Bimetallic Metal-organic Frameworks Research Articles

Tailoring the Electrochemical Responses of MOF-74 Via Dual-Defect Engineering for Superior Energy Storage.

Rationally designed defects in a crystal can confer unique properties. This study showcases a novel dual-defects engineering strategy to tailor the electrochemical response of metal-organic framework (MOF) materials used for electrochemical energy storage. Salicylic acid (SA) is identified as an effective modulator to control MOF-74 growth and induce structural defects, and cobalt cation doping is adopted for introducing a second type of defect. The resulting dual-defects engineered bimetallic MOF exhibits a discharging capacity of 218.6 mAh g-1, 4.4 times that of the pristine MOF-74, and significantly improved cycling stability. Moreover, the engineered MOF-74(Ni0.675Co0.325)-8//Zn aqueous battery shows top energy/power density performances for Ni-Zn batteries (266.5Wh kg-1, 17.22kW kg-1). Comprehensive investigations reveal that engineered defects modify the local coordination environment and promote the in situ electrochemical reconfiguration during operation to significantly boost the electrochemical activity. This work suggests that rational tailoring of the defects within the MOF crystal is an effective strategy to manipulate the coordination environment of the metal centers and the corresponding electrochemical reconfiguration for electrochemical applications.

Spin Crossover and Exchange Effects on Oxygen Evolution Reaction Catalyzed by Bimetallic Metal Organic Frameworks

Spin Crossover and Exchange Effects on Oxygen Evolution Reaction Catalyzed by Bimetallic Metal Organic Frameworks

Zinc–cobalt bimetallic metal-organic framework (Zn/Co-MOF) nanoparticles as potent pH stimuli anti-corrosive agent for development of a self-healable epoxy composite coating

The impressive BET-surface area and the design versatility have made Z67(ZIF-67) MOF a potent nanomaterial for anti-corrosion applications. Despite excellent anti-corrosion features the Z67(ZIF-67) suffers poor stability in water media, making it improper for application in polymeric systems. One strategy to enhance the stability of Z67 is its structure modification via a mixed-metal organic framework approach. This study involved the synthesis of a series of Z67 nanoparticles through the incorporation of zinc cation (Zn) at different percentages. Specifically, three different compositions were synthesized: Zn10-Z67, Zn20-Z67, and Zn30-Z67 denoting the addition of 10 %, 20 %, and 30 % molar percent of Zn, respectively. FTIR, FE-SEM, XRD, TEM, ICP-OES, and XPS, as well as BET analyses, were conducted for the Zinc–Cobalt bimetallic MOF structure. Subsequently, the properties attributed to the particles' active and barrier anti-corrosion feature in solution (NaCl) as well as coating (epoxy) phases were investigated. The EIS test performed in the solution phase, after 72h of metal exposure to Zn30-Z67 containing saline media, revealed a 590 % and 30 % increase in total resistance, respectively, compared to the uninhibited sample. Due to the increased stability of Zn10-Z67 in a saline environment, the active corrosion inhibition of the scratched coating containing these particles was increased by approximately 140 % compared to the Z67-containing composite. The incorporation of zinc cations into the structure of Z67 has enhanced the stability and control release features in aqueous environments, thereby enhancing the barrier properties of the epoxy coating. The reduction rate of log|Z|0.01Hz of the Zn10-Z67/EPC was 9 % which was lower than that of the Neat EPC (epoxy coating) (24 %).

Self-assembly Fe-Co MOF@BN and epoxy resin nano composites with highly enhanced flame retardancy and smoke suppression properties

A shuttle-shaped Fe-Co bimetallic metal organic frameworks (MOFs) on sheet-like hexagonal boron nitride (h-BN) was fabricated via an organic-inorganic hybrid strategy, forming a novel Fe-Co MOF@BN flame retardant, and the hybrids together with ammonium polyphosphate (APP) were incorporated into epoxy resins to explore their flame retardancy and smoke suppression effects. When combining 0.5 % Fe-Co MOF@BN with 9.5 % APP, the peak heat release rate, peak smoke release rate, CO production rate, and peak CO2 production rate of the EP composite (EP/APP/Fe-Co MOF@BN) were reduced by 73.7 %, 71.4 %, 70 %, and 80 % respectively, compared to epoxy. The limiting oxygen index increases to 30.2 %, indicating the EP/APP/Fe-Co MOF@BN composites have superior fire safety performance. The excellent fire performance of EP/APP/Fe-Co MOF@BN composites benefiting from the barrier effect of Fe-Co MOF@BN lamellar structure, the catalytic carbonization of Fe and Co, the gas phase dilution of APP and the enhancement of the cross-linking degree of the char layer. Meanwhile, Fe-Co MOF@BN improves the dispersion of APP in the EP composites, which broadens the application range of MOF and h-BN. Herein, the EP/APP/Fe-CoMOF@BN composites with high flame retardancy, low smoke production rate, and excellent mechanical properties provide a feasible solution for the use of EP under high temperatures.

