[(CH3)2NH2]7Pb4X15 (X = Cl- and Br-), 2D-Perovskite Related Hybrids with Dielectric Transitions and Broadband Photoluminiscent Emission.

We have prepared two new lead halides with the novel general formula of DMA7Pb4X15 (DMA = [(CH3)2NH2]+ and X = Cl- or Br-) by using an easy route under mild conditions at room temperature. These compounds exhibit an unprecedented crystal structure, are formed by layers of distorted [PbX6] octahedra, which share corners and faces, and contain intercalated DMA cations. Very interestingly, they display dielectric transitions, which are related to a partial order-disorder process of the DMA cations between 160 and 260 K. Additionally, these new layered hybrids exhibit a broadband photoluminiscent emission, which is related to the structural distortions of the [PbX6] octahedra. These findings not only open up large possibilities for future optoelectronic applications of these materials, but they also offer a novel playground for an easy modulation of electrical and optical properties of hybrid organic-inorganic materials. We anticipate that this novel A7Pb4X15 formula can be adequate to tune the family of the hybrid lead halides using other alkylammonium cations, such as methylammonium, formamidinium, or ethylammonium, to improve their photoelectronic properties.

Empowering CO2 Eco-Refrigeration With Colossal Breathing-Caloric-Like Effects in MOF-508b.

Today, ≈20% of the electric consumption is devoted to refrigeration; while, ≈50% of the final energy is dedicated to heating applications. In this scenario, many cooling devices and heat-pumps are transitioning toward the use of CO2 as an eco-friendly refrigerant, favoring carbon circular economy. Nevertheless, CO2 still has some limitations, such as large operating pressures (70-150 bar) and a critical point at 31 °C, which compromises efficiency and increases technological complexity. Very recently, an innovative breathing-caloric mechanism in the MIL-53(Al) compound is reported, which implies gas adsorption under CO2 pressurization boosted by structural transitions and which overcomes the limitations of stand-alone CO2. Here, the breathing-caloric-like effects of MOF-508b are reported, surpassing by 40% those of MIL-53(Al). Moreover, the first thermometry device operating at room temperature and under the application of only 26 bar of CO2 is presented. Under those conditions, this material presents values of ΔT ≈ 30 K, reaching heating temperatures of 56 °C and cooling temperatures of -10 °C, which are already useful for space heating, air-conditioning, food refrigeration, and freezing applications.

Discovery of Colossal Breathing-Caloric Effect under Low Applied Pressure in the Hybrid Organic-Inorganic MIL-53(Al) Material.

In this work, "breathing-caloric" effect is introduced as a new term to define very large thermal changes that arise from the combination of structural changes and gas adsorption processes occurring during breathing transitions. In regard to cooling and heating applications, this innovative caloric effect appears under very low working pressures and in a wide operating temperature range. This phenomenon, whose origin is analyzed in depth, is observed and reported here for the first time in the porous hybrid organic-inorganic MIL-53(Al) material. This MOF compound exhibits colossal thermal changes of ΔS ∼ 311 J K-1 kg-1 and ΔH ∼ 93 kJ kg-1 at room temperature (298 K) and under only 16 bar, pressure which is similar to that of common gas refrigerants at the same operating temperature (for instance, p(CO2) ∼ 64 bar and p(R134a) ∼ 6 bar) and noticeably lower than p > 1000 bar of most solid barocaloric materials. Furthermore, MIL-53(Al) can operate in a very wide temperature range from 333 K down to 254 K, matching the operating requirements of most HVAC systems. Therefore, these findings offer new eco-friendly alternatives to the current refrigeration systems that can be easily adapted to existing technologies and open the door to the innovation of future cooling systems yet to be developed.

Anomalous and colossal thermal expansion, photoluminescence, and dielectric properties in lead halide-layered perovskites with cyclohexylammonium and cyclopentylammonium cations.

A detailed study of lead halide-layered perovskites with general formula A2PbX4 (where A is cyclohexylammonium (CHA) or cyclopentylammonium (CPA) cation and X is Cl- or Br- anion) is presented. Using variable temperature synchrotron X-ray powder diffraction, we observe that these compounds exhibit diverse crystal structures above room temperature. Very interestingly, we report some unconventional thermomechanical responses such as uniaxial negative thermal expansion and colossal positive thermal expansion in a perpendicular direction. For the polymorphs of (CHA)2PbBr4, the volumetric thermal expansion coefficient is among the highest reported for any extended inorganic crystalline solid, reaching 480 MK-1. The phase transitions are confirmed by calorimetry and dielectric measurements, where the dielectric versus temperature curves show anomalies related with the order-disorder phase transitions. In addition, these compounds exhibit a broad photoluminescence (PL) emission with a large Stokes shift, which is related with an exciton PL emission.

Simple and Low-Cost Footstep Energy-Recover Barocaloric Heating and Cooling Device.

In this work, we design, build, and test one of the very first barocaloric devices. The here presented device can recover the energy generated by an individual's footstep and transform it into barocaloric heating and/or cooling. Accordingly, we present an innovative device that can provide eco-friendly and gas-free heating/cooling. Moreover, we test the device by measuring a new barocaloric organic polymer that exhibits a large adiabatic temperature change of ~2.9 K under the application of 380 bar. These results pave the way towards novel and more advanced barocaloric technologies and provide a simple and low-cost device to explore new barocaloric materials.