Precise Tuning of Hollow and Pore Size of Bimetallic MOFs Derivate to Construct High-Performance Nanoscale Materials for Supercapacitors and Sodium-Ion Batteries.

Precise control of pore volume and size of carbon nanoscale materials is crucial for achieving high capacity and rate performances of charge/discharge. In this paper, starting from the unique mechanism of the role of In, Zn combination, and carboxyl functional groups in the formation of the lumen and pore size, the composition of InZn-MIL-68 is regulated to precisely tune the diameter and wall pore size of the hollow carbon tubes. The hollow carbon nanotubes (CNT) with high-capacity storage and fast exchange of Na+ ions and charges are prepared. The CNT possess ultra-high specific capacitance and ultra-long cycle life and also offer several times higher Na+ ion storage capacity and rate performance than the existing CNTs. Density functional theory calculations and tests reveal that these superior characteristics are attributed to the spacious hollow structure, which provides sufficient space for Na+ storage and the tube wall's distinctive porosity of tube wall as well as open ends for facilitating Na+ rapid desorption. It is believed that precise control of sub-nanopore volume and pore size by tuning the composition of the carbon materials derived from bimetallic metal-organic frameworks (MOFs) will establish the basis for the future development of high-energy density and high-power density supercapacitors and batteries.

Microwave-Assisted Ultrafast Synthesis of Bimetallic Nickel-Cobalt Metal-Organic Frameworks for Application in the Oxygen Evolution Reaction.

Herein, a series of monometallic Ni-, Co- and Zn-MOFs and bimetallic NiCo-, NiZn- and CoZn-MOFs of formula M2(BDC)2DABCO and (M,M')2(BDC)2DABCO, respectively, (M, M'=metal) with the same pillar and layer linkers 1,4-diazabicyclo[2.2.2]octane (DABCO) and benzene-1,4-dicarboxylate (BDC) were prepared through a fast microwave-assisted thermal conversion synthesis method (MW) within only 12 min. In the bimetallic MOFs the ratio M:M' was 4 : 1. The mono- and bimetallic MOFs were selected to systematically explore the catalytic-activity of their derived metal oxide/hydroxides for the oxygen evolution reaction (OER). Among all tested bimetallic MOF-derived catalysts, the NiCoMOF exhibits superior catalytic activity for the OER with the lowest overpotentials of 301 mV and Tafel slopes of 42 mV dec-1 on a rotating disk glassy carbon electrode (RD-GCE) in 1 mol L-1 KOH electrolyte at a current density of 10 mA cm-2. In addition, NiCoMOF was insitu grown in just 25 min by the MW synthesis on the surface of nickel foam (NF) with, for example, a mass loading of 16.6 mgMOF/gNF, where overpotentials of 313 and 328 mV at current densities of 50 and 300 mA cm-2, respectively, were delivered and superior long-term stability for practical OER application. The low Tafel slope of 27 mV dec-1, as well as a low reaction resistance from electrochemical impedance spectroscopy (EIS) measurement (Rfar=2 Ω), confirm the excellent OER performance of this NiCoMOF/NF composite. During the electrocatalytic processes or even before upon KOH pre-treatment, the MOFs are transformed to the mixed-metal hydroxide phase α-/ß-M(OH)2 which presents the active species in the reactions (turnover frequency TOF=0.252 s-1 at an overpotential of 320 mV). Compared to the TOF from ß-M(OH)2 (0.002 s-1), our study demonstrates that a bimetallic MOF improves the electrocatalytic performance of the derived catalyst by giving an intimate and uniform mixture of the involved metals at the nanoscale.

Preparation of a high-performance H2S gas sensor based on CuO/Co3O4composite derived from bimetallic MOF.

The bimetallic metal-organic frameworks (MOFs), Cu/Co-MOF, was synthesized through a solvothermal method and calcined to obtain CuO/Co3O4composites. By adjusting the molar ratio between Cu and Co ions, a composite material of CuO/Co3O4(Cu:Co = 1:1) was developed and showed excellent sensing capabilities, and the response reached as high as 196.3 for 10 ppm H2S detection. Furthermore, the optimal operating temperature as low as 40 °C was found. In comparison with the sensors prepared by pristine CuO and pristine Co3O4, the sensor based on CuO/Co3O4composite exhibited a significant response. Additionally, the sensor can detect H2S gas down to 300 ppb. The gas sensing mechanism is discussed in depth from the perspective of p-p heterojunction formation between the p-type CuO and p-type Co3O4. The as-prepared CuO/Co3O4composite-based sensor is expected to find practical application in the low-power monitoring of H2S.

