Unsaturated Metal Sites Research Articles

Tailoring Ce-Centered Metal-Organic Frameworks for Fast Li+ Transport in Composite Polymer Electrolyte.

Regulating metal nodes to innovate the metal-organic framework (MOF) structure is of great interest to boost the performance of MOFs-incorporated composite solid electrolytes. Herein, Ce4+ with a low-lying 4f orbital is selected as metal center to coordinate with organic ligand to prepare MOF of Ce-UiO-66. The unsaturated open metal sites and defected oxygen vacancies furnish Ce-UiO-66 with strengthened Lewis acidity, which promotes Ce-UiO-66 interacting effectively with both poly(ethylene oxide) (PEO) and Li salt anions. Accordingly, Ce-UiO-66 as additive fillers can be uniformly dispersed in PEO matrix to form an advanced composite solid-state electrolyte (Ce-UiO@PEO) with accelerated Li+ transport. The optimized Ce-UiO@PEO displays a boosted ionic conductivity of 4.20 × 10-4 S cm-1 and an improved Li+ transference number of 0.39 at 60 °C, which are highly comparable to those of other MOFs@PEO electrolytes. Combined with the mechanical and thermal stabilities, such a Ce-UiO@PEO electrolyte enables Li/Li symmetric and Li/LiFePO4 full cells with superior cycling stability and rate performance. The Ce-UiO@PEO electrolytes are of great potential to be applied in high-performance lithium metal batteries.

Hierarchical Bifunctional NiO Electrocatalyst: Highly Porous Structure Boosting the Water Splitting Activity.

The development of an efficient, low-cost and earth-abundant electrocatalyst for water splitting is crucial for the production of sustainable hydrogen energy. However their practical applications are largely restricted by their limited synthesis methods, large overpotential and low surface area. Hierarchical materials with a highly porous three-dimensional nanostructure have garnered significant attention due to their exceptional electrocatalytic properties. These hierarchical porous frameworks enable the fast electron transfer, rapid mass transport, and high density of unsaturated metal sites and maximize product selectivity. Here the process involved obtaining monodispersed microrod-shaped Ni(OH)2 through a hydrothermal reaction, followed by a heat treatment to convert it into hierarchical microrod-shaped NiO materials. N2 sorption analysis revealed that the BET surface area increased from 9 to 89 m2/g as a result of the heat treatment. The hierarchical microrod-shaped NiO materials demonstrated outstanding bifunctional electrocatalytic water splitting capabilities, excelling in both HER and OER in basic solution. Overpotential of 347 mV is achieved at 10 mA/cm2 for OER activity, with a Tafel slope of 77 mV/dec. Similarly, overpotential of 488 mV is achieved at 10 mA/cm2 for HER activity, with a Tafel slope of 62 mV/dec.

DBD plasma assisted synthesis of Ce-MIL-88B(Fe) with electron-rich CUSs and mixed-valent bimetallic sites for enhanced photo-Fenton performance

Iron-based metal-organic frameworks (Fe-MOFs) are regarded as a kind of prospective catalysts for photo-Fenton process. However, high cost, rate-limiting Fe(III)/Fe(II) circulation and limited metal sites greatly restricted the application of Fe-MOFs in photo-Fenton system. Ce-MIL-88B(Fe) was synthesized with mixed-valent bimetallic sites and tunable coordinated unsaturated metal sites (CUSs) using dielectric barrier discharge (DBD) plasma with waste PET. The incorporation of Ce altered the structure and the electron aggregation, as well as induced structural defects. Ce substitution in Fe-MOFs induced the regulation of the ratio of Fe ions and formation of electron-rich CUSs, which were beneficial for the rapid adsorption and activation of H2O2, thus enhancing the photo-Fenton performance. The effect of reaction conditions on TC degradation was investigated by response surface methodology (RSM) combined with Box-Behnken design (BBD). This study demonstrates a new perspective on the construction of bimetallic MOFs for the photo-Fenton system.

Reusable fluorescence nanoprobe based on DNA-functionalized metal-organic framework for ratiometric detection of mercury (II) ions.

