Stimulus-Induced Dynamic Behavior Regulation of Flexible Crystals through the Tuning of Module Rigidity.

Introducing dynamic behavior into periodic frameworks has borne fruit in the form of flexible porous crystals. The detailed molecular design of frameworks in order to control their collective dynamics is of particular interest, for example, to achieve stimulus-induced behavior. Herein, by varying the degree of rigidity of ditopic pillar linkers, two isostructural flexible metal-organic frameworks (MOFs) with common rigid supermolecular building bilayers were constructed. The subtle substitution of single (in bibenzyl-4,4'-dicarboxylic acid; H2BBDC) with double (in 4,4'-stilbenedicarboxylic acid; H2SDC) C-C bonds in pillared linkers led to markedly different flexible behavior of these two MOFs. Upon the removal of guest molecules, both frameworks clearly show reversible single-crystal-to-single-crystal transformations involving the cis-trans conformation change and a resulting swing of the corresponding pillar linkers, which gives rise to Flex-Cd-MOF-1a and Flex-Cd-MOF-2a, respectively. Strikingly, a more favorable gas-induced dynamic behavior in Flex-Cd-MOF-2a was verified in detail by stepwise C3H6/C3H8 sorption isotherms and the corresponding in situ powder X-ray diffraction experiments. These insights are strongly supported by molecular modeling studies on the sorption mechanism that explores the sorption landscape. Furthermore, a consistency between the macroscopic elasticity and microscopic flexibility of Flex-Cd-MOF-2 was observed. This work fuels a growing interest in developing MOFs with desired chemomechanical functions and presents detailed insights into the origins of flexible MOFs.

Engineering Single-Atom Sites with the Irving-Williams Series for the Simultaneous Co-photocatalytic CO2 Reduction and CH3CHO Oxidation.

The bonding effects between 3d transition-metal single sites and supports originate from crystal field stabilization energy (CFSE). The 3d transition-metal atoms of the spontaneous geometrical distortions, that is the Jahn-Teller effect, can alter CFSE, thereby leading to the Irving-Williams series. However, engineering single-atom sites (SASs) using the Irving-Williams series as an ideal guideline has not been reported to date. Herein, alkynyl-linked covalent phenanthroline frameworks (CPFs) with phenanthroline units are developed to anchor the desired 3d single metal ions from d5 to d10 (Mn2+, Fe3+, Co2+, Ni2+, Cu2+, and Zn2+). The Irving-Williams series was employed to accurately predict the bonding effects between 3d transition-metal atoms and phenanthroline units. To verify this, theoretical calculations and experimental results reveal that Cu-SASs/CPFs exhibits higher stability and faster charge-transfer efficiency, far surpassing other metal-SASs/CPFs. As expected, Cu-SASs/CPFs demonstrates a high photoreduction of CO2-to-CO activity (~30.3 µmol·g-1·h-1) and an exceptional photooxidation of CH3CHO-to-CH3COOH activity (~24.7 µmol·g-1·h-1). Interestingly, the generated *O2- is derived from the process of CO2 reduction, thereby triggering a CH3CHO oxidation reaction. This work provides a novel design concept for designing SASs by the Irving-Williams to regulate the catalytic performances.

Fluorinated MOF-Based Hexafluoropropylene Nanotrap for Highly Efficient Purification of Octafluoropropane Electronic Specialty Gas.

High-purity octafluoropropane (C3F8) electronic specialty gas is a key chemical raw material in semiconductor and integrated circuit manufacturing industry, while selective removal of hexafluoropropylene (C3F6) impurity for C3F8 purification is essential but a challenging task. Here we report a fluorinated cage-like MOF Zn-bzc-CF3 (bzc=5-(trifluoromethyl)-1H-pyrazole-4-carboxylic acid) for C3F6/C3F8 separation. The incorporation of -CF3 groups not only provides suitable pore aperture size for highly efficient size-exclusive C3F6/C3F8 separation, but also creates hydrophobic microenvironments, endowing Zn-bz-CF3 high chemical stability. Remarkably, Zn-bzc-CF3 exhibits high C3F6 adsorption capacity while excluding C3F8, achieving ideal molecular-sieving C3F6/C3F8 separation. Breakthrough experiments show that Zn-bzc-CF3 can efficiently separate C3F6/C3F8 mixture and high-purity C3F8 (99.9 %) can be obtained.