A new strategy for PET depolymerization: Application of bimetallic MOF-74 as a selective catalyst.

Large-volume production of poly(ethylene terephthalate) (PET), especially in the form of bottles and food packaging containers, causes problems with polymer waste management. Waste PET could be recycled thermally, mechanically or chemically and the last method allows to obtain individual monomers, but most often it is carried out in the presence of homogeneous catalysts, that are difficult to separate and reuse. In view of this, this work reports for the first time, application of bimetallic MOF-74 - as heterogeneous catalyst - for depolymerization of PET with high monomer (bishydroxyethyl terephthalate, BHET) recovery. The effect of type and amount of second metal in the MOF-74 (Mg/M) was systematically investigated. The results showed increased activity of MOF-74 (Mg/M) containing Co2+, Zn2+ and Mn2+ as a second metal, while the opposite correlation was observed for Cu2+ and Ni2+. It was found that the highest catalytic activity was demonstrated by the introduction of Mg-Mn into MOF-74 with ratio molar 1:1, which resulted in complete depolymerization of PET and 91.8% BHET yield within 4 h. Furthermore, the obtained catalyst showed good stability in 5 reaction cycles and allowed to achieve high-purity BHET, which was confirmed by HPLC analysis. The as-prepared MOF-74 (Mg/Mn) was easy to separate from the post-reaction mixture, clean and reuse in the next depolymerization reaction.

Optimization and synthesis of a novel sorbent composite based on magnetic chitosan-amine-functionalized bimetallic MOF for the simultaneous dispersive solid-phase microextraction of four aflatoxins in real water, herbal distillate, and food samples.

Aflatoxins (AFs), an important category of pollutants, are formed in many foods and adversely affect human health. Therefore, their determination is critical to ensuring human food health. An efficient dispersive solid-phase microextraction technique was developed as a simple and straightforward sample preparation technique for determination of four aflatoxins using a high-performance liquid chromatography (HPLC) fluorescence detector. A novel efficient, green sorbent for extracting AFs was synthesized based on hydrothermal and chemical strategies. The amounts of three sorbent components were optimized using a mixture design (simplex lattice design), including 14 experiments. The optimal amount of amino-bimetallic Fe/Ni-MIL-53 nanospheres, chitosan, and magnetic Fe3O4 nanoparticles as sorbent components was 0.87, 0.67, and 0.47 g, respectively. Also, various factors affecting the process of AF determination were studied and optimized in two successive experimental designs, including the definitive screening design and the Box-Behnken design. Under optimal conditions, the linear ranges for measuring aflatoxin B1, aflatoxin B2, aflatoxin G1, and aflatoxin G2 were 0.05-82.6, 0.07-86.4, 0.08-85.7, and 0.07-89.5 ng mL-1, respectively. The relative standard deviations under inter-day and intra-day conditions for measuring AFs at three analyte concentrations were determined in triplicate analysis and were in the ranges of 3.7-4.6% and 4.9-6.1% for water sample analysis, respectively. The qualitative detection limits for determining AFs were between 0.01 and 0.05 ng mL-1. The pre-concentration factor of the method for measuring AFs ranged from 739.7 to 802.1. The proposed method was used for determining AFs in several real samples, including herbal distillate, black tea, corn, and real water samples. The relative recovery and standard deviation were 87.8-97.8% and 4.10-6.82%, respectively.

A sensitive fluorescence detection strategy for H2O2 and glucose by using aminated Fe-Ni bimetallic MOF as fluorescent nanozyme.

