Pristine MOF Research Articles

MOFite: A High-Density Lithiophilic and Scalable Metal-Organic Framework Anode for Rechargeable Lithium-Ion Battery.

Developing an anode material that has better performance efficiency than commercial graphite while keeping the features of economic scalability and environmental safety is highly desirable yet challenging. MOFs are a promising addition to the ongoing efforts, however, the relatively poor performance, chemical instability, and large-scale economic production of efficiency-proven pristine MOFs restrict their utility in real-life energy storage applications. Furthermore, hierarchical porosity for lucid mass diffusion, high-density lithiophilic sites are some of the structural parameters for improving the electrode performance. Herein, we have demonstrated the potential of economically scalable salicylaldehydate 3D-conjugated-MOF (Fe-Tp) as a high-performance anode in Li-ion batteries: the anode-specific capacity achieved up to 1447 mAh g-1 at 0.1 A g-1 and 89 % of cyclic stability after 500 cycles at 1.0 A g-1 for pristine MOF. More importantly, incorporating 10 % Fe-Tp doping in commercial graphite (MOFite) significantly enhanced lithium storage, doubling capacity after 400 cycles. It signifies the potential practical utility of Fe-Tp as a performance booster for commercial anode material.

Room temperature detection of n-butanol Ce-doped MOF:ZnO sensor under UV activation

Being one of toxic and flammable volatile organic compounds (VOC), n-butanol has brought about many potential health risks, there is an urgent demand for highly sensitive detection techniques to monitor its concentration in occupational environments and the air. In this paper, Ce-doped MOF:ZnO sensors under UV activation for room-temperature detection of n-butanol were synthesized by the co-precipitation method and systemically characterized by XRD, SEM, HRTEM, and XPS. The sensitive performances were evaluated by the use of a WS-30A gas sensor measurement system. The results showed that Ce doping has significantly enhanced the sensitivity of the MOF:ZnO sensors, and the response value of the 0.08 % Ce-doped ZnO sensor has achieved to 397.30, which was 9.32 times higher than that of the pristine MOF:ZnO. And the response and recovery times were 17 and 117 s respectively, demonstrating a speedy detection capability. In addition, the sensor gained excellent stability and reproducibility with special selectivity for n-butanol. The comprehensive achievements of this research would be promising to promote the development of volatile organic compound detection technology and beneficial to the well application in the fields of environmental monitoring, industrial safety, and public health.

Unveiling the power of defect engineering in MOF-808 to enhance efficient carbon dioxide adsorption and separation by harnessing the potential of DFT analysis

Defect engineering in metal–organic frameworks involves intentionally introducing defects to modify their properties. These defects create new active sites, increase surface area, and enhance overall performance in various applications. If properly designed, these intentional defects can create new active sites and increase the specific surface area and thus the overall performance in various applications. The defect engineering strategy in MOF-808 was evaluated using the second ligand agent in different ratios. The exceptional specific surface area obtained compared to the pristine MOF 808 indicates the realization of the improvement potential of MOFs and the increase of their performance capabilities, especially in adsorbing and sequestering carbon dioxide gas in order to achieve a carbon dioxide-free future. A comprehensive set of characterization tests was conducted on the synthesized compounds in order to determine their physical and chemical properties. The Langmuir isotherm and the Weber and Morris kinetic model were chosen as the most suitable models due to their consistent performance, with R2 values surpassing 0.95 across all linker concentrations. In MOF-808 with different linker ratios of 0 %, 5 %, 10 %, 15 %, and 20 %, adsorption capacities of 6.4, 5.9, 6.7, 8.3, and 6.4 mmol/g were determined at 25 °C and 110 kPa, respectively. Notably, MOF-808-15 % exhibited the highest adsorption capacity and a remarkable surface area of 3922 m2/g, indicating a substantial interaction between CO2 molecules and the available open metal sites. Also, MOF-808 variants showed great moisture stability after being exposed to moist air for 7 days. Furthermore, an assessment of this adsorbent’s performance under flue gas conditions, utilizing the Ideal Adsorption Solution Theory (IAST), underscored its outstanding selectivity, with a significant value of 760, representing a 115-fold increase compared to pristine MOF-808-0 %. Density Functional Theory (DFT) shows better adsorption energy for MOF-808-15 % compared to MOF-808-0 %, implying the effect of defects in CO2 adsorption. Isosteric heat of adsorption study shows chemisorption phenomenon for all MOF-808 variants. Lastly, an evaluation of the cyclic stability of these MOFs over ten adsorption–desorption cycles showcased their robust and enduring performance, offering promising prospects for industrial applications.

