Multifunctional and Ultrastable Co-MOF Effectively Separates Various Different Component Gas Mixtures.

Developing low-cost and multifunctional adsorbents for adsorption separation to obtain high-purity (>99.9%) gases is intriguing yet challenging. Notably, the ongoing trade-off between adsorption capacity and selectivity in separating multicomponent mixed gases still persists as a pressing scientific challenge requiring urgent attention. Herein, the ultrastable TJT-100 exhibits unique structural characteristics including uncoordinated carboxylate oxygen atoms, coordinated water molecules directed toward the pore surface, and sufficient Me2NH2+ cations in channels. TJT-100 exhibits a high adsorption capacity and exceptional separation performance, particularly notable for its high C2H2 capacity of 127.7 cm3/g and remarkable C2H2 selectivity over CO2 (5.4) and CH4 (19.8), which makes it a standout material for various separation applications. In a breakthrough experiment with a C2H2/CO2 mixture (v/v = 50/50), TJT-100 achieved a record-high C2H2 productivity of 69.33 L/kg with a purity of 99.9%. Additionally, TJT-100 demonstrates its effectiveness in separating CO2 from natural gas and flue gas. Its exceptional selectivity for CO2/CH4 (10.7) and CO2/N2 (11.9) results in a high CO2 productivity of 21.23 and 22.93 L/kg with 99.9% purity from CO2/CH4 (v/v = 50/50) and CO2/N2 (v/v = 15/85) mixtures, respectively.

DEM parameters of slope cultivated purple soil in Southwest China and interaction mechanism between very narrow tine.

The establishment of discrete element method (DEM) model for simulating the behavior of viscous soil can significantly contribute to the development of agricultural machinery, particularly in hilly areas worldwide. There is limited research on the parameter calibration of the DEM for purple soil in the Southwest China and its interaction mechanism between very narrow tine. Piling up test, rotating drum test and design-expert 12.0 software were used to design Plackett-Burman test, steepest climb test and Box-Behnken test successively. Combined with soil intrinsic parameter measurement test, soil simulation parameter calibration and optimization were completed. Based on the optimized DEM simulation parameters, the average relative errors of static repose angle and dynamic repose angle were 1.934 and 2.289%, respectively. The accuracy of parameter calibration results of DEM simulation was proved. Three kinds of very narrow tines were designed and processed. The interaction model and mechanism between soil-touch parts and soil was established. The average relative errors between the DEM simulation results of the forward resistance and disturbance area of the three soil-touch parts and the soil bin test results were 7.22% and 11.24%, respectively, which further proved that the calibration results of DEM parameters of purple soil and the interaction model with the soil-touch parts in this study were reliable. The physical and interaction parameters of slope cultivated purple soil in Southwest China were determined based on static-dynamic repose angle, providing more accurate parameters for study of soil-touch parts.

Enhancing Photoreduction of Cr(VI) through a Multivalent Manganese(II)-Organic Framework Incorporating Anthracene Moieties.

Exploiting a photocatalyst with high stability and excellent activity for Cr(VI) reduction under mild conditions is crucial yet challenging. Herein, the rigid aromatic multicarboxylate ligand with chromophore anthracene was selected to coordinate with multivalent metal ion manganese and to obtain a stable two-dimensional (2D) Mn-based metal-organic framework (MOF), LCUH-120, which can efficiently and quickly convert Cr(VI) into Cr(III) under light without the need for any additional photosensitizer. The efficient photosensitive anthracene group serves as a photosensitizer center and multivalent Mn(II) ion as a photocatalyst center in LCUH-120, and the conversion of Cr(VI) to Cr(III) can be realized completely in just 40 min. Specifically, the rate constant (k) and reduction rate of the Cr(VI) photocatalytic reaction can be high up to 0.134 min-1 and 2.50 mgCr(VI) g-1cata min-1 in an acidic environment (pH = 2), respectively. Compared to our previously reported three-dimensional (3D) Sm-MOF, LCUH-120 exhibits a significantly higher catalytic reaction rate, which might be ascribed to the fact that the photocatalyst center Mn node can improve the rate of electron transfer and promote the separation of holes and photogenerated electrons. In an acidic environment, the reaction mechanism can be verified through various contrast experiments and theoretical simulations.