An aminated Fe-Ni bimetallic metal-organic framework (Fe3Ni-MOF-NH2) with both peroxidase-like activity and fluorescence properties was developed. Fe3Ni-MOF-NH2 possessed the enhanced peroxidase-like activity through the enhanced electron transfer process and hydroxyl radical (·OH) generation. It was found that the amino group endowed the material with fluorescent property and the metal site Ni in Fe3Ni-MOF-NH2 could also enhance the fluorescence emission intensity (Ex = 345 nm, Em = 452 nm). Based on the dual excellent performance of Fe3Ni-MOF-NH2, a novel sensitive fluorescence detection strategy for H2O2 and glucose was designed and achieved. First, Fe3Ni-MOF-NH2 converted H2O2 to ·OH by exerting peroxidase-like activity, and ·OH converts catechol to o-benzoquinone. Then, the amino group in Fe3Ni-MOF-NH2 connected to o-benzoquinone, which resulted in its fluorescence quenching. The detection limit of H2O2 was as low as 5 nM. Combined with glucose oxidase which can oxidize glucose and produce H2O2 the glucose could be indirectly determined with a detection limit of 40 nM. The method was applied to the detection of low-level glucose in human urine samples with good recoveries and reproducibilities.

Differential sensitization toward lanthanide metal-organic framework for detection of an anthrax biomarker.

A novel Tb-doped Eu-based metal-organic framework (Eu-MOF@Tb) has been developed by incorporating hexanuclear europium cluster and 2,2'-bipyridine-5,5'-dicarboxylic acid as well as coordination with Tb(III). Owing to the diverse coordination status of Tb(III) and Eu(III) in MOF, antenna effect emission from Tb(III) can be invoked by dipicolinic acid (DPA), but the luminescence originating from Eu(III) remains unchanged. Taking advantage of this phenomenon, a ratiometric luminescent method for detection of DPA, a biomarker for Bacillus subtilis spores, was developed through differential sensitization toward lanthanide ions. This analysis method allowed for the detection of DPA in the 0.2-10 µM concentration range, with a detection limit of 60 nM. It was further validated by spiked recoveries (89.3-110%) of real-world samples with RSD values in the range 3.9-11%. Alongside this, a paper indicator test was prepared for naked-eye detection of DPA via a dose-sensitive color evolution from red to green under UV light. The effectiveness of the proposed approach was explored in the detection of bacterial spores in real biological and environmental samples and indicated great potential for applications as a real-time monitoring system against the anthrax threat.

Inlaying Ultrathin Bimetallic MOF Nanosheets into 3D Ordered Macroporous Hydroxide for Superior Electrocatalytic Oxygen Evolution.

Controllable synthesis of ultrathin metal-organic framework (MOF) nanosheets and rational design of their nano/microstructures in favor of electrochemical catalysis is critical for their renewable energy applications. Herein, an in situ growth method is proposed to prepare the ultrathin NiFe MOF nanosheets with a thickness of 1.5 nm, which are vertically inlaid into a 3D ordered macroporous structure of NiFe hydroxide. The well-designed composite delivers an efficient electrocatalytic performance with a low overpotential of 270 mV at a current density of 10 mA cm-2 and stable electrolysis as long as 10 h toward the electrochemical oxygen evolution reaction, much superior to the state-of-the-art RuO2 electrocatalyst. A comprehensive analysis demonstrates that the excellent performance originates from the desirable combination of the highly exposed active centers in the ultrathin bimetallic MOF nanosheets, effective electron conduction between MOF nanosheets and ordered macroporous hydroxide, and efficient mass transfer across the hierarchically porous hybridization. This study sheds light on the exploration of powerful protocols to gain diverse high-performance MOF nanosheets and may open a perspective to achieve their efficient electrocatalytic performance.

A Novel Approach to High-Performance Aliovalent-Substituted Catalysts-2D Bimetallic MOF-Derived CeCuOx Microsheets.

Mixed transition metal oxides (MTMOs) have enormous potential applications in energy and environment. Their use as catalysts for the treatment of environmental pollution requires further enhancement in activity and stability. This work presents a new synthesis approach that is both convenient and effective in preparing binary metal oxide catalysts (CeCuOx ) with excellent activity by achieving molecular-level mixing to promote aliovalent substitution. It also allows a single, pure MTMO to be prepared for enhanced stability under reaction by using a bimetallic metal-organic framework (MOF) as the catalyst precursor. This approach also enables the direct manipulation of the shape and form of the MTMO catalyst by controlling the crystallization and growth of the MOF precursor. A 2D CeCuOx catalyst is investigated for the oxidation reactions of methanol, acetone, toluene, and o-xylene. The catalyst can catalyze the complete reactions of these molecules into CO2 at temperatures below 200 °C, representing a significant improvement in performance. Furthermore, the catalyst can tolerate high moisture content without deactivation.