New Architecture Based on Metal-Organic Frameworks and Spin Crossover Complexes to Detect Volatile Organic Compounds.

We present here the encapsulation of a spin crossover complex C1 [FeII(L)] (L: 4-amino-, 2-(2-pyridinylmethylene)hydrazide) inside MOF-808(Zr), a chemically robust Metal-Organic Framework. The compound C1⊂MOF-808 retains its crystallinity as well as a partial porosity compared to pristine MOF and shows solvatochromism under Volatile Organic compounds (VOCs) sorption associated to a spin state change of the guest complex. More specifically, this compound shows an interesting reversible color change under formaldehyde and formic acid vapor sorption and can therefore be considered as a new kind of optical VOCs chemosensor, opening new doors for developing a broad range of VOCs optical sensors.

Construction of controllable multicomponent ZnO-ZnCo/MOF-PANI composites for supercapacitor applications

Supercapacitors, as new electrochemical energy storage (EES) devices, with the lower energy density seriously hinder their realization of the requirements for future high energy storage devices. Thus, It is crucial to develop straightforward and efficient approaches to address the aforementioned challenges in future EES devices. In this paper, controllable multi-component composites are designed and ZnO is used as a conductive carrier in preparing layered structured ZnO-Zn/Co-metal-organic framework-polyaniline (ZnO-Zn/Co-MOF-PANI, ZZCMP) electrode materials by solvothermal and electrodeposition methods. The abundant active sites and the high specific surface area of the MOF are used to create the conditions for the loading of PANI, while it can establish an effective ion/electron transport channel with PANI to enhance the material utilisation and the electrochemical performance of the overall material. Add to that, the advantages of flexibility and rigidity of pristine MOF are made use of to provide sufficient space during the process of long-term charging and discharging, thus facilitating resistance to the structural deformation and enhancing the mechanical stability of the material. The optimized integrated electrode ZZCMP-10 exhibits a capacitance of 458.9 F.g−1 when operated at a current density of 1 A.g−1. The asymmetric supercapacitor (ASC) is constructed with ZZCMP-10 as the positive electrode material and active carbon is used as the material for the negative electrode, which shows an energy density of 26 Wh.kg−1 at a current density of 1 A.g−1 and a retention of 75.3 % capacitance is achieved after 5000 cycles of long-term charging and discharging. This study provides a reasonable exploration for designing high-energy-density electrochemical energy storage devices.

A resistant and stable HKUST@MC composite for highly efficient gas adsorptive desulfurization

A novel HKUST-1 shaped composite with improved mechanical and water resistance produced by a technically feasible and cost-effective method preserving the pristine MOF porosity.

Mixed-valence bimetallic Ce/Zr-NH2-UiO-66 modified with CdIn2S4 to form S-scheme heterojunction for boosting photocatalytic CO2 reduction

A bimetallic Ce/Zr-UiO-66-NH2/CdIn2S4 (Ce-NU66/CIS) heterojunction close interfacial contact has been designed by in-situ hydrothermal co-synthesis of Ce/Zr-NH2-UiO-66 and CdIn2S4. The one-pot-synthesized heterojunction was employed for CO2 reduction without any sacrificial agent. The Ce-NU66/CIS exhibits visible-light-active characteristics accompanied by improved excited charge separation, along with high surface area and well-dispersed heterojunction structure compared to the pristine MOF and CdIn2S4. Doping Ce ions can produce some oxygen vacancies (OVs) and enhance the electron density surrounding Zr4+ ions, which ultimately resulted in an increase in the photocatalytic effect. In the absence of any sacrificial reagents, the optimized 8 wt% Ce0.2NU66/CIS sample exhibited significantly improved photocatalytic CO2 reduction activity, with CO production rate of 6.01 μmol‧g−1‧h−1 and a high CO selectivity of 54.98 %, which were 3.72 and 1.96 times contrasting to the original CdIn2S4, and 17.83 and 2.47 times in comparison of NU66, respectively. Consequently, the bimetallic Ce/Zr-UiO-66-NH2/CdIn2S4 could have the potential to be used as a photocatalyst with improved properties for studying CO2 reduction. It may provide a rational design for constructing mixed-valent bimetallic for soler-driven CO2 conversion.

