Metal-organic Framework Derivatives Research Articles

Ru-Doped Ultrasmall Cu Nanoparticles Decorated with Carbon for Electroreduction of Nitrate to Ammonia.

Electrocatalytic nitrate reduction reaction offers a sustainable approach to treating wastewater and synthesizing high-value ammonia under ambient conditions. However, electrocatalysts with low faradaic efficiency and selectivity severely hinder the development of nitrate-to-ammonia conversion. Herein, Ru-doped ultrasmall copper nanoparticles loaded on a carbon substrate (Cu-Ru@C) were fabricated by the pyrolysis of Cu-BTC metal-organic frameworks (MOFs). The Cu-Ru@C-0.5 catalyst exhibits a high faradaic efficiency (FE) of 90.4% at -0.6 V (vs RHE) and an ammonia yield rate of 1700.36 μg h-1mgcat.-1 at -0.9 V (vs RHE). Moreover, the nitrate conversion rate is almost 100% over varied pHs (including acid, neutral, and alkaline electrolytes) and different nitrate concentrations. The remarkable performance is attributed to the synergistic effect between Cu and Ru and the excellent conductivity of the carbon substrate. This work will open an exciting avenue to exploring MOF derivatives for ambient ammonia synthesis via selective electrocatalytic nitrate reduction.

Efficient metal–organic framework-based dual co-catalysts system assist CdS for hydrogen production from photolysis of water

Metal-organic framework materials (MOFs) and their derivatives have been widely used in the field of photocatalytic water decomposition for hydrogen production. In this study, NiS/CdS was initially acquired and subsequently combined with DUT-67 via ultrasound to create a unique ternary photocatalyst NiS/CdS@DUT-67. The rate of hydrogen production for NiS/CdS@DUT-67 is 9618 μmol·g NiS/CdS−1·h−1 for NiS/CdS@DUT-67, which is 32 times and 2.5 times higher than that for CdS and NiS/CdS, respectively. Of particular interest is the fact that even after 50 h of photocatalysis, the hydrogen production rate did not show a significant decrease, demonstrating its excellent stability compared to CdS and NiS/CdS. In this ternary system, NiS and DUT-67 function as dual co-catalysts for CdS, collaborating to enhance charge separation during the photocatalysis. This study presents a clear demonstration of the advantages of utilizing metal–organic framework derivatives (MOF-derivatives) cophotocatalysts and their synergistic effect, resulting in improved photocatalytic activity and stability of semiconductors. This innovative approach provides a new perspective on constructing photocatalytic materials with exceptional performance.

Non‐thermal Plasma for VOCs Abatement: Recent Advance

AbstractVolatile organic compounds (VOCs) emissions are a factor in a number of environmental issues. To reduce the associated negative consequences, it is crucial to develop efficient VOCs removal systems. Non‐thermal plasma (NTP) co‐catalytic technology has become a popular research topic in this field as a result of its ability to reduce the activation energy of the reaction while simultaneously improving product selectivity. Despite the huge number of studies synthesising the use of metals and their oxide catalysts in the degradation of VOCs, metal‐organic frameworks (MOFs) and MOF derivatives are the subject of comparatively few studies in this area. This paper reviews the basic principles and technological progress of NTP co‐catalytic VOCs degradation, with a focus on the use of MOFs and their derivatives in plasma VOCs degradation, as well as the use of other non‐metallic carbon materials in plasma VOCs degradation. It highlights the potential future development direction of NTP catalytic synergistic treatment of VOCs by focusing on the optimization of catalytic synergism on the treatment impact. In the end, the challenges faced, the prospects, and our personal perspective on future research directions are also estimated and elucidated.

Metal-organic-frameworks derived hollow carbon derivatives: Controllable configurations and optimized microwave absorption

Metal-organic-frameworks (MOFs) derivatives with diverse architectures and adjusted chemical compositions have been recognized as one of the promising candidates in the field of microwave absorption, especially carbon derivatives with hollow structure. Herein, the recent strategies in fabrication of hollow MOFs derivatives and the relationship between hollow structure and microwave absorption performance are briefly summarized. Then, the synthesized mechanism and crucial factors in the formation of hollow structure are systematically analyzed. Finally, the current challenges and future research trends are predicted, which provide guidelines for the regulation of hollow MOFs derivatives and the manipulation of microwave absorption performance.

3D carbon skeleton/MOF derivatives for efficient electromagnetic absorption and corrosion resistance.

