Growth Of Metal-organic Frameworks Research Articles

High-Valence Co Stabilized by In-Situ Growth of ZIF-67 on NiCo-LDH for Enhanced Performance in Oxygen Evolution Reaction.

The application of metal-organic frameworks (MOFs) in the electro-catalysis of heterogeneous structures is limited by the problems of low electrical conductivity and poor mechanical strength due to the complex synthesis process, although their high specific surface area and controllable structure. In this study, a method involving metal precipitation and ligand reaction is used during the electrochemical corrosion of hydroxides/oxy-hydroxides to obtain ZIF-67 in situ. The in situ growth technology not only effectively addresses the bonding strength and material conductivity challenges in the heterostructure between MOFs and the substrate but also enhances the catalyst's surface area and activity. Additionally, the exposure and protection of Co4+ by ZIF-67 contribute to the electrocatalyst's performance, demonstrating a low overpotential (η100) of 293mV, a Tafel slope of 25.8mV dec-1, and a charge transfer resistance of 3.9 Ω, with long-term robustness proven in continuous stability test exceeding 75000 s under the superhigh current density of 500mA cm-2. This work on binder-free in situ growth of MOFs not only provides relevant theoretical insights and experimental experience for cost-effective and controllable production of MOF-based catalysts but also offers ideas for the development of future electrocatalysts by exploring the exposure and protection of active site using MOFs materials.

Flexible MOF@fabrics composites: The in-situ growth of metal-organic frameworks on cotton and selectively adsorption of gold(III) from aqueous solution

Metal-organic frameworks (MOFs) show great potential applications in dealing with heavy metal pollution due to their unique large specific surface area, tunable pore size, and diverse active groups. However, the powder form of MOFs has suffered from the disadvantages of difficult recycling and secondary contamination after adsorption of heavy metals, which seriously limits their practical application. Therefore, in this work, we prepared a series of bifunctional zirconium-based MOFs cotton fabric composites (MCFC) via in situ growth of MOFs on carboxylated cotton fabric, exhibiting large specific surface area, adjustable pore size, and effective adsorption ability. The prepared CF-UiO-66-(OH)2-FA shows an excellent adsorption efficiency of Au(III) more than 99.990 %, and the saturated adsorption amount is up to 190.98 mg·g−1 at 25 °C. Meanwhile, the kinetic experiment analysis demonstrated that the Au(III) adsorption behavior of MCFC follows pseudo-second-order (PSO) kinetic model. More importantly, it also exhibits great selectivity in adsorbing Au(III) from the mixture of multiple metal ions coexisted solution. The results of adsorption thermodynamics and adsorption isotherms indicate that adsorption is monolayer and a spontaneous, exothermic process. And the ideal adsorption and separation process could be finished by quickly filtrating with a single or multi-layer MCFC. Excellent adsorption performance even after four cycles of adsorption. Therefore, the fabricated MCFC shows great processability, flexibility, collectability and reusability in adsorbing and recycling precious metal ion from wastewater.

Carbon nanotubes perpendicularly grown on graphene oxide nanosheets derived from metal-organic frameworks: Synergistic reinforcement of poly(l-lactic acid) scaffold

