The triclinic form of AlPO 4 -34, a microporous aluminophosphate with the chabazite (CHA) topology, adopts a rhombohedral symmetry upon calcination. The framework structure of this phase remains intact under ambient conditions, but it distorts dramatically, though reversibly, in the presence of water. Following these structural changes in situ by X-ray diffraction revealed that there are actually two stable rehydrated phases, which differ from each other by one water molecule in the channel. Both of these phases have triclinic unit cells that are closely related to that of the calcined rhombohedral phase. The structure of the low-temperature (10 °C), fully rehydrated phase (phase B) was elucidated by combining high-resolution synchrotron powder diffraction with solid-state NMR techniques. Coordination of three of the six Al atoms to water molecules causes the deformation of the framework and the reduction of the symmetry. Rietveld refinement of the structure of phase B in the triclinic space group P1 (a ) 9.026, b ) 9.338, c ) 9.508 Å, R ) 95.1°, β ) 104.1°, and γ ) 96.6°) converged with R F ) 0.079 and R WP ) 0.176 (R exp ) 0.087). Framework connectivities derived from the structure were used to assign 31 P NMR lines as well as part of the 27 Al NMR signal.
The utilization of the reversible chemical and physical sorption of water on solids provides a new thermal energy storage concept with a great potential for lossless long‐term storage. The performance of microporous aluminophosphates in heat storage applications is highlighted by a comparative thermogravimetric and calorimetric study of three known materials (SAPO‐34, AlPO4‐18, APO‐Tric) and is correlated with their structural features. The maximum water sorption capacity is similar for all three samples and results in a stored energy density of 240 kWh m−3 in the 40–140 °C range. The elemental composition influences the gradual (silicoaluminophosphate SAPO‐34) or sudden (aluminophosphates AlPO4‐18, APO‐Tric) water uptake, with the latter being favourable in storage systems. The driving force for the determined sorption process is the formation of highly ordered water clusters in the pores, which is enabled by rapid and reversible changes in the Al coordination and optimal pore diameters. The ease with which changes in the Al coordination can occur in APO‐Tric is related to the use of the fluoride route in the synthesis. The understanding of these fundamental structure/sorption relationships forms an excellent basis for predicting the storage potential of numerous known or new microporous aluminophosphates and other porous materials from their crystal structures.
Hydrophilic porous materials are recognized as very promising materials for water-sorption-based energy storage and transformation. In this study, a porous, zeolite-like aluminophosphate with LTA (Linde Type A) topology is inspected as an energy-storage material. The study is motivated by the material's high predicted pore volume. According to sorption and calorimetric tests, the aluminophosphate outperforms all other zeolite-like and metal-organic porous materials tested so far. It adsorbs water in an extremely narrow relative-pressure interval (0.10 < p/p 0 < 0.15) and exhibits superior water uptake (0.42 g g −1 ) and energy-storage capacity (527 kW h m −3 ). It also shows remarkable cycling stability; after 40 cycles of adsorption/desorption its capacity drops by less than 2%. Desorption temperature for this material, which is one of crucial parameters in applications, is lower from desorption temperatures of other tested materials by 10-15 °C. Furthermore, its heatpump performance is very high, allowing efficient cooling in demanding conditions (with cooling power up to 350 kW h m −3 even at 30 °C temperature difference between evaporator and environment). On the microscopic scale, sorption mechanism in AlPO 4 -LTA is elucidated by X-ray diffraction, nuclear magnetic resonance measurements, and first-principles calculations. In this aluminophosphate, energy is stored predominately in hydrogen-bonded network of water molecules within the pores.
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