical materials’ are central components of sustainable energy systems because they are the best performing. A few examples include the permanent magnets based on rare earth metals (Dy, Nd, Pr) used in wind turbines, Li and Co in Li-ion batteries, Pt and Ir in fuel cells and electrolysers, Si in solar cells just to mention a few. These materials are classified as ‘critical’ by the European Union and Department of Energy. Except in sustainable energy, materials are also key components in packaging, construction, and textile industry along with many other industrial sectors. This roadmap authored by prominent researchers working across disciplines in the very important field of sustainable materials is intended to highlight the outstanding issues that must be addressed and provide an insight into the pathways towards solving them adopted by the sustainable materials community. In compiling this roadmap, we hope to aid the development of the wider sustainable materials research community, providing a guide for academia, industry, government, and funding agencies in this critically important and rapidly developing research space which is key to future sustainability., The authors would like to thank The Faraday Institution ReLiB Project Grant Numbers FIRG005 and FIRG006, the UKRI Interdisciplinary Circular Economy Centre for Technology Metals (Met4Tech) Grant No. EP/V011855/1 and the EPSRC Critical Elements and Materials Network (CREAM) EP/R020140/1 for providing financial assistance for this research.

In this paper, hydrogen adsorption in metal-organic framework MIL-101(Cr) is investigated through a combination of sorption experiments, modeling of experimental isotherms, differential scanning calorimetry (DSC), neutron scattering, in situ synchrotron powder X-ray diffraction, and molecular simulations. The molecular simulations at 77 K for H2 adsorption in the material show excellent correspondence with excess uptakes determined from experimental isotherms. The simulations also indicate that H2 adsorption at a low pressure is mainly located in the 0.7 nm supertetrahedron and that, with increasing pressure, H2 starts to accumulate in the small (2.9 nm) and large (3.4 nm) cages. The inelastic neutron scattering results show that, in contrast to reports for hydrogen adsorption under the same conditions for microporous carbons, there is no solid-like H2 or any higher density H2 phases adsorbed in the pores of MIL-101(Cr). This indicates that, with increasing pressures, the adsorbed density of the MIL-101(Cr) remains constant but the volume of adsorbate increases and that higher densities for adsorbed hydrogen require pore sizes smaller than 0.7 nm, which is the size of the smallest pore in MIL-101(Cr). The enthalpies of adsorption are also investigated for this material using simulations, the Clapeyron equation applied to the isosteres and DSC, with the direct calorimetric method showing good agreement at zero coverage with the other two methods. The simulations and the Clapeyron equation are also in good agreement up to 6 wt % coverage.

Methane is touted as a replacement for fossil fuels in transport applications due to its lower costs of production and cleaner combustion. Storage of methane is still a problem and different technologies have been considered, including compression and liquefaction. Adsorption in a porous material is a potential alternative for methane storage, as it can increase densities at moderate pressures and temperatures. For practical applications, in addition to the quantities stored and working capacities, it is important to equally consider aspects such as kinetics of storage and thermal management of the storage system. In this paper, the kinetics and enthalpies of adsorption of methane in activated carbons AX-21 and TE7, and metal-organic framework MIL-101 (Cr) are extracted from readily available gas sorption data. The adsorption kinetics at 300 K and 325 K are analysed and fitted with the linear driving force (LDF) model, and mass transfer coefficients (MTC) and effective diffusivities are estimated. The effective diffusivities have a range of values from 1.79 × 10−13 m2 s−1 for the MIL-101 (Cr) at 300 K to 9.36 × 10−10 m2 s−1 for the TE7 at 325 K. The activation energies for the effective diffusivities based on an Arrhenius-type temperature dependence are calculated as 7.42, 7.09 and 5.38 kJ mol−1 for the AX-21, the MIL-101 (Cr) and the TE7, respectively. The enthalpies of adsorption are calculated with the Clausius-Clapeyron equation and the differences observed when calculating these with excess and absolute amounts are presented and discussed, with the results showing that enthalpies can have up to 10% differences if using excess amounts instead of absolute quantities. The isosteric enthalpies are also compared with enthalpies at zero-coverage obtained from differential calorimetry experiments for the MIL-101 (Cr), and a ∼3.5 kJ mol−1 difference is observed, which underlines the importance of refining calculation methods and bridging the gap between direct and indirect methods for calculating enthalpies of adsorption.