Construction of Coordination Spaces with Narrow Pore Windows in Co-Based Metal-Organic Frameworks toward CO2/N2 Separation.

Carbon emission reduction is an important measure to mitigate the greenhouse effect, which has become a hotspot in global climate change research. To contribute to this, here, we fabricated two Co-based metal-organic frameworks (Co-MOFs), namely, {[Co3(NTB)2(bib)]·(DMA)2·(H2O)4}n (DZU-211) and {[Co3(NTB)2(bmip)]·(DMA)2}n (DZU-212) (H3NTB = 4,4',4″-nitrilotribenzoic acid, bib = 1,4-bis(imidazol-1-yl)-butane, bmip = 1,3-bis(2-methyl-1H-imidazol-1-yl)propane) to realize efficient CO2/N2 separation by dividing coordination spaces into suitable pores with narrow windows. DZU-211 reveals a 3D open porous framework, while DZU-212 exhibits a 3D double-fold interpenetrated structure. The two MOFs both possess large coordination spaces and small open pore sizes, via the bib ligand insertion and framework interpenetration, respectively. Comparatively, DZU-211 reveals superior selective CO2 uptake properties due to its more suitable pore characteristics. Gas sorption experiments show that DZU-211 has a CO2 uptake of 52.6 cm3 g-1 with a high simulated CO2/N2 selectivity of 101.7 (298 K, 1 atm) and a moderate initial adsorption heat of 38.1 kJ mol-1. Moreover, dynamic breakthrough experiments confirm the potential application of DZU-211 as a CO2 separation material from postcombustion flue gases.

Comparative Study on the Proton Conduction Behaviors of Two Acidic Amphiphilic and Hydrophilic Coordination Compounds in Nafion Composite Membranes.

The acidic amphiphilic compound H[Co(H2L1)(HL1)(phen)]·3H2O (H4(Co-L1), H3L1 = 5-(3', 5'-dicarboxylphenyl)-pyridine-2-carboxylic, phen = phenanthroline) and the hydrophilic compound [Ni(HL2)(H2O)5]·H2O (H(Ni-L2), H3L2 = 5-(3',5'-dicarboxylphenyl)-pyridine-3-carboxylic) were synthesized via hydrothermal reactions at acidic conditions. The acidity of H4(Co-L1) is stronger than of H(Ni-L2); while the hydrogen bond continuity in H4(Co-L1) extended monodirectionally, which is smaller compared to the three-directional extension observed in H(Ni-L2). The proton conduction behaviors of these two compounds as fillers of Nafion composite membranes have been investigated. The results indicate that the optimal doping amounts of H4(Co-L1) and H(Ni-L2) are 2 and 1%, respectively; the proton conductivities of H4(Co-L1)/Nafion-2 and H(Ni-L2)/Nafion-1 composite membranes are 0.243 and 0.212 S·cm-1, respectively, which are approximately 50.2 and 30.6% higher than that of pure Nafion membrane, respectively. A higher doping amount of H4(Co-L1) can be attributed to its hydrophobic phen ligand, which promotes compatibility with Nafion membrane and reduces aggregation. Hydrogen bond continuity has a more significant effect on proton conductivity than acidity at relatively low doping amounts; conversely, this relationship reverses at relatively high doping amounts.

Correction: A robust and porous titanium metal-organic framework for gas adsorption, CO2 capture and conversion.

Correction for 'A robust and porous titanium metal-organic framework for gas adsorption, CO2 capture and conversion' by Xuze Pan, et al., Dalton Trans., 2023, 52, 3896-3906, https://doi.org/10.1039/D2DT03158B.

[Characteristics and Source Analysis of Carbonaceous Aerosols in PM2.5 in Huaxi District, Guiyang].

