Multivariate Metal-organic Frameworks Research Articles

In Situ Encapsulation of Atomically Precise Nanoclusters in Reticular Frameworks via Mechanochemical Synthesis.

The combination of atomically precise nanoclusters (APNCs) and reticular frameworks is promising for generating component-specific nanocomposites with emergent properties. However, traditional liquid-phase synthesis often hampers this potential by damaging APNCs and limiting combination diversity. Here, mechanochemical synthesis to explore the encapsulation of diverse oil- and water-soluble APNCs within various reticular frameworks is employed, establishing a database of 21 unique APNC-framework combinations, including metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), and multivariate MOFs. These framework coatings not only spatially immobilize APNCs but also secure their structures, preventing aggregation and degradation while enhancing stability and activity. Encapsulating Au25 in HOFs resulted in a remarkable 315-fold increase in catalytic activity compared to Au25 homogeneous catalyst, highlighting the framework's crucial role in catalytic enhancement. The mechanochemical synthesis strategy facilitates tailored support screening, catering to specific needs, and shows promise for developing multifunctional systems, including enzyme-APNC@frameworks material for cascade reactions.

Evaluation and screening of multivariate metal-organic frameworks for hydrogen storage

Multivariate metal-organic frameworks (MTV-MOFs) are characterized by their unique structural feature of incorporating multiple organic linkers and metal ions into a unified framework. This composite construction bestows MTV-MOFs with a broader spectrum of diverse and intricate properties compared to traditional single-component MOFs. In this study, the performance of 560 MTV-MOFs as hydrogen storage adsorbents has been thoroughly investigated. Firstly, the key structural parameters of materials, including density, pore occupied accessible volume, accessible surface area, and porosity were computed. Then, high-throughput Grand Canonical Monte Carlo (GCMC) simulations were employed to calculate hydrogen adsorption capacity of MTV-MOFs under hydrogen pressures of 100 bar at both 77 K and 298 K. Based on simulated results, the deliverable hydrogen capacity of these MTV-MOFs were deduced under both room temperature conditions (298 K, 97.2 bar → 298 K, 5 bar) and low-temperature conditions (77 K, 100 bar → 160 K, 5 bar). Through high-throughput screening, we identified top ten promising MTV-MOFs with the highest hydrogen storage capacity and conducted in-depth studies on their hydrogen adsorption properties. Furthermore, we developed a multivariate linear regression model to quantitatively predict the relationship between hydrogen adsorption capacity and their structural parameters for these MTV-MOFs. The predictions of this model align closely with the outcomes derived from GCMC simulations. The present study highlights the potential of MTV-MOFs as promising candidates for hydrogen storage applications, thereby providing valuable theoretical insights into the exploration of high-capacity hydrogen storage materials.

Regulating interaction with surface ligands on Au25 nanoclusters by multivariate metal–organic framework hosts for boosting catalysis

ABSTRACT While atomically precise metal nanoclusters (NCs) with unique structures and reactivity are very promising in catalysis, the spatial resistance caused by the surface ligands and structural instability poses significant challenges. In this work, Au25(Cys)18 NCs are encapsulated in multivariate metal–organic frameworks (MOFs) to afford Au25@M-MOF-74 (M = Zn, Ni, Co, Mg). By the MOF confinement, the Au25 NCs showcase highly enhanced activity and stability in the intramolecular cascade reaction of 2-nitrobenzonitrile. Notably, the interaction between the metal nodes in M-MOF-74 and Au25(Cys)18 is able to suppress the free vibration of the surface ligands on the Au25 NCs and thereby improve the accessibility of Au sites; meanwhile, the stronger interactions lead to higher electron density and core expansion within Au25(Cys)18. As a result, the activity exhibits the trend of Au25@Ni-MOF-74 > Au25@Co-MOF-74 > Au25@Zn-MOF-74 > Au25@Mg-MOF-74, highlighting the crucial roles of microenvironment modulation around the Au25 NCs by interaction between the surface ligands and MOF hosts.

Metal Variance in Multivariate Metal-Organic Frameworks for Boosting Catalytic Conversion of CO2.