Our investigations into molecular hydrogen (H2) confined in microporous carbons with different pore geometries at 77 K have provided detailed information on effects of pore shape on densification of confined H2 at pressures up to 15 MPa. We selected three materials: a disordered, phenolic resin-based activated carbon, a graphitic carbon with slit-shaped pores (titanium carbide-derived carbon), and single-walled carbon nanotubes, all with comparable pore sizes of < 1 nm. We show via a combination of in situ inelastic neutron scattering studies, high-pressure H2 adsorption measurements, and molecular modelling that both slit-shaped and cylindrical pores with a diameter of ~0.7 nm lead to significant H2 densification compared to bulk hydrogen under the same conditions, with only subtle differences in hydrogen packing (and hence density) due to geometric constraints. While pore geometry may play some part in influencing the diffusion kinetics and packing arrangement of hydrogen molecules in pores, pore size remains the critical factor determining hydrogen storage capacities. This confirmation of the effects of pore geometry and pore size on the confinement of molecules is essential in understanding and guiding the development and scale-up of porous adsorbents that are tailored for maximising H2 storage capacities, in particular for sustainable energy applications.

Introducing heterostructure to graphitic carbon nitrides (g-C3N4) can improve the activity of visible-light-driven catalysts for efficient treatment of multiple toxic pollutants in water. Here we report for the first time that a complex material can be constructed from an oxygen-doped g-C3N4 and MIL-53(Fe) metal-organic framework using a facile hydrothermal synthesis and recycled polyethylene terephthalate from plastic waste. The novel multi-walled nanotube structure of the O-g-C3N4/MIL-53(Fe) composite which enables unique interfacial charge transfer at the heterojunction showed an obvious enhancement in separation efficiency of the photochemical electron-hole pairs. This resulted in narrow bandgap energy (2.30 eV compared to 2.55 eV in O-g-C3N4), high photocurrent intensity (0.17 mA cm-2 compared to 0.12 mA cm-2 and 0.09 mA cm-2 in MIL-53(Fe) and O-g-C3N4, respectively), and excellent catalytic performance in the photodegradation of anionic azo dyes (95% RR 195 and 99% RY 145 degraded after 4 h, and only a minor change in the efficiency observed after four consecutive tests). These results demonstrate the development of new catalysts made from waste feedstocks that show high stability, ease of fabrication and can operate in natural light for environmental remediation.

Chabazite (CHA), one of the most common zeolite framework types, has a remarkable capacity to accommodate a wide range of different cations within the unique CHA framework. This has led to CHA being applied extensively in ion exchange, and studied for highly selective gas sorption, most notably through a trapdoor mechanism. Here, we report the systematic study of a series of six chabazite zeolites (i.e.K-CHA, Cs-CHA, Ca-CHA, Ba-CHA, Sr-CHA and Zn-CHA) obtained by subjecting the parent chabazite (KNa-CHA) to exchange operations with cations of different valences and atomic radii. These samples were examined using numerous techniques and it was found that the differences in valence and size between extra-framework cations exert a significant effect on the abundance of these cations positioned in the framework, resulting in differing nitrogen sorption ability measured in the synthesised chabazite zeolites. These findings will help to understand how the zeolite counter-cation affects the ability of the CHA material to selectively sequester and separate gases through the use of the trapdoor mechanism.

Controlling the assembly and disassembly of nanoscale protein cages for the capture and internalisation of protein or non-proteinaceous components is fundamentally important to a diverse range of bionanotechnological applications. Here, we study the reversible, pressure-induced dissociation of a natural protein nanocage,E. colibacterioferritin (Bfr), using synchrotron radiation small angle X-ray scattering (SAXS) and circular dichroism (CD). We demonstrate that hydrostatic pressures of 450 MPa are sufficient to completely dissociate the Bfr icositetramer into protein dimers, and the reversibility and kinetics of the reassembly process can be controlled by selecting appropriate buffer conditions. We also demonstrate that the heme B prosthetic group present at the subunit dimer interface influences the stability and pressure lability of the cage, despite its location being discrete from the inter-dimer interface that is key to cage assembly. This indicates a major cage-stabilising role for heme within this family of ferritins.