Biochar-Supported FeCo-MOF derivative catalyzes PDS-Mediated degradation of tetracycline

Bimetallic metal–organic framework (MOF) has gained wide attention in the field of advanced oxidative processes (AOPs), however, the agglomeration problem severely limits its active sites and its activation mechanism still needs to be further explored. This study developed the BC@CoFe composite material, utilizing biochar (BC) to support FeCo-MOF derivatives, effectively alleviating their agglomeration and structural collapse. The results of the BC@CoFe activated peroxydisulfate (PDS) system for the degradation of tetracycline (TC) revealed an excellent degradation efficiency up to 97.7 % in 2 h for TC solution (20 mg/L, degradation rate constants k = 7.066 mM-1min−1). Furthermore, the BC@CoFe/PDS system exhibits exceptionally high cyclic stability (73.23 % degradation efficiency after 12 h continuous degradation), a wide range of pH (3–11) and temperature tolerance (20-60℃), resistance to background ion interference (SO42-, H2PO4-, NO3– and HA), and reduced toxicity of the degradation products. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) analyses show that the exceptional catalytic performance of BC@CoFe primarily stems from the synergistic effect between Fe(II)/Co(III) and Fe(III)/Co(II). Regarding the reactive active species involved in TC degradation, the contribution rates of 1O2, SO4•- and ·OH were measured and calculated to be 73.6 %, 14.9 %, and 11.5 %, respectively. Thus, the BC@CoFe/PDS system exhibits outstanding catalytic activity and has broad practical applications in water treatment.

Heterogeneous strategy constructing a built-in electric field: CoP/FeP bifunctional electrode for overall water splitting

Development of non-noble bifunctional electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are of great significance under alkaline electrolytes for overall water splitting. In this work, CoP/FeP has been designed and constructed in situ on carbon fiber paper by using the bimetallic metal organic frameworks (MOFs) synthesis strategy. The heterogeneous CoP/FeP displays excellent catalytic activities in both HER and OER of the fully hydrolyzed semi-reaction. Remarkably, CoP/FeP is applied as the bifunctional electrode in anode and cathode to construct an overall water splitting apparatus, resulting in the low cell voltage and excellent stability. The exceptional electrocatalytic performance may be mainly attributed to the heterogeneous interface, which constructs a built-in electric field to provide electron to Co with electron-rich structure, resulting in the strong adsorption of H and weak adsorption of O2 on Co. This study provides an effective and controllable method for the design of self-supporting bimetal phosphide catalysts.

Construction of rose-type Co/Mo bimetal MOF and MOF-derived W embedded composites: structure, reactivity, and dynamic simulation

Transition metal organic framework-derived materials are potential catalysts for cycloolefins oxidation, and it is essential to develop them with sufficient intrinsic activity and more efficient structure. Herein, we designed Co/Mo bimetallic MOF with rose-type structure as a support for synthesizing CoMo-ZIF@IL/W catalyst with lamelliform structure and abundant Co, Mo, and W active sites for cyclopentene tandem oxidation to glutaraldehyde. Characterization results reveal that: 1) Mo implantation dramatically increases pore size (2.15 → 28.91 nm) of monometallic MOF Co-ZIF; 2) IL introduction significantly improves active (Co2+ + Co3+) / satellite content ratio from 1.85 to 2.5; 3) MOF morphology can be completely changed through post-synthetic modification via IL, rather than just during the synthesis process. Meanwhile, CoMo-ZIF@IL/W exhibits high activity and excellent reuse properties in cyclopentene oxidation. Remarkably, dynamic simulation supported via detailed kinetic parameters (pre-exponential factors A1-3 = 1.17 × 1012, 1.45 × 108, 9.58 × 106 L⋅mol−1⋅s−1, activation energies E1-3 = 89.4, 57.82, 86.01 kJ⋅mol−1) and possible synergistic catalysis mechanism of Co/Mo/W active species were first explored.

