Journal of Materials Chemistry. A, Materials for Energy and Sustainability

Compared to rigid physisorbents, switching coordination networks that reversibly transform between closed (non-porous) and open (porous) phases offer promise for gas/vapour storage and separation owing to their improved working capacity and desirable thermal management properties. We recently introduced a coordination network, X-dmp-1-Co, which exhibits switching enabled by transient porosity. The resulting "open" phases are generated at threshold pressures even though they are conventionally non-porous. Herein, we report that X-dmp-1-Co is the parent member of a family of transiently porous coordination networks [X-dmp-1-M] (M = Co, Zn and Cd) and that each exhibits transient porosity but switching events occur at different threshold pressures for CO2 (0...

In the search for novel solid polymer electrolytes (SPEs), primarily targeting battery applications, a range of different polymers is currently being explored. In this context, the non-coordinating poly(vinylidene fluoride- co -hexafluoropropylene) (PVdF-HFP) polymer is a frequently utilized system. Considering that PVdF-HFP should be a poor solvent for cation salts, it is counterintuitive that this is a functional host material for SPEs. Here, we do an in-depth study of the salt dissolution properties and ionic conductivity of PVdF-HFP-based electrolytes, using two different fabrication methods and also employing a low-molecular-weight solvent analogue...

Ca metal anode rechargeable batteries are seen as a sustainable high-energy density and high-voltage alternative to the current Li-ion battery technology due to the low redox potential of Ca metal and abundance of Ca. Electrolytes are key enablers on the path towards next-generation battery systems. Within this work, we synthesize a new calcium tetrakis(hexafluoroisopropyloxy) aluminate salt, Ca[Al(hfip)4 ]2 , and benchmark it versus the state-of-the-art boron analogue Ca[B(hfip)4 ]2 . The newly developed aluminate-based electrolyte exhibits improved performance in terms of conductivity, Ca plating/stripping efficiency, and oxidative stability as well as Ca battery cell performance...

A high-throughput computational screening approach combined with machine learning (ML) was introduced to unlock the potential of both synthesized and hypothetical COFs (hypoCOFs) for adsorption-based CH4 /H2 separation. We studied 597 synthesized COFs for adsorption of a CH4 /H2 mixture using Grand Canonical Monte Carlo (GCMC) simulations under pressure-swing adsorption (PSA) and vacuum-swing adsorption (VSA) conditions. Based on the simulation results, the CH4 /H2 selectivities, CH4 working capacities, adsorbent performance scores, and regenerabilities of the synthesized COFs were assessed and the structural properties of the top-performing COFs were identified...

Since its verification in 2019, there have been numerous high-profile papers reporting improved efficiency of lithium-mediated electrochemical nitrogen reduction to make ammonia. However, the literature lacks any coherent investigation systematically linking bulk electrolyte properties to electrochemical performance and Solid Electrolyte Interphase (SEI) properties. In this study, we discover that the salt concentration has a remarkable effect on electrolyte stability: at concentrations of 0.6 M LiClO4 and above the electrode potential is stable for at least 12 hours at an applied current density of -2 mA cm-2 at ambient temperature and pressure...

[This corrects the article DOI: 10.1039/D2TA07686A.].

Minimizing the overpotential at the air electrode of solid oxide fuel cells (SOFC) is one of the key challenges regarding a broad applicability of this technology. Next to novel materials and geometry optimization, surface modification is a promising and flexible method to alter the oxygen exchange kinetics at SOFC cathode surfaces. Despite extensive research, the mechanism behind the effect of surface decorations is still under debate. Moreover, for Sr decoration, previous studies yielded conflicting results, reporting either a beneficial or a detrimental impact on the oxygen exchange kinetics...

Short-range ordering in cation-disordered cathodes can have a significant effect on their electrochemical properties. Here, we characterise the cation short-range order in the antiperovskite cathode material Li2 FeSO, using density functional theory, Monte Carlo simulations, and synchrotron X-ray pair-distribution-function data. We predict partial short-range cation-ordering, characterised by favourable OLi4 Fe2 oxygen coordination with a preference for polar cis -OLi4 Fe2 over non-polar trans -OLi4 Fe2 configurations...

We report an additive-free one-pot hydrothermal synthesis of Au, Ag, Pd, and alloy AuPd nanoparticles (NPs) anchored on commercial polyurethane (PU) foams. While unable to reduce the precursor metal salts at room temperature, PU is able to serve as a reducing agent under hydrothermal conditions. The resulting NP@PU sponge materials perform comparably to reported state-of-the-art reduction catalysts, and are additionally very well suited for use in semi-automated synthesis: the NP anchoring is strong enough and the support flexible enough to be used as a 'catalytic sponge' that can be manipulated with a robotic arm, i...

Improving the perovskite/electron-transporting layer (ETL) interface is a crucial task to boost the performance of perovskite solar cells (PSCs). This is utterly fundamental in an inverted (p-i-n) configuration using fullerene-based ETLs. Here, we propose a scalable strategy to improve fullerene-based ETLs by incorporating high-quality few-layer graphene flakes (GFs), industrially produced through wet-jet milling exfoliation of graphite, into phenyl-C61-butyric acid methyl ester (PCBM). Our new composite ETL (GF:PCBM) can be processed into an ultrathin (∼10 nm), pinhole-free film atop the perovskite...

