UiO-66 is a zirconium-based metal–organic framework (MOF) that has numerous applications. Our group recently determined that UiO-66 is not as inert in aqueous dispersions as previously reported in the literature. The present work therefore assessed the behaviour of UiO-66 in buffers: 2-amino-2-(hydroxymethyl)-1,3-propanediol (TRIS), 4-(2-hydroxyethyl)piperazine-1-ethane sulfonic acid (HEPES), N-ethylmorpholine (NEM) and phosphate buffer (PB), all of which are commonly used in many UiO-66 applications. High performance liquid chromatography and inductively coupled plasma mass spectrometry were used to monitor degradation of the MOF at 25 °C. In each buffer, the terephthalate linker was released to some extent. The chemical nature of the buffer media played a decisive role in the stability with a more pronounced leaching effect in the saline forms of these buffers. The HEPES buffer was found to be the most benign, whereas NEM and PB should be avoided at any concentration as they were shown to rapidly degrade the UiO-66 framework. Low concentration TRIS buffers are also recommended, although these offer minimal buffer capacity to adjust pH. Regardless of the buffer used, rapid terephthalate release was observed, indicating that the UiO-66 was attacked immediately after mixing with the buffer. This process was even more pronounced at 37 °C, i.e., at typical temperature in biological and medical applications. In addition, the dissolution of zirconium, observed in some cases, intensified the UiO-66 decomposition process. These results demonstrate that sensitive analytical techniques have to be used to monitor the release of MOF components so as to quantify the stabilities of these materials in liquid environments.
In September 2018, the First European Workshop on Metal Phosphonates Chemistry brought together some prominent researchers in the field of metal phosphonates and phosphinates with the aim of discussing past and current research efforts and identifying future directions. The scope of this perspective article is to provide a critical overview of the topics discussed during the workshop, which are divided into two main areas: synthesis and characterisation, and applications. In terms of synthetic methods, there has been a push towards cleaner and more efficient approaches. This has led to the introduction of high-throughput synthesis and mechanochemical synthesis. The recent success of metal–organic frameworks has also promoted renewed interest in the synthesis of porous metal phosphonates and phosphinates. Regarding characterisation, the main advances are the development of electron diffraction as a tool for crystal structure determination and the deployment of in situ characterisation techniques, which have allowed for a better understanding of reaction pathways. In terms of applications, metal phosphonates have been found to be suitable materials for several purposes: they have been employed as heterogeneous catalysts for the synthesis of fine chemicals, as solid sorbents for gas separation, notably CO2 capture, as materials for electrochemical devices, such as fuel cells and rechargeable batteries, and as matrices for drug delivery.