Carbonaceous aerosol, as an important component of atmospheric aerosol, has a significant impact on atmospheric environmental quality, human health, and global climate change. To investigate the characteristics and sources of carbonaceous aerosol in atmospheric fine particulate matter (PM2.5) in Huaxi District of Guiyang, an in-situ observational study was conducted during different seasons in 2020, and the carbonaceous components of PM2.5 were measured using a thermal-optical carbon analyzer (DRI Model 2015). The results of the study showed that the average concentrations of PM2.5, total carbonaceous aerosol (TCA), organic carbon (OC), secondary organic carbon (SOC), and elemental carbon (EC) concentrations during the observation period were (39.7±22.3), (14.1±7.2), (7.6±3.9), (4.4±2.6), and (2.0±1.0) µg·m-3, respectively, and the mean value of OC/EC was (3.9±0.8). ρ(PM2.5), ρ(TCA), ρ(OC), ρ(SOC), and ρ(EC) showed a seasonal variation pattern with the highest in winter [(52.6±28.6), (17.0±9.6), (9.1±5.2), (6.1±3.9), and (2.4±1.2) µg·m-3, respectively] and the lowest in summer [(25.1±7.1), (11.6±3.6), (6.3±1.9), (3.7±1.2), and (1.6±0.6) µg·m-3, respectively]. The seasonal variation in OC/EC showed summer (4.2±0.8) > winter (3.8±0.9) > autumn (3.8±0.5) > spring (3.7±0.9), indicating the presence of SOC generation in all seasons in Huaxi District. SOC showed a significant correlation with OC (R2 =0.9), and the SOC concentration tended to increase with the increase in atmospheric oxidation. OC showed a good correlation with EC in all seasons, with the highest in autumn (R2 =0.9) and lower correlations in the other three seasons (R2 ranged from 0.74 to 0.75), indicating a common source. According to OC/EC ratio range, it was preliminarily determined that carbonaceous aerosol came from vehicle exhaust emissions, coal burning emissions, and biomass combustion emissions. In order to further quantify the contribution of major emission sources to carbonaceous aerosol, the results of this study using PMF to analyze the sources of carbonaceous aerosol showed that the main sources of carbonaceous aerosol in Huaxi District of Guiyang were coal combustion sources (29.3%), motor vehicle emission sources (21.5%), and biomass combustion sources (49.2%).

Two isostructural Zn/Co-MOFs with penetrating structures: multifunctional properties of both luminescence sensing and conversion of CO2 into cyclic carbonates.

Two new metal-organic frameworks (MOFs), namely, {[Zn(HL)(bpea)]·DMF}n (Zn-MOF-1) and {[Co(HL)(bpea)]·DMF}n (Co-MOF-2) (H3L = 3-(3,5-dicarboxybenzyloxy)benzoic acid, bpea = 1,2-di(pyridyl)ethane), were obtained by the reaction of H3L and N-containing ligand bpea with Zn(NO3)2·6H2O and Co(NO3)2·6H2O, respectively. The isomorphic Zn-MOF-1 and Co-MOF-2 featured a 3D penetrating framework with different stabilities, luminescence, and catalytic properties. Luminescence measurement indicated that Zn-MOF-1 could be used to detect Al3+ through a turn-on effect with a detection limit of 0.42 µM. The sensing mechanism experiments showed that the enhanced luminescence of Zn-MOF-1 toward Al3+ may be due to the weak interaction between Al3+ and Zn-MOF-1 and the absorbance-caused enhancement (ACE) mechanism. Meanwhile, both Zn-MOF-1 and Co-MOF-2 showed interesting CO2 adsorption properties and could catalyze the cycloaddition of CO2 to epoxides resulting in 96 and 92% ideal products within 12 hours, respectively. They can be cycled up to 5 times without significant loss of catalytic efficiency.

Cd-MOF and Its Ln3+-Post Modification Products: Regulation of Luminescence Properties and Improved Detection of Uric Acid, Quinine, and Quinidine.