Areusable fluorescent nanoprobewas developedusing DNA-functionalized metal-organic framework (MOF) for ratiometric detection of Hg2+. We utilized a zirconium-based MOF (UiO-66) to encapsulate tris(bipyridine) ruthenium(II) chloride (Ru(bpy)32+), resulting in Ru(bpy)32+@UiO-66 (RU) with red fluorescence. The unsaturated metal sites in UiO-66 facilitate the attachment of thymine-rich single-strand DNA (T-ssDNA) through Zr-O-P bond, producing T-ssDNA-functionalized RU complex (RUT). The T-ssDNA selectively binds to Hg2+, forming stable T-Hg2+-T base pairs and folding into double-stranded DNA, which permits the intercalation of SYBR Green I (SGI) and activates its green fluorescence. In the presence of Hg2+, SGI fluorescence increases in a dose-dependent manner, while Ru(bpy)32+ fluorescence remains constant. This fluorescence contrast enables RUT to serve as an effective ratiometric nanoprobe for Hg2+ detection, with a detection limit of 3.37 nM. Additionally, RUT demonstrates exceptional reusability due to the ability of cysteine to remove Hg2+, given its stronger affinity for thiol groups. The RUT was successfully applied to detect Hg2+ in real water samples. This work advances the development of ratiometric fluorescence nanoprobe based on DNA-functionalized MOFs.

Engineering Coordinatively Unsaturated Metal Sites in 2D Metal‐Porphyrin Frameworks for Initiator‐Free, Broadband Photocatalytic Synthesis of Ultrahigh Molecular Weight Polymers

Engineering Coordinatively Unsaturated Metal Sites in 2D Metal‐Porphyrin Frameworks for Initiator‐Free, Broadband Photocatalytic Synthesis of Ultrahigh Molecular Weight Polymers

Glass fiber-based metal organic gel composite electrolytes for solid-state lithium batteries

Abstract Quasi-solid-state electrolytes encounter great obstacles in structural stability due to their inherent heterogeneity. Here, we introduce a new composite structure of glass-fiber-based metal-organic gel as a solid-state electrolyte and explore its electrochemical properties in lithium-metal batteries. We use a straightforward in-situ sol-gel method to synthesize this composite electrolyte, where glass fiber acts as matrices, ferric nitrate reacts with trimeric acid to form interconnected channels with abundant unsaturated metal sites, while ionic liquid electrolyte is in-situ confined into interconnected channels. The as-prepared composite electrolyte membrane has a uniform structure and composition, exhibiting a high room-temperature ionic conductivity of 1.79×10−3 S cm−1 and a high electrochemical oxidation potential of 4.76 V vs Li/Li+. This composite has excellent cycling performance in LiFePO4//Li (99.5% after 100 cycles) and NCM811//Li (86.6% after 200 cycles) batteries.

Constructing binuclear sites to modulate the charge distribution of MIL-101 for enhanced toluene adsorption performance: experimental and theoretical studies

Toluene is a class of volatile organic compounds (VOCs) in the air that harm environmental quality and human health. To enhance the adsorption performance of adsorbents for toluene, based on the principle that unsaturated metal sites in MOFs can be replaced, nanoscale M@MIL-101(M represents Mg, Ca, Sr) with binuclear sites was prepared by a one-step solvothermal method. The second metal was successfully introduced into the topology of MIL-101 by partially substituting Cr sites. The results of the dynamic adsorption experiments showed that 20%Sr@MIL-101 exhibited the highest toluene adsorption capacity, which was about 60% higher than that of the undoped MIL-101. Analysis using a monolayer and multilayer model based on statistical physics theory indicated that the Sr/Cr binuclear sites could enhance the interaction strength of the adsorption system, promoting the adsorption of more layers of toluene molecules on the surface of MIL-101. Characterization and simulation together confirmed that constructing Sr/Cr binuclear sites in MIL-101 can cause significant redistribution of charge within the pores, enhancing the van der Waals interactions, π-π stacking interactions, hydrogen bonding, and Lewis acid-base interactions between the pore interior and the adsorbate molecules. Additionally, density functional theory (DFT) revealed that the adsorption sites of toluene in MIL-101 were distributed in a trigonal prism arrangement and were symmetrically aligned with a 180° rotation of the MIL-101 triangular cage.