Biomimetic Photodegradation of Glyphosate in Carborane-Functionalized Nanoconfined Spaces.

The removal of organophosphorus (OP) herbicides from water has been studied using adsorptive removal, chemical oxidation, electrooxidation, enzymatic degradation, and photodegradation. The OP herbicide glyphosate (GP) is one of the most used herbicides worldwide, leading to excess GP in wastewater and soil. GP is commonly broken down in environmental conditions to compounds such as aminomethylphosphonic acid (AMPA) or sarcosine, with AMPA having a longer half-life and similar toxicity to GP. Metal-organic frameworks (MOFs) are excellent materials for purifying OP herbicides from water due to their ability to combine adsorption and photoactivity within one material. Herein, we report the use of a robust Zr-based MOF with a meta-carborane carboxylate ligand (mCB-MOF-2) to examine the adsorption and photodegradation of GP. The maximum adsorption capacity of mCB-MOF-2 for GP was determined to be 11.4 mmol/g. Non-covalent intermolecular forces between the carborane-based ligand and GP within the micropores of mCB-MOF-2 are thought to be responsible for strong binding affinity and capture of GP. After 24 h of irradiation with ultraviolet-visible (UV-vis) light, mCB-MOF-2 selectively converts 69% of GP to sarcosine and orthophosphate, following the C-P lyase enzymatic pathway and biomimetically photodegrading GP. Circumventing the production of AMPA is desirable, as it has a longer half-life and similar toxicity to GP. The exceptional adsorption capacity of GP by mCB-MOF-2 and its biomimetic photodegradation to non-toxic sarcosine make it a promising material for removing OP herbicides from water.

Tuning the Trade-Off between Ethane/Ethylene Selectivity and Adsorption Capacity within Isoreticular Microporous Metal-Organic Frameworks by Linker Fine-Fluorination.

The pore dimension and surface property directly dictate the transport of guests, endowing diverse gas selective adsorptions to porous materials. It is highly relevant to construct metal-organic frameworks (MOFs) with designable functional groups that can achieve feasible pore regulation to improve their separation performances. However, the role of functionalization in different positions or degrees within framework on the separation of light hydrocarbon has rarely been emphasized. In this context, four isoreticular MOFs (TKL-104-107) bearing dissimilar fluorination are rationally screened out and afforded intriguing differences in the adsorption behavior of C2 H6 and C2 H4 . Ortho-fluoridation of carboxyl allows TKL-105-107 to exhibit enhanced structural stabilities, impressive C2 H6 adsorption capacities (>125 cm3 g-1 ) and desirable inverse selectivities (C2 H6 over C2 H4 ). The more modified ortho-fluorine group and meta-fluorine group of carboxyl have improved the C2 H6 /C2 H4 selectivity and adsorption capacity, respectively, and the C2 H6 /C2 H4 separation potential can be well optimized via linker fine-fluorination. Meanwhile, dynamic breakthrough experiments proved that TKL-105-107 can be used as highly efficient C2 H6 -selective adsorbents for C2 H4 purification. This work highlights that the purposeful functionalization of pore surfaces facilitates the assembly of highly efficient MOF adsorbents for specific gas separation.

Trace removal of benzene vapour using double-walled metal-dipyrazolate frameworks.