The construction of the nanohybrid composed of two carbonaceous nanomaterials is a promising strategy to inhibit their aggregation, and effectively exert the advantages of their excellent mechanical properties as reinforcement for polymers. Here, carbon nanotubes (CNTs) were in situ perpendicularly growing on the surface of graphene oxide (GO) through metal-organic frameworks (MOF)-derived strategy by chemical vapor deposition (CVD), aiming to facilitate their dispersion on poly(l-lactic acid) (PLLA) bone scaffold fabricated by selective laser sintering (SLS). Specifically, GO provided nucleation sites for the growth of MOF, and worked as the templates when CNTs grew, in which MOF provided catalysts and carbon sources simultaneously. The precursor was heated to 550 °C and kept for 2 h, then heated to 900 °C and kept for 2 h before cooling. The obtained nanohybrid (GO@CNT) exhibited a superior dispersion state than the pure GO in the scaffold at the same loading, especially when the loading was 0.75 wt%. Adding 0.75 wt% GO@CNT endowed the scaffold with a remarkable increment in tensile strength and compressive strength of 13.36 MPa and 24.72 MPa with enhancement of 55.35% and 18.85%, respectively, compared to the scaffold containing 0.75 wt% GO. A crack extension model combined with experiment results was proposed to better understand reinforcement mechanisms. Additionally, the scaffold containing GO@CNT exhibited benign cytocompatibility with a cell-spreading area of 86.31% and cell density of 564 cells/mm2 after culturing for 5 d according to the results of cell adhesion and immunofluorescence tests, making it a promising candidate for bone defect repair.

Enhancing the charge storage capacity of ultrathin metal–organic framework nanosheets with CO2-derived carbon nanotubes

Metal-organic frameworks (MOFs) hold promise as efficient electrode materials for supercapacitors, but their practical application is hindered by the intrinsic low electrical conductivity. Here, we employ CO2-derived carbon nanotubes based on molten salt electrolysis (MSE-CNTs) as the framework to guide the growth of nickel-based MOF (Ni-MOF). The resulting MSE-CNTs/Ni-MOF composite exhibits an impressive specific capacitance of 1714.2 F g−1 at 1 A g−1, 1.45 and 1.26 times greater than bare Ni-MOF (1185.7 F g−1) and CVD-CNTs/Ni-MOF (1364.3 F g−1, the composite of Ni-MOF and commercial CNTs produced by chemical-vapor-deposition), respectively. Moreover, the assembled hybrid supercapacitor (MSE-CNTs/Ni-MOF//active carbon) achieves a remarkable specific capacitance of 136.5 F g−1 at 1 A g−1 and an energy density of 54.8 Wh kg−1 at 850 W kg−1, standing among the best of the state-of-the-art. The superior capacitive performance of MSE-CNTs/Ni-MOF than CVD-CNTs/Ni-MOF can be attributed to the better electrical conductivity of MSE-CNTs, the thinner nanosheet architecture of MSE-CNTs/Ni-MOF, and the effective electrically conductive network within the composite. This work marks a paradigm shift from greenhouse gas CO2 to excellent energy storage materials, paving the way for addressing both the energy and climate issues simultaneously.

Rational design of continuous and short-range lithium ion pathways based on polydopamine-anchored metal-organic frameworks for all-solid-state electrolytes

The immerging three dimensional (3D) metal-organic framework (MOF)-reinforced composite solid-state electrolytes have attracted great interest because of the enhanced ionic conductivity and mechanical properties. However, the defective spatial arrangement of MOFs restricted by fabrication methodology leads to insufficient lithium ion transport in electrolytes. Herein, a 3D interconnected MOF framework tailored for all-solid-state electrolytes is rationally designed by a universal polydopamine (PDA)-engineered “double-sided tape” strategy. The PDA serves as a double-sided tape, firmly adhering on the special single-layer Nylon grid as well as offering uniform nucleation sites to anchor the metal nodes to ensure continuous growth of well-ordered MOFs. Benefiting from the Lewis acid feature of MOFs and its cage effect toward TFSI−, a fast and homogeneous lithium ion transport can be achieved through the internal channels within neighboring MOFs and the continuous MOFs/polymer interfaces both along the short-range circumferential boundary of Nylon fiber. The resultant composite electrolytes exhibit high lithium ion conductivity and prominent mechanical properties, rendering excellent cyclic stability whether used in coin or pouch cells. This work demonstrates a widely applicable “double-sided tape” strategy for controllable spatial arrangement of MOF nanoparticles on optional substrates, which provides a scalable approach to rationally construct desired lithium ion pathways within composite electrolytes.