Design and development of diamond-shaped Silver-Trimesic acid based Metal-Organic framework for high-performance supercapacitor application

A metal–organic framework serves as one of the promising electrode materials for supercapacitor applications due to its tunable porous structures. The concentration of silver salt and trimesic acid plays a vital role in the formation of the Ag-TA metal–organic framework. Herein, we successfully synthesized the orthorhombic crystal structured Ag-TA with high surface area which enhances the ions intercalation and deintercalation during charging/discharging process. The prepared material exhibits diamond shaped morphology with a large surface area of 106.569 m2 g−1. The Ag-TA electrode exhibits a maximum specific capacity of 917 C g−1 at a current density of 1 A g−1 and also has excellent cycling stability of 90 % capacity retention with an efficiency of 99.8 % after 5000 cycles. In addition to that the asymmetric (Ag-TA//AC) supercapacitor device is constructed which delivers a maximum energy density of 77.46 W h kg−1 at a power density of 0.65 kW kg−1 and also exhibits a remarkable specific capacity of 408 C g−1 at 1 A/g with excellent capacity retention of 97 % of its initial capacity and 98.4 % of Coulombic efficiency. The results of this work suggest that the possibility of using pristine Ag-TA MOF serves as a suitable electrode material for supercapacitor application.

Hierarchical nanocomposites derived from UiO-66 framework and zeolite for enhanced CO2 adsorption

In this study, a new nanocomposite composed of zeolite Y incorporated into the UiO-66 framework has been synthesized by solvothermal growth of UiO-66 on the support of zeolite Y, and investigated for CO2 adsorption and separation of CO2/CH4 gas mixtures. The aim of this work was to increase the CO2 uptake and the selectivity of the base framework, as well as to increase its thermal stability. Various weight ratios of UiO-66/zeolite Y were prepared to achieve the optimal composition subject to the highest adsorption capacity. The formation of UiO-66/zeolite Y nanocomposites was verified with different characterization methods. It was observed that UiO-66/zeolite Y with a weight ratio of 90:10 has the same morphology as pristine UiO-66 but with superior porosity. Compared to base UiO-66, its surface area and micropore volume increased by about 80 % and 50 %, respectively. Moreover, the results indicate a substantial improvement of 50 % in the CO2 adsorption capacity of nanocomposite (14.6 mmol/g, 298 K, 30 bar) compared to pristine UiO-66. To our knowledge, the newly synthesized nanocomposites exhibited the record-highest CO2 adsorption capacity among the reported UiO-66 composites. The predicted CO2/CH4 adsorption selectivity of the nanocomposite based on IAST is also higher than that of the pristine MOF. Finally, the cyclic adsorption/desorption test revealed more than 95 % desorption efficiency after ten cycles. Due to the high capacity, selectivity, and reversibility of CO2 adsorption on the UiO-66/zeolite Y, and also the high thermal stability of the nanocomposite, it is suggested as an excellent potential adsorbent for the practical application of biogas and natural gas purification. Furthermore, this contribution also presents an insight into the role of zeolite Y in the nanocomposite framework which could comprehend pore size distribution control by varying its amount.

Preparation, characterization, and application of stable naphthalenediimide‐based metal–organic framework for cooperative capture low concentration uranium from wastewater

AbstractExtracting uranium from real water samples remains a great challenge due to low uranium concentration, concentrated competing ions and volumes of water. The design and preparation of uranium adsorbents with high efficiency and affinity are still difficult. Herein, we presented a facile one‐pot strategy to obtain a novel metal organic framework (denoted as Mn‐NDISA) for stable and efficient trapping of low concentration uranium. Mn‐NDISA with a built‐in hydrophobic cavity can boost the absorption affinity to 1.99 × 106 mL g−1 through the cooperative capture composed of electrostatic interaction, coordination force and hydrogen binding. Owing to the coordination‐available oxygen sites in flexible framework, a rapid kinetic equilibrium was achieved in just 25 min. Moreover, these exceptional adsorption features enabled Mn‐NDISA to successfully capture the naturally occurring uranium traces (~ppb) in wastewater samples, making it one of the most influential absorbents toward UO22+ ever reported. The experimental and theoretical studies revealed that the electrostatic attraction came from the surface negatively charged Mn‐NDISA and the positively charged UO22+. The coordination originated from Lewis basic hydroxyl, carbonyl groups, and Lewis acid UO22+, while hydrogen bonds further reinforced the as‐formed uranium binding complex. This research offered a promising cooperative capture strategy to improve the uranium affinity of the pristine MOF for trace contaminants removal in environmental remediation fields.