Metal-organic framework (MOF) derivatives have attracted tremendous attention in electromagnetic (EM) wave absorption owing to their unique properties such as structural diversity, tailorable components and light weight. However, they fail to demonstrate decent EM attenuation performance due to inadequate heterostructures and multiple reflections. Here, 3D carbon skeleton (CS)/MOF derivatives are prepared via an in situ growth and pyrolysis strategy which is based on chitosan derived CS and the MOFs ZIF-8 and ZIF-67. As a result, CS/ZIF-8 600 °C demonstrates excellent EM absorption, whose minimum reflection loss is -41.85 dB with an effective absorption bandwidth of 2.56 GHz. In addition, the CS/MOF composites exhibit splendid corrosion resistance in complex environments such as neutral, acidic and alkaline.

Metal–organic framework derivatives with gradient structures via multidimensional assembly engineering for tunable efficient microwave absorption

Multidimensional assembly strategy facilitates the preparation of MOF-derived Co-doped carbon-based composites assembled with 1D nanowires/rods and 0D nanobubbles to enhance and optimize microwave attenuation.

Recent progress of metal-organic framework-based nanozymes with oxidoreductase-like activity.

Nanozymes, a class of synthetic nanomaterials possessing enzymatic catalytic properties, exhibit distinct advantages such as exceptional stability and cost-effectiveness. Among them, metal-organic framework (MOF)-based nanozymes have garnered significant attention due to their large specific surface area, tunable pore size and uniform structure. MOFs are porous crystalline materials bridged by inorganic metal ions/clusters and organic ligands, which hold immense potential in the fields of catalysis, sensors and drug carriers. The combination of MOFs with diverse nanomaterials gives rise to various types of MOF-based nanozyme, encompassing original MOFs, MOF-based nanozymes with chemical modifications, MOF-based composites and MOF derivatives. It is worth mentioning that the metal ions and organic ligands in MOFs are perfectly suited for designing oxidoreductase-like nanozymes. In this review, we intend to provide an overview of recent trends and progress in MOF-based nanozymes with oxidoreductase-like activity. Furthermore, the current obstacles and prospective outlook of MOF-based nanozymes are proposed and briefly discussed. This comprehensive analysis aims to facilitate progress in the development of novel MOF-based nanozymes with oxidoreductase-like activity while serving as a valuable reference for scientists engaged in related disciplines.

Hydrogen sulfide sensor based on NiWO4-NiO nanoflowers prepared from metal-organic framework derivatives

Hydrogen sulfide sensor based on NiWO₄-NiO nanoflowers prepared from metal-organic framework derivatives

Why Ceria Nanoparticles Obtained from Ce-MOFs Exhibit Higher Catalytic Efficient in Soot Combustion? Understanding the Role of Intrinsic Properties of a Cerium-Organic Framework to Produce CeO2

Metal-organic framework (MOF) derivatives, such as porous metal oxides with controlled morphology have received great attention for applications in various fields. In this paper, the experimental results show that porous CeO2 with high specific surface area (90.5 m2 g-1) and nanorod morphology can be obtained by calcining a Ce-MOF template at optimized temperature (300-500 °C). The formation mechanism of this porous structure as well as the influence of the calcination temperature are well explained by taking into account thermal behavior and intrinsic structural features of the Ce-MOF precursor. We employed the oxides formed as heterogeneous catalysts to reduce the soot originating from the incomplete combustion of diesel or diesel/biodiesel blends. The CeO2 materials exhibit outstanding catalytic activity, lowering the temperature of soot combustion from 610 to 370 °C. Compared with similar work, our catalyst exhibits enhanced soot oxidation activity, making it highly promising for diesel particulate filter applications. Such outstanding catalytic performance of the porous CeO2 nanorods benefits from their large specific surface area, and morphological and structural characteristics.

Fabrication of flower-like CoFe/C composites derived from ferrocene-based metal-organic frameworks: an in situ growth strategy toward high-efficiency electromagnetic wave absorption.

Magnetic/dielectric composites can achieve high-efficiency electromagnetic wave (EMW) absorption performance by integrating multiple mechanisms such as dielectric loss and magnetic loss. The bimetallic metal-organic frameworks (MOFs) assembled from ferrocene (Fc) derivative-based bridging ligands are considered ideal precursors for the preparation of magnetic/dielectric composites due to tailored alloy components with magnetic losses. Herein, a novel CoFe/C composite with nanoflower structures is successfully obtained via an in situ growth strategy to decompose an Fc-based bimetallic MOF assembled from 1,1'-ferrocene dicarboxylic acid as bridging ligands and Co2+ ions. Notably, the nanoflower structures of the obtained composites provide an effective path for the scattering and reflection of the EMW, thereby improving the impedance matching by combining dielectric and magnetic loss. The CoFe/C composite exhibits excellent EMW absorption performance and has a minimum reflection loss of -61.6 dB at 3.7 mm and an effective absorption bandwidth of 6.24 GHz at a corresponding thickness of 2.2 mm. Moreover, the obtained composite exhibits lightweight characteristics and a low radar cross-section. This work presents a novel method through Fc-based bimetallic MOF derivatives to design and develop novel magnetic/dielectric composites with efficient EMW absorption properties for comprehensive applications.