In-situ immobilization of ZIF-67/ZIF-8 on wood biomass for degradation of methylene blue and formaldehyde

Metal-organic frameworks (MOFs) have been extensively studied for the removal of pollutants in wastewater and air. However, the existence of MOF materials in powder form with easy agglomeration and difficult separation has greatly confined their application potential. To address this challenge, ZIF-67/ZIF-8 composites were in-situ grown on wood biomass, with its porous structure providing channels for the growth of MOFs and active sites for MOFs catalysis. The structure, i.e., morphology, crystallinity and chemical components, and optical properties were characterized. The degradation efficiency of methylene blue (MB) by the ZIF-67/ZIF-8@wood composites photocatalyst was more than 85.7 % under visible light irradiation within 90 mins, reflecting the good photocatalytic activity of the composites. The ZIF-67/ZIF-8@wood composites completely adsorbed and decomposed HCHO (22.3 ppm) within 30 mins. The high catalytic performance of the ZIF-67/ZIF-8@wood composites can be attributed to the high surface area of wood that results in a high absorption of contaminants. This simple, low-cost, and green preparation method has promoted the sustainable utilization of biomass resources with great significance for practical environmental remediation.

Spray technique inspired fabrication of metal-organic framework/aerogel composite for catalytic CO2 cycloaddition

Growing metal–organic framework (MOF) on the appropriate porous matrix can effectively circumvent its poor processability and recyclability owing to its powder state by providing more exposed area and enhanced stability. A feasible and efficient spray technique was applied to prepare five kinds of MOF/aerogel composites by spraying the MOF precursor droplet sequentially onto the aerogel, including carboxylate-based MOF/aerogel composites and azolate-based MOF/aerogel composites. The sprayed precursor droplets render MOF growth concentrated on the aerogel walls with resulting continuous and homogeneous MOF film, and avoid the waste of precursor solution, which is scalable with industrial potential. MOF/aerogel composites integrates the porous nature of aerogels with excellent mass transfer property and MOF film grown on aerogel walls with more active sites, which exhibit excellent catalytic activity and stability in CO2 cycloaddition.

Cellulose nanofiber-induced metal–organic framework “armor” for the fabrication of carbon fibre composites with enhanced mechanical properties and electrical conductivity

Metal-organic frameworks (MOFs) possess significant potential in enhancing the interfacial performance of composites owing to their exceptional skeletal structures and substantial specific surface area. Herein, we prepared typical conductive MOFs (Ni-HHTP, HHTP = 2, 3, 6, 7, 10, 11-hexahydroxybenzene) at the interface by in situ synthesis using cellulose nanofibers (CNFs) assembled on the surface of carbon fibres (CFs) as precursors. CNFs can not only act as a smart cushion to promote stress release but also provide abundant oxygen-containing functional groups, such as hydroxyl and carboxyl groups, which can facilitate the growth of MOF on the surface of CFs. Furthermore, MOFs with porous structure and large specific surface area increase the interphase region for interfacial load transmission. The CF composites prepared using this strategy exhibited improvements in interlaminar shear strength (ILSS), interfacial shear strength (IFSS), flexural strength and flexural modulus by 57.9 %, 54.9 %, 35.1 % and 46.7 %, respectively. Additionally, the electrical conductivities of the composites in both thickness and in-plane directions were 1.04 × 10−4 S/cm and 7.3770 S/cm, respectively, which was attributed to the MOFs on the surface of the fibres facilitating the formation of good conductive channels between the fibres and resin. This study proposes an advanced interfacial modification approach to prepare CF composites with excellent mechanical and electrical conductivity properties.

