Metal-organic Framework Nanorods Research Articles

Conductive Zinc-Based Metal–Organic Framework Nanorods as Cathodes for High-Performance Zn-Ion Capacitors

Zinc-ion capacitors (ZICs), combining the merits of both high-energy zinc-ion batteries and high-power supercapacitors, are known as high-potential electrochemical energy storage (EES) devices. However, the research on ZICs still faces many challenges because of the lack of appropriate cathode materials with robust crystal structures and rich channels for stable and fast Zn2+ ion transport. In this study, we synthesized a robust, conductive, two-dimensional metal–organic framework (MOF) material, zinc-benzenehexathiolate (Zn-BHT), and investigated its electrochemical performance for zinc storage. Zn2+ ions could insert into/extricate from the host structure with a high diffusion rate, enabling the Zn-BHT cathode to exhibit a surface-controlled charge storage mechanism. Due to its unique structure, Zn-BHT exhibited a good reversible discharge capacity approaching 90.4 mAh g−1 at 0.1 A g−1, as well as a desirable rate capability and good cycling performance. In addition, a ZIC device was fabricated using the Zn-BHT cathode and a polyaniline-derived porous carbon (PC) anode, which depicted a high working voltage of up to 1.8 V and a high energy density of ~37.2 Wh kg−1. This work shows that conductive MOFs are high-potential electrode materials for ZICs and provide new enlightenment for the development of electrode materials for EES devices.

Effect of pore structure in bismuth metal-organic framework nanorod derivatives on adsorption and organic pollutant degradation.

This study explores the synthesis, characterization, and photocatalytic properties of bismuth metal-organic framework (Bi-MOF) nanorods and their derivatives such as Ag/Bi-MOF and Ag/Bi2O3. Bi-MOF nanorods exhibit significant photocatalytic activity under visible light, with the addition of silver (Ag) enhancing electron-hole pair separation and reducing their recombination. This leads to improved photocatalytic performance, particularly in the degradation of organic pollutants such as Rhodamine B (RhB) and Methylene Blue (MB). The results show that Bi-MOF and its derivatives demonstrate excellent chemical stability and high performance in photocatalytic applications, even when subjected to high temperatures and tested across a wide pH range. The large surface area and microporous structure facilitate selective adsorption of small organic molecules like MB. The pores and large surface area not only provide numerous active sites but also enhance the interaction between reactants and the catalyst surface, improving photocatalytic efficiency. Bi-MOF and its derivatives perform optimally across a broad pH range, from acidic to alkaline environments, where strong oxidizing hydroxyl radicals (·OH) are easily formed, aiding in the effective degradation of organic compounds. The study also shows that Bi-MOF and its derivatives can be reused multiple times without significant loss in performance. This research contributes to the development of advanced materials for environmental remediation, highlighting the potential of Bi-MOF-based nanocomposites in practical applications.

Low-coordinated Co–Mn diatomic sites derived from metal–organic framework nanorods promote electrocatalytic CO2 reduction

The diatomic L-Co1Mn1-NC catalyst, featuring low-coordinated Co/Mn centers on nanorod-shaped carbon, boosts CO2-to-CO conversion. Its unique microenvironment enhances d–d interaction and charge delocalization, facilitating CO desorption in the CO2RR.

Metal-organic frameworks' latent potential as High-Efficiency osmotic power generators in Thin-Film nanocomposite membranes

This study investigates enhanced osmotic power generation by incorporating metal–organic framework (MOF) nanorods into the thin-film nanocomposite (TFN) membranes for pressure retarded osmosis (PRO) applications. The spotlight is on an innovative membrane, NH2-Ce-BTC-500, which is fabricated utilizing amine-functionalized MOFs (NH2-Ce-BTC), showcasing the synergistic effects of structure and chemistry in optimizing membrane properties for power generation. The NH2-Ce-BTC-500 membrane exhibits a remarkable increase in hydrophilicity, setting a new power density benchmark of 6.9 W/m2. NH2-Ce-BTC-500 outperforms Ce-BTC-500 and pristine TFC membranes by 15 % and 109.1 %, demonstrating the superior performance of amine-functionalized membranes. Furthermore, through physical and chemical characterizations, it is revealed that the MOF-based membranes exhibit increased surface roughness and porosity, indicating the formation of additional water pathways. This enhancement leads to a substantial increase in the water flux, reaching 31.0 LMH in PRO mode, which is a 106 % improvement compared to pristine TFC membranes. This remarkable increase in water flux directly translates to enhanced power generation capacity. In essence, the NH2-Ce-BTC-500 membrane exhibits promising advancements in PRO performance, offering the potential to lower downstream energy consumption and increase power generation efficiency. This research opens up a new paradigm for developing next-generation osmotic power generation. This renewable and energy-efficient solution can address the global energy crisis by leveraging the potential of MOF nanorods in TFN membranes.

