Electrocatalysts Derived from Metal–Organic Frameworks for Oxygen Reduction and Evolution Reactions in Aqueous Media

Electrochemical energy conversion and storage devices such as fuel cells and metal–air batteries have been extensively studied in recent decades for their excellent conversion efficiency, high energy capacity, and low environmental impact. However, sluggish kinetics of the oxygen‐related reactions at air cathodes, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), are still worth improving. Noble metals such as platinum (Pt), iridium (Ir), ruthenium (Ru) and their oxides are considered as the benchmark ORR and OER electrocatalysts, but they are expensive and prone to be poisoned due to the fuel crossover effect, and may suffer from agglomeration and leaching after long‐term usage. To mitigate these limits, it is highly desirable to design alternative ORR/OER electrocatalysts with prominent performance. Metal–organic frameworks (MOFs) are a class of porous crystalline materials consisting metal ions/clusters coordinated by organic ligands. Their crystalline structure, tunable pore size and high surface area afford them wide opportunities as catalytic materials. This Review covers MOF‐derived ORR/OER catalysts in electrochemical energy conversion, with a focus on the different strategies of material design and preparation, such as composition control and nanostructure fabrication, to improve the activity and durability of MOF‐derived electrocatalysts.     

MOF-derived ZnO and ZnO@C composites with high photocatalytic activity and adsorption capacity

Nanostructured ZnO materials have unique and highly attractive properties and have inspired interest in their research and development. This paper presents a facile method for the preparation of novel ZnO-based nanostructured architectures using a metal organic framework (MOF) as a precursor. In this approach, ZnO nanoparticles and ZnO@C hybrid composites were produced under several heating and atmospheric (air or nitrogen) conditions. The resultant ZnO nanoparticles formed hierarchical aggregates with a three-dimensional cubic morphology, whereas ZnO@C hybrid composites consisted of faceted ZnO crystals embedded within a highly porous carbonaceous species, as determined by several characterization methods. The newly synthesized nanomaterials showed relatively high photocatalytic decomposition activity and significantly enhanced adsorption capacities for organic pollutants.     

A New Architecture for Fibrous Organic Transistors Based on a Double‐Stranded Assembly of Electrode Microfibers for Electronic Textile Applications

Herein, a unique device architecture is proposed for fibrous organic transistors based on a double‐stranded assembly of electrode microfibers for electronic textile applications. A key feature of this work is that the semiconductor channel of the fiber transistor comprises a twist assembly of the source and drain electrode microfibers that are coated by an organic semiconductor. This architecture not only allows the channel dimension of the device to be readily controlled by varying the thickness of the semiconductor layer and the twisted length of the two electrode microfibers, but also passivates the device without affecting interconnections with other electrical components. It is found that the control of crystalline nanostructure of the semiconductor layer is critical for improving both the production yield of the device and the charge‐carrier transport in the device. The resulting fibrous organic transistors show a high output current of over ?5 mA at a low operation voltage of ?1.3 V and a good on/off current ratio of 10⁵. The device performance is maintained after repeated bending deformation and washing with a strong detergent solution. Application of the fibrous organic transistors to switch current‐driven LED devices and detection of electrocardiography signals from a human body are demonstrated.     

Graphite nanoplatelets/multiwalled carbon nanotubes hybrid nanostructure for electrochemical capacitor

Recently, the focus on carbon based nanostructures for various applications has been due to their novel properties such as high electrical conductivity, high mechanical strength and high surface area. In the present work, we have investigated the charge storage capacity of modified graphite nanoplatelets and hybrid structure of graphite nanoplatelets-multiwalled carbon nanotubes (MWNTs). These MWNTs can be used as spacers to reduce the possibility of restacking of graphite nanoplatelets and hence increases the surface area of the hybrid carbon nanostructure thereby high degree of metal oxide decoration is achieved over the hybrid structure. MWNTs were prepared by catalytic chemical vapor deposition technique and further purified with air oxidation and acid treatment. Graphite was treated with conc. nitric acid and sulphuric acid in the volumetric ratio of 1:3 for 3 days and these modified graphite nanoplatelets were further stirred with MWNTs in equal weight ratio to form hybrid nanostructure. Further, ruthenium oxide (RuO2) nanoparticles were decorated on this hybrid structure using chemical route followed by calcination. RuO2 decorated hybrid carbon nanostructure was characterized by using X-ray diffraction, Electron microscopy and Raman spectroscopy. The performance of the hybrid structure based nanocomposite as electrochemical capacitor electrodes was analyzed by studing its capacitive and charge-discharge behaviours using cyclic voltammetry and chronopotentiometry techniques and the results have been discussed.     

Multiple Bio-Actives Loaded Gellan Gum Microfibers from Microfluidics for Wound Healing

Wound healing, known as a fundamental healthcare issue worldwide, has been attracting great attention from researchers. Here, novel bioactive gellan gum microfibers loaded with antibacterial peptides (ABPs) and vascular endothelial growth factor (VEGF) are proposed for wound healing by using microfluidic spinning. Benefitting from the high controllability of microfluidics, bioactive microfibers with uniform morphologies are obtained. The loaded ABPs are demonstrated to effectively act on bacteria at the wound site, reducing the risk of bacterial infection. Besides, sustained release of VEGF from microfibers helps to accelerate angiogenesis and further promote wound healing. The practical value of woven bioactive microfibers is demonstrated via animal experiments, where the wound healing process is greatly facilitated because of the excellent circulation of air and nutritious substances. Featured with the above properties, it is believed that the novel bioactive gellan gum microfibers would have a remarkable effect in the field of biomedical application, especially in promoting wound healing.     