Missing-Linker Defect Functionalized Metal-Organic Frameworks Accelerating Zinc Ion Conduction for Ultrastable All-Solid-State Zinc Metal Batteries.

Solid-state polymer electrolytes (SPEs) are promising for high-performance zinc metal batteries (ZMBs), but they encounter critical challenges of low ionic conductivity, limited Zn2+ transference number (tZn2+), and an unstable electrolyte-electrode interface. Here, we present an effective approach involving a missing-linker metallic organic framework (MOF)-catalyzed poly(ethylene glycol) diacrylate (PEGDA)/polyacrylamide (PAM) copolymer SPE for single Zn2+ conduction and seamless electrolyte-electrode contact. The single-Zn2+ conduction is facilitated by the anchoring of the OTF- anions onto the unsaturated metal sites of missing-linker MOF, while the PEGDA and PAM chains in competitive coordination with Zn2+ ions promote rapid Zn ion transport. Our all-solid-state electrolyte simultaneously achieves a superior ionic conductivity of 1.52 mS cm-1 and a high tZn2+ of 0.83 at room temperature, alongside uniform Zn metal deposition (1000 cycles in symmetric cells) and high Zn plating/striping efficiencies (>99% after 600 cycles in asymmetric cells). Applications of our SPE in Zn//VO2 full cells are further demonstrated with a long lifespan of 2000 cycles and an extremely low-capacity degradation rate of 0.012% per cycle. This work provides an effective strategy for using a missing-linker MOF to catalyze competitively coordinating copolymers for accelerating Zn2+ ion conduction, assisting the future design of all-solid-state ZMBs.

Dual structure cobalt sites on surface hydroxyl and oxygen vacancy of BiOCl for cooperative CO2 reduction and tetracycline oxidation

Metal ion cocatalysts have huge prospect for photocatalytic CO2 reduction coupled with organic decomposition because of their cost effectiveness and abundant active sites. Herein, we exploit a defect−group oriented tactic to induce dual−structured Co sites on BiOCl with rich surface hydroxyls (OHs) and oxygen vacancies (OVs) (labeled as BiO1−xCl−OH), in which the surface OHs and OVs acted as anchoring points to anchor Co2+ ions. Density functional theory calculations manifested that surface OHs anchored Co2+ ions via hydrogen bonding to produce tight OH−Co sites, meanwhile, surface OVs with unsaturated metal sites and unpaired electrons captured Co2+ ions through chemical bonding to form close−knit OV−Co site. The as−generated OV−Co and OH−Co site served as reductive and oxidative cocatalyst for CO2 reduction and tetracycline oxidation, respectively, thereby achieving high−efficiency redox activity. This work provided a novel strategy to devise progressive dual functional metal ions cocatalysts for high−efficiency CO2 reduction and organic pollutants oxidation.

Crosslinked microporous membrane with pore compensation for efficient and long-term gas separation

Utilizing polymers of intrinsic microporosity (PIMs) to construct microporous membranes with high free volume fraction and surface area is a promising strategy to realize high-performance carbon capture. However, plasticization and physical aging remarkably limits the practical applications of PIM-based membrane separation. This work proposed a pore-compensation crosslinking strategy to fabricate a crosslinked microporous membrane with firmly inter-/intra-chain arrangement and highly-preserved CO2 permeation for efficient and long-term gas separation. Amino-functionalized UiO-66 (UiO-66-NH2) was employed to play the dual-function of crosslinker and pore compensation in the construction of crosslinking network among the bromomethylated PIM (BM-PIM) matrix via multiple covalent-crosslinking reactions. Compared with conventional crosslinking agents, the porous structure of UiO-66-NH2 crosslinkers provided additional gas transport channels for compensating the reduction of free volume during the formation of crosslinking network. Meanwhile, the unsaturated metal sites on UiO-66-NH2 crosslinkers enhanced the CO2 transport. Accordingly, the crosslinked microporous membrane with pore compensation achieved an excellent gas separation (CO2/N2 and CO2/CH4 separation factors of 32.2 and 49.3) and structural stability with superior anti-plasticization (plasticizing pressure up to 0.8 MPa) and anti-aging (CO2 permeability loss <15 % after 180 days). The pore-compensation crosslinking strategy offers a novel method to fabricate high-performance microporous membrane for efficient carbon capture.