One 3D Cd-MOF, namely, {[(HDMA)2][Cd3(L)2]·5H2O·2DMF}n (LCU-124, LCU indicates Liaocheng University), was synthesized from an ether-containing ligand 1,3-bis(3,5-dicarboxylphenoxy)benzene (H4L). Its Ln3+-postmodified samples, Eu3+@LCU-124 and Tb3+@LCU-124, were obtained through cation exchange of dimethylamine cation (HDMA) with Eu3+ and Tb3+. The successful entry of rare earth into LCU-124 by cation exchange modification was verified by IR, XRD, XPS, EDS mapping, and luminescence spectra. The proportion of Eu3+/Tb3+ was adjusted during the modification process, leading to fluorescent materials with different emissions. Luminescence measurements indicated that these complexes exhibited interesting multiresponsive sensing activities toward biomarkers urine acid (UA), quinine (QN), and quinidine (QND). First, LCU-124 has a pronounced quenching effect toward UA with the detection limit of 31.01 µM. After modification, the visualization of the detection was improved significantly and the detection limit of Eu3+@LCU-124 was reduced to 0.868 µM. Second, when QN and QND were present in the suspensions of Eu3+@LCU-124 and Tb3+@LCU-124, strong blue light emission peaks occurred, while the characteristic emission of Eu3+/Tb3+ decreased, forming ratiometric fluorescent sensors with the detection limit in the range of 0.199-9.49 µM. The fluorescent probes have high selectivity, excellent sensitivity recycling, and fast response time (less than 1 min). Besides, a simple logic gate circuit and a range of luminescent mixed matrix membranes were designed to provide simple and fast detection of above biomarkers. Our work indicated that modification of Eu3+/Tb3+ could improve the detection ability significantly.

A simple MOF constructed using Pb(II) with strong polarizing force: a filler of Nafion membrane to increase proton conductivity.

Metal-organic frameworks (MOFs) are promising competitive candidates as fillers for Nafion proton exchange membrane (PEM). Increasing efforts have been made to explore methods for synthesizing MOF fillers and the mechanism by which MOF doping improves the proton conductivity (σH+) values of composite membranes. In this study, a Pb(II) cation with strong polarizing force was selected for the hydrothermal reaction with a simple sulfoterephthalate ligand (H3L). Pb-MOF [Pb2L(OH)]n was obtained, which was constructed using Pb-O layers and deprotonated sulfoterephthalate L3- and exhibited good thermal and water stability. Different amounts of Pb-MOF particles were doped into Nafion to fabricate Pb-MOF/Nafion-x composite membranes, which were characterized using SEM, PXRD, IR spectroscopy, TGA, and other methods. It was found that doping Pb-MOF can apparently improve the water absorbability and thermal stability of the composite membrane. The σH+ of the Pb-MOF/Nafion-7 composite membrane was the highest and 2.14 times that of the pure Nafion membrane at 353 K. The higher proton conduction properties may be explained by the strong polarization force, and Pb(II) cations on the surface of Pb-MOF can decrease the bond energy of the O-H bond of absorbed water molecules and increase the acidity of the composite membrane. The phenomena in this study and our previous study confirm that acidity is the most important factor in favor of proton conductivity.

Two-Dimensional Lanthanide Metal-Organic Frameworks as a Platform for Sensing Pollutant and Nitrophenols Reduction.