Bidirectional redox catalyst with rambutan-like structure for advanced lithium-sulfur battery

The lithium polysulfide (LiPSs) shuttle effect and sluggish conversion kinetics hinder the commercial viability of lithium-sulfur (Li-S) batteries. To improve the properties of Li-S batteries, it is imperative to establish efficient pathways for Li-ions transmission by constructing conductivity channels of high quality, and to expedite the conversion kinetics of LiPSs by employing catalysts of exceptional activity. In this study, we synthesized a spherical superstructure of metal–organic framework nanorods (SS-MOFNR) using a self-assembly strategy with zinc-metal–organic framework (Zn-MOF) nanoparticles, followed by carbonization to obtain the spherical superstructure of carbon nanorods (SS-CNR). Subsequently, palladium nanoparticles were synthesized through the reduction and uniformly dispersed onto SS-CNR. The hollow porous structure facilitates the efficient utilization of sulfur and ensures the rapid diffusion of Li-ions. Additionally, Pd nanoparticles exhibit significant catalytic activity, effectively adsorbing LiPSs and bidirectional catalytic conversion of sulfur species, thereby effectively suppressing the shuttle effect of LiPSs. Therefore S/Pd@SS-CNR electrode demonstrates commendable electrochemical efficacy, as evidenced by its initial specific capacity of 1627.7 mAh g−1 at 0.1C and maintaining a specific capacity of 766.2 mAh g−1 even after 600 cycles at 0.5C. Moreover, it exhibits favorable cycle stability at 2C, retaining a reversible capacity of 502.3 mAh g−1 after undergoing 1000 cycles.

Europium/1,3,5-Benzenetricarboxylic Acid Metal–Organic Framework Nanorods Decorated with CdSe Quantum Dots as Coatings for Noncontact Ratiometric Optical Temperature Sensing

Europium/1,3,5-Benzenetricarboxylic Acid Metal–Organic Framework Nanorods Decorated with CdSe Quantum Dots as Coatings for Noncontact Ratiometric Optical Temperature Sensing

Semiconductive (Cu–S)n metal–organic framework incorporated polyimide nanocomposite coatings forming an oxide barrier for durable anticorrosion effects

A semiconductive (Cu–S)n metal–organic framework (MOF) possesses redox property, which enables polyimide (PI)/(Cu–S)n MOF nanocomposite coatings to form a passivation layer on a metal substrate to prevent corrosion. This study successfully synthesised (Cu–S)n MOF nanorods by using a one-pot microwave-assisted reaction. The functionalised (Cu–S)n MOF nanorods exhibited excellent dispersion in solution and could polymerise with the PI matrix through chemical bonding to form PI/functionalised (Cu–S)n MOF (PI/FMOF) nanocomposites. The as-prepared nanocomposites exhibited multifunctional properties with remarkable flexibility and excellent thermal, mechanical, and corrosion protection effect, as well as anticorrosion against high temperatures. The nanocomposites exhibited a corrosion rate and corrosion protection efficiency of 4.66 × 10−3 milli-inches per year and 99.93 %, respectively. Furthermore, long-term (21 days) anticorrosion durability tests revealed that the PI/FMOF nanocomposites maintained their anticorrosion performance throughout the tests. This study is the first to use polymer/redox MOF–based nanocomposites in anticorrosion applications, successfully reducing the corrosion rate and inhibiting corrosion through the induction of a passivation barrier.