Ethylenediamine-entrapped defective UiO-66(Zr) frameworks for improved CO2 adsorption and selectivity

In this work, ethylenediamine was entrapped to defected UiO-66(Zr) frameworks to harvest defective amine@UiO-66(Zr) adsorbent (ED@DUiO) that showed improved CO2 performance and good renewability owing to a synergetic effect of creating defects and introducing amine molecules. The UiO-66(Zr) framework was in-situ modified using an acetic acid modulator, followed by grafting of ethylenediamine into the defected UiO-66(Zr) in n-hexane media. Results indicated that the defected UiO-66(Zr) framework had enhanced porosity and exposed more coordinatively unsaturated sites of Zr4+, favouring grafting amine molecules. Gas adsorption experiments revealed that ED@UiO exhibited significantly enhanced CO2 performance compared to the pristine MOF. At 25 °C and 100 kPa, the optimized ED@DUiO entrapped with ∼ 38.3 wt% amines exhibited a CO2-absorbing amount of ∼ 3.48 mmol/g, and IAST-CO2/CO and CO2/N2 selectivity of ∼ 46 and ∼ 78, respectively. Furthermore, the defected UiO-66 entrapped with ethylenediamine exhibited good separation of CO2 in the mixture with CO or N2 under dynamic flow adsorption conditions. The study provides a new strategy combining engineering defects and grafting alkylamine within MOF, which is a promising strategy for developing CO2-selective adsorbent materials.

Self‐sacrificial Templated Synthesis of Fe/N Co‐doping TiO2 for Enhanced CO2 Photocatalytic Reduction

AbstractAs a green photocatalyst, TiO2 has been widely used in adsorption, desorption and redox reactions, but the wide energy band and moderate visible light absorption have greatly inhibited its applications in photocatalysis. The effective method of enhancing the performance of catalysts is the development of heterojunction and metal‐nonmetal co‐doping. Herein, Fe−N co‐doped TiO2 heterojunction photocatalysts (FexTi@C) were successfully synthesized by calcining a self‐sacrificial template (NH2−MIL‐125(Ti)) injected with Fe3+ solution. X‐ray diffraction (XRD), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), N2 adsorption/desorption analysis, and photoelectrochemical tests were used to characterize FexTi@C, showing multiple rutile/anatase TiO2 heterojunction structure, low bandgap, and significant absorption in visible light. In addition, the Ti−O−Fe tetrahedra and more oxygen vacancies were provided since the doped N is from the pristine MOF and the radii of Fe3+ and Ti4+ are similar, which improved the photocatalytic efficiency of CO2 reduction to CH4, especially the Fe0.8Ti@C reached 7.8‐fold and 10.2‐fold CH4 yield increase compared with the original TiMOF template and the undoped Ti@C, respectively. This work presents a simple method for the fabrication of low bandgap semiconductors, and also makes a new attempt at the synergistic effect between the in‐situ elements and valence bonds of MOF‐derived catalysts.

Adsorption investigation of a composite of metal-organic framework and polyethylene oxide hydrogel

Though adsorption techniques are eco-environmentally friendly, most lack the effectiveness of complete contaminant elimination leading to increasing concerns about the presence of aqueous contaminants on humans. Thus, synergistic combination of low adsorption capacity adsorbents may be an effective method to enhance their aqueous contaminant uptake. Sol-gel synthesized lanthanum-1,4-benzene dicarboxylate metal organic framework (LaBDC MOF) and polyethylene oxide (PEO) hydrogel were combined to prepare a synergistic composite adsorbent (PEO-LaBDC) for aqueous methylene blue (MB) adsorption. Major properties of the pristine LaBDC MOF and PEO hydrogel were expressed in the characterized composite indicating successful preparation. PEO-LaBDC composite MB removal rate of MB was at least twice as fast (60 min) to those of the pristine LaBDC MOF (120 min) and PEO hydrogel (125 min). The fitting of kinetics model was fractal in nature, and optimum adsorption was on the alkaline end of the pH spectrum for all adsorbents (pH = 12, 10, and 10, respectively). Comparatively, the composite exhibited a better adsorption performance of ≈177% higher than the pristine LaBDC MOF; buttressing the idea that synergistic combination of adsorbents in composites could enhance adsorption processes. Therefore, the PEO-LaBDC composite is a promising adsorbent for the remediation of aqueous MB.