In principle, porous physisorbents are attractive candidates for the removal of volatile organic compounds such as benzene by virtue of their low energy for the capture and release of this pollutant. Unfortunately, many physisorbents exhibit weak sorbate-sorbent interactions, resulting in poor selectivity and low uptake when volatile organic compounds are present at trace concentrations. Herein, we report that a family of double-walled metal-dipyrazolate frameworks, BUT-53 to BUT-58, exhibit benzene uptakes at 298 K of 2.47-3.28 mmol g-1 at <10 Pa. Breakthrough experiments revealed that BUT-55, a supramolecular isomer of the metal-organic framework Co(BDP) (H2BDP = 1,4-di(1H-pyrazol-4-yl)benzene), captures trace levels of benzene, producing an air stream with benzene content below acceptable limits. Furthermore, BUT-55 can be regenerated with mild heating. Insight into the performance of BUT-55 comes from the crystal structure of the benzene-loaded phase (C6H6@BUT-55) and density functional theory calculations, which reveal that C-H···X interactions drive the tight binding of benzene. Our results demonstrate that BUT-55 is a recyclable physisorbent that exhibits high affinity and adsorption capacity towards benzene, making it a candidate for environmental remediation of benzene-contaminated gas mixtures.

Theoretical Screening of CO2 Electroreduction over MOF-808-Supported Self-Adaptive Dual-Metal-Site Pairs.

Electrochemical CO2 reduction to transportation fuels and valuable platform chemicals provides a sustainable avenue for renewable energy storage and realizes an artificially closed carbon loop. However, the rational design of highly active and selective CO2 reduction electrocatalysts remains a challenging task. Herein, a series of metal-organic framework (MOF)-supported flexible, self-adaptive dual-metal-site pairs (DMSPs) including 21 pairwise combinations of six transition metal single sites (MOF-808-EDTA-M1M2, M1/M2 = Fe, Cu, Ni, Pd, Pt, Au) for the CO2 reduction reaction (CO2RR) were theoretically screened using density functional theory calculations. Against the competitive hydrogen evolution reaction, MOF-808-EDTA-FeFe and MOF-808-EDTA-FePt were identified as the promising CO2RR electrocatalysts toward C1 and C2 products. The calculated limiting potential for CO2 electroreduction to C2H6 and C2H5OH over MOF-808-EDTA-FeFe is -0.87 V. Compared with an applied potential of -0.56 eV toward CH4 production over MOF-808-EDTA-FeFe, MOF-808-EDTA-FePt exhibits an even better activity for CO2 reduction to C1 products at a limiting potential of -0.35 V. The present work not only identifies promising candidates for highly selective CO2RR electrocatalysts leading to C1 and C2 products but also provides mechanistic insights into the dynamic nature of DMSPs for stabilizing various reaction intermediates in the CO2RR process.

Stepwise Engineering the Pore Aperture of a Cage-like MOF for the Efficient Separation of Isomeric C4 Paraffins under Humid Conditions.

The separation of isomeric C4 paraffins is an important task in the petrochemical industry, while current adsorbents undergo a trade-off relationship between selectivity and adsorption capacity. In this work, the pore aperture of a cage-like Zn-bzc (bzc=pyrazole-4-carboxylic acid) is tuned by the stepwise installation methyl groups on its narrow aperture to achieve both molecular-sieving separation and high n-C4 H10 uptake. Notably, the resulting Zn-bzc-2CH3 (bzc-2CH3 =3,5-dimethylpyrazole-4-carboxylic acid) can sensitively capture n-C4 H10 and exclude iso-C4 H10 , affording molecular-sieving for n-C4 H10 /iso-C4 H10 separation and high n-C4 H10 adsorption capacity (54.3 cm3 g-1 ). Breakthrough tests prove n-C4 H10 /iso-C4 H10 can be efficiently separated and high-purity iso-C4 H10 (99.99 %) can be collected. Importantly, the hydrophobic microenvironment created by the introduced methyl groups greatly improves the stability of Zn-bzc and significantly eliminates the negative effect of water vapor on gas separation under humid conditions, indicating Zn-bzc-2CH3 is a new benchmark adsorbent for n-C4 H10 /iso-C4 H10 separation.