High-Strength MOF-Based Polymer Electrolytes with Uniform Ionic Flow for Lithium Dendrite Suppression.

The uneven formation of lithium dendrites during electroplating/stripping leads to a decrease in the utilization of active lithium, resulting in poor cycling stability and posing safety hazards to the battery. Herein, introducing a 3D continuously interconnected zirconium-based metal-organic framework (MOF808) network into a polyethylene oxide polymer matrix establishes a synergistic mechanism for lithium dendrite inhibition. The 3D MOF808 network maintains its large pore structure, facilitating increased lithium salt accommodation, and expands anion adsorption at unsaturated metal sites through its diverse large-space cage structure, thereby promoting the flow of Li+. Infrared-Raman and synchrotron small-angle X-ray scattering results demonstrate that the transport behavior of lithium salt ion clusters at the MOF/polymer interface verifies the increased local Li+ flux concentration, thereby raising the mobility number of Li+ to 0.42 and ensuring uniform Li+ flux distribution, leading to dendrite-free and homogeneous Li+ deposition. Furthermore, nanoindentation tests reveal that the high modulus and elastic recovery of MOF-based polymer electrolytes contribute to forming a robust, dendrite-resistant interface. Consequently, in symmetric battery systems, the system exhibits minimal overpotential, merely 35mV, while maintaining stable cycling for over 1800 h, achieving low-overpotential lithium deposition. Moreover, it retains redox stability under high voltages up to 5.3V.

Reasonable construction of low migration energy barrier and continuous proton transfer channels via bimetallic MOFs nanofibers (MIL-(Cr Al)–NH2) for its composite proton exchange membrane

Reasonable construction of low migration energy barrier and continuous proton transfer channel is the key to improving the performance of composite proton exchange membranes. In this paper, we prepared a novel bimetallic MOFs (MIL-(Cr Al)–NH2) nanofibers (MCANs) consisting of Cr and Al elements by electro-blown spinning method (EBS) and hydrothermal synthesis, and subsequently introduced them into non-fluorinated sulfonic acid polymer sulfonated polysulfone (SPSF) matrix to obtain composite proton exchange membranes (MCANs@SPSF). Importantly, MCANs successfully constructed relatively long-range continuous unsaturated metal site proton transfer channels provided by the Cr-based MOFs, thereby reducing the proton migration energy barrier in the MCANs@SPSF, which confirmed by the density functional theory (DFT) calculation. In detail, DFT studies indicated that the migration energy barrier between H+ and MCANs was 1.677 eV, while that of single Al-based MOF (MAN) and single Cr-based MOF (MCN) were 1.879 eV and 1.762 eV respectively. The existence of efficient low migration energy barrier and continuous proton transfer channels made the proton conduction efficiency of MCANs@SPSF greatly improved, that was under the condition of 80 °C and 100 % RH, the proton conductivity of MCANs@SPSF reached the maximum value of 0.358 S cm−1 and the power density reached 104 mW cm−2. Moreover, MCANs@SPSF-5 displayed best DMFC durability performance with only 14.65 % voltage loss under 24h test. In addition, due to the acid-base pair interaction between MCANs and SPSF enhanced the interface binding force between the two phases, meanwhile, the pore structure of MOFs also had a certain adsorption effect on methanol, thus reducing the methanol permeability, and the addition of 5 wt% MCANs in SPSF was tested to reduce the methanol permeability to 5.53 × 10-7 cm2 s−1. Overall, this work provided a new strategy for construction of low migration energy barrier and continuous proton transfer channels, which was beneficial for the development of high performance proton exchange membranes.