Lignin, a natural biopolymer and abundant by-product, is a particularly promising feedstock for carbon-based materials and a potentially sustainable alternative to phenolic resins, which are typically derived from crude oil. The source and method used to isolate lignin have a large impact on the thermal properties of the polymer, and can affect resultant materials prepared from lignin. Previous investigations into lignin characterisation often utilise a variety of feedstocks and isolation methods, which can make robust comparisons challenging. We present a systematic investigation into the chemical composition of lignins extracted using an identical Organosolv isolation method but from different biomass feedstocks: hemp hurds, eucalyptus chips, flax straw, rice husk and pine. We show how the aromatic structure of lignin can affect the thermal behaviour of the polymer, which correlates to the structure of resulting carbons. Carbons from lignins with a high syringyl unit content display a pronounced foaming behaviour which, on activation, results in a high-surface area material with hierarchical porosity.

Porous superhydrophobic nanofibrous networks based on cellulose acetate butyrate (CAB) were prepared using electrospinning. The morphology and wettability of the prepared fibrous networks was studied using scanning electron microscopy and static contact angle measurements. The porous nanofiber networks exhibited superhydrophobicity and superoleophilicity with a water contact angle of ∼165° and an oil contact angle of ∼0°. The porous nature of the nanofibres themselves is thought to lead to an increased surface area making them suitable for sorption applications. Due to their hydrophobic and oleophilic nature, they were tested for their oil sorption capacity. They demonstrated an oil sorption capacity of ∼60 g/g for motor oil, which is four times that of commercially used polypropylene. The nanofibrous mats also demonstrated excellent reusability, retaining ∼80% of their sorption capacity for up to 5 cycles of use.

Activated carbons are promising sorbents that have been heavily investigated for the physisorptive storage of hydrogen. The industrial process for production of activated carbons is finely tuned and requires a reliable and uniform feedstock. While the natural biopolymer lignin, a by-product of several industries, has received increasing interest as a potentially sustainable and inexpensive activated carbon feedstock, the ratio of the three aromatic monomers (S, G, and H) in lignin can be heavily affected by the lignin source and growing conditions. The aromatic ratio is known to influence the thermal behavior of the polymer, which could be problematic for production of consistent activated carbons at scale. With the goal of improving the consistency of activated carbons produced from lignins derived from different feedstocks, here we present a route to limiting the influence of lignin feedstock on activated carbon porosity and performance, resulting in a carbonization process that is resilient to changes in lignin source. Two different types of organosolv lignin (representing high S-unit content and high G-unit content feedstocks) were investigated. Resulting activated carbons exhibited a high surface area (> 1000 m2·g-1) with consistent adsorptive properties and reasonable hydrogen uptake of up to 1.8 wt.% at 1 bar and -196 °C. These findings indicate that low temperature carbonization conditions can be used to produce a consistent carbon material using organosolv lignins from any source, paving the way for more widespread use of lignin in large-scale carbon production.

Lignin is a significant by-product of the paper pulping and biofuel industries. Upgrading lignin to a high-value product is essential for the economic viability of biorefineries for bioethanol production and environmentally benign pulping processes. In this work, the feasibility of lignin-derived activated carbons for hydrogen storage was studied using a Design of Experiments methodology, for a time and cost-efficient exploration of the synthesis process. Four factors (carbonisation temperature, activation temperature, carbonisation time, and activation time) were investigated simultaneously. Development of a mathematical model allowed the factors with the greatest impact to be identified using regression analysis for three responses: surface area, average pore size, and hydrogen uptake at 77 K and 1 bar. Maximising the surface area required activation conditions using the highest settings, however, a low carbonisation temperature was also revealed to be integral to prevent detrimental and excessive pore widening. A small pore size, vital for efficient hydrogen uptake, could be achieved by using low carbonisation temperature but also low activation temperatures. An optimum was achieved using the lowest carbonisation conditions (350 °C for 30 min) to retain a smaller pore size, followed by activation under the severest conditions (1000 °C for 60 min) to maximise surface area and hydrogen uptake. These conditions yielded a material with a high surface area of 1400 m2 g−1 and hydrogen uptake of 1.9 wt.% at 77 K and 1 bar.