Multifunctional bimetallic MOF with oxygen vacancy synthesized by microplasma for rapid total antioxidant capacity assessment in agricultural products.

The assessment of total antioxidant capacity (TAC) is crucial for evaluating overall antioxidant potential, predicting the risk of chronic diseases, guiding dietary and nutritional interventions, and studying the effectiveness of antioxidants. However, achieving rapid TAC assessment with high sensitivity and stability remains a challenge. In this study, Ce/Fe-MOF with abundant oxygen vacancies was synthesized using microplasma for TAC determination. The microplasma synthesis method was rapid (30 min) and cost-effective. The presence of oxygen vacancies and the collaboration between iron and cerium in Ce/Fe-MOF not only enhanced the catalyst's efficiency but also conferred multiple enzyme-like properties: peroxidase-like, oxidase-like, and superoxide dismutase mimetic activities. Consequently, a simple colorimetric assay was established for TAC determination in vegetables and fruits, featuring a short analysis time of 15 min, a good linear range of 5-60 µM, a low detection limit of 1.3 µM and a good recovery of 91 %-107 %. This method holds promise for rapid TAC assessment in agricultural products.

Spindle shaped Fe-Ni metal organic frameworks wrapped with f-MWCNTs for the efficacious sensing of tartrazine.

A facile hydrothermal route was employed for the synthesis of iron-nickel bimetal organic frameworks (Fe-Ni bi-MOFs) and composite with an acid functionalized multi-walled carbon nanotubes (Fe-Ni MOF/f-MWCNTs) for electrochemical detection of tartrazine. The as-prepared Fe-Ni MOF/f-MWCNTs was confirmed by the several physicochemical studies. A micro spindle shaped, highly porous, and crystalline Fe-Ni MOF/f-MWCNTs was noticed. The high sensitivity and stability of Fe-Ni MOF/f-MWCNTs/GCE modified electrode was analyzed. Due to its high porosity nature, the analyte molecule effectively gets adsorbed on the modified electrode and undergo electrochemical oxidation effectively. The modified electrode exhibits low limit of detection (LOD) and limit of quantification (LOQ) as 0.04 × 10-6 mol/L and 0.13 × 10-6 mol/L towards tartrazine. These results reveal the potential applications of Fe-Ni MOF/f-MWCNTs/GCE as modified electrode material for sensitive detection of tartrazine along with its robust reproducibility, stability, and effective sensing properties.

Fast skin healing chitosan/PEO hydrogels: In vitro and in vivo studies.

Due to its outstanding qualities, particularly when it takes the shape of hydrogels, chitosan is a well-known biological macromolecule with many applications. When chitosan hydrogels are modified with other polymers, the desirable function as skin regeneration hydrogels is compromised; nevertheless, the mechanical properties can be improved, which is crucial for commercialization. In this study, for the first time, bimetallic zinc silver metal-organic frameworks (ZAg MOF) loaded with ascorbic acid were added to chitosan/polyethylene oxide (PEO) based interpenetrating polymer network (IPN) hydrogels that were crosslinked with biotin to improve their antimicrobial activity, mechanical characteristics, and sustainable treatment of wounds. Significant changes in the microstructure, hydrophilicity level, and mechanical properties were noticed. Ascorbic acid release patterns were upregulated in an acidic environment pH (5.5) that mimics the initial wound pH. Impressive cell viability (98 %), antimicrobial properties, and almost full skin healing in a short time were achieved for the non-replaceable chitosan/PEO developed hydrogels. Enhancing the wound healing of the treated animals using the prepared CS/PEO hydrogel dressing was found to be a result of the inhibition of dermal inflammation via decreasing IL-1ß, suppressing ECM degradation (MMP9), stimulating proliferation through upregulation of TGF-ß and increasing ECM synthesis as it elevates collagen 1 and α-SMA contents. The findings support the implementation of developed hydrogels as antimicrobial hydrogels dressing for fast skin regeneration.