Hierarchical two‐dimensional Ti‐MOF derived from MXene for hybrid supercapacitor electrodes

Presently, two‐dimensional (2D) metal–organic framework (MOF) are drawing increasing attention in energy‐storage areas. However, more and complexed factors would affect the nucleation and growth of 2D MOFs, and subsequently affect the final performance. Particularly, it is important to control the coordination rate between ions and ligands. In this paper, MXene was directly used as titanium source to coordinate with an organic ligand to form Ti‐MOF sheets. To further boost the performance, mesopores were introduced in preparing 2D Ti‐MOF, constructing hierarchical porous Ti‐MOF@Ti3C2TX hybrids. Results showed that diffusion‐controlled behaviors play a dominant role over surface capacitive behaviors during the charge storage process of the hierarchical porous hybrids. A hybrid supercapacitor (HSC) assembled with the obtained HP‐Ti‐MOF@Ti3C2TX and activated carbon (AC) exhibited an energy density of 22.9 Wh kg−1 at a power density of 850 W kg−1 (1 A g−1), and a power density of 4.25 kW kg−1 at an energy density of 15.3 Wh kg−1 (5 A g−1). The present strategy is expected to provide design ideas for novel energy‐storage electrode materials.

Synergistic Construction of Sub-Nanometer Channel Membranes through MOF–Polymer Composites: Strategies and Nanofiltration Applications

The selective separation of small molecules at the sub-nanometer scale has broad application prospects in the field, such as energy, catalysis, and separation. Conventional polymeric membrane materials (e.g., nanofiltration membranes) for sub-nanometer scale separations face challenges, such as inhomogeneous channel sizes and unstable pore structures. Combining polymers with metal–organic frameworks (MOFs), which possess uniform and intrinsic pore structures, may overcome this limitation. This combination has resulted in three distinct types of membranes: MOF polycrystalline membranes, mixed-matrix membranes (MMMs), and thin-film nanocomposite (TFN) membranes. However, their effectiveness is hindered by the limited regulation of the surface properties and growth of MOFs and their poor interfacial compatibility. The main issues in preparing MOF polycrystalline membranes are the uncontrollable growth of MOFs and the poor adhesion between MOFs and the substrate. Here, polymers could serve as a simple and precise tool for regulating the growth and surface functionalities of MOFs while enhancing their adhesion to the substrate. For MOF mixed-matrix membranes, the primary challenge is the poor interfacial compatibility between polymers and MOFs. Strategies for the mutual modification of MOFs and polymers to enhance their interfacial compatibility are introduced. For TFN membranes, the challenges include the difficulty in controlling the growth of the polymer selective layer and the performance limitations caused by the “trade-off” effect. MOFs can modulate the formation process of the polymer selective layer and establish transport channels within the polymer matrix to overcome the “trade-off” effect limitations. This review focuses on the mechanisms of synergistic construction of polymer–MOF membranes and their structure–nanofiltration performance relationships, which have not been sufficiently addressed in the past.

A Real-Time LSPR-Based Study of Metal-Organic Framework (MOF) Growth.

MOFs are known for their absorption properties and widely used for accumulation, filtering, sensorics, photothermal, catalytical and other applications. Their combination with plasmonic metal nanoparticles leads to hybrid structures that profit from the stabilizing effect and high porosity of the MOF as well as the optical and electronic properties of the nanoparticles. The growth of MOFs on plasmonic nanoparticles can be monitored in-situ using LSPR spectroscopy, simultaneously applying microfluidic reaction conditions for the fabrication of NP@MOF structures. Here, a systematic study is conducted using LSPR spectroscopy for the monitoring of the Layer-by-Layer deposition of twelve different MOFs, determining the suitability of LSPR spectroscopy for this purpose. In addition to some well-investigated materials like HKUST-1, other MOFs such as MIL-53, MIL-88 A and Cu-BDC are deposited successfully. For some MOFs such as Zn-Fum, the LSPR experiment indicates that no deposition had taken place. The results are confirmed with AFM, SEM and XPS measurements. This work shows that LSPR spectroscopy is suitable for the in-situ monitoring of LbL MOF growth and the microfluidic setup is a very promising method for the controlled manufacturing of NP@MOF hybrid structures. Further studies may include the optimization of the synthesis process or the transfer to other materials.