Introducing additional meso- or macroporosity into traditionally microporous metal-organic frameworks (MOFs) is a very promising way to improve the catalytic performance of these materials, mostly due to the resultant reductions of diffusional barriers during liquid-phase or gas-phase reactions. Here we show that HKUST-1 can be successfully synthesised either via post-synthetic treatment (etching prepared HKUST-1 samples in phosphoric acid, here called HKUST AE) or via in situ crystallisation (exposing the MOF precursor solution to supercritical CO2, here called HKUST CO2) to produce hierarchically porous structures that are highly beneficial for catalysis. These hierarchical MOFs were characterised by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM) and gas sorption to confirm the preservation of the microscopic structure and the appearance of macropores in the crystallites. More importantly, the benefits of introducing these hierarchical porous structures into this MOF for improving the diffusion accessibility of reagents to the sample in catalysed liquid- and gas-phase reactions were quantified for the first time. It was found that the hierarchical pore structure helped to increase the reaction conversion of styrene oxide methanolysis (by ~65 % using either HKUST AE and HKUST CO2, at 40 oC in 25 min) and CO oxidation (by 55 % using HKUST CO2 at 260 oC). These findings demonstrate the advantage of using hierarchical porous MOFs in catalysis.

Introducing hierarchical pore structure to microporous materials such as metal-organic frameworks (MOFs) can be beneficial for reactions where the rate of reaction is limited by low rates of diffusion or high pressure drop. This advantageous pore structure can be obtained by defect formation, mostly via post-synthetic acid etching, which has been studied extensively on water-stable MOFs. Here we show that a water-unstable HKUST-1 MOF can also be modified in a corresponding manner by using phosphoric acid as a size-selective etching agent and a mixture of dimethyl sulfoxide and methanol as a dilute solvent. Interestingly, we demonstrate that the etching process which is time- and acidity- dependent, can result in formation of defective HKUST-1 with extra interconnected hexagonal macropores without compromising on the bulk crystallinity. These findings suggest an intelligent scalable synthetic method for formation of hierarchical porosity in MOFs that are prone to hydrolysis, for improved molecular accessibility and diffusion for catalysis., 14 pages, 8 figures

While metal-organic frameworks (MOFs) exhibit excellent potential in extensive catalytic reactions, predictably synthesizing MOF nanoparticles (NPs) with desired and uniform sizes remains a great challenge. Here, a mild and efficient ultrasound-assisted synthetic method has been developed to prepare ZIF-8, ZIF-67, and Co/ZIF-8 with well-designed particle size and morphology. By adjusting the cobalt content doped into a heterometallic ZIF-8 structure, tunable particle sizes ranging from 35 nm to over 300 nm have been achieved, resulting from the differences in nucleation and growth rates of zinc and cobalt ZIFs. Impressively, this as-obtained bimetallic Zn/Co-ZIF shows hierarchical porous structure with modified physicochemical properties, leading to a change of nitrogen adsorption-desorption characteristics. In addition, when used as a heterogenous catalyst, the bimetallic Co-doped ZIF-8 is demonstrated to have both enhanced catalytic performance for the activation of peroxymonosulfate (PMS) in organic dye degradation compared to pure ZIF-8, as well as superior structural stability, when compared to monometallic ZIF-67. This work provides a novel strategy for the predictable design and controlled fabrication of bimetallic MOF nanostructures with desired structures and compositions. Ministry of Education (MOE) Submitted/Accepted version The authors gratefully acknowledge the financial support from the Ministry of Education (MOE) Singapore AcRF Tier 1 grant (2018-T1- 001-077) and the UK Engineering and Physical Sciences Research Council (EP/R01650X/1).