The discharge of harmful and toxic pollutants in water is destroying the ecosystem balance and human being health at an alarming rate. Therefore, the detection and removal of water pollutants by using stable and efficient materials are significant but challenging. Herein, three novel lanthanide metal-organic frameworks (Ln-MOFs), [La(L)(DMF)2(H2O)2]·H2O (LCUH-104), [Nd(L)(DMF)2(H2O)2]·H2O (LCUH-105), and [Pr(L)(DMF)2(H2O)2]·H2O (LCUH-106) [H3L = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid (H3TZI)] were solvothermally constructed and structurally characterized. In the three Ln-MOFs, dinuclear metallic clusters {Ln2} were connected by deprotonated tetrazol-containing dicarboxylate TZI3- to obtain a 2D layered framework with a point symbol of {42·84}·{46}. Their excellent chemical and thermal stabilities were beneficial to carry out fluorescence sensing and achieve the catalytic nitrophenols (NPs) reduction. Especially, the incorporation of the nitrogen-rich tetrazole ring into their 2D layered frameworks enables the fabrication of Pd nanocatalysts (Pd NPs@LCUH-104/105/106) and have dramatically enhanced catalytic activity by using the unique metal-support interactions between three Ln-MOFs and the encapsulating palladium nanoparticles (Pd NPs). Specifically, the reduction of NPs (2-NP, 3-NP, and 4-NP) in aqueous solution by Pd NPs@LCUH-104 exhibits exceptional conversion efficiency, remarkable rate constants (k), and outstanding cycling stability. The catalytic rate of Pd NPs@LCUH-104 for 4-NP is nearly 8.5 times more than that of Pd/C (wt 5%) and its turnover frequency value is 0.051 s-1, which indicate its excellent catalytic activity. Meanwhile, LCUH-105, as a multifunctional fluorescence sensor, exhibited excellent fluorescence detection of norfloxacin (NFX) (turn on) and Cr2O72- (turn off) with high selectivity and sensitivity at a low concentration, and the corresponding fluorescence enhancement/quenching mechanism has also been systematically investigated through various detection means and theoretical calculations.

Notably Stable Bifunctional Europium-Centered Metal-Organic Framework for Instant Sensing of Uric Acid and 1-Hydroxypyrene in Human Urine.

A new Eu-centered metal-organic framework, [(CH3)2NH2][Eu(cdip)(H2O)] (compound 1), was fabricated by the reaction of Eu(NO3)3·6H2O and a high-symmetry ligand, 5,5'-carbonyldiisophthalic acid (H4cdip). Interestingly, compound 1 exhibits extraordinary stability, including air, thermal, and chemical stabilities, in an aqueous solution with a broad pH range of 1-14, which is rarely seen in the field of metal-organic framework materials. Notably, compound 1 is proved to be an exceptional prospective luminescent sensor for recognizing 1-hydroxypyrene and uric acid both in DMF/H2O solution and human urine with a fast response (1-HP: 10 s; UA: 80 s), high quenching efficiency Ksv (7.01 × 104 M-1 for 1-HP and 5.46 × 104 M-1 for UA in DMF/H2O solution; 2.10 × 104 M-1 for 1-HP and 3.43 × 104 M-1 for UA in human urine), low limit of detection (1.61 µM for 1-HP and 0.54 µM for UA in DMF/H2O solution; 0.71 µM for 1-HP and 0.58 µM for UA in human urine), and remarkable anti-interference ability based on luminescence-quenching effects observable by the naked eye. This work provides a new strategy for the exploration of potential luminescent sensors based on Ln-MOFs for 1-HP, UA, or other biomarkers in biomedical and biological fields.

Constructing interface engineering and tailoring a nanoflower-like FeP/CoP heterostructure for enhanced oxygen evolution reaction.

The inexpensive and highly efficient electrocatalysts toward oxygen evolution reaction (OER) in water splitting electrolysis have displayed promising practical applications to relieve energy crisis. Herein, we prepared a high-yield and structurally regulated bimetallic cobalt-iron phosphide electrocatalyst by a facile one-pot hydrothermal reaction and subsequent low-temperature phosphating treatment. The tailoring of nanoscale morphology was achieved by varying the input ratio and phosphating temperature. Thus, an optimized FeP/CoP-1-350 sample with the ultra-thin nanosheets assembled into a nanoflower-like structure was obtained. FeP/CoP-1-350 heterostructure displayed remarkable activity toward the OER with a low overpotential of 276 mV at a current density of 10 mA cm-2, and a low Tafel slope of only 37.71 mV dec-1. Long-lasting durability and stability were maintained with the current with almost no obvious fluctuation. The enhanced OER activity was attributed to the presence of copious active sites from the ultra-thin nanosheets, the interface between CoP and FeP components, and the synergistic effect of Fe-Co elements in the FeP/CoP heterostructure. This study provides a feasible strategy to fabricate highly efficient and cost-effective bimetallic phosphide electrocatalysts.