Fabrication of NiCo Bimetallic MOF Films on 3D Foam with Assistance of Atomic Layer Deposition for Non-Invasive Lactic Acid Sensing.

Lactic acid (LA) is an important downstream product of glycolysis in living cells and is abundant in our body fluids, which are strongly associated with diseases. The development of enzyme-free LA sensors with high sensitivity and low consumption remains a challenge. 2D metal-organic frameworks (MOFs) are considered to be promising electrochemical sensing materials and have attracted much attention in recent years. Compared to monometallic MOFs, the construction of bimetallic MOFs (BMOFs) can obtain a larger specific surface area, thereby increasing the exposed active site. 3D petal-like NixCoy MOF films on nickel foams (NixCoy BMOF@Ni foams) are successfully prepared by combining atomic layer deposition-assisted technology and hydrothermal strategy. The established NixCoy BMOF@Ni foams demonstrate noticeable LA sensing activity, and the study is carried out on behalf of the Ni1Co5 BMOF@Ni foam, which has a sensitivity of up to 9030 µA mM-1 cm-2 with a linear range of 0.01-2.2 mM and the detection limit is as low as 0.16 µM. Additionally, the composite has excellent stability and repeatability for the detection of LA under a natural air environment with high accuracy and reliability. Density functional theory calculation is applied to study the reaction process between composites and LA, and the result suggests that the active site in the NiCo BMOF film favors the adsorption of LA relative to the active site of monometallic MOF film, resulting in improved performance. The developed composite has a great potential for the application of noninvasive LA biosensors.

Bimetal-organic framework/GOx-based hydrogel dressings with antibacterial and inflammatory modulation for wound healing.

Antibiotic resistance of bacteria and persistent inflammation are critical challenges in treating bacteria infected wounds. Thus, it is urgent to develop versatile wound dressings that possess high-efficiency antibacterial performance and inflammation regulation. Herein, we have successfully constructed a hydrogel wound dressing consisting of the bimetallic metal-organic framework (MOF) loaded with glucose oxidase (GOx), termed as MOF(Fe-Cu)/GOx-polyacrylamide (PAM) gel. Hydrogel dressings can provide an efficient cascade-catalyzed system to accelerate wound healing via synergistic antibacterial and inflammatory modulation. Importantly, the catalytic property of the bimetallic MOF(Fe-Cu) is about five times that of the monometallic MOF(Fe). Based on such a cascade-catalyzed system, the abundant gluconic acid and H2O2 can be continuously produced by decomposing glucose via GOx. Such gluconic acid can notably improve the peroxidase performance of MOF(Fe-Cu), which can further efficiently decompose H2O2 to achieve the antibacterial. Meanwhile, MOF (Fe Cu)/GOx PAM gel can induce macrophages to change into an M2 phenotype, which can accelerate the transformation of the wound microenvironment to a remodeling state and then accelerate angiogenesis and neurogenesis. This work provides multifunctional bioactive materials for accelerating wound healing and will have great potential in clinical applications. STATEMENT OF SIGNIFICANCE: Antibiotic resistance and persistent inflammation are still the critical reasons for the slow healing of bacteria infected wounds. Herein, we prepared a hydrogel wound dressing composed of bimetallic metal organic framework (MOF) loaded with glucose oxidase (GOx). The catalytic activity of the bimetallic MOF(Fe-Cu) is significantly enhanced due to doping of copper, which makes it possess outstanding antibacterial ability based on cascade catalysis. Such dressing can promote the remodeling of inflammatory immunity by regulating macrophage polarization to suppress over-reactive inflammation, further accelerating the healing of bacteria-infected wounds. This study provides an innovative and effective way to accelerate the healing of bacteria infected wound by combining bacteria killing and inflammation modulation.

Oxidase mimicking Co/2Fe MOF included biosensor for sialic acid detection.