Facile Tuned TSCT-TADF in Donor-Acceptor MOF for Highly Adjustable Photonic Modules based on Heterostructures Crystals.

Highly adjustable photonic modules were constructed based on the heterostructures crystals of a new series of donor-acceptor metal-organic framework (D-A MOF) featuring highly tunable thermally activated delayed fluorescence (TADF). By introducing N-phenylcarbazole and derivatives as donor guests into the acceptor host NKU-111, highly tunable through-space charge transfer based TADF could be achieved through the engineering of heavy atom effect, which result in modulatable emission wavelength (540 to 600 nm) and enhanced quantum yield (up to 30.86 %). Furthermore, by rationally integrating the D-A MOFs with distinctive emissions, rod-like heterostructures crystals featuring excitation position dependent tip emissions in wide wavelength range (495 to 598 nm) could be fabricated, which could serve as highly potential photonic modules for photonic circuit applications.

Synthesis, Characterization, and Electrochemistry of Copper Dibenzoporphyrin(2.1.2.1) Complexes.

Three copper dibenzoporphyrin(2.1.2.1) complexes having two dipyrromethene units connected through o-phenylen bridges and 4-MePh, Ph, or F5Ph substituents at the meso positions of the dipyrrins were synthesized and characterized according to their spectral, electrochemical, and structural properties. As indicated by the single-crystal X-ray structures, all three derivatives have highly bent molecular structures, with angles between each planar dipyrrin unit ranging from 89° to 85°, indicative of a nonaromatic molecule. The insertion of copper(II) into dibenzoporphyrins(2.1.2.1) induced a change in the macrocyclic cavity shape from rectangular in the case of the free-base precursors to approximately square for the metalated copper derivatives. Solution electron paramagnetic resonance (EPR) spectra at 100 K showed hyperfine coupling of the Cu(II) central metal ion and the N nucleus in the highly bent molecular structures. Electrochemical measurements in CH2Cl2 or N,N-dimethylformamide (DMF) containing 0.1 M tetrabutylammonium perchlorate (TBAP) were consistent with ring-centered electron transfers and, in the case of reduction, were assigned to electron additions involving two equivalent π centers on the bent nonaromatic molecule. The potential separation between the two reversible one-electron reductions ranged from 230 to 400 mV in DMF, indicating a moderate-to-strong interaction between the equivalent redox-active dipyrrin units of the dibenzoporphyrins(2.1.2.1). The experimentally measured highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps ranged from 2.14 to 2.04 eV and were smaller than those seen for the planar copper tetraarylporphyrins(1.1.1.1), (Ar)4PCu.

Student's t-Kernel-Based Maximum Correntropy Kalman Filter.

The state estimation problem is ubiquitous in many fields, and the common state estimation method is the Kalman filter. However, the Kalman filter is based on the mean square error criterion, which can only capture the second-order statistics of the noise and is sensitive to large outliers. In many areas of engineering, the noise may be non-Gaussian and outliers may arise naturally. Therefore, the performance of the Kalman filter may deteriorate significantly in non-Gaussian noise environments. To improve the accuracy of the state estimation in this case, a novel filter named Student's t kernel-based maximum correntropy Kalman filter is proposed in this paper. In addition, considering that the fixed-point iteration method is used to solve the optimal estimated state in the filtering algorithm, the convergence of the algorithm is also analyzed. Finally, comparative simulations are conducted and the results demonstrate that with the proper parameters of the kernel function, the proposed filter outperforms the other conventional filters, such as the Kalman filter, Huber-based filter, and maximum correntropy Kalman filter.

A Peptide HEPFYGNEGALR from Apostichopus japonicus Alleviates Acute Alcoholic Liver Injury by Enhancing Antioxidant Response in Male C57BL/6J Mice.