Developing efficient, low-cost, MOF catalysts for CO2 conversion at low CO2 concentrations under mild conditions is particularly interesting but remains highly challenging. Herein, we prepared an isostructural series of two-dimensional (2D) multivariate metal-organic frameworks (MTV-MOFs) containing copper- and/or silver-based cyclic trinuclear complexes (Cu-CTC and Ag-CTC). These MTV-MOFs can be used as efficient and reusable heterogeneous catalysts for the cyclization of propargylamine with CO2. The catalytic performance of these MTV-MOFs can be engineered by fine-tuning the Ag/Cu ratio in the framework. Interestingly, the induction of 10% Ag remarkably improved the catalytic efficiency with a turnover frequency (TOF) of 243 h-1, which is 20-fold higher than that of 100% Cu-based MOF (i.e., TOF = 10.8 h-1). More impressively, such a bimetallic MOF still exhibited high catalytic activity even for simulated flue gas with 10% CO2 concentration. Furthermore, the reaction mechanism has been examined through the employment of NMR monitoring experiments and DFT calculations.

Laser-forged transformation and encapsulation of nanoalloys: pioneering robust wideband electromagnetic wave absorption and shielding from GHz to THz

The emergence of the internet of things has promoted wireless communication’s evolution towards multi-band and multi-area utilization. Notably, forthcoming sixth-generation (6G) communication standards, incorporating terahertz (THz) frequencies alongside existing gigahertz (GHz) modes, drive the need for a versatile multi-band electromagnetic wave (EMW) absorbing and shielding material. This study introduces a pivotal advance via a new strategy, called ultrafast laser-induced thermal-chemical transformation and encapsulation of nanoalloys (LITENs). Employing multivariate metal-organic frameworks, this approach tailors a porous, multifunctional graphene-encased magnetic nanoalloy (GEMN). By fine-tuning pulse laser parameters and material components, the resulting GEMN excels in low-frequency absorption and THz shielding. GEMN achieves a breakthrough of minimum reflection loss of −50.6 dB in the optimal C-band (around 4.98 GHz). Computational evidence reinforces GEMN’s efficacy in reducing radar cross sections. Additionally, GEMN demonstrates superior electromagnetic interference shielding, reaching 98.92 dB under THz band (0.1–2 THz), with the mean value result of 55.47 dB. These accomplishments underscore GEMN’s potential for 6G signal shielding. In summary, LITEN yields the remarkable EMW controlling performance, holding promise in both GHz and THz frequency domains. This contribution heralds a paradigm shift in EM absorption and shielding materials, establishing a universally applicable framework with profound implications for future pursuits.

Zr-based multivariate metal-organic framework for rapid extraction of sulfonamide antibiotics from water and food samples

Based on multiple ligands strategy, a series of multivariate metal organic frameworks (MTV-MOFs) named as PCN-224-DCDPSx were prepared using one-pot solvothermal method to extract and remove sulfonamide antibiotics (SAs). The pore structure and adsorption performance can be further regulated by modulating the doping ratios of medium-tetra(4-carboxylphenyl) porphyrin and 4,4′-dicarboxydiphenyl sulfones. The MTV-MOFs of PCN-224-DCDPS1.0 possesses very large specific surface area (1625 m2/g). Using PCN-224-DCDPS1.0 as sorbent, a dispersive solid-phase extraction method was developed to extract and preconcentrate SAs from water, eggs, and milk prior to high performance liquid chromatography analysis. The limits of detection of method were determined between 0.17 and 0.27 ng/mL with enrichment factors ranging 214–327. The adsorption can be finished within 30 s, and the recovery rate remains above 80 % after 10 repeated uses. The adsorption capacities of sorbent were determined from 300 to 621 mg/g for sulfadiazine, sulphapyridine, sulfamethoxydiazine, sulfachlorpyridazine, sulfabenzamide, and sulfadimethoxine. The adsorption mechanisms were investigated and can be attributed to π-π interactions, hydrogen bonds, and electrostatic interactions. This work represents a method for preparation of MTV-MOFs and uses as sorbent for extraction and enrichment of trace pollutants from complex samples.

Diffusional Electron Transport Coupled to Thermodynamically Driven Electron Transfers in Redox-Conductive Multivariate Metal-Organic Frameworks.