High-vacuum-calcined multi-MOF mixed-matrix membrane for CH4/N2 separation

Methane/nitrogen (CH4/N2) separation remains a persistent challenge owing to the similar polarities, kinetic diameters, and boiling points of CH4 and N2. Herein, a novel method is proposed for enhancing the separation performance of CH4/N2 via vacuum resistance calcination, which uses surface-carbonized and hardened ZIF-8 (SCH-Z), MOF-74-Ni (SCH-M), and UiO-66-NH2 (SCH–U). The nanoparticles treated by vacuum resistance calcination remain the microporous characteristics of MOF, while introducing additional mesoporous structure and unsaturated metal sites. Such multistage pore structure and rich metal sites display a significant improvement in the CH4 adsorption over N2. In addition, the separation performance of multiple metal–organic frameworks (MOFs) mixed matrix membranes (MMMs) fabricated by homogeneously mixing the alkaline polymer polyvinylamine (PVAm) with SCH-M/SCH-Z and SCH-M/SCH–U was investigated, respectively. When the measured pressure was 0.1 MPa and the binary filler loading was 48 %, the PVAm/(SCH-M)0.7(SCH-Z)0.3/MPSf MMM exhibited outstanding CH4/N2 separation performance (CH4 permeance of 2888.48 GPU and selectivity of 4.38). Furthermore, when the loading of the binary filler was 45 %, the ideal CH4/N2 selectivity and CH4 permeance of PVAm/(SCH-M)0.67(SCH–U)0.33/MPSf MMM are 5.57 and 2263.94 GPU, respectively. This study provides a novel idea that introducing multi-MOF nanoparticles into MMMs for optimizing gas separation performance.

Enhanced catalytic performance for CO2 cycloaddition and Knoevenagel condensation reactions via stable Eu3+ modified Mn-MOF

The construction of MOF-based catalysts containing simultaneous Lewis acid and Lewis base sites has been considered as an efficient approach to enhance chemical fixation of CO2 into value-added products and Knoevenagel condensation reaction. Herein, one novel Eu3+-modified Mn-MOF (Eu3+@Mn-MOF-1) was successfully synthesized by solvothermal synthesis and post-synthesis modification. In Mn-MOF-1, the alternating chains with single and double carboxylate bridges are connected by H2L4− ligands to form a three-dimensional framework with 1D channels along a axis. Interestingly, the activated state of Eu3+@Mn-MOF-1 (noted as Eu3+@Mn-MOF-1a) with the removal of coordinated and lattice H2O molecules displayed excellent thermal stability. Furthermore, it is worth emphasizing that the inner surfaces of Eu3+@Mn-MOF-1a are functionalized by pentiful Lewis acid sites (tri- and penta-coordinated Mn2+ ions and modified Eu3+ ions) and Lewis base sites (uncoordinated Ocarboxylate and Npyridine). By virtue of the abundant co-existing Lewis acid-base sites, Eu3+@Mn-MOF-1a exhibited high catalytic performance for the cycloaddition of CO2 with epoxides and Knoevenagel condensation of aldehydes and malononitrile with preferable repeatability under mild conditions without the requirement of any solvent. Moreover, Eu3+@Mn-MOF-1a performed much higher activity for the cycloaddition of CO2 with epoxides than Mn-MOF-1a under the same conditions. In addition, Eu3+@Mn-MOF-1a also shows the yield of benzylidenemalononitrile can reach 99.9 % at room temperature within 1 h, representing about 1.3-fold increase compared to that of Mn-MOF-1a (76.0 %). The improvement of catalytic performance suggested the contribution of Eu3+ ions to the reaction. Hence, this work provides an efficient approach for the construction of MOFs with Lewis base sites by elaborately designing organic ligands and Lewis acid sites by post-synthetic modification to expose and/or introduce more unsaturated metal sites.