Liver-related disease caused by alcohol is a frequent disorder of the hepatic tract. Heavy consumption of alcohol in a short period causes oxidative damage to the liver. Sea cucumber is abundant in nutrients and its various extracts have been studied for antioxidant properties. One peptide was isolated and identified from Apostichopus japonicus in our recent study. We investigated the benefits of the peptide in a model of acute ethanol-induced male C57BL/6J mice. Dietary intake of the peptide could attenuate hepatomegaly, hepatitis and the accumulation of lipid droplets, and increase antioxidant enzyme activities in mice with acute alcoholic liver injury. The results indicated that a 20 mg/kg peptide supplement could activate the Nrf2/HO-1 pathway and block the nuclear translocation of NF-κB to alleviate oxidative stress and inflammation. In addition, the preventive effects of peptide supplementation may be related to autophagy. This study suggests that dietary supplementation with a sea cucumber-derived peptide is one of the potential candidates to alleviate acute alcoholic liver injury.

Synergistic effect of carboxyl and sulfate groups for effective removal of radioactive strontium ion in a Zr-metal-organic framework.

Rapid removal of radioactive strontium from nuclear wastewater is of great significance for environmental safety and human health. This work reports the effective adsorption of strontium ion in a stable dual-group metal-organic framework, Zr6(OH)14(BDC-(COOH)2)4(SO4)0.75 (Zr-BDC-COOH-SO4), which contains strontium-chelating groups (-COOH and SO4) and a strongly ionizable group (-COOH). Zr-BDC-COOH-SO4 exhibits very rapid adsorption kinetics (<5 min) and a maximum adsorption capacity of 67.5 mg g-1. The adsorption behaviors can be well fitted to the pseudo-second-order model and the Langmuir isotherm model. Further investigations indicate that the adsorption of Sr2+ onto Zr-BDC-COOH-SO4 would not be obviously affected by solution pH and adsorption temperature. The feasible regeneration of the adsorbent was also demonstrated using a simple elution method. Mechanism investigation suggests that free -COOH contributes to the rapid adsorption based on electrostatic interaction, while the introduction of -SO4 significantly enhanced the adsorption capacity. Thus, these results suggest that Zr-BDC-COOH-SO4 is a potential candidate for Sr2+ removal. They also introduce dual groups as an effective strategy for designing high-efficiency adsorbents.

[Effective medicinal ingredients and screening of excellent germplasm in Rubus chingii].

In order to provide rationale for selection of good germplasm in Rubus chingii, main effective medicinal ingredients of green fruit such as gallic acid, ellagic acid, kaempferol-3-rutinoside, astragalin and tiliroside were measured using UPLC for the samples collected from Chun'an county of Zhejiang province, and such parameters as soluble solid contents of ripe fruit of some samples were also measured to study variation among individuals and correlation. It has been found that there were differences among individuals in the contents of gallic acid, ellagic acid, kaempferol-3-rutinoside, astragalin and tiliroside, which ranged from 0.010 2%-0.027 4%, 0.089 5%-0.291 1%, 0.010 5%-0.114 8%, 0.005 8%-0.041 2% and 0.010 9%-0.086 3%, respectively, with a CV of 18.60%, 27.02%, 44.23%, 44.17% and 47.29%, respectively. Gallic acid was positively correlated with ellagic acid, but negatively with kaempferol-3-rutinoside and astragalin significantly. Significantly positive correlation existed between kaempferol-3-rutinoside, astragalin and linden glycoside as well as between ellagic acid and fruit shape index of ripe fruit and between linden glycoside and the content of soluble solids. 51.35% of the individuals had a content of soluble solids more than 15%. Therefore, abundant variations have been found among individuals in effective medicinal ingredients in R. chingii, which shows great potential for selection, but only do 7.61% of the individuals meet the requirement of Chinese pharmacopoeia in terms of the contents of effective medicinal ingredients. Therefore, selection could be first performed in terms of fruit shape index of ripe red fruit, followed by the contents of ellagic acid and kaempferol-3-rutinoside measured. The individuals, in which the contents of effective medicinal ingredients don't meet the requirement of Chinese pharmacopoeia, could be considered for the selection in terms of edible fresh fruit.

