The building sector is responsible for a third of the global energy consumption and a quarter of greenhouse gas emissions. Phase change materials (PCMs) have shown high potential for latent thermal energy storage (LTES) through their integration in building materials, with the aim of enhancing the efficient use of energy. Although research on PCMs began decades ago, this technology is still far from being widespread. This work analyses the main contributions to the employment of PCMs in the building sector, to better understand the motivations behind the restricted employment of PCM-based LTES technologies. The main research and review studies are critically discussed, focusing on: strategies used to regulate indoor thermal conditions, the variation of mechanical properties in PCMs-based mortars and cements, and applications with ground-coupled heat pumps. The employment of materials obtained from wastes and natural sources was also taken in account as a possible key to developing composite materials with good performance and sustainability at the same time. As a result, the integration of PCMs in LTES is still in its early stages, but reveals high potential for employment in the building sector, thanks to the continuous design improvement and optimization driven by high-performance materials and a new way of coupling with tailored envelopes.

In the field of sustainable construction materials, the production of eco-friendly concretes, obtained by the addition of waste products such as biochar and recycled polymer particles, offers interesting alternatives to traditional materials. Biochar is a carbonaceous solid by-product obtained from the thermo-chemical conversion of biomass and its addition into concrete admixtures can offer an eco-friendly carbon sequestration solution, capable to slightly improve concrete properties. Recycled polymer materials can be used to partially replace conventional aggregates with the aim of obtaining lighter concretes that help to face the disposal challenge presented by this non-degradable plastic waste. However, the influence of these waste additions on the corrosion behavior of steel rebars embedded in these “eco-concretes” is still unexplored. Within this context, this work presents some results of an extensive study dealing with the concrete mechanical and physical properties and the rebar corrosion resistance during cyclic exposures to chloride-containing solutions.

Fluids under extreme confinement show characteristics significantly different from those of their bulk counterpart. This work focuses on water confined within the complex cavities of highly hydrophobic metal-organic frameworks (MOFs) at high pressures. A combination of high-pressure intrusion-extrusion experiments with molecular dynamic simulations and synchrotron data reveals that supercritical transition for MOF-confined water takes place at a much lower temperature than in bulk water, ∼250 K below the reference values. This large shifting of the critical temperature (T_c) is attributed to the very large density of confined water vapor in the peculiar geometry and chemistry of the cavities of Cu₂tebpz (tebpz = 3,3',5,5'-tetraethyl-4,4'-bipyrazolate) hydrophobic MOF. This is the first time the shift of T_c is investigated for water confined within highly hydrophobic nanoporous materials, which explains why such a large reduction of the critical temperature was never reported before, neither experimentally nor computationally.

Proton-coupled electron-transfer (PCET) plays a key role in many biological processes and a thorough comprehension of its subtle mechanistic complexity requires the synthesis and characterization of suitable artificial systems capable of mimicking this fundamental, elementary step. Herein we report on a detailed photophysical investigation of conjugate 1, based on a tin(IV) tetraphenylporphyrin (SnTPP) chromophore bound to two L-tyrosinato amino acids, in CH2Cl2 in combination with organic bases of different strength and the preparation of a novel conjugate 3, based on a tin(IV) octaethylporphyrin (SnOEP) in place of the tetraphenyl analog, and its photophysical characterization in CH2Cl2 in the presence of pyrrolidine. In the case of compound 1 with all bases examined quenching of both the singlet and triplet excited states is observed and attributed to the occurrence of concerted proton-electron transfer (CPET). Rates and quenching yields decrease with the strength of the base used, consistent with the decrease of the driving force for the CPET process. Conjugate 3 with pyrrolidine is quenched only at the triplet level by CPET, albeit with slower rates than its parent compound 1, ascribable to the smaller driving force as a result of SnOEP being more difficult to reduce than SnTPP. For both systems, the quenching mechanism is confirmed by suitable blank experiments, specific kinetic treatments, and the observation of kinetic isotope effects (KIEs). Differently from what previously proposed, a detailed reinvestigation of the triplet quenching of 1 with pyrrolidine shows that no long-lived radical pair state is formed, as diradical recombination is always faster than formation. This is true for both 1 and 3 and for all bases examined. The kinetics of the CPET pathways can be well described according to Marcus theory and point toward the involvement of substantial reorganization energy as typically observed for PCET processes of concerted nature.

Hydrophobicity has proven fundamental in an inexhaustible amount of everyday applications. Material hydrophobicity is determined by chemical composition and geometrical characteristics of its macroscopic surface. Surface roughness or texturing enhances intrinsic hydrophilic or hydrophobic characteristics of a material. Here we consider crystalline surfaces presenting molecular-scale texturing typical of crystalline porous materials, e.g., metal-organic frameworks. In particular, we investigate one such material with remarkable hydrophobic qualities, ZIF-8. We show that ZIF-8 hydrophobicity is driven not only by its chemical composition but also its sub-nanoscale surface corrugations, a physical enhancement rare amongst hydrophobes. Studying ZIF-8’s hydrophobic properties is challenging as experimentally it is difficult to distinguish between the materials’ and the macroscopic corrugations’ contributions to the hydrophobicity. The computational contact angle determination is also difficult as the standard “geometric” technique of liquid nanodroplet deposition is prone to many artifacts. Here, we characterise ZIF-8 hydrophobicity via: (i) the “geometric” approach and (ii) the “energetic” method, utilising the Young–Dupré formula and computationally determining the liquid–solid adhesion energy. Both approaches reveal nanoscale Wenzel-like bathing of the corrugated surface. Moreover, we illustrate the importance of surface linker termination in ZIF-8 hydrophobicity, which reduces when varied from sp3 N to sp2 N termination. We also consider halogenated analogues of the methyl-imidazole linker, which promote the transition from nanoWenzel-like to nanoCassie–Baxter-like states, further enhancing surface hydrophobicity. Present results reveal the complex interface physics and chemistry between water and complex porous, molecular crystalline surfaces, providing a hint to tune their hydrophobicity.