The development of redox-conductive metal-organic frameworks (MOFs) and the fundamental understanding of charge propagation through these materials are central to their applications in energy storage, electronics, and catalysis. To answer some unresolved questions about diffusional electron hopping transport and redox conductivity, mixed-linker MOFs were constructed from two statistically distributed redox-active linkers, pyromellitic diimide bis-pyrazolate (PMDI) and naphthalene diimide bis-pyrazolate (NDI), and grown as crystalline thin films on conductive fluorine-doped tin oxide (FTO). Owing to the distinct redox properties of the linkers, four well-separated and reversible redox events are resolved by cyclic voltammetry, and the mixed-linker MOFs can exist in five discrete redox states. Each state is characterized by a unique spectroscopic signature, and the interconversions between the states can be followed spectroscopically under operando conditions. With the help of pulsed step-potential spectrochronoamperometry, two modes of electron propagation through the mixed-linker MOF are identified: diffusional electron hopping transport between linkers of the same type and a second channel that arises from thermodynamically driven electron transfers between linkers of different types. Corresponding to the four redox events of the mixed-linker MOFs, four distinct bell-shaped redox conductivity profiles are observed at a steady state. The magnitude of the maximum redox conductivity is evidenced to be dependent on the distance between redox hopping sites, analogous to the situation for apparent electron diffusion coefficients, Deapp, that are obtained in transient experiments. The design of mixed-linker redox-conductive MOFs and detailed studies of their charge transport properties present new opportunities for future applications of MOFs, in particular, within electrocatalysis.

Enhanced Electrocatalytic Oxygen Evolution by In Situ Growth of Tetrametallic Metal-Organic Framework Electrocatalyst FeCoNiMn-MOF on Nickel Foam.

Developing highly efficient, cost-effective, non-noble-metal-based electrocatalysts with superior performance and stability for oxygen evolution reactions is of immense challenge as well as great importance for the upcoming sustainable and green energy conversion technologies. The multivariate metal-organic frameworks with hierarchical porous structures and unsaturated coordination modes are considered to be promising emerging energy materials. In this work, a series of multimetallic MOFs were directly grown on nickel foam (NF) through the solvothermal method. Notably, the optimized tetrametallic FeCoNiMn-MOF/NF shows a low overpotential of 239 mV to achieve a current density of 50 mA cm-2 with a Tafel slope of 62.05 mV dec-1 for OER in 1 M KOH. It also exhibits excellent stability and durability over 100 h in chronoamperometric studies. The enhanced performance is closely tied to the high activity of iron and nickel ions and the decomposed and reconstructed Ni/Fe-OOH intermediates of the FeCoNiMn-MOF/NF during the OER process, which are revealed by XPS analysis and in situ Raman spectroscopy. This present work demonstrates the feasibility and advantage of utilizing highly efficient and durable multimetallic MOFs for electrocatalytic oxygen evolution.

Multivariate Metal–Organic Frameworks for Programming Functions

AbstractMultivariate metal–organic frameworks (MTV‐MOFs) provide a handle over programming MOF's physicochemical properties for use in functional applications. In this review, the state‐of‐art design features of MTV‐MOFs are summarized, including multivariate functionalities, mixed metals, and post‐synthetic modification, and highlight their resulting fine‐tuned performance in practical applications, such as gas storage, gas separation, water harvesting, luminescence sensing, heterogeneous catalysis, and drug delivery. Furthermore, a vision is provided for future research avenues, in which MTV‐MOFs enable the incorporation of a variety of functionalities, metals, linkers, secondary building units (SBUs), and pore metrics along a specific crystallographic direction with respect to the ordered backbone. Future directions focus on mechanistic and kinetics investigations into the formation of MTV‐MOFs in addition to high‐throughput screening with the aim of automation and artificial intelligence.

Metal-Organic Frameworks Constructed from Branched Oligomers.

Metal-organic frameworks (MOFs) prepared from oligomeric or polymeric organic ligands have been studied and are termed oligoMOFs and polyMOFs, respectively. Herein, several oligoMOFs are described that have been prepared from branched oligomers with dendritic or star-like architectures. Branched oligomeric ligands with four (4(H2bdc)-b) or eight (8(H2bdc)-b) 1,4-benzene dicarboxylic acid (H2bdc) groups were prepared and used to synthesize isoreticular-type Zn(II)-based MOFs (IRMOF). A branched tetramer (4(H2bdc)-b) produced an oligoIRMOF-1 with improved ambient stability compared with IRMOF-1 or previously described oligoMOFs. To understand the effect of the ligand architecture, oligoIRMOFs were also prepared from a linear tetramer (4(H2bdc)-l). For a branched octamer (8(H2bdc)-b), it was found that the addition of an organic base was required to produce crystalline oligoIRMOFs. Multivariate MOFs (MTV-MOFs) could also be readily prepared with a combination of an octamer (8(H2bdc)-b) and H2bdc.