N-doped branched metal–organic framework derivatives to boost multiband microwave absorption with ultrathin thickness

CoNi@NPC/NCNTs composites with a rod-like N-doped carbon matrix and branched N-doped CNTs, prepared via melamine-assisted CVD pyrolysis, demonstrate superior dual-band electromagnetic wave absorption (2–18 and 26.5–40 GHz) with ultrathin thickness.

Structural engineering of rare earth metal-organic frameworks derivatives with high anisotropy for high-efficiency electromagnetic wave absorption

Structural engineering and component design are crucial for conceiving outstanding metal-organic frameworks (MOFs)-based electromagnetic wave (EMW) absorption materials. However, an efficient and direct clarification of the structural influences on the EMW absorption performance of MOF-based absorption materials remains highly challenging and still awaits exploration. To this end, we synthesized a new type of rare earth (RE) MOFs with hexagonal-bipyramidal, snowflake-like, and dendritic structures through facilely controlling the solvent ratios in a scalable coprecipitation approach. The MOF-derived CeO2/Co/C hybrids with the same component content inheriting the morphological structures showcased tunable dielectric property and EMW absorption performance. The dendritic MOF derivatives with the highest anisotropy achieved a superior EMW absorption performance, manifesting a minimum reflection loss value of −71.5 dB at 1.7 mm and an effective absorption bandwidth of 5.2 GHz at 1.6 mm thickness, comparable to those of the best EMW absorbers. This work not only confirmed the high potential of RE MOF derivatives for EMW absorption, but also directly and efficiently unveiled the mechanism of morphological structure on the dielectric property and EMW absorption performance for the MOF-based EMW absorption material.

Hierarchical Electrode Constructed by carbon-coated Metal-Organic Framework Derivatives Supported on two-dimensional Ti3C2 nanosheets for Hybrid Li-ion Capacitors

BackgroudMetal-organic frameworks (MOFs) (e.g., Co-MOF) had been a popular platform for synthesis electrode materials for lithium-ion capacitors (LICs) because of their high theoretical specific capacity and unique structural advantages. Recent researches have focused on the development of MOFs derivative-based composites with high specific surface area, high structural stability, and high electrical conductivity. Methods: Here a distinct Ti3C2/Co3O4@C heterostructure composite was prepared by a straightforward method via hydrogen bonding with carbon-coated Co-MOF derivative anchored on Mxene-Ti3C2 nanosheets. The carbon-coated hollow Co3O4 polyhedra could shorten Li+ diffusion paths, increase the specific surface area and mitigate structural changes during the Li+ storage process. Moreover, Ti3C2 sheets were acted as a conductive network, which could increase the Li+ transport rate and stability of the structure. SignificantServing as anode material, Ti3C2/Co3O4@C electrode showed a specific capacity of 1341 mAh/g at current density of 0.1 A/g, with 93% capacity maintenance at 2 A/g after 1000 cycles in the lithium-ion half cell. Furthermore, Ti3C2/Co3O4@C//AC LIC delivered a high energy of 106 Wh/kg at 7632 W/kg. The distinct heterostructure, straightforward, and excellent performance of the Ti3C2/Co3O4@C composite as anode could provide application prospects in LICs with high energy/power density.

Facile synthesis of cobalt, nickel and manganese-based metal organic framework derived layered double hydroxides on Ni foam as effective binder-free electrodes of energy storage devices

Metal organic framework (MOF) derivatives have attracted intensive attention as the active material of energy storage devices. Layered double hydroxide (LDH) with large surface area, high redox capability and good cycling stability is regard as one of efficient active materials. Developing MOF-derived LDH with multiple metals can possibly achieve excellent surface properties, high electrical conductivity and abundant redox reactions. However, synthesizing MOF-derived LDH is time-consuming and requires high temperature environments. In this work, a simple and time-effective precipitation and etching process is proposed to synthesize MOF-derived LDH on nickel foam (NF) as binder-free electrodes of energy storage devices. The cobalt, nickel and manganese are utilized to design MOF-derived LDH with different metal species and numbers. The trimetallic MOF-derived LDH based on Co, Ni and Mn presents a high specific capacitance (CF) of 1113.7 F/g at 20 mV/s, due to abundant electroactive sites and multiple redox states for carrying out large numbers of redox reactions. The energy storage device composed of the trimetallic MOF-derived LDH and carbon on NF as electrodes presents the maximum energy density of 61.5 Wh/kg at the power density of 750 W/kg, and the CF retention of 92.5% and Coulombic efficiency of 95% after 10,000 charge/discharge cycles.

