Avoiding the Kinetic Inertness of Chromium Ions Using a Coordination Substitution Strategy for the Rapid Synthesis of Chromium-Based Metal-Organic Frameworks.

Chromium-based metal-organic frameworks (Cr-MOFs) are very attractive in a wide range of applications due to their robustness and high porosity. However, the kinetic inertness of chromium ions results in the synthesis of Cr-MOFs often taking prolonged reaction times, which limit their industrial applications. Herein, we report a novel synthesis strategy based on coordination substitution, which overcomes the kinetic inertness of chromium ions and can synthesize Cr-MOFs in a shorter time. The versatility of this strategy has been demonstrated by producing several known Cr-MOFs, such as TYUT-96Cr, MIL-100Cr, MIL-101Cr, and MIL-53Cr. PXRD, SEM, TEM, 77 K N2 adsorption, and TGA have proved that the Cr-MOFs synthesized using this new strategy have good crystallinity, high porosity, and excellent thermal stability. The synthesis mechanism was investigated using theoretical calculations.

Effect of the Number of Methyl Groups in DMOF on N2O Adsorption and N2O/N2 Separation.

Nitrous oxide (N2O), as the third largest greenhouse gas in the world, also has great applications in industry, so the purification of N2O from N2 in industrial tail gas is a crucial process for achieving environmental protection and giving full play to its economic value. Based on the polarity difference of N2O and N2, N2O adsorption was researched on DMOF series materials with different polarities and methyl numbers of the ligand. N2O adsorption at 0.1 bar is enhanced, attributed to an increase of the methyl group densities at the benzenedicarboxylate linker. Grand canonical Monte Carlo simulations demonstrate the key role of methyl groups within the pore surface in the preferential N2O affinity. Methyl groups preferentially bind to N2O and thus enhanced low (partial) pressure N2O adsorption and N2O/N2 separation. The result shows that DMOF-TM has the highest N2O adsorption capacity (19.6 cm3/g) and N2O/N2 selectivity (23.2) at 0.1 bar. Breakthrough experiments show that, with an increase of the methyl number, the coadsorption time and retention time also increase, and DMOF-TM has the best N2O/N2 separation performance.

Tuning Piezoelectricity via Thermal Annealing at a Freestanding Ferroelectric Membrane.

Tuning the ferroelectric domain structure by a combination of elastic and electrostatic engineering provides an effective route for enhanced piezoelectricity. However, for epitaxial thin films, the clamping effect imposed by the substrate does not allow aftergrowth tuning and also limits the electromechanical response. In contrast, freestanding membranes, which are free of substrate constraints, enable the tuning of a subtle balance between elastic and electrostatic energies, giving new platforms for enhanced and tunable functionalities. Here, highly tunable piezoelectricity is demonstrated in freestanding PbTiO3 membranes, by varying the ferroelectric domain structures from c-dominated to c/a and a domains via aftergrowth thermal treatment. Significantly, the piezoelectric coefficient of the c/a domain structure is enhanced by a factor of 2.5 compared with typical c domain PbTiO3. This work presents a new strategy to manipulate the piezoelectricity in ferroelectric membranes, highlighting their great potential for nano actuators, transducers, sensors and other NEMS device applications.

Inverse Adsorption Separation of N2 O/CO2 in AgZK-5 Zeolite.

Nitrous oxide (N2 O), as the third largest greenhouse gas in the world, also has great applications in daily life and industrial production, like anesthetic, foaming agent, combustion supporting agent, N or O atomic donor. The capture of N2 O in adipic acid tail gas is of great significance but remains challenging due to the similarity with CO2 in molecular size and physical properties. Herein, the influence of cation types on CO2 -N2 O separation in zeolite was studied comprehensively. In particular, the inverse adsorption of CO2 -N2 O was achieved by AgZK-5, which preferentially adsorbs N2 O over CO2 , making it capable of trapping N2 O from an N2 O/CO2 mixture. AgZK-5 shows a recorded N2 O/CO2 selectivity of 2.2, and the breakthrough experiment indicates excellent performance for N2 O/CO2 separation. The density functional theory (DFT) calculation shows that Ag+ has stronger adsorption energy with N2 O, and the kinetics of N2 O is slightly faster than that of CO2 on AgZK-5.

A Customized Hydrophobic Porous Shell for MOF-5.

The susceptibility to moisture of metal-organic frameworks (MOFs) is a critical bottleneck for their wider practical application. Constructing core-shell composites has been postulated as an effective strategy for enhancing moisture resistance, but for fragile MOFs this has rarely been accomplished. We report herein, for the first time, the construction of a customized hydrophobic porous shell, NTU-COF, on the particularly fragile MOF-5 by a "Plug-Socket Anchoring" strategy. Notably, the pore structure of MOF-5 was well maintained, and it could still achieve complete CO2/N2 separation under humid conditions. The homogeneous interface between MOF-5 and NTU-COF has been inspected at atomic resolution by a combination of cryogenic focused ion beam (cryo-FIB) and ultralow-dose (scanning) transmission electron microscope giving profound insight into the mechanism of assembly of the core-shell structure. This work presents a facile strategy for the fabrication of a hydrophobic porous shell for labile MOFs, and provides a general approach for solving the problem of moisture instability of porous materials for practical applications.

Prominent Size Effects without a Depolarization Field Observed in Ultrathin Ferroelectric Oxide Membranes.

