Metal-organic frameworks (MOFs) are microporous materials with huge potential for chemical processes, including retention or separation of guest molecules. Structural collapse at high-pressure, and transitions to liquid states at high temperature, have recently been observed in this family. Here, we show that the effect of simultaneous high pressure and temperature application on ZIF-62 and ZIF-4 results in complex behaviour, with distinct high-and low-density amorphous phases occurring over different regions of the pressure-temperature phase diagram. In-situ powder X-ray diffraction, Raman spectroscopy and optical microscopy reveal that the stability of the liquid MOF-state expands significantly towards lower temperatures at intermediate, industrially achievable pressures. Furthermore, the MOF-glass formed by melt quenching the high temperature liquid is shown to demonstrate permanent, accessible porosity. Our results thus imply a novel route to the synthesis of functional MOF glasses at low temperatures, avoiding decomposition upon heating at ambient pressure.

We present an in situ powder X-ray diffraction study on the phase stability and polymorphism of the metal− organic framework ZIF-4, Zn(imidazolate) 2 , at simultaneous high pressure and high temperature, up to 8 GPa and 600 °C. The resulting pressure−temperature phase diagram reveals four, previously unknown, high-pressure−high-temperature ZIF phases. The crystal structures of two new phasesZIF-4cp-II and ZIF-hPT-IIwere solved by powder diffraction methods. The total energy of ZIF-4-cp-II was evaluated using density functional theory calculations and was found to lie in between that of ZIF-4 and the most thermodynamically stable polymorph, ZIF-zni. ZIF-hPT-II was found to possess a doubly interpenetrated diamondoid topology and is isostructural with previously reported Cd(Imidazolate) 2 and Hg(Imidazolate) 2 phases. This phase exhibited extreme resistance to both temperature and pressure. The other two new phases could be assigned with a unit cell and space group, although their structures remain unknown. The pressure−temperature phase diagram of ZIF-4 is strikingly complicated when compared with that of the previously investigated, closely related ZIF-62 and demonstrates the ability to traverse complex energy landscapes of metal−organic systems using the combined application of pressure and temperature.

Accumulation of radiation damage from synchrotron X-rays leads to complete amorphization of the initially crystalline metal–organic frameworks ZIF-4, ZIF-62, and ZIF-zni. The mechanism of this transformation is studied as a function of time and temperature and is shown to be non-isokinetic.

Metal-organic frameworks (MOFs) are microporous materials with huge potential as host structures for chemical processes, including retention, catalytic reaction, or separation of guest molecules. Structural collapse at high-pressure, and unusual behaviours at elevated temperatures, such as melting and transitions to liquid states, have recently been observed in the family. Here, we show that the effect of the application of simultaneous high-pressure and -temperature on a MOF can be understood in terms of silicate analogues, with crystalline, amorphous and liquid states occurring across the pressure - temperature phase diagram. The response of ZIF-62, the MOF on which we focus, to simultaneous pressure and temperature reveals a complex behaviour with distinct high- and low- density amorphous phases occurring over different regions of the pressure-temperature space. In-situ powder X-ray diffraction, Raman spectroscopy and optical microscopy reveal that the stability of the liquid MOF-state expands significantly towards lower temperatures at intermediate, industrially achievable pressures. Our results imply a novel route to the synthesis of functional MOF glasses at low temperatures, avoiding decomposition upon heating at ambient pressure.

Earth’s deep carbon cycle affects atmospheric CO2, climate, and habitability. Owing to the extreme solubility of CaCO3, aqueous fluids released from the subducting slab could extract all carbon from the slab. However, recycling efficiency is estimated at only around 40%. Data from carbonate inclusions, petrology, and Mg isotope systematics indicate Ca2+ in carbonates is replaced by Mg2+ and other cations during subduction. Here we determined the solubility of dolomite [CaMg(CO3)2] and rhodochrosite (MnCO3), and put an upper limit on that of magnesite (MgCO3) under subduction zone conditions. Solubility decreases at least two orders of magnitude as carbonates become Mg-rich. This decreased solubility, coupled with heterogeneity of carbon and water subduction, may explain discrepancies in carbon recycling estimates. Over a range of slab settings, we find aqueous dissolution responsible for mobilizing 10 to 92% of slab carbon. Globally, aqueous fluids mobilise $${35}_{-17}^{+20}$$ 35 − 17 + 20 % ($${27}_{-13}^{+16}$$ 27 − 13 + 16 Mt/yr) of subducted carbon from subducting slabs.