Selective Reduction of Multivariate Metal-Organic Frameworks for Advanced Electrocatalytic Cathodes in High Areal Capacity and Long-Life Lithium-Sulfur Batteries.

Lithium-sulfur batteries hold great promise as next-generation high-energy-density batteries. However, their performance has been limited by the low cycling stability and sulfur utilization. Herein, we demonstrate that a selective reduction of the multivariate metal-organic framework, MTV-MOF-74 (Co, Ni, Fe), transforms the framework into a porous carbon decorated with bimetallic CoNi alloy and Fe3O4 nanoparticles capable of entrapping soluble lithium polysulfides while synergistically facilitating their rapid conversion into Li2S. Electrochemical studies on coin cells containing 89 wt % sulfur loading revealed a reversible capacity of 1439.8 mA h g-1 at 0.05 C and prolonged cycling stability for 1000 cycles at 1 C/1060.2 mA h g-1 with a decay rate of 0.018% per cycle. At a high areal sulfur loading of 6.9 mg cm-2 and lean electrolyte/sulfur ratio (4.5 μL:1.0 mg), the battery based on the 89S@CoNiFe3O4/PC cathode provides a high areal capacity of 6.7 mA h cm-2. The battery exhibits an outstanding power density of 849 W kg-1 at 5 C and delivers a specific energy of 216 W h kg-1 at 2 C, corresponding to a specific power of 433 W kg-1. Density functional theory shows that the observed results are due to the strong interaction between the CoNi alloy and Fe3O4, facilitated by charge transfer between the polysulfides and the substrate.

Multivariate Metal–Organic Frameworks Ranging from a Homogeneous Uniform Distribution to Heterogeneous 1D, 2D, and 3D Distributions of Mixed Building Blocks

Multivariate Metal–Organic Frameworks Ranging from a Homogeneous Uniform Distribution to Heterogeneous 1D, 2D, and 3D Distributions of Mixed Building Blocks

Tuning the Electrochemical Performance of Multiple Phased Selenides@C/MXene Composites via Controllable Synthesis of Multivariate Metal‐Organic Frameworks

AbstractMetal‐organic frameworks (MOFs) are excellent precursors for electrode materials preparations. Synergistic effects may exist between different metal centers in multivariate MOFs, making them often more effective than single‐metal MOFs. Herein, we propose an atom economic mechanochemical method to realize the efficient component regulation of target multivariate MOFs. Moreover, by combining the synthesis of multivariate MOFs and exfoliating MXene, multivariate MOF/MXene composites can be obtained via a one‐step strategy. A further selenization process can derive them into selenides@C/MXene composites. These derived composites contain multiple nanostructured metal selenides embedded in multi‐heteroatom doped carbon matrix. For these composites, abundant heterojunction structures are formed, which can build internal self‐built electric field and enhance the reaction kinetics effectively for sodium‐ion storage. More importantly, the electrochemical performance of NCMS@C/MX composites can be optimized due to the intrinsic characteristics of the containing metal selenides. Overall, experimental results demonstrate the universality of this solvent‐free synthesis route for controllable preparation of high‐performance selenides@C/MXene electrode materials. It provides a feasible and environmentally friendly method to adjust metal ratios for optimal energy storage performance. We hope this research inspires optimization strategies for high‐performance electrode materials and leads to the development of energy storage materials with more rational structures and better performance.

The Use of Rapid Precipitation to Synthesise Multivariate UiO-66 Metal–Organic Frameworks for Photocatalysis