Microporous Hydrogen-Bonded Organic Framework for Highly Efficient Turn-Up Fluorescent Sensing of Aniline.

A microporous three-dimensional (3D) hydrogen-bonded organic framework (HOF-20) has been constructed from an aromatic-rich tetratopic carboxylic acid, 5-(2,6-bis(4-carboxyphenyl)pyridin-4-yl)isophthalic acid (H4BCPIA). The activated HOF-20a has a moderately high Brunauer-Emmett-Teller (BET) surface area of 1323 m2 g-1 and excellent stability in water and HCl aqueous solution. HOF-20 exhibits highly efficient turn-up fluorescent sensing of aniline in water with a detection limit of 2.24 µM and is selective toward aniline in the presence of aromatic interferents, owing to the hydrogen bonding and edge-to-face π-π stacking interactions between the HOF-20 host and the guest aniline molecules, as demonstrated in the single-crystal X-ray structure of HOF-20⊃aniline. Density functional theory (DFT) calculations further demonstrate that the recognition of aniline molecules by HOF-20 could restrict the rotation of the aromatic rings in H4BCPIA linkers, reducing the nonradiative decay pathways upon photoexcitation and subsequently enhancing the fluorescence intensity.

A Highly Water-Stable meta-Carborane-Based Copper Metal-Organic Framework for Efficient High-Temperature Butanol Separation.

Biofuels are considered sustainable and renewable alternatives to conventional fossil fuels. Biobutanol has recently emerged as an attractive option compared to bioethanol and biodiesel, but a significant challenge in its production lies in the separation stage. The current industrial process for the production of biobutanol includes the ABE (acetone-butanol-ethanol) fermentation process from biomass; the resulting fermentation broth has a butanol concentration of no more than 2 wt% (the rest is essentially water). Therefore, the development of a cost-effective process for separation of butanol from dilute aqueous solutions is highly desirable. The use of porous materials for the adsorptive separation of ABE mixtures is considered a highly promising route, as these materials can potentially have high affinities for alcohols and low affinities for water. To date, zeolites have been tested toward this separation, but their hydrophilic nature makes them highly incompetent for this application. The use of metal-organic frameworks (MOFs) is an apparent solution; however, their low hydrolytic stabilities hinder their implementation in this application. So far, a few nanoporous zeolitic imidazolate frameworks (ZIFs) have shown excellent potential for butanol separation due to their good hydrolytic and thermal stabilities. Herein, we present a novel, porous, and hydrophobic MOF based on copper ions and carborane-carboxylate ligands, mCB-MOF-1, for butanol recovery. mCB-MOF-1 exhibits excellent stability when immersed in organic solvents, water at 90 °C for at least two months, and acidic and basic aqueous solutions. We found that, like ZIF-8, mCB-MOF-1 is non-porous to water (type II isotherm), but it has higher affinity for ethanol, butanol, and acetone compared to ZIF-8, as suggested by the shape of the vapor isotherms at the crucial low-pressure region. This is reflected in the separation of a realistic ABE mixture in which mCB-MOF-1 recovers butanol more efficiently compared to ZIF-8 at 333 K.

The First Genome Survey of the Antarctic Krill (Euphausia superba) Provides a Valuable Genetic Resource for Polar Biomedical Research.