WOx boosted hollow Ni nanoreactors for the hydrodeoxygenation of lignin derivatives

Reasonable design of non-noble metal catalysts with hollow open structure for hydrodeoxygenation (HDO) of lignin derivatives to value-added chemicals is of great significance but challenging. Herein, a novel MOF-derived multilayer hollow sphere coated nickel‑tungsten bimetallic catalyst (Ni2-WOx@CN-700) was fabricated via by confined pyrolysis strategy using bimetallic MOFs as a self-sacrificial template, which exhibits robust activity for the typical model HDO of vanillin to 2-methoxy-4-methylphenol (Yield of 100 % at 140 °C for no less than 10 cycles). The characterizations revealed that WOx facilitated the dispersion of Ni nanoparticles and adjusted the acidic capacity of the catalyst through the formed Ni-WOx heterojunction. Density functional theory (DFT) calculations confirms that WOx species enhanced the electron-rich nature of the active sites, while the adsorption energies of H2 and vanillin on Ni-WOx decreased from −0.572 eV and − 0.622 eV on Ni to −3.969 eV and − 4.92254 eV, respectively. These results further indicated that the high activity of Ni2-WOx@CN-700 was attributed to the Ni-WOx heterojunction. Based on the characterizations and the thermodynamic calculations, the reaction mechanism was proposed. In addition, the catalyst shows good substrate universality, which enables its good commercial application prospect.

A novel hierarchic hydrothermal strategy to enhance the performance of nickel-cobalt metal-organic framework for supercapacitors

The study presents a novel hierarchical hydrothermal strategy, which can not only ensure the morphology characteristics of the initial hydrothermal products, but also enhance the properties of the materials. Here, the hierarchical hydrothermal treatment was carried out with bimetallic nickel cobalt metal organic framework (NiCo-MOF) as the representative. The results of characterization and electrochemical tests showed that NiCo-MOF after hierarchical hydrothermal treatment (NCM-H) not only exhibits enhanced stability in crystal morphology but also an increased number of active sites in the material. At the same time, compared with the initial hydrothermal NiCo-MOF (NCM-F), the rate performance and cycle stability of NCM-H have been greatly improved. The prepared NCM-H electrode demonstrates a remarkable specific capacity of 1006F g−1 at 1 A/g. Furthermore, the assembled NCM-H//AC asymmetric supercapacitor (ASC) device demonstrates a remarkable energy density of 100.8 Wh kg−1 at a power density of 750 W kg−1. Excellent rate performance (76.4 % retention from 1 A/g to 20 A/g) and cycling stability (83.8 % after 5000 cycles). This unique hierarchical hydrothermal strategy is convenient, efficient, environmentally friendly and low-cost, and can provide a meaningful reference for the performance improvement of MOF-based and other related materials.

Investigation of the kinetics of imidacloprid adsorption onto bimetallic Cu-BTC MOF

Imidacloprid, which is harmful for humans as well as many other aquatic invertebrate species, is extensively present in water worldwide. Hydrophobic Cu-BTCIPA and a novel composite, Ag@Cu-BTCIPA, was synthesized for adsorption of imidacloprid from water. The synthesis of the composite and the increase in surface area and pore volume were confirmed by FTIR, XRD, SEM, and BET analysis. A comparative study of the adsorption efficiencies of the synthesized composites was performed. The maximum adsorption efficiency achieved was 83.6 % at pH 7 by the Ag@Cu-BTCIPA composite. Kinetic and isotherm analyses suggested multilayer chemisorption involving p-p conjugation and pore-filling mechanisms. Intra-particle diffusion was the rate limiting step. Release studies of imidacloprid from water showed that the percentage release amount was 90.2 % at 70 min. Kinetic analysis of the release process suggested release through chemisorption, with swelling-controlled release from the dosage form, corresponding to the super case II transport mechanism.

