Autonomous indoor humidity control is gaining more and more attention but is limited by the trade-offs among pore volume,pore size and water stability of water adsorbents.We solve this problem by using a unique coordi...Autonomous indoor humidity control is gaining more and more attention but is limited by the trade-offs among pore volume,pore size and water stability of water adsorbents.We solve this problem by using a unique coordination network topology combined with hydrolytically stable M(Ⅲ)carboxylate clusters.By extending the ligand length from 9.0 to 11.2 and 13.7?,the pore volume significantly increases from 0.99 to 1.40 and 1.78 cm^(3)g^(-1),which proportionally increases the saturated water adsorption capacity.Meanwhile,the pore size slightly increases from 10.4 to 11.0 and 13.5A,which restricts the isotherm inflection pressure and hysteresis width to meet the requirement of indoor humidity control.Large single-crystals suitable for Xray diffraction studies were obtained by using Fe(Ⅲ)salts,while isostructural frameworks with sufficiently high water stabilities were synthesized by using Cr(Ⅲ)salts,which offer record working capacity of 0.90 and 1.10 g g^(-1)for indoor humidity control.展开更多
Hybrid ferroelastic crystals have garnered considerable interest due to their promising potential as mechanical switches and sensors.The anomalous ferroelastic phase transitions,in which ferroelasticity occurs in the ...Hybrid ferroelastic crystals have garnered considerable interest due to their promising potential as mechanical switches and sensors.The anomalous ferroelastic phase transitions,in which ferroelasticity occurs in the hightemperature phase rather than the low-temperature phase,are of particular interest,but they are sporadically-documented and none of them is involved in breaking of the chemical bonds.Herein,a hydroxyl-containing cation,i.e.,Me_(3)NOH^(+),is employed to construct a three-dimensional hybrid crystal(Me_(3)NOH)_(2)KBiCl_(6)(1).This crystal undergoes distinct twostep structural phase transitions with space-group changes of Pna21–P112_(1)–P63mc,belonging to an anomalous temperaturereversed mm2F2 ferroelastic transition and a normal 6mmF2 ferroelastic transition,respectively.The anomalous ferroelastic transition is entirely driven by switchable K–O coordination bonds involving breaking and reformation.Notably,the dynamic behavior of Me_(3)NOH^(+)cations along with the distortion of inorganic framework enables the manifestation of unusual“high-low-medium”second-harmonic generation-switching behaviors.This study presents the enormous benefits of switchable coordination bonds for inducing anomalous ferroelastic phase transitions,offering valuable insight for the exploration of new multifunctional ferroelastic materials.展开更多
基金supported by the National Natural Science Foundation of China(22090061,22231012,21821003,22071272)。
文摘Autonomous indoor humidity control is gaining more and more attention but is limited by the trade-offs among pore volume,pore size and water stability of water adsorbents.We solve this problem by using a unique coordination network topology combined with hydrolytically stable M(Ⅲ)carboxylate clusters.By extending the ligand length from 9.0 to 11.2 and 13.7?,the pore volume significantly increases from 0.99 to 1.40 and 1.78 cm^(3)g^(-1),which proportionally increases the saturated water adsorption capacity.Meanwhile,the pore size slightly increases from 10.4 to 11.0 and 13.5A,which restricts the isotherm inflection pressure and hysteresis width to meet the requirement of indoor humidity control.Large single-crystals suitable for Xray diffraction studies were obtained by using Fe(Ⅲ)salts,while isostructural frameworks with sufficiently high water stabilities were synthesized by using Cr(Ⅲ)salts,which offer record working capacity of 0.90 and 1.10 g g^(-1)for indoor humidity control.
基金supported by the National Natural Science Foundation Of China(22071273 and 21821003)the Fundamental Research Funds for the Central Universities,Sun Yat-Sen University(23lgzy001).
文摘Hybrid ferroelastic crystals have garnered considerable interest due to their promising potential as mechanical switches and sensors.The anomalous ferroelastic phase transitions,in which ferroelasticity occurs in the hightemperature phase rather than the low-temperature phase,are of particular interest,but they are sporadically-documented and none of them is involved in breaking of the chemical bonds.Herein,a hydroxyl-containing cation,i.e.,Me_(3)NOH^(+),is employed to construct a three-dimensional hybrid crystal(Me_(3)NOH)_(2)KBiCl_(6)(1).This crystal undergoes distinct twostep structural phase transitions with space-group changes of Pna21–P112_(1)–P63mc,belonging to an anomalous temperaturereversed mm2F2 ferroelastic transition and a normal 6mmF2 ferroelastic transition,respectively.The anomalous ferroelastic transition is entirely driven by switchable K–O coordination bonds involving breaking and reformation.Notably,the dynamic behavior of Me_(3)NOH^(+)cations along with the distortion of inorganic framework enables the manifestation of unusual“high-low-medium”second-harmonic generation-switching behaviors.This study presents the enormous benefits of switchable coordination bonds for inducing anomalous ferroelastic phase transitions,offering valuable insight for the exploration of new multifunctional ferroelastic materials.