Lithium-metal electrodes are promising for developing next-generation lithium-based batteries with high energy densities. However, their implementation is severely limited by dendritic growth during battery cycling, which eventually short-circuits the battery. Replacing conventional liquid electrolytes with solid polymer electrolytes (SPEs) can suppress dendritic growth. Unfortunately, in SPEs the high stiffness required for suppressing dendrites comes at the expense of efficient lithium-ion transport. Some polymer-based composite electrolytes, however, enable the decoupling of stiffness and ionic conductivity...

In this work, we report the synthesis, structural characterisation and sorption properties of an 8-fold interpenetrated diamondoid (dia) metal-organic framework (MOF) that is sustained by a new extended linker ligand, [Cd(Imibz)2 ], X-dia-2-Cd, HImibz or 2 = 4-((4-(1 H -imidazol-1-yl)phenylimino)methyl)benzoic acid. X-dia-2-Cd was found to exhibit reversible single-crystal-to-single-crystal (SC-SC) transformations between four distinct phases: an as-synthesised (from N , N -dimethylformamide) wide-pore phase, X-dia-2-Cd-α; a narrow-pore phase, X-dia-2-Cd-β, formed upon exposure to water; a narrow-pore phase obtained by activation, X-dia-2-Cd-γ; a medium-pore CO2 -loaded phase X-dia-2-Cd-δ...

Antimony selenide (Sb2 Se3 ) is an auspicious material for solar energy conversion that has seen rapid improvement over the past ten years, but the photovoltage deficit remains a challenge. Here, simple and low-temperature treatments of the p-n heterojunction interface of Sb2 Se3 /TiO2 -based photocathodes for photoelectrochemical water splitting were explored to address this challenge. The FTO/Ti/Au/Sb2 Se3 (substrate configuration) stack was treated with (NH4 )2 S as an etching solution, followed by CuCl2 treatment prior to deposition of the TiO2 by atomic layer deposition...

High-voltage cathode materials are important for the implementation of high-energy-density Li-ion batteries. However, with increasing cut-off voltages, interfacial instabilities between electrodes and the electrolyte limit their commercial development. This study addresses this issue by proposing a new electrolyte additive, (3-aminopropyl)triethoxysilane (APTS). APTS stabilises the interface between the LiNi0.5 Mn1.5 O4 (LNMO) cathode and the electrolyte in LNMO‖Li half-cells due to its multifunctional character...

The effects of sulphur adsorbates and other typical solid oxide fuel cell (SOFC) poisons on the electronic and ionic properties of an SrO-terminated (La,Sr)CoO3 (LSC) surface and on its oxygen exchange kinetics have been investigated experimentally with near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), low energy ion scattering (LEIS) and impedance spectroscopy as well as computationally with density functional theory (DFT). The experiment shows that trace amounts of sulphur in measurement atmospheres form SO2- 4 adsorbates and strongly deactivate a pristine LSC surface...

We elucidate the underlying cause of a commonly observed increase in the rate of oxygen release of an oxygen carrier with redox cycling (here specifically for the perovskite Sr0.8 Ca0.2 FeO3- δ ) in chemical looping applications. This phenomenon is often referred to as activation. To this end we probe the evolution of the structure and surface elemental composition of the oxygen carrier with redox cycling by both textural and morphological characterization techniques (N2 physisorption, microscopy, X-ray powder diffraction and X-ray absorption spectroscopy)...

Adsorbents able to uptake large amounts of gases within a narrow range of pressure, i.e. , phase-change adsorbents, are emerging as highly interesting systems to achieve excellent gas separation performances with little energy input for regeneration. A recently discovered phase-change metal-organic framework (MOF) adsorbent is F4_MIL-140A(Ce), based on CeIV and tetrafluoroterephthalate. This MOF displays a non-hysteretic step-shaped CO2 adsorption isotherm, reaching saturation in conditions of temperature and pressure compatible with real life application in post-combustion carbon capture, biogas upgrading and acetylene purification...

Two ultramicroporous 2D and 3D iron-based Metal-Organic Frameworks (MOFs) have been obtained by solvothermal synthesis using different ratios and concentrations of precursors. Their reduced pore space decorated with pendant pyridine from tangling isonicotinic ligands enables the combination of size-exclusion kinetic gas separation, due to their small pores, with thermodynamic separation, resulting from the interaction of the linker with CO2 molecules. This combined separation results in efficient materials for dynamic breakthrough gas separation with virtually infinite CO2 /N2 selectivity in a wide operando range and with complete renewability at room temperature and ambient pressure...

Directly fused nickel(ii) porphyrins are successfully investigated as heterogeneous single-site catalysts for the oxygen evolution reaction (OER). Conjugated polymer thin films from Ni(ii) 5,15-(di-4-methoxycarbonylphenyl)porphyrin (pNiDCOOMePP) and Ni(ii) 5,15-diphenylporphyrin (pNiDPP) showed an OER onset overpotential of 270 mV, and current densities of 1.6 mA cm-2 and 1.2 mA cm-2 at 1.6 V vs. RHE, respectively, representing almost a hundred times higher activity than those of monomeric thin films. The fused porphyrin thin films are more kinetically and thermodynamically active than their non-polymerized counterparts mainly due to the formation of conjugated structures enabling a dinuclear radical oxo-coupling (ROC) mechanism at low overpotential...

The application of gas diffusion electrodes (GDEs) for the electrochemical reduction of CO2 to value-added products creates the possibility of achieving current densities of a few hundred mA cm-2 . To achieve stable operation at such high reaction rates remains, however, a challenging task, due to the flooding of the GDE. In order to mitigate flooding in a zero-gap membrane-electrode assembly (MEA) configuration, paths for effective electrolyte perspiration inside the GDE structure have to be kept open during the electrolysis process...