Purpose: Microalgae have a high potential as a feedstock for the production of biofuels, either indirectly, through the extraction of lipids, which can be transformed into biodiesel, or directly via whole cell conversion using hydrothermal liquefaction (HTL). Both approaches have disadvantages, due to the high cost of cultivating microalgae with sufficient lipid content (>40%), while the whole cell conversion produces low quality oils, which require significant further upgrading. This work investigated the possibility of realising the benefits of both processes, by studying the liquefaction reaction of a lipid-extracted algae hydrolysate. Methods: In order to enhance oil yields, the reaction was conducted in the presence of varying loadings of iso-propyl alcohol (IPA) and applied two waste steel furnace residues as potential liquefaction catalysts. Results: Primarily, The lipid extraction process needs to be optimized to reduce the amount of acid contaminant within the liquefaction medium. For the HTL process, the addition of 50 vol% IPA resulted in remarkably high oil yields of up to 60.2 wt% on an organic basis, whereas the two furnace residues had no positive effect on the product distribution, and instead favoured the formation of solid reaction products. Nevertheless, the results suggested that the presence of iron potentially reduced the nitrogen and oxygen content of the bio-oil. Conclusions: As such, HTL is a suitable method for valorising lipid-extracted algal biomass, where the bio-oil yields can be enhanced substantially by using IPA in conjunction with the water.

Synthetic K+ chabazite (KCHA), Cs+ chabazite (CsCHA) and Zn2+ chabazite (ZnCHA) have been synthesized and investigated in order to relate the differences in their crystalline structures to their thermal stability, moisture content and frequency dependent alternating current (AC) conductivity, permittivity and phase angle at a range of temperatures. The materials are shown to exhibit the universal dielectric response, which is typical of materials consisting of both conductive and insulating regions. Due to the presence of porosity, the three chabazites were hydrated significantly at room temperature and so the dehydrated state was achieved by heating the chabazites to high temperatures to ensure that all different energetic types of water were removed. Cation migration activation energies for KCHA (0.66 ± 0.10) eV, CsCHA (0.88 ± 0.01) eV and ZnCHA (0.90 ± 0.01) eV were determined during the cooling cycle from the fully dehydrated state to provide an accurate measurement of the activation energies. Good thermal stability of the materials was observed up to 710 °C and below 200 °C the electrical properties can be strongly influenced by hydration level. Overall, it was determined that when either hydrated or dehydrated, KCHA had the highest conductivity and lowest cation migration activation energy of the three studied chabazites and thus has the most promising electrical properties for potential use as a gas sensing material in next-generation electrical-based gas sensors.

Current state-of-the-art methods consist of containing high-pressure compressed hydrogen in composite cylinders, with solid-state hydrogen storage materials an alternative that could improve on storage performance by enhancing volumetric densities. A new strategy that uses cryogenic temperatures to load hydrogen (cryocharging) is proposed and analysed in this work, comparing densities and final storage pressures for empty cylinders and containers with the high-surface area materials MIL-101 (Cr) and AX-21. Results show cryocharging as a viable option, as it can substantially lower the charging (at 77 K) and final pressures (at 298 K) for the majority of the cases considered. Kinetics are an equally important requirement for hydrogen storage systems, so the effective diffusivities at these conditions for both materials were calculated, and showed values comparable to the ones estimated in metal–organic frameworks and zeolites from quasielastic neutron scattering and molecular simulations. High-surface area materials tailored for hydrogen storage are a promising route for storage in mobile applications and results show that cryocharging is a promising strategy for hydrogen storage systems, since it increases volumetric densities and avoids energy penalties of operating at high pressures and/or low temperatures. Keywords: Hydrogen storage, Nanoporous materials, Hydrogen storage systems, Adsorption

Here we report direct physical evidence that confinement of molecular hydrogen (H2) in an optimized nanoporous carbon results in accumulation of hydrogen with characteristics commensurate with solid H2 at temperatures up to 67 K above the liquid-vapour critical temperature of bulk H2. This extreme densification is attributed to confinement of H2 molecules in the optimally-sized micropores, and occurs at pressures as low as 0.02 MPa. The quantities of contained, solid-like H2 increased with pressure and were directly evaluated using in-situ inelastic neutron scattering and confirmed by analysis of gas sorption isotherms. The demonstration of the existence of solid-like hydrogen challenges the existing assumption that supercritical hydrogen confined in nanopores has an upper limit of liquid H2 density. Thus, this insight offers opportunities for the development of more accurate models for the evaluation and design of nanoporous materials for high capacity adsorptive hydrogen storage.