A robust and porous titanium metal-organic framework for gas adsorption, CO2 capture and conversion.

A robust and porous titanium metal-organic framework (Ti-MOF; LCU-402) has been hydrothermally synthesized through combining a tetranuclear Ti2Ca2(µ3-O)2(µ2-H2O)1.3(H2O)4(O2C-)8 cluster and a tritopic 1,3,5-benzene(tris)benzoic (BTB) ligand. LCU-402 shows remarkable stability and permanent porosity for CO2, CH4, C2H2, C2H4, and C2H6 gas adsorption. Moreover, LCU-402 as a heterogeneous catalyst can smoothly convert CO2 under a simulated flue atmosphere into organic carbonate molecules by cycloaddition reactions of CO2 and epoxides, indicating that LCU-402 might be a promising catalyst candidate in practical applications. We are confident that the identification of a persistent titanium-oxo building unit would accelerate the development of new porous Ti-MOF materials.

Series of Dual Functional Two-Dimensional RE-OFs for Nitrophenol Reduction and Dye Separation.

The rational design and preparation of stable and multifunctional metal-organic frameworks (MOFs) with excellent catalysis and adsorption properties are desirable but are great challenges. The nitrophenol (NP) reduction to aminophenols (APs) by using the catalyst Pd@MOFs is an effective strategy, which has attracted extensive attention in recent years. Here, we report four stable isostructural two-dimensional (2D) rare earth metal-organic frameworks [RE4(AAPA)6(DMA)2 (H2O)4][DMA]3[H2O]8 (namely LCUH-101, RE = Eu, Gd, Tb, Y; AAPA2- = 5-[(anthracen-9-yl-methyl)-amino]-1,3-isophthalate), which feature a 2D layer structure with sql topology of point symbol {44·62} and exhibit excellent chemical stability and thermostability. The as-synthesized Pd@LCUH-101 was utilized for the catalytic reduction of 2/3/4-nitrophenol, which indicates high catalytic activity and recyclability attributed to the synergistic effect between Pd nanoparticles and the 2D layered structure. Of note, the turnover frequency (TOF), the reaction rate constant (k), and the activation energy (Ea) of Pd@LCUH-101 (Eu) in the reduction of 4-NP, respectively, are 1.09 s-1, 2.17 min-1, and 50.2 kJ·mol-1, which show that it has superior catalytic activity. Remarkably, LCUH-101 (Eu, Gd, Tb, and Y) are multifunctional MOFs that can effectively absorb and separate mixed dyes. The appropriate interlayer spacing enables them to efficiently adsorb methylene blue (MB) and rhodamine B (RhB) in aqueous solution, with adsorption capacities of 0.97 and 0.41 g·g-1, respectively, which is one of the highest values among those of the reported MOF-based adsorbers. Meanwhile, LCUH-101 (Eu) can be used for the separation of the dye mixture MB/MO and RhB/MO, and the excellent reusability enables LCUH-101 (Eu) to be used as chromatographic column filters to quickly separate and recover dyes. Therefore, this work provides a new strategy for the exploitation of stable and efficient catalysts for NP reduction and adsorbents for dyes.

Detection Enhancement of One Multifunctional Cd-Metal-Organic Framework toward Tetracycline Antibiotics by Simply Mixing Eu3+ in Suspension.