Abundant Surface Defects in Cobalt Hydroxides/Oxyhydroxides Induced by Zinc Species Facilitate Water Oxidation.

The complex process of the anodic oxygen evolution reaction (OER) severely hinders overall water splitting, which further limits the large-scale production and application of hydrogen energy. In this work, one type of bimetallic coordination polymer of ZnCoBTC using the MOF-on-MOF strategy has been synthesized where both Co(II) and Zn(II) cations exhibit the same coordination environment. By applying an electric potential, the predesigned bimetallic MOF precursor can be conveniently degraded into CoOxHy as an active species for efficient OER. Owing to the dissolution of ZnOxHy species, in situ formed disordered defects on the external surface of the catalyst increase the specific surface area as well as expose abundant active materials. Therefore, the ZnCoOxHy nanosheet shows excellent OER performance and reaches an overpotential of only 334 mV at 10 mA cm-2 with a Tafel slope of 66.4 mV dec-1, indicating fast reaction kinetics. The results demonstrate that metals with the same coordination environment can undergo in situ replacement or secondary growth on the pristine MOF, and they can be electrochemically degraded into highly efficient catalysts for future energy applications.

Fabrication of visible light responsive nitrogen-doped carbon quantum dots/MIL-101(Cr) composites for enhanced photodegradation of Rhodamine B

In this study, an environmentally friendly hydrothermal process was successfully utilized for the fabrication of MIL-101(Cr) (MIL-Cr) and nitrogen-doped carbon quantum dots (N-CQDs) without employing toxic and hazardous hydrofluoric acid and organic solvents. Then, a simple solvent-deposition technique was used to prepare MIL-Cr/N-CQDs(x) composites without requiring specialized equipment. To assess the photocatalytic capabilities of the synthesized materials, Rhodamine B (RhB) was chosen as one of the wastewater toxic organic dye pollutants for photo-degradation experiments. The optimum amount of N-CQDs in composite structure was determined by mixing different volumes of N-CQDs with MIL-Cr, in which MIL-Cr/N-CQDs(2) composite exhibited the highest photocatalytic performance (95%) under visible light illumination. Also, all composites showed better photocatalytic activity in comparison with pristine MOF and N-CQDs individually because N-CQDs can operate as electron acceptors when coupled with MOF, which can prevent the fast electron-hole recombination and increase the visible light absorption. Based on the results of the kinetic investigation, the MIL-Cr/N-CQDs(2) depicted the highest kinetic rate, which is 2.63 and 9.5 times larger than pristine MIL-Cr and N-CQDs under the same experimental conditions. Furthermore, a photocatalytic mechanism was postulated through reactive species scavenging experiments, and it was found that •OH and photo-generated h+ were crucial to the degradation process.

Cerium-based metal–organic framework-conducting polymer nanocomposites for supercapacitors

Nanocomposites consisting of a cerium-based metal–organic framework (Ce-MOF-808) and a conducting polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), are synthesized by performing the pulse electrodeposition of PEDOT within the Ce-MOF-808 thin films. Ratios between MOF and PEDOT in the composites are tunable by simply adjusting the charge density used for electropolymerization, and the crystallinity, morphology, and elemental distributions of the resulting nanocomposites are characterized. Electrochemical behaviors and capacitive performances of the pristine MOF, pristine PEDOT thin films, and composite thin films are investigated with the use of the neutral sodium sulfate aqueous electrolytes. The reversible electrochemical reactivity of the highly porous Ce-MOF-808 provides a pseudocapacitance, and the electronically conducting PEDOT can not only offer a remarkable double-layer capacitance but also facilitate the electronic conduction between the redox-active cerium sites present in the MOF. As a result, the composite can outperform both the pristine MOF and pristine electrodeposited PEDOT as the active materials for supercapacitors. Findings here suggest that the highly porous and redox-active cerium-based MOF thin films are capable to enhance the capacitive performances of the electrodeposited PEDOT thin films.