Experimental results for methane adsorption on two high-surface area carbons (TE7-20 and AX-21) and one metal-organic framework (MIL-101(Cr)) are presented, with isotherms obtained at temperatures ranging from 250 to 350 K and at pressures up to 15 MPa. The isotherms were analysed to determine if these materials could be viable alternatives for on-board solid-state storage of methane. The results show a very high adsorbate density in the pores of all materials, which for some can even exceed liquid methane density. At moderate pressures below 5 MPa, the calculated total energy densities are close to the energy density of methanol, and are almost 40% of the energy density of gasoline (petrol). Compared with standard compression at the same conditions, the results show that adsorption can be a competitive storage alternative, as it can offer equal volumetric capacities at much lower pressures, hence reducing the energy penalty associated with compression. It is shown that the optimal conditions for adsorptive methane storage in these materials are at moderate pressure ranges, where the gains in amounts stored when using an adsorbent are more pronounced when compared to cylinders of compressed methane gas at the same operating conditions. Finally, a study on deliverable capacities for adsorbed methane was carried out, simulating two charging pressure scenarios of 3.5 and 6.5 MPa and discharge at 0.5 MPa. The results show that some of the tested materials have high working volumetric capacities, with some materials displaying more than 140 kg m(-3) volumetric working capacity for charging at 6.5 MPa and delivery at 0.5 MPa. (C) 2015 Elsevier B.V. All rights reserved.

This work demonstrates the potential of zeolite Y supported nickel phosphide materials as highly active catalysts for the upgrading of bio-oil as an improved alternative to noble metal and transition metal sulphide systems. Our systematic work studied the effect of using different counterions (NH4 +, H+, K+ and Na+) and Si/Al ratios (2.56 and 15) of the zeolite Y. It demonstrates that whilst the zeolite counterion itself has little impact on the catalytic activity of the bare Y-zeolite, it has a strong influence on the activity of the resulting nickel phosphide catalysts. This effect is related to the nature of the nickel phases formed during the synthesis process Zeolites containing K+ and Na+ favour the formation of a mixed Ni12P5/Ni2P phase, H+ Y produces both Ni2P and metallic Ni, whereas NH4 + Y produces pure Ni2P, which can be attributed to the strength of the phosphorus-aluminium interaction and the metal reduction temperature. Using quinoline as a model for the nitrogen-containing compounds in bio-oils, it is shown that the hydrodenitrogenation activity increases in the order Ni2P > Ni0 > Ni12P5. While significant research has been dedicated to the development of bio-oils produced by thermal liquefaction of biomass, surprisingly little work has been conducted on the subsequent catalytic upgrading of these oils to reduce their heteroatom content and enable processing in conventional petrochemical refineries. This work provides important insights for the design and deployment of novel active transition metal catalysts to enable the incorporation of bio-oils into refineries.

A highly porous carbon was synthesised using a coordination complex as an unusual precursor. During controlled pyrolysis a trinuclear copper complex, [CuII3Cl4(H2L)2]•CH3OH, undergoes phase changes with melt and expulsion of different gases to produce a unique morphology of copper-doped carbon which, upon acid treatment, produces highly porous graphitic carbon with a surface area of 857 m2g-1 and a gravimetric hydrogen uptake of 1.1 wt% at 0.5 bar pressure at 77 K.

Recently, much research has been published on the hydrothermal liquefaction (HTL) of microalgae to form bio-crude, which can be further upgraded into sustainable 3rd generation biofuels. However, most of these studies have been conducted in batch reactors, which are not fully applicable to large-scale industrial production. In this investigation an inexpensive laboratory scale continuous flow system was designed and tested for the liquefaction of microalgae produced during wastewater treatment. The system was operated at a range of temperatures (300 °C–340 °C) and flow rates (3–7 mL min− 1), with the feed being delivered using high pressure N2 rather than a mechanical pump. The design incorporated the in-situ collection of solids through a double tube design. The algae was processed at 5 wt% and the results were compared to those from a batch reactor operated at equivalent conditions. By combining high heating rates with extended reaction times, the continuous system was able to yield significantly enhanced bio-crude yields compared to the batch system. This demonstrates the need for inexpensive continuous processing in the lab, to aid in scale up decision making.