Portable electrochemical sensor for adrenaline detection using CoNi-MOF-based CS-PAM hydrogel

The development of a portable smartphone-based electrochemical sensor for analyzing adrenaline levels in real samples can make a great contribution to the research community worldwide. In order to achieve this goal, the key challenge is to build sensing interfaces with excellent electrocatalytic properties. In this work, microspherical bimetallic metal–organic frameworks (CoNi-MOF) consisting of nanoclusters were first synthesized using a hydrothermal method. On this basis, the catalytic activity of pure chitosan-polyacrylamide hydrogel (CS-PAM) was modulated by adding different amounts of CoNi-MOF during the in-situ synthesis of CS-PAM. Finally, a portable electrochemical detection system based on CS-PAM was established for the detection of adrenaline. A series of resulting composite hydrogels with a large specific surface area, abundant active sites, and unique network structure facilitate the enrichment and catalysis of adrenaline molecules. Under optimal conditions, the analytical platform constructed by using CoNi-MOF-based CS-PAM has the advantages of a wide detection range (0.5–10 and 10–2500 μM), a low detection limit (0.167 μM), and high sensitivity (0.182 and 0.133 μA·μM·cm−2). In addition, the sensor maintains selective detection of the target in the presence of many different types of interferences, and the current response is not significantly reduced even after 60 cycles of testing. We strongly believe that the designed smart portable sensing can realize the accurate determination of adrenaline in complex systems, and this study can provide new ideas for the research of MOFs-based hydrogels in electrochemical analysis.

Efficient calcium sulfite oxidation treatment by a highly active iron-manganese bimetallic metal-organic frameworks (MOFs)

Calcium sulfite (CaSO3) oxidation is the key step in the resource utilization of flue gas desulfurization (FGD) ash waste. However, under natural conditions the oxidation rate of CaSO3 is very low, limiting its conversion into calcium sulfate, an acceptable product for construction material. This study was devoted to the investigation of the synthesis and performance of a bimetallic MOFs with potential catalytic activity, namely, Fe/Mn(BDC)(DMF,F) catalysts. A combination of techniques including SEM, EDS, XRD, FT-IR, etc. were used to characterize the catalysts. The excellent catalytic performance examined in a gas-liquid-solid three-phase oxidation system are due to the special flexible respiratory architecture and homogeneous distribution of active sites, which allows the reactants to fully contact with the catalyst. Mn incorporated in the backbone of the metal-organic framework significantly enriches the catalytic active species that participate in a radical chain reaction with activated SO32- as ·SO3-, which in turn generates the key radical ·SO5- that reacts with SO32- to form SO42-. In the presence of Fe/Mn(BDC)(DMF, F)-13, the oxidation ratio of CaSO3 could reach 90.71%, which is more than 30-fold compared to non-catalytic oxidation and almost 5 times the effects of the single metal Fe(BDC)(DMF, F) catalyst. In addition, the study of kinetics shows that the oxidation rate of Fe/Mn(BDC)(DMF,F)-13 can reach 0.042mmol·L-1·s-1 with an apparent activation energy of 10.86kJ/mol. The oxidation rate is mainly affected by reaction temperature, pH value, catalyst concentration, and air flow rate. This study provides a potentially sustainable way for utilization of CaSO3-containing desulfurization ash.

Glucose sensing performance of bimetallic MOFs CoFe-ZIF/CC for enzyme-free saliva sensor applications

Co-ZIF is widely believed as a promising material which shows potential in MOFs based enzyme-free sensors. However, the research of Co-ZIF in glucose sensor filed has been hampered, due to its poor electronic conductivity and slow ion diffusion caused by closed rhombohedral dodecahedron structure. In this work, the obtained Co0.95Fe0.05-ZIF presents highly opened nanosheet structure on CC, resulting in rich open active sites and ions moving channels. Compared with other reported ZIFs, the Co0.95Fe0.05-ZIF/CC exhibits excellent sensing performance with a high sensitivity of 3232.30 μA mM−1 cm−2 in the range of 0.20-1.00mM and a low detection limit of less than 5μM, due to its highly opened nanosheet structure. The Co0.95Fe0.05-ZIF/CC also shows excellent selectivity, repeatability and reproducibility for glucose detection. Furthermore, the variation trend of test results measured by this saliva sensor without any sample pre-treatment, is consistent with that of commercial blood glucose meter, indicating its potential in real applications. This synthesis strategy also provides a new direction of structure construction for high performance MOFs in enzyme-free glucose sensor field.