It is necessary to find more simple methods to improve the detection selectivity and sensitivity of antibiotics. Herein, we constructed a novel three-dimensional (3D) Cd-MOF LCU-117 assembled from p-terphenyl-4,2″,5″,4'-tetracarboxylic acid, which showed a special 3D helical structure with carboxylic acid ligands and nitrogen-containing ligands crossing each other vertically. Luminescence measurements indicated that LCU-117 has high selectivity and sensitivity toward Eu3+ through the ratiometric effect. Meanwhile, this complex itself could detect antibiotics oxytetracycline (OTC) through the turn-off mechanism. When Eu3+ was added in suspensions of LCU-117 (noted as Eu3+@LCU-117), the detection toward OTC was enhanced significantly and visually. The sensing mechanism was investigated in detail by various measurements and theoretical calculations. LCU-117 has a good effect on the logic gate, potential fingerprint detection, and mixed-matrix membranes (MMMs). The practical application for monitoring OTC in water samples also provided a satisfactory result.

A "Pre-Division Metal Clusters" Strategy to Mediate Efficient Dual-Active Sites ORR Catalyst for Ultralong Rechargeable Zn-Air Battery.

To conquer the bottleneck of sluggish kinetics in cathodic oxygen reduction reaction (ORR) of metal-air batteries, catalysts with dual-active centers have stood out. Here, a "pre-division metal clusters" strategy is firstly conceived to fabricate a N,S-dual doped honeycomb-like carbon matrix inlaid with CoN4 sites and wrapped Co2 P nanoclusters as dual-active centers (Co2 P/CoN4 @NSC-500). A crystalline {CoII 2 } coordination cluster divided by periphery second organic layers is well-designed to realize delocalized dispersion before calcination. The optimal Co2 P/CoN4 @NSC-500 executes excellent 4e- ORR activity surpassing the benchmark Pt/C. Theoretical calculation results reveal that the CoN4 sites and Co2 P nanoclusters can synergistically quicken the formation of *OOH on Co sites. The rechargeable Zn-air battery (ZAB) assembled by Co2 P/CoN4 @NSC-500 delivers ultralong cycling stability over 1742 hours (3484 cycles) under 5 mA cm-2 and can light up a 2.4 V LED bulb for ≈264 hours, evidencing the promising practical application potentials in portable devices.

Two Co-Based Metal-Organic Framework Isomers with Similar Metal-Carboxylate Sheets: Turn-On Ratiometric Luminescence Sensing Activities toward Biomarker N-Acetylneuraminic Acid and Discrimination of Ga3+ and In3.

Two supramolecular Co-MOF isomers, namely, {[Co(L)0.5(m-bimb)]·3H2O}n (LCU-115) and {[Co(L)0.5(p-bimb)]·3H2O}n (LCU-116), were synthesized from an amide-containing carboxylic acid N,N″-(3,5-dicarboxylphenyl)benzene-1,4-dicarboxamide (H4L) and two flexible positional isostructural N-containing ligands m-bimb and p-bimb (m-bimb = 1,3-bis((1H-imidazol-1-yl)methyl)benzene; p-bimb = 1,4-bis((1H-imidazol-1-yl)methyl)benzene). The carboxylate ligands connect Co(II) centers to form 2D metal-carboxylate sheets, which are extended further by m-bimb and p-bimb to form a 2D bilayer with parallel stacking (LCU-115) and a 3D framework (LCU-116), respectively. Luminescence measurements indicated that these two complexes exhibited interesting multiresponsive sensing activities toward pH, biomarker N-acetylneuraminic acid, and trivalent cations Ga3+/In3+. They show highly sensitive turn-on fluorescence responses in the acidic range and can also be regarded as on-off-on vapoluminescent sensors to typical acidic and basic gases HCl and Et3N. It is worth noting that these complexes have excellent turn-on ratiometric fluorescence sensing ability for N-acetylneuraminic acid (NANA) with detection limits as low as 7.39 and 8.06 µM, respectively. Furthermore, they were successfully applied for the detection of NANA in simulated urine and serum samples with satisfactory results. For ion detection, LCU-116 could detect both Ga3+ and In3+, while LCU-115 could distinguish Ga3+ from In3+ with the latter showing luminescence quenching. The sensing mechanism was investigated in detail by XRD, UV-vis, EDS, XPS, SEM, and TEM. The results of interday and intraday precision studies gave low RSD values in the range of 1.19-3.53%, ascertaining the reproducibility of these sensors. The recoveries for the sensing analytes in simulated urine/serum or real water are satisfactory from 96.7 to 103.3% (toward NANA) and 96.6 to 115.0% (toward Ga3+ and In3+), indicating that these two complexes also possess acceptable reliability for monitoring in real samples. The results indicated that the supramolecular isomers LCU-115 and LCU-116 are promising material candidates for application in biological and environmental monitoring.