Superhydrophobic cellulose paper with sustained antibacterial activity prepared by in-situ growth of carvacrol-loaded zinc-based metal organic framework nanorods for food packaging application

Cellulose paper packaging materials have gained considerable attention as substitutes for petroleum-based plastics owing to their biodegradability, renewability, flexibility, and good mechanical strength. However, high hydrophilicity and the absence of essential antibacterial activity limit their application in food packaging. In this study, a facile and energy-saving method was developed to improve the hydrophobicity of cellulose paper and endow it with a long-acting antibacterial effect by integrating cellulose paper substrate with metal–organic frameworks (MOFs). A dense and homogenous coating of regular hexagonal ZnMOF-74 nanorods was in-situ formed on a paper surface by layer-by-layer assembly followed by low-surface-energy polydimethylsiloxane (PDMS) modification to prepare a superhydrophobic PDMS@(ZnMOF-74)5@paper. Excellent anti-fouling, self-cleaning, and antibacterial adhesion performances were obtained for this superhydrophobic paper. In addition, active carvacrol was loaded into the pores of ZnMOF-74 nanorods on PDMS@(ZnMOF-74)5@paper to combine antibacterial adhesion together with bactericidal ability, ultimately resulting in a completely “bacteria-free” surface and sustained antibacterial performance. The resultant superhydrophobic papers not only showed overall migration values within the limit of 10 mg/dm2 but also good stability against various harsh mechanical, environmental, and chemical treatments. This work gave insights into the potential of in-situ-developed MOFs-dopped coating as a functionally modified platform for preparing active superhydrophobic paper-based packaging.

An ordered conductive Ni-CAT nanorods array as all-round polysulfide regulator for lithium-sulfur batteries

The effective suppression of polysulfide shuttle is indispensable for the commercialization of lithium-sulfur batteries (LSBs). In this work, an ordered conductive metal-organic framework (MOF) Ni-CAT nanorods array rooted on carbon nanotube film (Ni-CAT/CNTF) is proposed for this subject. The well-aligned MOF nanorods array possesses a unique vertical structure, presenting an incompact upper part and dense root, which guarantee the highly efficient adsorption and selective sieving towards polysulfides, respectively, as well as a fast Li+ transfer. What's more, the good electrical property and fully exposed Ni-based catalytic sites are qualified to boost the electrochemical kinetics. Consequently, LSBs with this fully functional MOF nanorods array exhibit an astonishing capacity of 1087 mAh g−1 and an extraordinary cyclability with a finite capacity-fading of only 0.026% per cycle for 1000 cycles at 1 C, along with an exceptional rate performance of 754 mAh g−1 at 5 C. Moreover, outstanding cycle and rate performance can be maintained under elevated sulfur loadings with a reduced electrolyte content. This work offers new insights into the rational design of polyfunctional nanostructures in LSBs.

Stacked conductive metal–organic framework nanorods for high-performance vacuum electronic devices

Metal-organic frameworks (MOFs) possessing many unique features have been utilized in several fields in recent years. However, their application in field emission (FE) vacuum electronic device is hindered by their poor electrical conductivity. Herein, a novel conductive MOF of Cu-catecholate (Cu-CAT) with the nanorod length of 200 nm and conductivity of 0.01 S/cm is grown on the graphite paper (GP). Under an applied electric field, a large number of electrons can be emitted from the nanoscale emitter tips of MOF surface to the anode. The great field emission performance of Cu-CAT@GP cold cathode film including a low turn-on field of 0.59 V/μm and ultra-high field enhancement factor of 29622, even comparable to most carbon-based materials that have been widely investigated in FE studies, is achieved in this work. Meanwhile, Cu-CAT@GP film has a good electrical stability with a current attenuation of 9.4% in 2 h. The findings reveal the cathode film fabricated by conductive MOF can be a promising candidate of cold electron source for vacuum electronic applications.

Integrating Bi@C Nanospheres in Porous Hard Carbon Frameworks for Ultrafast Sodium Storage.

Sodium-ion batteries (SIBs) have emerged as an alternative technology because of their merits in abundance and cost. Realizing their real applications, however, remains a formidable challenge. One is that among the limitations of anode materials, the alloy-type candidates tolerate fast capacity fading during cycling. Here, a 3D framework superstructure assembled with carbon nanobelt arrays decorated with a metallic bismuth (Bi) nanospheres coated carbon layer by thermolysis of Bi-based metal-organic framework nanorods is synthesized as an anode material for SIBs. Due to the unique structural superiority, the anode design promotes excellent sodium-storage performance in terms of high capacity, excellent cycling stability, and ultrahigh rate capability up to 80Ag-1 with a capacity of 308.8mAhg-1 . The unprecedented sodium-storage ability is not only attributed to the unique hybrid architecture, but also to the production of a homogeneous and thin solid electrolyte interface layer and the formation of uniform porous nanostructures during cycling in the ether-based electrolyte. Importantly, deeper understanding of the underlying cause of the performance improvement is illuminated, which is vital to provide the theoretical basis for application of SIBs.