A facile amperometric biosensor that included oxidase mimicking Co/2Fe metal-organic framework (MOF) for sialic acid (SA) detection was prepared. Amperometric SA biosensor was constructed on a gold screen-printed electrode via immobilization of Co/2Fe MOF and N-acetylneuraminic Acid Aldolase (NANA-Aldolase) enzyme, respectively. NANA-Aldolase enzyme converts free SA into pyruvate and N-acetyl-d-mannosamine. After this conversion, oxidase mimicking Co/2Fe bimetallic MOF converts pyruvate into acetylphosphate and O2 into H2O2. Investigation of analytical characteristics resulted with the linear range of 0.02 mM-1.00 mM of SA concentration with limit of detection value of 0.026 mM. Sample application studies with developed SA biosensor were carried out with GD3 ganglioside and HeLa cancer cell lines which have high SA concentrations while A549 cell lines were also used as control group. Before detecting free SA, the bound SA was freed from SA sources where every step was monitored via electron impedance spectroscopy. Then, free SA was successfully detected with the amperometric SA biosensor and as a result, more practical and accurate system was developed.

Accelerated electron transfer process via MOF-derived FeCo/C for enhanced degradation of antibiotic contaminants towards heterogeneous electro-Fenton system.

The Fe(III) to Fe(II) process limits the rate of the electro-Fenton system. In this study, MIL-101(Fe) derived porous carbon skeleton-coated FeCo bimetallic catalyst Fe4/Co@PC-700 was prepared as a heterogeneous electro-Fenton (EF) catalytic process. The experimental results showed its good performance in catalytic removal of antibiotic contaminants, the rate constant of tetracycline (TC) degradation catalyzed by Fe4/Co@PC-700 was 8.93 times higher than that of Fe@PC-700 under the pH conditions of raw water (pH = 5.86), exhibited good removal of TC, oxytetracycline (OTC), hygromycin (CTC), chloramphenicol (CAP) and ciprofloxacin (CIP). It was shown that the introduction of Co promoted more Fe0 production, allowing the material to exhibit faster Fe(III)/Fe(II) cycling rates. 1O2 and high-priced metal oxygen species were identified as the main active species of the system, in addition to the analysis of possible degradation pathways and toxicity of intermediates of TC. Finally, the stability and adaptability of Fe4/Co@PC-700 and EF systems to different water matrices were evaluated, showing that Fe4/Co@PC-700 was easy to recover and could be applied to different water matrices. This study provides a reference for the design and system application of heterogeneous EF catalysts.

Rational construction of a robust metal-organic framework nanozyme with dual-metal active sites for colorimetric detection of organophosphorus pesticides.

While nanomaterials with enzyme-mimicking activities are emerging as promising candidates in the colorimetric detection of organophosphorus pesticides (OPs), the catalytic activities and recognition ability to analyte of most nanozymes are inherently deficient. In this work, we introduced manganese ions into a typical iron based MOF (Fe-MIL(53)) via a one-pot hydrothermal reaction strategy, which brought out a catalytically favorable bimetallic Mn/Fe-MIL(53) MOF nanozyme. The catalytic performance of Mn/Fe-MIL(53) is superior to that of pure Fe-MIL (53) and the mechanism for superior catalytic activity of material is revealed by active species scavenging experiments and X-ray photoelectron spectroscopy (XPS). Besides, the introduction of manganese endows the material with the characteristic of being specially destroyed by choline, which motivates the establishment of a simple, selective and sensitive colorimetric strategy for OPs detection. The proposed colorimetric strategy could quantify the methyl parathion and chlorpyrifos in the concentration range of 10-120 nM and 5-50 nM, respectively. The low detection limit of 2.8 nM for methyl parathion and 0.95 nM (3 S/N) for chlorpyrifos were achieved. Good recoveries were obtained when applied in the real sample detection. Our work paves the way to boost catalytic performance of MOF nanozymes, which will be useful in biosensing.

Degradation of Tetracycline Hydrochloride by Cu-Doped MIL-101(Fe) Loaded Diatomite Heterogeneous Fenton Catalyst.