ZIF derived nanosheet copper-cobalt oxide/nitrogen-doped carbon via promote peroxymonosulfate activation for the rapid degradation of metronidazole

In recent years, metal-organic framework derivatives have been regarded as materials with great potential for water treatment applications. In this study, we employed a polyvinylpyrrolidone (PVP)-assisted copper-cobalt bimetallic zeolitic imidazole framework (ZIF) as a template to rationally design nanosheet-like mixed metal oxide embedded nitrogen-doped carbon (CuCoO-PC). CuCoO-PC exhibited excellent degradation potential towards metronidazole (MNZ) and achieved almost complete degradation within 7 min through the activation of peroxymonosulfate (PMS). Importantly, the introduction of copper into CuCoO-PC established strong interactions between copper and cobalt, accelerating the activation performance of PMS. Furthermore, PVP, rich in nitrogen atoms, formed strong coordination interactions with ZIF precursors, which effectively protected the morphological stability of ZIF at high temperature, preventing collapse and aggregation. Meanwhile, the formation of nitrogen-doped carbon networks provides a pathway for the generation of non-radical. The study found that CuCoO-PC continuously activated PMS, generating various reactive oxygen species (ROS), among which SO4•- and 1O2 played decisive roles. By calculating the HOMO, LUMO, and Fukui functions, we identified the reactive sites of MNZ and proposed possible degradation pathways. CuCoO-PC demonstrated excellent catalytic performance, reduced toxicity of intermediate products, and good reusability, all of which highlight its enormous potential in practical applications.

A photoelectrochemical sensor based on copper-based metal organic framework derivatives for the homogeneous detection of L-cysteine

Due to their outstanding advantages, photoelectrochemical (PEC) sensors have gained significant attention, which can realize the rapid and accurate detection of target. However, the semiconductor as its core component has a strong influence on the analysis and detection performance. Herein, we developed a simple and efficient method to prepare heterojunction for the construction of PEC sensor detecting L-cysteine (L-Cys). The rod-like copper-based metal organic framework was prepared by room temperature synthesis method, which was used to derive rod-like CuO/Cu2O/C heterojunction with excellent photoelectric property. Due to L-Cys interacts with CuO/Cu2O/C heterojunction to form steric hindrance effect through Cu-S bond, which reduces the photocurrent signal and realizes the selective and homogeneous detection of L-Cys. Inspired by this steric strategy, a PEC sensing platform was fabricated by CuO/Cu2O/C heterojunction for the homogeneous detection of L-Cys, showing linear responses in the range of 0.2 μM to 50 μM with the detection limit of 0.12 μM. Our work shed light on the advancement of better PEC sensor and the method of constructing heterojunction.

Research Progress on Metal–Organic Framework-Based Electrode Materials for Supercapacitors

Supercapacitors play an important role in power systems since they are a key part of electrochemical energy storage devices. To assemble high-performance supercapacitors, it is crucial to discover and innovate high-capacitive electrode materials. Recently, metal–organic frameworks (MOFs) and their derivatives have received wide concerns as electrode materials for supercapacitors, not only because of their high pore volume and large surface area for ions and electrons insertion and transportation, but also due to the intrinsic metal active sites that possibly offer extra faradaic pseudocapacitance. Additionally, the abundant species of MOFs with various morphologies also feature advantages in enriching the structural diversity of electrodes. In this paper, we first report the latest research progress and demonstrate the feasibility of pure MOFs for directly constructing supercapacitor electrodes. Furthermore, different MOF derivatives, including porous carbons, transition metal oxides, metal hydroxides and MOF composites for supercapacitors, are summarized, and their electrochemical performances with corresponding energy storage mechanisms are presented in detail. Finally, the perspectives for MOF-based materials applied in supercapacitors are discussed, aiming to provide a guideline for further research based on these promising materials.