The world-famous Antarctic krill (Euphausia superba) plays a fundamental role in the Antarctic food chain. It resides in cold environments with the most abundant biomass to support the Antarctic ecology and fisheries. Here, we performed the first genome survey of the Antarctic krill, with genomic evidence for its estimated genome size of 42.1 gigabases (Gb). Such a large genome, however, is beyond our present capability to obtain a good assembly, although our sequencing data are a valuable genetic resource for subsequent polar biomedical research. We extracted 13 typical protein-coding gene sequences of the mitochondrial genome and analyzed simple sequence repeats (SSRs), which are useful for species identification and origin determination. Meanwhile, we conducted a high-throughput comparative identification of putative antimicrobial peptides (AMPs) and antihypertensive peptides (AHTPs) from whole-body transcriptomes of the Antarctic krill and its well-known counterpart, the whiteleg shrimp (Penaeus vannamei; resident in warm waters). Related data revealed that AMPs/AMP precursors and AHTPs were generally conserved, with interesting variations between the two crustacean species. In summary, as the first report of estimated genome size of the Antarctic krill, our present genome survey data provide a foundation for further biological research into this polar species. Our preliminary investigations on bioactive peptides will bring a new perspective for the in-depth development of novel marine drugs.

Specific K+ Binding Sites as CO2 Traps in a Porous MOF for Enhanced CO2 Selective Sorption.

Metal-organic frameworks (MOFs) can be fine-tuned to boost sorbent-sorbate interactions in order to improve gas sorption and separation performance, but the design of MOFs with ideal structural features for gas separation applications remains a challenge. Herein it is reported that unsaturated alkali metal sites can be immobilized in MOFs through a tetrazole based motif and that gas affinity can thereby be boosted. In the prototypal MOF of this type-NKU-521 (NKU denotes Nankai University), K+ cations are effectively embedded in a trinuclear Co2+ -tetrazole coordination motif. The embedded K+ sites are exposed to the pores of NKU-521 through water removal, and the isosteric heat (Qst ) for CO2 is boosted to 41 kJ mol-1 . The nature of the binding site is validated by molecular simulations and structural characterization. The K+ cations in effect serve as gas traps and boost the CO2 -framework affinity, as measured by the Qst , by 24%. In addition, the impact of unsaturated alkali metal sites upon the separation of hydrocarbons is evaluated for the first time in MOFs using ideal adsorbed solution theory (IAST) calculations and column breakthrough experiments. The results reveal that the presence of exposed K+ sites benefits gas sorption and hydrocarbon separation performances of this MOF.

Direct Observation of Li+ Ions Trapped in a Mg2+-Templated Metal-Organic Framework.

Herein we report the first example of a metal-organic framework (MOF) in which the location of Li+ ions trapped in the porous confinement can be unambiguously defined by single-crystal X-ray diffraction. Furthermore, the Li+-doped MOF shows significant enhancement in gas uptake as well as selective adsorption of CO2 over CH4.

Highly Chemically Stable MOFs with Trifluoromethyl Groups: Effect of Position of Trifluoromethyl Groups on Chemical Stability.

Metal-organic frameworks (MOFs) are a class of advanced porous crystalline materials. However, numerous MOFs have poor chemical stability, significantly restricting their industrial application. The introduction of trifluoromethyl groups around clusters of MOFs results in a shielding effect caused by their hydrophobicity and bulkiness, thus preventing guest molecules from attacking the coordination bonds. To prove such a shielding effect, the position of the trifluoromethyl groups is rationally adjusted, with trifluoromethyl groups at the ortho positions of carboxyl groups significantly improving the chemical stability of UiO-67. The prepared UiO-67- o-2CF3 remains intact after treatment with boiling water, 8 M HCl, 10 mM NaOH, and 50 ppm of NaF aqueous solutions. As the control experiment, trifluoromethyl groups at the meta positions of carboxyl groups have no shielding effect; hence, UiO-67- m-2CF3 has a stability that is lower than that of UiO-67- o-2CF3. In addition, the shielding effect is also applied to other MOFs, including DUT-5- o-2CF3 and Al-TPDC- o-2CF3, confirming the universality of this strategy.