A rapid synthesis method is used to form multivariate metal–organic frameworks (MTV-MOFs) with the UiO-66 structure, where precipitation occurs upon mixing solutions of ligands and metal salts at temperatures less than 60 °C. The materials include mixtures of metals and ligands, Ce/Zr-UiO-66(1,4-NDC/BDC), Ce/Zr-UiO-66(1,4-NDC/2,6-NDC), Ce/Zr-UiO-66(1,4-NDC), Ce/Ti-UiO-66(1,4-NDC), and Ce/Ti-UiO-66(BDC-NH2) (NDC = naphthalene dicarboxylate, BDC = benzene-1,4-dicarboxylate, BDC-NH2 = 2-amino-benzene-1,4-dicarboxylate). Phase purity was determined by powder X-ray diffraction (PXRD), with a broadening of the profile indicative of nanoscale crystallites, verified by scanning electron microscopy (SEM). The molar ratio of metals and organic ligands in Ce/Zr-UiO-66(1,4-NDC/2,6-NDC) was confirmed by X-ray fluorescence (XRF) and solution 1H nuclear magnetic resonance (NMR) after digestion, respectively. Analysis of the adsorption of dyes by the MTV-MOFs showed that a pseudo-first-order model accounts for the kinetics. The effectiveness of photocatalytic degradation of two cationic (methylene blue and rhodamine B) and two anionic (Congo red and Alizarin Red S (AR)) dyes was studied under UV and visible light. The most effective photocatalytic degradation was found between 1 and 15 min towards both cationic and anionic dyes by Ce/Zr-UiO-66(1,4-NDC/2,6-NDC). Measurements of recyclability and photostability showed retention of crystallinity after five cycles of use and exposure to light for 17 h, as confirmed by PXRD.

Design of magnetic multivariate metal–organic framework for high-efficient adsorption and rapid magnetic separation of bisphenol pollutants

Herein, a magnetic multivariate metal–organic framework (MTV-MOF) named as 95.7 %BTB/MOF-525@Fe3O4 was synthesized by one-pot mixing ligand strategy. The magnetic MTV-MOF exhibited large specific surface area (320 m2·g−1) and high porosity. The 95.7 %BTB/MOF-525@Fe3O4 was used as sorbent for extraction and enrichment of bisphenol pollutants (BPs). The experimental results demonstrated that adsorption kinetics and isotherms conform to pseudo-second-order model and Langmuir model. The maximum adsorption capacities for bisphenol F, bisphenol A, bisphenol B, bisphenol AF were 275.1, 233.6, 302.1 and 277.2 mg·g−1, respectively. With 95.7 %BTB/MOF-525@Fe3O4 as sorbent, the magnetic solid phase extraction coupling HPLC was used to detect trace BPs in environmental water. The limits of detection were determined as between 0.067 and 0.167 ng·mL−1. The enrichment factors were in the range of 242–295. The recoveries were ranged from 79.4 to 103 % with relative standard deviations not higher than 8.85 %. In addition, the recovery rate of sorbent remained above 80 % after 21 times of reuse. The work provides an effective material for extraction and removal of BPs in the environment.

Multivariate Metal-Organic Frameworks Prepared by Simultaneous Metal/Ligand Exchange for Enhanced C2-C3 Selective Recovery from Natural Gas.

Recovering light alkanes from natural gas is a critical but challenging process in petrochemical production. Herein, we propose a postmodification strategy via simultaneous metal/ligand exchange to prepare multivariate metal-organic frameworks with enhanced capacity and selectivity of ethane (C2H6) and propane (C3H8) for their recovery from natural gas with methane (CH4) as the primary component. By utilizing the Kuratowski-type secondary building unit of CFA-1 as a scaffold, namely, {Zn5(OAc)4}6+, the Zn2+ metal ions and OAc- ligands were simultaneously exchanged by other transition metal ions and halogen ligands under mild conditions. Inspiringly, this postmodification treatment can give rise to improved capacity for C2H6 and C3H8 without a noticeable increase in CH4 uptake, and consequently, it resulted in significantly enhanced selectivity toward C2H6/CH4 and C3H8/CH4. In particular, by adjusting the species and amount of the modulator, the optimal sample CFA-1-NiCl2-2.3 demonstrated the maximum capacities of C2H6 (5.00 mmol/g) and C3H8 (8.59 mmol/g), increased by 29 and 32% compared to that of CFA-1. Moreover, this compound exhibited excellent separation performance toward C2H6/CH4 and C3H8/CH4, with high uptake ratios of 6.9 and 11.9 at 298 K and 1 bar, respectively, superior to the performance of a majority of the reported MOFs. Molecular simulations were applied to unravel the improved separation mechanism of CFA-1-NiCl2-2.3 toward C2H6/CH4 and C3H8/CH4. Furthermore, remarkable thermal/chemical robustness, moderate isosteric heat, and fully reproducible breakthrough experiments were confirmed on CFA-1-NiCl2-2.3, indicating its great potential for light alkane recovery from natural gas.