In this work, the combination of high surface area diatomite with Fe and Cu bimetallic MOF material catalysts (Fe0.25Cu0.75(BDC)@DE) were synthesized by traditional solvothermal method, and exhibited efficient degradation performance to tetracycline hydrochloride (TC). The degradation results showed: Within 120 min, about 93% of TC was degraded under the optimal conditions. From the physical-chemical characterization, it can be seen that Fe and Cu play crucial roles in the reduction of Fe3+ because of their synergistic effect. The synergistic effect can not only increase the generation of hydroxyl radicals (•OH), but also improve the degradation efficiency of TC. The Lewis acid property of Cu achieved the pH range of reaction system has been expanded, and it made the material degrade well under both neutral and acidic conditions. Loading into diatomite can reduce agglomeration and metal ion leaching, thus the novel catalysts exhibited low metal ion leaching. This catalyst has good structural stability, and less loss of performance after five reaction cycles, and the degradation efficiency of the material still reached 81.8%. High performance liquid chromatography-mass spectrometry was used to analyze the degradation intermediates of TC, it provided a deep insight of the mechanism and degradation pathway of TC by bimetallic MOFs. This allows us to gain a deeper understanding of the catalytic mechanism and degradation pathway of TC degradation by bimetallic MOFS catalysts. This work has not only achieved important progress in developing high-performance catalysts for TC degradation, but has also provided useful information for the development of MOF-based catalysts for rapid environmental remediation.

Structural and Electronic Modulation of Iron-Based Bimetallic Metal-Organic Framework Bifunctional Electrocatalysts for Efficient Overall Water Splitting in Alkaline and Seawater Environment.

Metal-organic frameworks (MOFs) are considered potential electrocatalysts for efficient water splitting. However, the structure-activity relationship of most MOFs is not systematically analyzed for electrocatalysis for anodes and cathodes. In this paper, we provide a strategy to modulate the electronic microstructure of iron-based bimetallic MOFs (MFe-BDC (M: Mg, Zn, Cd)) grown on the nickel foam (NF) as bifunctional electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The optimal bimetallic CdFe-BDC via modulating appropriate metal cations of IIA and IIB possesses excellent OER and HER performance with the lowest overpotentials of 290 mV at 100 mA cm-2 and 148 mV at 10 mA cm-2, respectively. The overall water splitting performance of the as-prepared CdFe-BDC requires 1.68 V to achieve a current density of 10 mA cm-2 in the real seawater media, and it exhibits the competitive H2 and O2 production rates of 6.4 and 3.1 µL s-1, respectively, in ambient alkaline conditions, suggesting its potential practical applications. Density functional theory (DFT) calculations demonstrate the relationship between microstructure and electrocatalytic performance of bimetallic MFe-BDC. This work emphasizes the significance of tailoring the electronic microstructure of bimetallic MOFs for efficient overall water splitting in alkaline and seawater environment.

Bimetallic Fe/Al-MOF for the adsorptive removal of multiple dyes: optimization and modeling of batch and hybrid adsorbent-river sand column study and its application in textile industry wastewater.

Bimetallic metal organic framework (MOF) has garnered interest over the years with its applications in industrial wastewater treatment. In this work, Fe-Al-1,4-benzene-dicarboxylic acid (FeAl(BDC)) MOF was synthesized, and adsorptive removal of Rhodamine B dye in batch and unique hybrid FeAl (BDC)-river sand fixed-bed column was studied. The experimental data from the batch studies corroborated well with the pseudo-second-order (PSO) (R2: 0.97) and Freundlich adsorption isotherm models (R2: 0.98) and achieved a maximum adsorption capacity of 48.59 mg/g in 90 min. Furthermore, a fixed-bed column study was conducted to assess the effect of varying flow rate (2, 5, 8 mL/min), bed height (5, 9, 13 cm), and feed concentration (10, 20, 30 mg/L) on the adsorption performance of FeAl(BDC) in continuous mode of operation. A uniform mixture of river sand and FeAl(BDC) by weight ratio (9:1) was packed into the column. The sand-FeAl(BDC) fixed-bed column could achieve the maximum adsorption capacity (qexp) of 113.05 mg/g at a 5 mL/min flow rate, feed concentration of 20 mg/L, and a bed height of 13 cm. The experimental data of the column study were successfully fitted well with BDST, Thomas (qcal: 114.94 mg/g), Yoon-Nelson, and dose-response models (qcal: 113.41 mg/g) and R2: 0.97-0.99. The fitting parameter values from the BDST model raise the scope of viable upscaling of the fixed-bed column. In all, it is proposed that these river sand-FeAl(BDC)-based filters can be widely used in areas facing critical contamination and in poor communities with a high demand for water.