Active site modulation in UiO-66(Ce) MOFs by Al3+ doping for boosting photocatalysis

A series of Al3+-doped UiO-66(Ce) MOFs (U(CexAl1−x)) was developed to reveal the roles of metal doping on active site formation and substrate activation in photocatalytic selective transformation of amines to imines. Al3+ doping induced crystal structure distortion to form coordinately unsaturated metal (Al, Ce) sites as Lewis acid sites to chemisorb and activate benzylamine (BA). In situ FTIR revealed that the Al site with stronger acid strength facilitated BA activation. The activation degree of N–H bonds in BA was evaluated by changes of calculated force constant. The intermediate products were confirmed through time-dependent in situ FTIR. The Al3+-doped sample U(Ce0.90Al0.10), the optimal catalyst, showed a significantly increased BA conversion (97.6 %) than that (47.5 %) of undoped sample, which was attributed to enough active sites and the optimal charge mobility. Finally, the present study proposes a synergistic photocatalytic mechanism associated with molecular activation to demonstrate selective oxidation pathways at the molecular level.

Enhanced catalytic reduction of 4-nitrophenol using bimetallic MOFs: a one-pot synthesis approach

ABSTRACT Several organic pollutants can harm the environment and human health. A typical environmentally toxic contaminant, 4-Nitrophenol (4-NP), may cause serious health issues. Therefore, catalytic reduction (hydrogenation) of 4-nitrophenol into less toxic 4-aminophenol (4-AP) is mostly preferred. A three-dimensional (3D) metal-organic framework of Ni-MOF-74 is mostly used which contains maximum unsaturated metal sites and the catalytic activity is enhanced due to partial exchange at the node position in MOF. In order to study the catalytic hydrogenation/reduction of organic dye, 4-nitrophenol as a model reaction, a bimetallic MOF, FeNi-MOF-74 was prepared by partially substituting Ni with Fe metal. The catalyst was synthesised using a one-pot solvothermal technique, and 4-nitrophenol was then reduced catalytically in aqueous media. For the reduction of nitrophenol, the FeNi-MOF-74 catalyst surpassed Ni-MOF (9.3 × 10−3 s−1) and Fe-MOF (5.4 × 10−3 s−1) with a lower reduction time and a higher rate constant; (1.6 × 10−2 s−1). The high conversion rate and economical induction time are attributed to the bimetallic synergistic effect.

Defect and doping engineering mediated M-D-MIL(Fe)/Cu-C3N4 heterojunction with dual active centers for efficient tetracycline hydrochloride removal

It is essential to explore Fe-MOFs catalysts containing both multiple active sites and rapid charge separation for improving photo-Fenton performance. Herein, a defect and doping engineering mediated M-D-MIL(Fe)/Cu-C3N4 heterojunction with dual active centers was prepared and its removal performance was investigated against tetracycline hydrochloride. Characterization confirms that: (1) The ligand vacancies in M-D-MIL(Fe) can expose plenty of coordinatively unsaturated metal sites (Fe CUS), which enhance the Lewis acidity and optimize the adsorption of H2O2. Meanwhile, the built-in dual redox centers (Fe3+/Fe2+ and Cu+/Cu2+) can synergistically promote the activation of H2O2. (2) The ligand vacancies in M-D-MIL(Fe) and copper ion in C3N4 as electron trapping sites can optimize the carrier separation of single-component materials. Furthermore, the composites exhibit a suitable energy band structure, an oriented built-in electric field, and tight interfacial contacts, all of which collectively create an optimal pathway and driving force for the efficient transport of photoinduced charges. This, in turn, accelerates the Fe3+/Fe2+ redox cycle. Finally, M-D-MIL(Fe)/Cu-C3N4 demonstrates excellent photo-Fenton performance at low H2O2 concentrations (5 mM), with a kinetic rate (k) of 0.035 min⁻¹, which is 14.58, 18.42, 1.94, and 15.21 times higher than those of MIL-100(Fe), C3N4, M-D-MIL(Fe), and Cu-C3N4, respectively. The study presents an innovative idea with potential applications in environmental restoration.