Pt Nanoparticles Confined in a 3D Porous FeNC Matrix as Efficient Catalysts for Rechargeable Li-CO2/O2 Batteries.

The cathodic product Li2CO3, due to its high decomposition potential, has hindered the practical application of rechargeable Li-CO2/O2 batteries. To overcome this bottleneck, a Pt/FeNC cathodic catalyst is fabricated by dispersing Pt nanoparticles (NPs) with a uniform size of 2.4 nm and 8.3 wt % loading amount into a porous microcube FeNC support for high-performance rechargeable Li-CO2/O2 batteries. The FeNC matrix is composed of numerous two-dimensional (2D) carbon nanosheets, which is derived from an Fe-doping zinc metal-organic framework (Zn-MOF). Importantly, using Pt/FeNC as the cathodic catalyst, the Li-CO2/O2 (VCO2/VO2 = 4:1) battery displays the lowest overpotential of 0.54 V and a long-term stability of 142 cycles, which is superior to batteries with FeNC (1.67 V, 47 cycles) and NC (1.87 V, 23 cycles) catalysts. The FeNC matrix and Pt NPs can exert a synergetic effect to decrease the decomposition potential of Li2CO3 and thus enhance the battery performance. In situ Fourier transform infrared (FTIR) spectroscopy further confirms that Li2CO3 can be completely decomposed under a low potential of 3.3 V using the Pt/FeNC catalyst. Impressively, Li2CO3 exhibits a film structure on the surface of the Pt/FeNC catalysts by scanning electron microscopy (SEM), and its size can be limited by the confined space between the carbon sheets in Pt/FeNC, which enlarges the better contacting interface. In addition, density functional theory (DFT) calculations reveal that the Pt and FeNC catalysts show a higher adsorption energy for Li2CO3 and Li2CO4 intermediates compared to the NC catalyst, and the possible discharge pathways are deeply investigated. The synergetic effect between the FeNC support and Pt active sites makes the Li-CO2/O2 battery achieve optimal performance.

Enhancing Proton Conductivity of Nafion Membrane by Incorporating Porous Tb-Metal-Organic Framework Modified with Nitro Groups.

A rigid carboxylate ligand with a nitro functional group was selected to coordinate with Tb(III) cation, and Tb-MOF ({[Tb4(L)4(OH)4(H2O)3]·8H2O}n, H2L = 2-nitroterephthalic acid) with large porous and excellent hydrophilicity was obtained successfully. The obtained Tb-MOF was filled into the Nafion matrix to improve its proton conduction performance. The Tb-MOF/Nafion composite membrane was characterized by PXRD, IR, and thermogravimetry (TG) and for water uptake, area swelling, and proton conductivity. The activity energy, Ea, value of the composite membrane, which is a very important factor affecting the proton conduction performance of the membrane, was fitted and calculated. It was revealed that Tb-MOF can improve the proton conductivities of composite membranes, and the improvement degree and Ea value were both affected by Tb-MOF content. When Tb-MOF content was 5%, the proton conductivity of the composite membrane was 1.53 × 10-2 S·cm-1 at 100% RH and 80 °C, which is 1.81 times that of the pure Nafion membrane. A MOF containing a nitro functional group was first doped into Nafion in this study and exhibited excellent performance for improving composite membrane proton conductivity. This study will provide a valuable reference for designing different functionalized MOFs to promote the proton conductivities of proton exchange membranes.