One-Step Synthesis of Ultrathin Carbon Nanoribbons from Metal–Organic Framework Nanorods for Oxygen Reduction and Zinc–Air Batteries

Two-dimensional (2D) carbon nanostructures play a critical role in energy-related applications, but developing facile and efficient strategies to synthesize these kinds of nanostructures is extreme...

A new generation of solid-phase microextraction based on breathing of metal organic framework nanorods MOF-508 for the determination of diazinon and chlorpyrifos in wheat samples

Flexible MOFs with reversible transformations between open- and closed-pore forms are a new generation of materials that have been applied for gas separation, catalysis, and molecular sensing. This article introduces smart SPME (SSPME) as a new generation of SPME based on the breathing behavior of flexible MOFs with nanorod structures. Stainless-steel (SS) wires were coated with zinc (II)-based MOF, namely MOF-508, with benzene dicarboxylic acid and 4,4-bipyridine. The prepared SSPMEs were investigated to determine some pesticides in wheat samples. The results showed a low limit of detection (4 and 20 µg Kg−1) and a wide linear dynamic range (20–4000 and 200–4000 µg Kg−1) for the determination of diazinon and chlorpyrifos analytes using the SSPME-GC-FID method. The acceptable relative standard deviation for one-fiber, fiber-to-fiber, intraday, and interday modes was obtained 5.6–15%. The use of SSPME during the extraction process led to the minimum desorption time and complete desorption of pesticides analytes from the SSPME fiber.

Cerium-Based Metal–Organic Framework Nanorods Nucleated on CeO2 Nanosheets for Photocatalytic N2 Fixation and Water Oxidation

Cerium-Based Metal–Organic Framework Nanorods Nucleated on CeO₂ Nanosheets for Photocatalytic N₂ Fixation and Water Oxidation

Continuous-flow rapid synthesis of wavelength-tunable luminescent lanthanide metal-organic framework nanorods by a microfluidic reactor

Lanthanide metal-organic frameworks (Ln-MOFs) have been widely used in fluorescence sensing, bioimaging and light emitting diode due to their excellent optical properties. However, the preparation of Ln-MOFs is energy and time-consuming due to the constraints of the conventional wet chemical methods. In this paper, a synthetic strategy for the rapid preparation of Ln-MOFs nanorods with adjustable emission wavelength in a microchannel reactor is proposed. Compared with the wet chemical methods, the efficient mass and heat transfer capability of the microchannel shortens the reaction time from 12 h to 50 min. More importantly, Ln-MOFs nanorods with different emission wavelengths can be easily prepared by adjusting the flow rate of different components of the microchannel, which can be adjusted in real-time according to the preparation needs. The result shows that the Ln-MOFs prepared by microfluidic method is in the shape of nanorods with widely emission wavelength from 470 nm (blue light) to 615 nm (red light). In addition, the fluorescence emission intensity of Ln-MOFs is confirmed to have a wide reversible temperature (30–220 ℃) and is expected to be used for high-precision temperature sensing in the future.

Instantaneous Sonophotocatalytic Degradation of Tetracycline over NU-1000@ZnIn2S4 Core-Shell Nanorods as a Robust and Eco-friendly Catalyst.