The rapid pace of development in biotechnology has placed great importance on controlling cell-material interactions. In practice, this involves attempting to decouple the contributions from adhesion molecules, cell membrane receptors, and scaffold surface chemistry and morphology, which is extremely challenging. Accordingly, a strategy is presented in which different chemical, biochemical, and morphological properties of 3D biomaterials are systematically varied to produce novel scaffolds with tuneable cell affinities. Specifically, cationized and surfactant-conjugated proteins, recently shown to have non-native membrane affinity, are covalently attached to 3D scaffolds of collagen or carboxymethyl-dextran, yielding surface-functionalized 3D architectures with predictable cell immobilization profiles. The artificial membrane-binding proteins enhance cellular adhesion of human mesenchymal stem cells (hMSCs) via electrostatic and hydrophobic binding mechanisms. Furthermore, functionalizing the 3D scaffolds with cationized or surfactant-conjugated myoglobin prevents a slowdown in proliferation of seeded hMSCs cultured for seven days under hypoxic conditions.

The suitability of biodiesel produced from spent Vietnamese coffee was examined. Previous work shows that the geographical origin of coffee beans has little effect on the composition and physical properties of the biodiesel produced Jenkins et al. [1]. Vietnamese coffee, however, is roasted in a range of fats and oils for flavour enhancement and therefore has a unique fatty acid profile. The oil yield and biodiesel properties of three Vietnamese coffees were assessed and compared to a coffee of more typical composition—Colombian—and traditional biodiesel feedstocks (rapeseed, sunflower and palm). The oil yield from fresh Vietnamese coffee was higher (12.0–14.0 %) than Colombian coffee (9.3 %), while the oil yield from spent Vietnamese coffee (9.3–10.4 %) was comparable to the Colombian coffee (9.5 %). The unsaponifiable matter was only present in low levels in the Vietnamese coffee (1.9–4.9 %) compared to Colombian coffee (30.4 % fresh, 21.4 % spent). Vietnamese coffee biodiesel was more saturated than Columbian coffee biodiesel. It was therefore more viscous and had a higher pour point than the Colombian coffee, and possessed properties more akin to palm biodiesel. Vietnamese coffee biodiesel would therefore be a suitable feedstock for use locally due to the more suitable climate and compatibility with the palm feedstock that is currently used. Spent coffee grounds from Vietnam is demonstrated to be a suitable source of biodiesel

Microbial lipids offer a promising feedstock for renewable biofuels. However, one of the major concerns with their conversion from lipids into suitable fuels is the high sterol content of the lipid. This is especially problematic for lipids obtained from oleaginous yeasts, as there are some indications that the sterol content could inhibit catalyst performance during hydrotreating. In this investigation a sterol-rich model feedstock (a 50:50 mixture of cholesterol and rapeseed oil, “RC50”) and an unrefined microbial lipid derived from the oleaginous yeast Metschkownia pulcherrima were converted to a diesel-like fuel in a single step via catalytic cracking. Far from reducing catalyst performance the cracking of the sterol groups liberated hydrogen, resulting in a reduction in the olefin content as well as an increase in the aromatic content of the fuel. The cracking of RC50 over Pd/C resulted in a fuel with a comparable product distribution to ultra-low sulphur diesel (ULSD), with high levels of linear alkanes and approximately 10 wt% aromatics. Cracking of unrefined yeast lipid over Pd/C was shown to result in an energy dense, hydrocarbon fuel suitable for marine applications (unblended) or a road transport fuel at 50% v/v blends with ULSD.

Multifunctional composites offer the ability to increase the efficiency, autonomy and lifespan of a structure by performing functions that would have been considered by designers as mutually exclusive. In the present perspective paper, a subclass of multifunctional composites is considered: metamaterials. In this perspective, a multifunctional composite is defined as ‘made of two or more materials that perform two or more functions in a manner that is constructive to the overall purpose of the structure’ where there is no differentiation between structural or non-structural functions. Equally, we define metamaterials are a class of man-made structures that display properties that are opposite to those typically found in nature. These ‘engineered’ architected materials continue to revisit and extend the boundaries of traditional materials science, opening up a wealth of new opportunities impacting on all aspects of human life. In our work, multifunctional metamaterials are delineated: electrodynamic, acoustic and mechanical. We review the current progress in these types of multifunctional metamaterials in terms of their bandwidth, fabrication techniques and applicability; noting that lattice structures offer considerable potential across all three functionalities. It culminates in the discussion of three key challenges which are seen by the authors as critical in the development of the next generation of lattice-type multifunctional metamaterials; namely, bandwidth, fabrication technique and proof of applicability. Success by the scientific community in these areas will lead to 3D multi-scale and multimedia lattice frameworks capable of influencing all three types of waves instantly; such a system would be a major technological breakthrough and will redefine our concept and understanding of multifunctional metamaterials in the next 10–20 years.