Straw-bundle-like rare earth metal-organic frameworks derivatives for high-efficiency electromagnetic wave absorption

Metal-organic frameworks (MOFs) derivatives have been widely developed as electromagnetic wave (EMW) absorption materials. Nevertheless, owing to the diverse metal ions, organic ligands, and crystal morphologies of MOFs precursors, challenges still remain to overcome towards directly ascertaining the contribution of metal components on EMW absorption for precisely designing high EMW absorption performance of MOF derivatives. Here, we synthesize a series of rare earth (RE) MOF derivatives via a facile, scalable coprecipitation followed by carbonization approach. Thanks to the similar chemical property derived from lanthanide shrinkage of RE elements, the MOF-derived RE oxides (REO)/carbon (REO = CeO2, La2O3, Nd2O3) hybrids exhibit the identical straw-bundle-like microstructure, efficiently assisting the elucidation of the roles of metal components in promoting EMW absorption. Benefiting from the tunable bandgap of various REO as well as carbonization temperature, the 800 °C-carbonized CeO2/carbon shows a minimum reflection loss of − 58.7 dB at a thickness of 1.7 mm and an effective absorption bandwidth of 5.0 GHz, comparable to the best EMW absorbers. This work not only demonstrates novel, high-performance RE-MOF derivatives, but also offers a general yet efficient strategy for designing metal components to achieve high-efficiency MOF-based EMW absorbers.

Synergistic Effect of Nickel Nanoparticles Dispersed on MOF-Derived Defective Co3O4 In Situ Grown over TiO2 Nanowires toward UV and Visible Light Driven Photothermal CO2 Methanation.

Catalytic CO2 hydrogenation is an effective approach to producing clean fuels, but this process is expensive, in addition to the low efficiency of catalysts. Thus, photothermal CO2 hydrogenation can effectively utilize solar energy for CH4 production. Metal-organic framework (MOF) derived materials with a controlled structure and morphology are promising to give a high number of active sites and photostability in thermal catalytic reactions. For the first time, a novel heterostructure catalyst was synthesized using a facile approach to in situ grow MOF-derived 0D Co3O4 over 1D TiO2 nanowires (NWs). The original 3D dodecahedral structure of the MOF is engineered into novel 0D Co3O4 nanospheres, which were uniformly embedded over Ni-dispersed 1D TiO2 NWs. In situ prepared 10Ni-7Co3O4@TiO2 NWs-I achieved an excellent photothermal CH4 evolution rate of 8.28 mmol/h at 250 °C under low-intensity visible light, whereas UV light treatment further increased activity by 1.2-fold. UV irradiations promoted high CH4 production while improving the susceptibility of the catalyst to visible light irradiation. The photothermal effect is prominent at lower temperatures, due to the harmonization of both solar and thermal energy. By paralleling with mechanically assembled 10Ni-7Co3O4/TiO2 NWs-M, the catalytic performance of the in situ approach is far superior, attributing to the morphological transformation of 0D Co3O4, which induced intimate interfacial interactions, formation of oxygen vacancies and boosted photo-to-thermal effects. The co-existence of metallic/metal oxide Ni-Co provided beneficial synergies, enhanced photo-to-thermal effects, and improved charge transfer kinetics of the composite. This work uncovers a facile approach to engineering the morphology of MOF derivatives for efficient photothermal CO2 methanation.

Ni3S4/FeNi2S4 heterostructure-embedded metal-organic framework-derived nanosheets interconnected by carbon nanotubes for boosting oxygen evolution reaction

The efficiency of electrolytic water splitting is hampered by the slow kinetics of the oxygen evolution reaction (OER). Addressing this challenge, we present a novel catalyst with rich Ni3S4/FeNi2S4 heterostructures anchored metal-organic framework-derived nanosheets interconnected by carbon nanotubes (NiFe–S@CNT). The NiFe–S@CNT electrocatalyst shows an ultralow overpotential of 246 mV at a current density of 10 mA/cm2 (η10), surpassing the benchmark RuO2 (η10 = 291 mV) as well as many reported sulfide electrocatalysts. The strong heterointerface interaction between Ni3S4 and FeNi2S4 induce synergistic effects, modifying the electronic structure of active sites and generating a large number of lattice defects. Additionally, the carbon nanotubes skeleton facilitates efficient electron transfer and enhances electrical conductivity during the catalytic process. Moreover, the metal-organic framework derivative inherits a porous structure, aiding in electrolyte penetration and efficient bubble release. This study provides a facile and scalable strategy to develop nonprecious transition-metal-based OER catalysts with abundant heterointerfaces and active sites for efficient water splitting.