RESUMEN
Zeolitic imidazolate framework (ZIF) microporous materials have already been employed in many fields of energetic and environmental interest since the last decade. The commercial scale production of some of these materials makes them more accessible for their implementation in industrial processes; however, their massive synthesis may entail modifications to the preparation protocols, which may result in a loss in the optimization of this process and a drop in the material's quality. This fact may have implications for the performance of these materials during their lifetime, especially when they are used in applications such as energy dissipation, in which they are subjected to several operating cycles under high pressures. This study focuses on ZIF-67, a material that has demonstrated in the past its ability to dissipate energy through the water intrusion-extrusion process under high pressure. Two ZIF-67 samples were synthesized using different protocols, and 2 batches of different qualities (labelled as high quality (HQ) and low quality (LQ)) were obtained and analysed by water porosimetry to study their performance in the intrusion-extrusion process. Unexpectedly, minor structural differences, which are typically neglected especially under production conditions, had a dramatic effect on their performance. The results presented in this study reiterate the importance of quality control with respect to reproducibility of experimental results. In a broader perspective, they are critical to the technology transfer from academia to industry.
RESUMEN
Wetting of a solid by a liquid is relevant for a broad range of natural and technological processes. This process is complex and involves the generation of heat, which is still poorly understood especially in nanoconfined systems. In this article, scanning transitiometry was used to measure and evaluate the pressure-driven heat of intrusion of water into solid ZIF-8 powder within the temperature range of 278.15-343.15 K. The conditions examined included the presence and absence of atmospheric gases, basic pH conditions, solid sample origins, and temperature. Simultaneously with these experiments, molecular dynamics simulations were conducted to elucidate the changing behavior of water as it enters into ZIF-8. The results are rationalized within a temperature-dependent thermodynamic cycle. This cycle describes the temperature-dependent process of ZIF-8 filling, heating, emptying, and cooling with respect to the change of internal energy of the cycle from the calculated change in the specific heat capacity of the system. At 298 K the experimental heat of intrusion per gram of ZIF-8 was found to be -10.8 ± 0.8 J·g-1. It increased by 19.2 J·g-1 with rising temperature to 343 K which is in a reasonable match with molecular dynamic simulations that predicted 16.1 J·g-1 rise. From these combined experiments, the role of confined water in heat of intrusion of ZIF-8 is further clarified.
RESUMEN
Heat and the work of compression/decompression are among the basic properties of thermodynamic systems. Being relevant to many industrial and natural processes, this thermomechanical energy is challenging to tune due to fundamental boundaries for simple fluids. Here via direct experimental and atomistic observations, we demonstrate, for fluids consisting of nanoporous material and a liquid, one can overcome these limitations and noticeably affect both thermal and mechanical energies of compression/decompression exploiting preferential intrusion of water from aqueous solutions into subnanometer pores. We hypothesize that this effect is due to the enthalpy of dilution manifesting itself as the aqueous solution concentrates upon the preferential intrusion of pure water into pores. We suggest this genuinely subnanoscale phenomenon can be potentially a strategy for controlling the thermomechanical energy of microporous liquids and tuning the wetting/dewetting heat of nanopores relevant to a variety of natural and technological processes spanning from biomedical applications to oil-extraction and renewable energy.
RESUMEN
Although coveted in applications, few materials expand when subject to compression or contract under decompression, i.e., exhibit negative compressibility. A key step to achieve such counterintuitive behaviour is the destabilisations of (meta)stable equilibria of the constituents. Here, we propose a simple strategy to obtain negative compressibility exploiting capillary forces both to precompress the elastic material and to release such precompression by a threshold phenomenon - the reversible formation of a bubble in a hydrophobic flexible cavity. We demonstrate that the solid part of such metastable elastocapillary systems displays negative compressibility across different scales: hydrophobic microporous materials, proteins, and millimetre-sized laminae. This concept is applicable to fields such as porous materials, biomolecules, sensors and may be easily extended to create unexpected material susceptibilities.