There is much current interest in the storage of hydrogen in porous materials for mobile energy applications. Despite significant hydrogen storage capacities having been observed recently for some synthesised materials, the identification of optimal operating conditions (pressure and temperature) is perhaps an even more important consideration from an engineering and applied science perspective. There will be pressure and temperature limits for effective use of an adsorptive storage system, because the adsorbent will always displace a volume in the storage container, and so at very high pressures the amount of hydrogen stored at a given temperature will be greater for a container with no adsorbent. In order for an adsorbent to be used there has to be some gain in the amount of the hydrogen stored to compensate for the cost and mass of the solid. We present a methodology by which the pressure and temperature ranges where it is advantageous to use adsorptive storage can be easily identified and the real gain of using such systems in terms of the absolute amount of hydrogen stored can be quantified. Using a well-characterised commercial activated carbon as an example system, we modelled high pressure hydrogen sorption isotherms and identified the operating conditions for which there is a significant increase in storage capacity from using an adsorbent as opposed to storage in the same volume via compression of hydrogen at the same temperature. A novel comparison of the density enhancement in the micropores with respect to the bulk hydrogen gas, as well as the influence of incorporating different amounts of adsorbent into a high pressure storage container is also presented.

This study of the effect of support of Co-Na-Mo based catalysts on the direct hydrogenation of CO$_2$ into hydrocarbons (HC) provides guidelines for the design of catalysts for CO$_2$ conversion. We demonstrate that the surface area of the support and the metal-support interaction have a key role determining the cobalt crystallite size and consequently the activity of the system. Cobalt particles with sizes

Visible light promoted photocatalytic water oxidations were conducted using a homogenous cobalt complex as a catalyst that was absorbed onto a silica gel substrate. The porous SiO2 contained Ru(bpy)3 2+ as a light harvester and the redox quinone analogue DCPIP as a reversible electron mediator as a step towards utilization of protons and electrons liberated in water oxidations for solar fuels.

Three highly porous Zr(IV)-based metal–organic frameworks, UBMOF-8, UBMOF-9, and UBMOF-31, were synthesized by using 2,2′-diamino-4,4′-stilbenedicarboxylic acid, 4,4′-stilbenedicarboxylic acid, and combination of both linkers, respectively. The mixed-linker UBMOF-31 showed excellent hydrogen uptake of 4.9 wt% and high selectivity for adsorption of CO2 over N2 with high thermal stability and moderate water stability with permanent porosity and surface area of 2552 m2 g−1.

The continually growing profile of energy issues in the 21st century is closely linked to the challenges of national and global development, international economy, and the emphasis on goods transport and human travel all around us. These challenges make headlines and are reflected in the social trends towards environmentally friendly practices and responsible use of energy. However, major advances and large-scale improvements in the infrastructure can only be achieved by engaging all aspects of engineering research and development, with particular emphasis on the design and incorporation of new materials. The Special Issue was commissioned at Materials & Design since the strategic themes in energy materials research are closely aligned with the scope and priorities of the journal [1]. In the transport sector, energy efficiency has been recognized as a major issue, and continues to gain importance. A number of materials-related developments have already taken place, bringing significant reductions in fossil fuel consumption and CO2 emissions. However, to meet the ever more stringent targets ahead there is a need to develop new materials and to optimise the use of existing ones. Advances in this area require considerable concerted research effort and sustaining synergy across the interconnected disciplines of composites, metallurgy, mechanics, and energy storage and generation. This Virtual Special Issue contains a collection of contributed papers on the following topics: (i) materials for lightweight structures including alloys and composites, (ii) materials for energy storage and the use of alternative energy sources, (iii) materials for energy harvesting technologies, (iv) materials for novel sensors.