The universal pollution of diverse water bodies and declined water quality represent very important environmental problems. The development of new and efficient photocatalytic water treatment systems based on the Z-scheme mechanisms can contribute to tackling such problems. This study reports the preparation, full characterization, and detailed sonophotocatalytic activity of a new series of hybrid NU@ZIS nanocomposites, which comprise a p-n heterojunction of 3D Zr(IV) metal-organic framework nanorods (NU-1000) and photoactive ZnIn2S4 (ZIS) nanostars. Among the obtained materials with varying content of ZIS (5, 10, 20, and 30%) on the surface of NU-1000, the NU@ZIS20 nanocomposite revealed an ultrahigh catalytic performance and recyclability in a quick visible-light-induced degradation of the tetracycline antibiotic in water under sonophotocatalytic conditions. Moreover, increased activity of NU@ZIS20 can be ascribed to the formation of a p-n heterojunction between NU-1000 and ZIS, and a synergistic effect of these components, leading to a high level of radical production, facilitating a Z-scheme charge carrier transfer and reducing the recombination of charge carriers. The radical trapping tests revealed that •OH, •O2-, and h+ are the major active species in the sonophotocatalytic degradation of tetracycline. Possible mechanism and mineralization pathways were introduced. Cytotoxicity of NU@ZIS20 and aquatic toxicity of water samples after tetracycline degradation were also assessed, showing good biocompatibility of the catalyst and efficacy of sonophotocatalytic protocols to produce water that does not affect the growth of bacteria. Finally, the obtained nanocomposites and developed photocatalytic processes can represent an interesting approach toward diverse environmental applications in water remediation and the elimination of other types of organic pollutants.

Orientation-Adjustable Metal-Organic Framework Nanorods for Efficient Oxygen Evolution Reaction.

A series of orientation-adjustable metal-organic framework (MOF) nanorods, CoFe(dobpdc)-I to CoFe(dobpdc)-III (dobpdc = 4,4'-dihydroxybiphenyl-3,3'-dicarboxylate), is developed on a 3D nickel foam (NF) template. By modulating the solvent composition for synthesis, the feature of MOF nanorods on the template can be varied from disorganized to a unidirectional orientation perpendicular to the NF. Well-aligned, vertically oriented CoFe(dobpdc)-III nanorods are hydrophilic and have more exposed active sites and interfacial charge transfer ability. Consequently, they exhibit a superior activity for oxygen evolution reaction (OER) with ultralow overpotentials of 176 and 240 mV at 10 and 300 mA cm-2 in 1.0 M KOH (aq), respectively. CoFe(dobpdc)-III also shows a record low overpotential of 204 mV at J10 mA cm-2 among the electrocatalysts based on CoFe MOF and an excellent overpotential at a high current density (100 mA cm-2) of 312 mV in 0.1 M KOH (aq). This is the first report of a convenient method to straighten up MOF nanorods on a template for highly efficient OER.

Ni-Based Metal–Organic Framework Nanorods Self-assembled into Hollow Architecture and Decorated with Pt Nanoparticles as Nanocatalysts for CO Oxidation

Herein, we fabricate a new type of Ni-based metal–organic frameworks (Ni-MOFs) with self-assembled nanorods to form hollow architectures, which were then used as excellent supports to load uniform ...

One-dimensional conductive metal–organic framework nanorods: a highly selective electrocatalyst for the oxygen reduction to hydrogen peroxide

Mn–TCNQ acts as an efficient electrocatalyst to boost 2e− oxygen reduction reaction, capable of achieving an outstanding H2O2 selectivity over 98% and a high H2O2 yield of 142.6 ppm h−1 in an alkaline medium.

The fluorescence imaging and precise suppression of bacterial infections in chronic wounds by porphyrin-based metal-organic framework nanorods.

Nano-antibacterial agents can play a critical role in chronic wound management. However, the design of an intelligent nanosystem that can provide both a visual warning of infection and precise sterilization remains a hurdle. Herein, a rod-like porphyrin-based metal-organic framework theranostic nanosystem (Zn-TCPP nanorods) is fabricated via coordination chelation between tetrakis(4-carboxylphenyl)porphyrin and zinc ions. This system can show significant fluorescence activation in response to the local elevated pH shown by chronic wounds, a main indicator of wound infection. Meanwhile, under the guidance of fluorescence imaging, the highly spatiotemporally precise photodynamic inactivation of microorganisms can be carried out without the destruction of surrounding normal cells and nascent cells. The results demonstrated that the Zn-TCPP nanorods were a highly sensitive and reversible probe for sensing alkaline pH levels. Alterations in the fluorescence of the Zn-TCPP nanorods can accurately indicate the infection status and heterogeneity of infection within the wound bed. Under specific light irradiation, the Zn-TCPP nanorods can exterminate 97% of Staphylococcus aureus via the generation of reactive oxygen species (ROS). Assays of extensive wounds demonstrate that the precise fluorescence-imaging-guided suppression of bacterial infection can significantly reduce the mouse mortality rate and accelerate wound healing. This system provides the opportunity for "precision medicine" relating to chronic wounds and some large-area wounds.