Core-shell nanomedicine based on multifunctional tetrahedral DNA nanostructures for synergistic enhancement of tumor chemodynamic/chemo-immunotherapy

Immune checkpoint blockade therapy has made great strides in cancer treatment, but conventional immune checkpoint blockade antibodies often lead to overactivation of the immune system and severe immune-related adverse effects. Herein, we report the design of a nanomedicine (denoted as CPD@M−TDN) based on multifunctional tetrahedral DNA nanostructures (M−TDN). In this system, a bimetallic metal–organic framework (Cu/ZIF-8) is synthesized as the core; doxorubicin-loaded polydopamine acts as a shell to reduce the immunogenicity of the nanomaterials in peripheral blood. Finally, the CpG oligodeoxynucleotides and PD-L1 aptamer-based M−TDN are coupled to the core–shell structure nanomedicine through the biotin-avidin-system. Under the acidic tumor microenvironment, the decomposition of Cu/ZIF-8 and the release of copper ions and doxorubicin can lead to immunogenic death of tumor cells through chemodynamic/chemotherapy. Furthermore, the M−TDN has the dual effects of weakening the immunosuppressive microenvironment with PD-L1 aptamer and promoting dendritic cell activation with the immunostimulant CpG. Overall, the developed CPD@M−TDN can effectively enhance the response rate to immunotherapy and has excellent potential in the field of integrated tumor treatment.

Bimetallic Copper-Cerium-Based Metal-Organic Frameworks for Selective Carbon Dioxide Capture.

Metal-organic frameworks (MOFs) are highly regarded as valuable adsorbent materials in materials science, particularly in the field of CO2 capture. While numerous single-metal-based MOFs have demonstrated exceptional CO2 adsorption capabilities, recent advancements have explored the potential of bimetallic MOFs for enhanced performance. In this study, a CuCe-BTC MOF was synthesized through a straightforward hydrothermal method, and its improved properties, such as high surface area, smaller pore size, and larger pore volume, were compared with those of the bare Ce-BTC. The impact of the Cu/Ce ratio (1:4, 1:2, 1:1, and 3:2) was systematically investigated to understand how adding a second metal influences the CO2 adsorption performance of the Ce-BTC MOF. Various characterization techniques, including scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and N2 BET surface area analysis, were employed to assess the physical and chemical properties of the bare Ce-BTC and CuCe-BTC samples. Notably, CuCe-BTC-1:2 exhibited superior surface area (133 m2 g-1), small pore size (3.3 nm), and large pore volume (0.14 cm3 g-1) compared to the monometallic Ce-BTC. Furthermore, CuCe-BTC-1:2 demonstrated a superior CO2 adsorption capacity (0.74 mmol g-1), long-term stability, and good CO2/N2 selectivity. This research provides valuable insights into the design of metal-BTC frameworks and elucidates how introducing a second metal enhances the properties of the monometallic Ce-BTC-MOF, leading to improved CO2 capture performance.

Cobalt metal replaces Co-ZIF-8 mesoporous material for effective adsorption of arsenic from wastewater.

The high cost and low adsorption capacity of primary metal-organic frameworks (ZIF-8) limit their application in heavy metal removal. In this paper, Co/Zn bimetallic MOF materials were synthesized with excellent adsorption performance for As5+. The adsorption reached equilibrium after 180 min and the maximum adsorption was 250.088 mg/g. In addition, Co-ZIF-8 showed strong selective adsorption of As5+. The adsorption process model of Co-ZIF-8 fits well with the pseudo-second-order kinetic model (R2=0.997) and Langmuir isotherm model (R2=0.994), and it is demonstrated that the adsorption behavior of the adsorbent is a single layer of chemical adsorption. In addition, when the adsorbent enters the arsenic-containing solution, the surface of Co-ZIF-8 is hydrolyzed to produce a large number of Co-OH active sites, and As5+ arrives at the surface of Co-ZIF-8 by electrostatic adsorption and combines with the active sites to generate the arsenic-containing complex As-O-Co. After four cycles, Co-ZIF-8 showed 80% adsorption of As5+. This study not only provides a new method to capture As5+ in water by preparing MOF with partial replacement of the central metal, but also has great significance for the harmless disposal of polluted water.

Antioxidant and antimicrobial potentials of biosynthesized Ag-Doped Ni-MOF as a novel hybrid nanocomposite

Metal-organic frameworks (MOFs) are organic–inorganic crystalline compounds that have attracted much attention due to their wide range of applications. Bimetallic MOFs offer more possibilities than MOFs based on single metal. This study focuses on the synthesis and characterization of a Ni-MOF doped with silver nanoparticles (Ag NPs) as potent antioxidant and antimicrobial agent. Red cabbage extract was used as a reducing agent to synthesize Ag NPs. Ag@Ni-MOF nanocomposite exhibited significant growth inhibition of bacteria and fungi, and demonstrated the best antioxidant properties among the synthesized compounds. These results suggest that designed Ag@Ni-MOF nanostructure can be applied in the treatment of oxidative stress-related diseases as well as bacterial/fungal infections.