The increasing miniaturization of electronics requires a better understanding of material properties at the nanoscale. Many studies have shown that there is a ferroelectric size limit in oxides, below which the ferroelectricity will be strongly suppressed due to the depolarization field, and whether such a limit still exists in the absence of the depolarization field remains unclear. Here, by applying uniaxial strain, we obtain pure in-plane polarized ferroelectricity in ultrathin SrTiO_{3} membranes, providing a clean system with high tunability to explore ferroelectric size effects especially the thickness-dependent ferroelectric instability with no depolarization field. Surprisingly, the domain size, ferroelectric transition temperature, and critical strain for room-temperature ferroelectricity all exhibit significant thickness dependence. These results indicate that the stability of ferroelectricity is suppressed (enhanced) by increasing the surface or bulk ratio (strain), which can be explained by considering the thickness-dependent dipole-dipole interactions within the transverse Ising model. Our study provides new insights into ferroelectric size effects and sheds light on the applications of ferroelectric thin films in nanoelectronics.

Synergistic Nitrogen Binding Sites in a Metal-Organic Framework for Efficient N2 /O2 Separation.

Porous materials with d3 electronic configuration open metal sites have been proved to be effective adsorbents for N2 capture and N2 /O2 separation. However, the reported materials remain challenging to address the trade-off between adsorption capacity and selectivity. Herein, we report a robust MOF, MIL-102Cr, that features two binding sites, can synergistically afford strong interactions for N2 capture. The synergistic adsorption site exhibits a benchmark Qst of 45.0 kJ mol-1 for N2 among the Cr-based MOFs, a record-high volumetric N2 uptake (31.38 cm3 cm-3 ), and highest N2 /O2 selectivity (13.11) at 298 K and 1.0 bar. Breakthrough experiments reveal that MIL-102Cr can efficiently capture N2 from a 79/21 N2 /O2 mixture, providing a record 99.99 % pure O2 productivity of 0.75 mmol g-1 . In situ infrared spectroscopy and computational modelling studies revealed that a synergistic adsorption effect by open Cr(III) and fluorine sites was accountable for the strong interactions between the MOF and N2 .

Ultramicroporous Hydrogen-Bonded Organic Framework Material with a Thermoregulatory Gating Effect for Record Propylene Separation.

Propane/propylene separation is one of the most challenging and energy-consuming but most important tasks in the petrochemical industry. Herein, a stable hydrogen-bonded organic framework (HOF-FJU-1) was tailor-made for highly efficient propylene separation from binary C3H6/C3H8 and even seven component CH4/C2H4/C2H6/C3H6/C3H8/CO2/H2 mixtures. The temperature-controllable diffusion channels in HOF-FJU-1 have enabled the porous material to completely exclude propane to reach high-performance propylene purification under energy-efficient operation conditions. Single-crystal structural analysis revealed that the well-matched pore aperture of HOF-FJU-1 can exactly accommodate propylene molecules via multiple intermolecular interactions, exhibiting a very high propylene/propane selectivity of 616 at 333 K. The propylene purity and productivity are over 99.5% and 30.2 L kg-1 from the binary C3H6/C3H8 (50/50) mixture at 333 K. Through a follow-up column separation of C3H6/C2H4 at 353 K, not only high-purity propylene (99.5%) but also ethylene (98.3%) can be readily collected from the seven component CH4/C2H4/C2H6/C3H6/C3H8/CO2/H2 (31/10/25/10/10/1/13) cracking gas mixtures. The great potential of HOF-FJU-1 for the industrial propylene separation process has been further supported by the high stability of this porous material under different environments and straightforward processibility and regeneration feasibility.

CO2 Capture from High-Humidity Flue Gas Using a Stable Metal-Organic Framework.

The flue gas from fossil fuel power plants is a long-term stable and concentrated emission source of CO2, and it is imperative to reduce its emission. Adsorbents have played a pivotal role in reducing CO2 emissions in recent years, but the presence of water vapor in flue gas poses a challenge to the stability of adsorbents. In this study, ZIF-94, one of the ZIF adsorbents, showed good CO2 uptake (53.30 cm3/g), and the calculated CO2/N2 (15:85, v/v) selectivity was 54.12 at 298 K. Because of its excellent structural and performance stability under humid conditions, the CO2/N2 mixture was still well-separated on ZIF-94 with a separation time of 30.4 min when the relative humidity was as high as 99.2%, which was similar to the separation time of the dry gas experiments (33.2 min). These results pointed to the enormous potential applications of ZIF-94 for CO2/N2 separation under high humidity conditions in industrial settings.

K-Chabazite Zeolite Nanocrystal Aggregates for Highly Efficient Methane Separation.

Methane (CH4 ) enrichment and purification is of great significance for increasing the heating value of unconventional natural gas sources and curtailing its effect on global warming. For a long time, commercial adsorbents for CH4 separation have been hampered by low adsorption capacities, sub-optimal adsorption selectivities, or slow diffusion rates, which have significantly restricted separation productivity. Herein, we report a facile and green seed-passaging method to fabricate donut-like macro-meso-micro hierarchical zeolite K-Chabazite nanocrystal aggregates. This consecutive seed-inducing method requires no organic template. By utilizing this unique nanocrystallization technique, the CH4 adsorption capacity, gas diffusion rate, and separation productivity of the resultant material are dramatically increased compared with those of commercially available adsorbents, thus setting a new benchmark in CH4 /N2 separation. More importantly, production of this adsorbent can be easily scaled-up to the order of 100 kg using readily available raw materials in this environmentally friendly synthetic route, enabling potential industrial implementation.