Construction of Well-Defined Two-Dimensional Architectures of Trimetallic Metal-Organic Frameworks for High-Performance Symmetric Supercapacitors.

The high surface-to-volume ratio and extraordinarily large-surface area of two-dimensional (2D) metal-organic framework (MOF) architectures have drawn particular interest for use in supercapacitors. To achieve an excellent electrode material for supercapacitors, well-defined 2D nanostructures of novel trimetallic MOFs were developed for supercapacitor applications. Multivariate MOFs (terephthalate and trimesate MOF) with distinctive nanobrick and nanoplate-like structures were successfully synthesized using a straightforward one-step reflux condensation method by combining Ni, Co, and Zn metal species in equimolar ratios with two different ligands. Furthermore, the effects of the tricarboxylic and dicarboxylic ligands on cyclic voltammetry, charge-discharge cycling, and electrochemical impedance spectroscopy were studied. The derived terephthalate and trimesate MOFs are supported with stainless-steel mesh and provide a suitable electrolyte environment for rapid faradaic reactions with an elevated specific capacity, excellent rate capability, and exceptional cycling stability. It shows a specific capacitance of 582.8 F g-1, a good energy density of 40.47 W h kg-1, and a power density of 687.5 W kg-1 at 5 mA cm-2 with an excellent cyclic stability of 92.44% for 3000 charge-discharge cycles. A symmetric BDC-MOF//BDC-MOF supercapacitor device shows a specific capacitance of 95.22 F g-1 with low capacitance decay, high energy, and power densities which is used for electronic applications. These brand-new trimetallic MOFs display outstanding electrochemical performance and provide a novel strategy for systematically developing high-efficiency energy storage systems.

Nanoscale Multivariate Metal–Organic Frameworks Amplify Oxidative Stress for Efficient Photodynamic Therapy of Cancer

Nanoscale Multivariate Metal–Organic Frameworks Amplify Oxidative Stress for Efficient Photodynamic Therapy of Cancer

Stepwise Assembly of Quinary Multivariate Metal-Organic Frameworks via Diversified Linker Exchange and Installation.

Multivariate MOFs (MTV-MOFs) constructed from multiple components with atomistic precision hold the promise for many fascinating developments in both fundamental sciences and applications. Sequential linker installation can be an effective method to introduce different functional linkers into an MOF that contains coordinatively unsaturated metal sites. However, in many cases, these linkers must be installed according to a specific sequence and the complete synthetic flexibility and freedom is yet to be realized. Here, we rationally decreased the size of the primary ligand used in NPF-300, a Zr-MOF with scu topology (NPF = Nebraska Porous Framework), and synthesized its isostructure, NPF-320. NPF-320 exhibits optimized pocket sizes which allow for the post-synthetic installation of three secondary linkers in all six permuted sequences via both linker exchange and installation, forming a final quinary MTV-MOF via single-crystal-to-single-crystal transformation. With the functionalization of the linkers from the quinary MOF system, one will be able to construct MTV-MOFs not only with variable porosity but also with unprecedented complexity and encoded synthetic sequence information. The utility of sequential linker installation was further demonstrated by the construction of a donor-acceptor pair-based energy transfer system.

A Self-Templated Design Approach toward Multivariate Metal-Organic Frameworks for Enhanced Oxygen Evolution.

Multivariate metal-organic framework (MOF) is an ideal electrocatalytic material due to the synergistic effect of multiple metal active sites. In this study, a series of ternary M-NiMOF (M = Co, Cu) through a simple self-templated strategy that the Co/Cu MOF isomorphically grows in situ on the surface of NiMOF is designed. Owing to the electron rearrange of adjacent metals, the ternary CoCu-NiMOFs demonstrate the improved intrinsic electrocatalytic activity. At optimized conditions, the ternary Co3 Cu-Ni2 MOFs nanosheets give the excellent oxygen evolution reaction (OER) performance of current density of 10mA cm-2 at low overpotential of 288mV with a Tafel slope of 87mV dec-1 , which is superior to that of bimetallic nanosheet and ternary microflowers. The low free energy change of potential-determining step identifies that the OER process is favorable at Cu-Co concerted sites along with strong synergistic effect of Ni nodes. Partially oxidized metal sites also reduce the electron density, thus accelerating the OER catalytic rate. The self-templated strategy provides a universal tool to design multivariate MOF electrocatalysts for highly efficient energy transduction.