Directionally Exfoliated Ni/Co Hydroxide-Organic Framework Nanosheets for Enhanced Wearable Glucose Sensing.

We report two-dimensional (2D) Ni/Co-based metal hydroxide-organic framework nanosheets (Ni/Co-MHOF NSs) for the construction of an efficient electrochemical nonenzymatic glucose sensor. The nanosheet architecture maximizes the exposure of coordinatively unsaturated metal sites, which enables a largely improved electrocatalytic performance toward the glucose oxidation reaction. The as-designed nonenzymatic sensor exhibits a high sensitivity of 235.71 μA·mM-1·cm-2 and a wide linear range of 1-3000 μM. The sensor presents excellent selectivity against several potential interferences and a short response time of 3.0 s. Of interest, a high-performance flexible sensor is developed by depositing the Ni/Co-MHOF NSs on screen-printed electrodes, which reveal decent bending stability. The designed glucose sensor patch can attach to the human body and realize noninvasive glucose monitoring in human sweat. This work may shed light on the application of novel MHOFs in the field of wearable electrochemical sensing.

Defect Engineering in Ce-Based Metal-Organic Frameworks toward Enhanced Catalytic Performance for Hydrogenation of Dicyclopentadiene.

Defective metal-organic frameworks (MOFs) have shown great potential for catalysis due to abundant active sites and adjustable physical and chemical properties. A series of Ce-based MOFs with different defect contents were synthesized via a modulator-induced defect engineering strategy with the aid of the cell pulverization technique. The effects of modulators on the pore structure, morphology, valence distribution of Ce, and Lewis acidity of Ce-MOF-801 were systematically investigated. Among the different samples studied, the optimal Ce-MOF-801-50eq sample exhibited remarkable catalytic activity for DCPD hydrogenation, achieving a conversion rate of 100%, which is significantly higher compared to other Ce-MOF-801-neq samples as well as the Zr-MOF-801-50eq and Hf-MOF-801-50eq samples. The enhanced catalytic performance of Ce-MOF-801-50eq can be attributed to advantages provided by defect engineering, such as the high specific surface area, proper pore size distribution, abundant unsaturated metal sites, and Ce3+/Ce4+ atom ratio, which have been supported by various characterizations. This study provides important insights into the rational design of Ce-MOFs in the field of catalytic DCPD hydrogenation.

Defect-Engineered Metal-Organic Framework/Polyimide Mixed Matrix Membrane for CO2 Separation.

Defect-engineered metal-organic frameworks (MOFs) with outstanding structural and chemical features have become excellent candidates for specific separation applications. The introduction of structural defects in MOFs as an efficient approach to manipulate their functionality provides excellent opportunities for the preparation of MOF-based mixed matrix membranes (MMMs). However, the use of this strategy to adjust the properties and develop the separation performance of gas separation membranes is still in its early stages. Here, a novel defect-engineered MOF (quasi ZrFum or Q-ZrFum) was synthesized via a controlled thermal deligandation process and incorporated into a CO2-philic 6FDA-durene polyimide (PI) matrix to form Q-ZrFum loaded MMMs. Defect-engineered MOFs and fabricated MMMs were investigated regarding their characteristic properties and separation performance. The incorporation of defects into the MOF structure increases the pore size and provides unsaturated active metal sites that positively affect CO2 molecule transport. The interfacial compatibility between the Q-ZrFum particles and the PI matrix increases via the deligandation process, which improves the mechanical strength of Q-ZrFum loaded membranes. MMM containing 5 wt.% of defect-engineered Q-ZrFum exhibits excellent CO2 permeability of 1308 Barrer, which increased by 99 % compared to the pure PI membrane (656 Barrer) at a feed pressure of 2 bar. CO2/CH4 and CO2/N2 selectivity reached 44 and 26.6 which increased by about 70 and 16 %, respectively. This study emphasizes that defect-engineered MOFs can be promising candidates for use as fillers in the preparation of MMMs for the future development of membrane-based gas separation applications.