Enhancement of oxygen evolution reaction by in situ growth PMo12@ZIF-67 on MWCNTs via perylene bisimide-based dispersant

The combination of metal organic frameworks (MOFs) and multi-walled carbon nanotubes (MWCNTs) can significantly improve their electrochemical performance. However, in most cases, chemical pre-treatment of MWCNTs is inevitable, which may compromise the ideal performance of the final composites. Herein, via a noncovalent functionalization method, PMo12@ZIF-67 was in situ grown on the surfaces of MWCNTs with the assistance of a new dispersant containing two triethylenetetramine (TETA) segments. In order to enhance the coordination of Co metal ions with the surface of MWCNTs, phenolic hydroxyl groups were incorporated into the dispersant through reaction with gallic acid (GA). After annealing, homogeneous CNT/Co6Mo6C2/Co composites were obtained, and they showed excellent performance on oxygen evolution reaction (OER). At a current density of 10 mA cm−2, the lowest overpotential is 263 mV, of which the performance is superior to that achieved by other in situ growth methods. The uniform distribution of coordination sites and subsequent in situ growth of MOFs on MWCNTs improved the electrical conductivity of the derivatives, thereby enhanced the utilization of catalytic active sites. This study presents a novel approach for synthesizing carbon-doped electrocatalytic materials, which demonstrates significant potential in various electrochemical applications.

Layer-by-layer growth of Cu3(HHTP)2 films on Cu(OH)2 nanowire arrays for high performance ascorbic acid sensing

Growing three-dimensional (3D) metal organic frameworks (MOFs) via heterogeneous epitaxial growth on metal hydroxide arrays are effective for constructing electrochemical sensor. However, the growth of MOFs is difficult to control, resulting in thick and irregular morphologies and even damage the metal hydroxide template. In this work, Cu3(HHTP)2 (HHTP = 2, 3, 6, 7, 10, 11-hexahydroxytriphenylene) films with controllable thickness and morphology were successfully prepared on Cu(OH)2 nanowire arrays (NWAs) through layer-by-layer (LBL) growth method. We have discovered that the LBL cycle and the reaction solvent composition are crucial for growing homogenous MOF thin films. The Cu3(HHTP)2 based ascorbic acid (AA) sensor, fabricated in ethanol within 10 LBL cycles, generated an ultrahigh sensitivity of 821.64 μA mM−1 cm−2 in the range of 6–981.41 μM, a low detection limit of 60 nM as well as the great selectivity, stability and reproducibility. Moreover, the relative deviation for AA detection in two fruit juices were 3.22 % and 3.71 %, and the test result for human sweat fall within the normal AA concentration range, verifying the feasibility of as-prepared sensor for practical application.

Protein–polyphenol nanoassemblies modulated construction of zeolitic imidazole framework-67 based nanofiltration membrane for effective separation of dye/salt mixtures

Metal–organic frameworks (MOFs) show great potential in various separation applications. However, fast nucleation rate and crystallization of MOFs, produce non-uniform and uncontrollable sized crystals, which are not suitable for the formation of MOF-based membranes. Herein, we propose the concept of utilizing protein polyphenol nanoassemblies (PPNs) as the building blocks for the confined growth of MOFs to fabricate zeolitic imidazolate frameworks (ZIF-67)-based membranes. We first demonstrated that colloidal PPNs as modulators in solution enables the formation of ZIF-67 MOFs with uniform and controllable crystal sizes. Subsequently, we utilized the metal salt coordinated PPNs (Co2+@PPN) as the precursor layer matrix deposited on porous polymeric support to fabricate ZIF-67 membranes via in-situ growth strategy at room temperature. The resultant membrane features a robust heterogeneous and well-integrated ZIF-67-reinforced PPN (ZIF-67@PPN) microporous networks. Benefiting from the rigid and multidimensional micropores of ZIF-67, the optimized ZIF-67@PPN1 composite membrane with improved water stability exhibited good water permeance (45.68 L m−2 h−1 bar−1), excellent dye desalination performance (Na2SO4/Congo red selectivity of 1271.47), and good antibiotic desalination performance (NaCl/Erythromycin selectivity of 21.46). The findings in this work provide important engineering concepts for the development of MOF-based membranes using sustainable nature-derived building blocks for emergent environment-relevant desalination applications in the chemical process industry.