Design and development of a porous nanorod-based nickel-metal–organic framework (Ni-MOF) for high-performance supercapacitor application

Fabrication of a pristine MOF for the development of an asymmetric supercapacitor device for energy-storage applications.

Novel isostructural iron‐series‐MOF calcined derivatives as positive and negative electrodes: A new strategy to obtain matched electrodes in a supercapacitor device

AbstractThe performance of asymmetric supercapacitors (ASCs) is strongly restricted by the capacity gap between the positive and negative electrodes. To address this issue, two new electrode materials deriving from Co‐ and Fe‐based metal–organic frameworks (MOFs, Co‐TAMBA‐d, and Fe‐TAMBA‐d) through a single‐step sintering method have been developed by considering the superiorities of the derivatives of MOFs including large surface areas, sufficient metal‐atom‐doping content, and extreme surface wettability to the bath solution. The as‐prepared Co‐TAMBA‐d as a positive electrode delivers typical pseudocapacitive behavior with the improvement of capacity, which is better than those of pristine MOF materials, while Fe‐TAMBA‐d as negative electrodes displays better electrochemical behavior than those of activated carbon. ASCs based on these two electrodes exhibits excellent energy density and power density of 47 W h/kg and 1658 W/kg, respectively, where this device can maintain prominent cycling stability with capacity retention after 5000 cycles being about 75%. Furthermore, the capacity can feed a series of red light‐emitting diodes, which gives solid evidence of the potential utilization. These results can afford the feasibility of isostructural MOF derivatives as promising electrodes in novel ASCs.

Cobalt Iron-Metal Organic Framework Coordinated to CMC Aerogel by Solvothermal Method and Application to Tetracycline Antibiotics Adsorption

In order to minimize the adverse impacts on the aquatic environment after treatment process, several attempts have been made to develop biodegradable, easy-to-recover, and environmentally friendly materials. The metal-organic framework material (CoFe-MOF) was developed in the CMC aerogel matrix by solvothermal method and applied in tetracycline antibiotic (TCC) adsorption. The morphological and structural properties of the materials were analyzed by scanning electron microscope (SEM), x-ray diffraction (XRD), Fourier Transform Infra Red (FT-IR), and (Brunauer-Emmett-Teller) (BET) to identify the crystals formed relative to the pristine MOF. The effects of various factors of the adsorption process such as time, pH, amount of adsorbent, and initial concentration of antibiotics were investigated. Results have shown that the adsorption capacity was 188.7 mg.g-1 at pH 4, the initial TCC concentration of 80 g.L-1 and equilibration time of 120 min. The experimental data describing the antibiotic adsorption process follows the Pseudo-second-order kinetic model and the Langmuir isothermal model. The CoFe-MOF aerogel material can recover and reuse all four cycles, thus it can be considered as a promising material for environmental remediation and other applications. Copyright © 2022 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0).

Constructing heterostructures of ZIF-67 derived C, N doped Co2P and Ti2VC2Tx MXene for enhanced OER

Oxygen evolution reaction (OER) is central to technologies such as electrochemical water splitting, and developing efficient and low-cost non-precious metal electrocatalysts for OER is of great significance to reducing cell voltage and developing hydrogen production by electrochemical water splitting. Herein, we prepared a carbon, nitrogen co-doped porous Co2P derived from the metal-organic framework (ZIF-67), which is anchored on bimetallic MXene nanosheets (named MX@MOF-Co2P). It was used as the OER catalyst and exhibited great electrocatalytic performance with very small overpotentials (246 mV at 10 mA–2 and 407 mV at 200 mA cm–2) as well as ultralow Tafel slope (28.18 mV dec–1). Combining characterizations and theoretical calculations, it was found that the remarkable performance was from follows: the obtained MX@MOF-Co2P inherited the porous structure of the pristine MOF with a large number of open active sites; carbon and nitrogen doping also modulated the electronic structure of the active center; the synergistic effect between cobalt phosphide and MXenes booted the electronic transfer. This work represents a promising strategy for the development of non-precious metal catalysts derived from metal-organic frameworks to achieve efficient energy conversion.