Enhanced Gas Adsorption on Cu3(BTC)2 Metal-Organic Framework by Post-Synthetic Cation Exchange and Computational Analysis.

Increased gas adsorption in a series of post-synthetically modified metal-organic frameworks (MOFs) of the type HKUST-1 was achieved by the partial cation exchange process. Manipulation of post-synthetic conditions demonstrates high tunability in the site substitution and gas adsorption properties during the dynamic equilibrium process. In this work, post-synthetic modification of Cu3(BTC)2 is carried on by exposure to TM2+ solutions (TM = Mn, Fe, Co, Ni) at different time intervals. The crystal structure, composition, and morphology were studied by powder X-ray diffraction, Fourier-transform infrared spectroscopy, inductively coupled plasma optical emission spectroscopy, and scanning electron microscopy. Structural analysis supports the retention of the crystal structure and partial substitution of the Cu metal nodes within the framework. A linear increase in the transmetalation process is observed with Fe and Co with a maximum percentage of 39 and 18%, respectively. Conversely, relatively low cation exchange is observed with Mn having a maximum percentage of 2.40% and Ni with only 2.02%. Gas adsorption measurements and surface area analysis were determined for each species. Interestingly, (Cu/Mn)3(BTC)2 revealed the highest CO2 adsorption capacity of 5.47 mmol/g, compared to 3.08 mmol/g for Cu3(BTC)2. The overall increased gas adsorption can be attributed to the formation of defects in the crystal structure during the cation exchange process. These results demonstrate the outstanding potential of post-synthetic ion exchange as a general approach to fine-tuning the physical properties of existing MOF architectures.

From Laves Phases to Quasicrystal Approximants in the Na-Au-Cd System.

The exploratory synthesis of gold-based polar intermetallic phases has revealed many new compounds with unprecedented crystal structures, unique bonding arrangements, and interesting electronic features. Here, we further understand the complexity of gold's crystal chemistry by studying the Na-Au-Cd ternary composition space. A nearly continuous structure transformation is observed between the seemingly simple binary NaAu2-NaCd2 phases, yielding three new intermetallic compounds with the compositions Na(Au0.89(5)Cd0.11(5))2, Na(Au0.51(4)Cd0.49(4))2, and Na8Au3.53(1)Cd13.47(1). Two compounds adopt different Laves phases, while the third crystallizes in a complex decagonal quasicrystal approximant. All three compounds are related through Friauf-Laves polyhedral building units with the gold/cadmium ratio found to control the transition among the unique crystal structures. Electronic structure calculations subsequently revealed the metallic nature of all three compounds with a combination of polar covalent Na-(Au/Cd) interactions and covalent (Au/Cd)-(Au/Cd) bonding interactions stabilizing each structure. These results highlight the crystal and electronic structure relationship among Laves phases and quasicrystal approximants enabled by the unique chemistry of gold.

From simple to complex crystal chemistry in the RE-Au-Tt systems (RE = La, Ce, Pr, Nd; Tt = Ge, Pb).

Polar intermetallics are an intriguing class of compounds with complex relationships between composition and structure that are not fully understood. This work reports a systematic study of the underexplored ternary composition space RE-Au-Tt (RE = La, Ce, Pr, Nd; Tt = Ge, Pb) to expand our knowledge of the intriguing chemistry and diversity achievable with these metallic constituents. These composition spaces are particularly interesting because of the potential to find Au-bearing, highly polar intermetallic compounds. The elements were first reacted through arc welding under an inert atmosphere, followed by annealing at 850 °C. X-ray diffraction of the products identified seven unreported compounds ranging from the simple NaTl-type compounds La1.5Au2Pb0.5 and Nd2-x Au2Pb x to the more structurally complex La5AuPb3 in the Hf5CuSn3-type structure and Pu3Pd4-type RE3Au3Ge (RE = La, Ce, Pr, Nd). First-principles electronic structure calculations investigate the combination of Fermi surface-Brillouin zone interactions, electrostatic interactions, and delocalized metallic bonding that contributes to the formation of these phases. These calculations show that a mixture of electrostatic and metallic bonding plays a dominant role in these phases. The RE-Au-Tt composition space remains full of potential for discovering materials with relevant magnetic and quantum properties, provided the crystal chemistry can be comprehended.

Superparamagnetic MOF@GO Ni and Co based hybrid nanocomposites as efficient water pollutant adsorbents.

A series of highly efficient adsorbents were developed using Ni3(BTC)2 and Co3(BTC)2 metal-organic frameworks (MOFs) and Fe3O4 magnetic nanoparticles (MNPs) to functionalize graphene oxide (GO). XRD results show high crystallinity of the prepared nanomaterials and the successful decoration of Ni3(BTC)2 and Co3(BTC)2 MOFs over the GO substrate (BTC = benzene-1,3,5-tricarboxylic acid). SEM and TEM imaging show the successful formation of nanoscale MOFs and Fe3O4 MNPs over GO. IR spectroscopy supports the characterization and successful preparation of the Fe3O4/MOF@GO hybrid composite nanoadsorbents. The prepared composite nanoadsorbents were used to sorb Methylene Blue (MB) as a model for common organic pollutants in water and common ions (Na+, Ca2+, Mg2+, SO42-, SiO32-) from a brackish water model. The adsorbed concentration at equilibrium of MB of the prepared composite nanoadsorbents increases by an average of 30.52 and 13.75 mg/g for the Co and Ni composite, respectively, when compared to the MOFs parent materials. The adsorbed amount of sulfate ions increases by 92.1 mg/g for the Co composite and 112.1 mg/g for the Ni composite, when compared to graphene oxide. This adsorption enhancement is attributed to suppressed aggregation through increased dispersive forces in the MOFs due to the presence of GO, formation of nanoscale MOFs over the GO platform, and the hindering of stacking of the graphene layers by the MOFs. Leaching tests show that the release of Co and Ni ions to water is reduced from 105.2 and 220 mg/L, respectively, in the parent MOF materials to 0.5 and 16.4 mg/L, respectively, in the composite nanoadsorbents. These findings show that the newly developed composite nanoadsorbents can sorb organic pollutants, and target sulfate and silicate anions, which makes them suitable candidates for water and wastewater treatments.