Locally controlled MOF growth on functionalized carbon nanotubes

Metal-organic frameworks (MOFs) are highly versatile materials because of their tunable properties. However, the typically poor electrical conductivity of MOFs presents challenges for their integration into electrical devices. By adding carbon nanotubes to MOF synthesis, a highly intergrown material with increased conductivity and chemiresistive sensing properties can be obtained. Here, we present a patterning technique to control MOF growth on predefined areas of one particular carbon nanotube. We found that electron beam pretreatment of -COOH functionalized multi-walled carbon nanotubes inhibits the growth of UiO-66 MOF on these multi-walled carbon nanotubes. By irradiating individual multi-walled carbon nanotubes, we show that MOF growth can be inhibited in predefined tube areas, creating MOF-free spaces on the nanotube. In this way, our method shows a possibility to pattern MOF growth on individual nanotubes.

Universal Strategy for Metal-Organic Framework Growth: From Cascading-Functional Films to MOF-on-MOFs.

Transformation of metal-organic framework (MOF) particles into thin films is urgently needed for the persistent development of well-applicable devices, and recently emerging functional-integrated hybrid frameworks. Although some flexible polymers and exclusive modification approaches have been proposed, the additive-free and widely applicable strategy has not been reported, hampering the deep investigation of the structure-performance relationship. A universal strategy for the in situ growth of large-area and continuous MOF films with controllable microstructures is introduced, through the modification of multi-scale and multi-structure substrates with poly(4-vinylpyridine) as the anchor to capture metal ions via Coulomb attraction. Based on the clarified structure-adsorption-separation mechanisms, the customized devices fabricated by in situ growth can achieve highly selective adsorption and excellently synergetic separation of various industrially relevant isomers. In addition, this strategy is also feasible for the construction of MOF-on-MOFs with varied lattice parameters. This strategy is easy to implement and will be widely applicable to the surface growth of diverse MOFs on desired substrates, and provides a new concept for developing hybrid MOFs integrating with customized functionalities.

In Situ Growth of MOF from Wood Aerogel toward Bromide Ion Adsorption in Simulated Saline Water.

Utilizing metal-organic framework (MOF) materials for the extraction of bromide ions (Br-) from aqueous solutions, as an alternative to chlorine gas oxidation technology, holds promising potential for future applications. However, the limitations of powdered MOFs, such as low utilization efficiency, ease of aggregation in water, and challenging recovery processes, have hindered their practical application. Shaping MOF materials into application-oriented forms represents an effective but challenging approach to address these drawbacks. In this work, a novel Ag-UiO-66-(OH)2@delignified wood cellulose aerogel (CA) adsorbent is synthesized using an oil bath impregnation method, involving the deposition of UiO-66-(OH)2 nanoparticles onto CA and the uniform dispersion of Ag0 nanoparticles across its surface. CA, characterized by the intertwined cellulose nanofiber structure and a highly hydrophilic surface, serves as an ideal substrate for the uniform growth of UiO-66-(OH)2 nanoparticles, which, in turn, spontaneously reduce Ag+ to form distributed Ag0 nanoparticles due to the abundant hydroxyl groups provided. Leveraging the well-defined biological structure of CA, which offers excellent mass transfer channels, and the highly dispersed Ag adsorption sites, Ag-UiO-(OH)2/CA exhibits remarkable adsorption capacity (642 mg/gAg) under optimized conditions. Furthermore, an integrated device is constructed by interconnecting Ag-UiO-(OH)2/CA adsorbents in series, affirming its potential application in the continuous recovery of Br-. This study not only presents an efficient Ag-UiO-(OH)2/CA adsorbent for Br- recovery but also sheds light on the extraction of other valuable elements from various liquid ores.

