RESUMEN
Diamine-functionalized metal-organic frameworks (MOFs) based on Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobihyenyl-3,3'-dicarboxylate) have been frequently reported as promising CO2 adsorbents due to their characteristic step-shaped adsorption behavior. However, high CO2 desorption temperatures for diamine-Mg2(dobpdc)-based adsorbents led to gradual diamine loss while the existence of an exotic CO2 adsorption mode remains experimentally unanswered. Herein, we present CO2 adsorbents obtained by functionalizing Mn2(dobpdc) with a diaminopropane series. These adsorbents offer low regeneration energies, allowing CO2 desorption at lower temperatures than the reported Mg-based analogs. Our first-principles density functional theory calculations showed that the binding strength between the diamine and Mn ions in Mn2(dobpdc) was stronger than that between the diamine and Mg ions in Mg2(dobpdc), preventing diamine loss even at high temperatures and enabling efficient regeneration. Additionally, the computational and experimental data demonstrated that primary-tertiary diamine-functionalized MOFs exhibit one-channel flipped adsorption structures that have not been experimentally revealed. Our findings provide insights into the role of metal ions in diamine loss for the future development of efficient amine-based CO2 adsorbents.
RESUMEN
Postsynthetic modifications (PSMs) of metal-organic frameworks (MOFs) play a crucial role in enhancing material performance through open metal site (OMS) functionalization or ligand exchange. However, a significant challenge persists in preserving open metal sites during ligand exchange, as these sites are inherently bound by incoming ligands. In this study, for the first time, we introduced alkoxides by exchanging bridging chloride in Ni2Cl2BTDD (BTDD=bis (1H-1,2,3,-triazolo [4,5-b],-[4',5'-i]) dibenzo[1,4]dioxin) through PSM. Rietveld refinement of synchrotron X-ray diffraction data indicated that the alkoxide oxygen atom bridges Ni(II) centers while the OMSs of the MOF are preserved. Due to the synergy of the existing OMS and introduced functional group, the alkoxide-exchanged MOFs showed CO2 uptakes superior to the pristine MOF. Remarkably, the tert-butoxide-substituted Ni_T exhibited a nearly threefold and twofold increase in CO2 uptake compared to Ni2Cl2BTDD at 0.15 and 1â bar, respectively, as well as high water stability relative to the other exchanged frameworks. Furthermore, the Grand Canonical Monte Carlo simulations for Ni_T suggested that CO2 interacts with the OMS and the surrounding methyl groups of tert-butoxide groups, which is responsible for the enhanced CO2 capacity. This work provides a facile and unique synthetic strategy for realizing a desirable OMS-incorporating MOF platform through bridging ligand exchange.
RESUMEN
The development of adsorbents for Kr and Xe separation is essential to meet industrial demands and for energy conservation. Although a number of previous studies have focused on Xe-selective adsorbents, stimuli-responsive Xe/Kr-selective adsorbents still remain underdeveloped. Herein, a Hofmann-type framework Co(DABCO)[Ni(CN)4 ] (referred to as CoNi-DAB; DABCO = 1,4-diazabicyclo[2,2,2]octane) that provides a temperature-dependent switchable Xe/Kr separation performance is reported. CoNi-DAB showed high Kr/Xe (0.8/0.2) selectivity with significant Kr adsorption at 195 K as well as high Xe/Kr (0.2/0.8) selectivity with superior Xe adsorption at 298 K. Such adsorption features are associated with the temperature-dependent rotational configuration of the DABCO ligand, which affects the kinetic gate-opening temperature of Xe and Kr. The packing densities of Xe (2.886 g cm-3 at 298 K) and Kr (2.399 g cm-3 at 195 K) inside the framework are remarkable and comparable with those of liquid Xe (3.057 g cm-3 ) and liquid Kr (2.413 g cm-3 ), respectively. Breakthrough experiments confirm the temperature-dependent reverse separation performance of CoNi-DAB at 298 K under dry and wet (88% relative humidity) conditions and at 195 K under dry conditions. The unique adsorption behavior is also verified through van der Waals (vdW)-corrected density functional theory (DFT) calculations and nudged elastic band (NEB) simulations.
RESUMEN
INTRODUCTION: The aims of this study were to assess the biologic stability of a newly designed hollow (H-type) miniscrew compared with conventional (C-type) miniscrews through histomorphometric and histologic analysis. METHODS: Both types of miniscrews were placed into the maxillae and the mandibles of 12 beagles. Maximum insertion torque, Periotest (Siemens AG, Bensheim, Germany) value, bone-implant contact, and bone volume were measured. RESULTS: The overall success rates of the H-type were 78.3% in the maxilla and 60.0% in the mandible. Mean maximum insertion torque values of the H-type were 14.2 N-cm in the maxilla and 20.9 N-cm in the mandible. The Periotest values of the H-type were -1.5 in the maxilla and -6.4 in the mandible. Mean maximum insertion torque and Periotest values of the H-type were higher than those of the C-type. In the maxilla, the bone-implant contact values of the H-type were 37.3% and 32.3% at 3 and 12 weeks, respectively. In the mandible, the bone-implant contact values were 31.4% and 18.5% at 3 and 12 weeks, respectively. CONCLUSIONS: Considering the lower success rate and the insufficient bone-implant contact and bone volume of the H-type in the mandible, the clinician should choose a suitable combination of miniscrews depending on local bone quality and implantation site, such as an H-type in the maxilla and a C-type in the mandible.