Enhancing photocatalytic performance of Ni-Ti bimetallic metal-organic frameworks for tetracycline degradation under visible light irradiation

Antibiotic wastewater poses a significant threat to the global environment and human health. In this work, Ni-Ti bimetallic Metal-Organic Frameworks (NT-MOF) were synthesized as effective photocatalysts to remove tetracycline (TC) from water under visible light irradiation. The photocatalysts underwent characterization using techniques such as Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), N2 adsorption-desorption, and X-Ray Photoelectron Spectroscopy (XPS). Photocatalytic tests were conducted under visible light conditions (λ>420 nm). The enhanced performance is mainly due to the presence of Ni in NT-MOF changing the shape and structure of the samples, reducing electron-hole recombination, thus promoting the charge separation process. These findings have significant implications for the development of efficient and sustainable methods for the removal of TC from wastewater.

Assembly of Amorphizing Porous Bimetallic Metal‐Organic Frameworks Spheres with Zn─O─Fe Cluster and Coordination Deficiency via Ligand Competition for Efficient Electro‐Fenton Catalysis

AbstractElectro‐Fenton process stands out as a highly promising approach for generating reactive oxygen‐containing radicals to address the escalating issue of environmental pollution. However, the long‐term goal of application necessitates ongoing pursuit of high‐quality catalysts with both sufficient activity and stability. Herein, a general route is reported for large‐scale synthesis of amorphizing porous bimetallic metal‐organic framework (MOF) spheres with Zn─O─Fe structure and coordination deficiency through facile and low‐cost synthesis of ligand competition. Assisted by a coordination modulator, deprotonation of terephthalic acid is accelerated and rapid synthesis of amorphous bimetallic MOF spheres is successfully achieved at room temperature. As inactive metal Zn is introduced into metal clusters of MOFs, the cycling efficiency of Fe3+/Fe2+ is improved and a secondary building unit of Zn─O─Fe is constructed, greatly accelerating electron conduction rate. Compared to crystalline spindle cMIL‐88B(Fe2Zn) by traditional solvothermal route, amorphous aMIL‐88B(Fe2Zn) has a unique spherical porous structure with larger surface area, higher conductivity, and more exposed active sites. Endowed with unique textural and surface chemistry, aMIL‐88B(Fe2Zn) exhibits superior catalytic activity in the degradation of refractory organic pollutants. The progress offers a feasible way to rational design of iron‐based hybrid MOF materials with tunable structures and enhance properties for various applications.

Dual-confinement regulating ternary metal-oxide activity sites derived from Co-MOF for enhanced electrocatalytic activity for glucose oxidation

Based on a dual-confinement strategy on a cobalt-metal-organic framework (Co-MOF), a series of trimetallic-oxide catalysts of Cux-O-Niy-O-Co3-x-y (x/y = 1/1, 1/3, 1/5 and 1/7) were developed for glucose oxidation. By chemical confinement regulation of ion exchange, diverse metal catalytic sites of Cu2+ and Ni2+ were introduced into Co-MOF, respectively; Then by spatial confinement synthesis of pyrolysis, trimetallic MOF of CuxNiyCo3-x-y-MOF was transformed into trimetallic-oxide of Cux-O-Niy-O-Co3-x-y, which maintained the regular morphology and highly ordered lattice structure of Co-MOF. The Cux-O-Niy-O-Co3-x-y composite modified glassy carbon electrode (Cux-O-Niy-O-Co3-x-y/GCE) exhibited enhanced electrocatalytic activity towards glucose oxidation when compared with Co-MOF/GCE, bimetallic MOFs of CuCo-MOF/GCE and NiCo-MOF/GCE, trimetallic MOF of CuxNiyCo3-x-y-MOF/GCE, as well as monometallic oxide Co3O4/GCE and bimetallic oxides of CuCo2O4/GCE and NiCo2O4/GCE, which was mainly due to the synergistic catalysis of electrocatalytically active Co-O-Cu-O-Ni bridges. With Cu2+/Ni2+ molar ratio of 1/3, Cux-O-Niy-O-Co3-x-y/GCE (x/y = 1/3) displayed excellent sensing behaviours on glucose detection. This work not only designed well-performed electrocatalysts for enhancing catalytic activity towards glucose oxidation, but also provided a new perspective to realize the controlled preparation of high-performance electrocatalysts.