New insight into the effect of layer-by-layer & in-situ growth of MOF on alginate vs preformed MOF mixed alginate composites on dye adsorption

Over the past years, the processing of metal–organic frameworks (MOFs) into body-shaped materials has received remarkable research interest to overcome the difficulties of using MOFs in powder form for advanced applications. In this work, shaped MOF-biopolymer composites are prepared from Iron (Fe), trimesic acid (BTC) for the MOF named Fe-BTC and sodium alginate as biopolymer using different strategies including the conventional mixed phases, the in-situ growth and layer-by-layer synthetic strategies to highlight the role of each method for the accessibility of active sites and determine which one is better for the adsorption capability. The obtained samples were characterized to reveal the interaction between the biopolymer and the MOF and subsequently tested for methylene blue dye adsorption to elucidate the effect of each strategy on the adsorption performance. The results indicated that the layer-by-layer synthetic strategy showed better accessibility for the active sites and thus an enhanced adsorption performance of the dye achieving 88.779 mg/g, surpassing the efficiency of the other strategies.

In situ growth of a redox-active metal-organic framework on electrospun carbon nanofibers as a free-standing electrode for flexible energy storage devices.

The rational construction of free-standing and flexible electrodes for application in electrochemical energy storage devices and next-generation supercapacitors is an emerging research focus. Herein, we prepared a redox-active ferrocene dicarboxylic acid (Fc)-based nickel metal-organic framework (MOF) on electrospun carbon nanofibers (NiFc-MOF@CNFs) via an in situ approach. This in situ approach avoided the aggregation of the MOF. The NiFc-MOF@CNF flexible electrode showed a high redox-active behavior owing to the presence of ferrocene and flexible carbon nanofibers, which led to unique properties, including high flexibility and lightweight. Furthermore, the prepared electrode was utilized in a supercapacitors (SC) without the use of any binder, which achieved a specific capacity of 460 C g-1 at 1 A g-1 with an excellent cyclic retention of 82.2% after 25 000 cycles and a good rate capability. A flexible asymmetric supercapacitor device was assembled, which delivered a high energy density of 56.25 W h kg-1 and a long-lasting cycling performance. Also, the prepared electrode could be used as a freestanding electrode in flexible devices at different bending angles. The obtained cyclic voltammetry curves showed negligible changes, indicating the high stability and good flexibility of the electrode. Thus, the use of the in situ strategy can lead to the uniform growth of redox-active MOFs or other porous materials on CNFs.

Improved optical quality of heteroepitaxially grown metal-organic framework thin films by modulating the crystal growth.

Fabricating high-quality thin films of metal-organic frameworks (MOFs) is important for integrating MOFs in various applications. Specifically, optical/electrical devices require MOF thin films that are crystallographically oriented, with closely packed crystals and smooth surfaces. Although the heteroepitaxial growth approach of MOFs on metal hydroxides has been demonstrated to control the orientation of the three crystallographic axes, the fabrication of MOF thin films with both three-dimensional crystallographic orientation and smooth surfaces remains a challenge. In this study, we report the fabrication of high-quality thin films of MOFs with closely packed MOF crystals, smooth surfaces, optical transparency, and crystal alignment by modulating the crystal growth of MOFs using the heteroepitaxial growth approach. High-quality thin films of Cu-paddlewheel-based pillar-layered MOFs are fabricated on oriented Cu(OH)2 thin films via epitaxial growth using acetate ions as modulators to control the crystal morphology. Increasing the modulator concentration results in a uniform crystal shape with a relatively long one-dimensional pore direction and uniform heterogeneous nucleation over the entire film. The MOF thin films fabricated using the modulator exhibit high optical transparency. High-quality MOF thin films with dense and flat surfaces will pave the way for integrating MOFs into sophisticated optical and electrical devices.