Crack growth resistance of hybrid fiber reinforced cement composites

Crack propagation in cement-based matrices carrying hybrid fiber reinforcement was studied using contoured double cantilever beam (CDCB) specimens. Influence of fiber type and combination was quantified using crack growth resistance curves. It was demonstrated that a hybrid combination of steel and polypropylene fibers enhances the resistance to both nucleation and growth of cracks, and that such fundamental fracture tests are very useful in developing high performance hybrid fiber composites. The influence of number of variables which would otherwise have remained obscured in normal tests for engineering properties become apparent in the fracture tests. The paper emphasizes the desired durability characteristics of these composites and discusses their current and future applications.     

Metal-organic framework-derived Mg-Zn hybrid nanocatalyst for biodiesel production

Controlled synthesis of metal–organic framework (MOF)-derived Mg-Zn hybrid nanostructure was demonstrated for the development of basic catalysts applied in biodiesel production from soybean oil. Two types of Mg-Zn hybrid nanostructures were successfully fabricated under different atmospheres (Ar, air), (1) MgO nanoparticles encapsulated in Zn-based MOF (MgO@Zn-MOF) and (2) MgO nanoparticles uniformly decorated on ZnO nanoparticles derived from Zn-MOF (MgO@ZnO), respectively. Ultrafine MgO nanoparticles (<5 nm for MgO@Zn-MOF and ≈10 nm for MgO@ZnO) were successfully synthesized and homogeneously dispersed in the MOF-derived Mg-Zn hybrid nanostructures. Significant increases in the specific surface area (i.e., a maximum of 1048.5 m²/g) and corresponding basicity (i.e., by a maximum of 2.1 times) were achievable by using MOF-based strategy comparing to the Mg-Zn catalyst prepared by a conventional solution-based approach. High 3-cycle stability and high yields of fatty acid methyl esters at a stoichiometric feed ratio 3 were both achievable, 67.6% and 73.3%, by using MgO@Zn-MOF and MgO@ZnO as the catalysts, respectively. The work demonstrates a prototype study of utilizing MOF to develop high-performance basic nanocatalysts through fundamental understanding of material synthesis by design versus their corresponding activities.     

Anion‐Sorbent Composite Separators for High‐Rate Lithium‐Ion Batteries

Novel composite separators containing metal–organic‐framework (MOF) particles and poly(vinyl alcohol) are fabricated by the electrospinning process. The MOF particles containing opened metal sites can spontaneously adsorb anions while allowing effective transport of lithium ions in the electrolyte, leading to dramatically improved lithium‐ion transference number t_Li⁺ (up to 0.79) and lithium‐ion conductivity. Meanwhile, the incorporation of the MOF particles alleviates the decomposition of the electrolyte, enhances the electrode reaction kinetics, and reduces the interface resistance between the electrolyte and the electrodes. Implementation of such composite separators in conventional lithium‐ion batteries leads to significantly improved rate capability and cycling durability, offering a new prospective toward high‐performance lithium‐ion batteries.     

Metal organic framework (MOF) in aqueous energy devices

Aqueous energy devices are under the spotlight of current research due to their safety, low cost and ease of handling. Metal-organic frameworks (MOFs) and their derivatives have spurred extensive exploration as they provide a library of new electrode materials. The rich and structural flexibilities (such as metal nodes, ligands, pore structure) endow MOFs and MOFs-derivatives with vast opportunities for various energy devices. In this review, we discuss the correlation between MOF structural parameters and electrochemical performance for aqueous energy devices in the scope of zinc-based batteries (Zn-ion, Zn-alkaline and Zn-air batteries), potassium-ion batteries and supercapacitors. For each energy device, the effect of determinative factors and structural modulating strategies of MOFs and derivatives are highlighted. Finally, we summarize the challenges and provide our perspective about MOFs and derivatives for future aqueous energy devices.     

Foldable Electrode Architectures Based on Silver‐Nanowire‐Wound or Carbon‐Nanotube‐Webbed Micrometer‐Scale Fibers of Polyethylene Terephthalate Mats for Flexible Lithium‐Ion Batteries

A crumply and highly flexible lithium‐ion battery is realized by using microfiber mat electrodes in which the microfibers are wound or webbed with conductive nanowires. This electrode architecture guarantees extraordinary mechanical durability without any increase in resistance after folding 1000 times. Its areal energy density is easily controllable by the number of folded stacks of a piece of the electrode mat. Deformable lithium‐ion batteries of lithium iron phosphate as cathode and lithium titanium oxide as anode at high areal capacity (3.2 mAh cm^?2) are successfully operated without structural failure and performance loss, even after repeated crumpling and folding during charging and discharging.     

Ni‐Fe Nitride Nanoplates on Nitrogen‐Doped Graphene as a Synergistic Catalyst for Reversible Oxygen Evolution Reaction and Rechargeable Zn‐Air Battery

Obtaining bifunctional electrocatalysts with high activity for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is a main hurdle in the application of rechargeable metal‐air batteries. Earth‐abundant 3d transition metal‐based catalysts have been developed for the OER and ORR; however, most of these are based on oxides, whose insulating nature strongly restricts their catalytic performance. This study describes a metallic Ni‐Fe nitride/nitrogen‐doped graphene hybrid in which 2D Ni‐Fe nitride nanoplates are strongly coupled with the graphene support. Electronic structure of the Ni‐Fe nitride is changed by hybridizing with the nitrogen‐doped graphene. The unique heterostructure of this hybrid catalyst results in very high OER activity with the lowest onset overpotential (150 mV) reported, and good ORR activity comparable to that for commercial Pt/C. The high activity and durability of this bifunctional catalyst are also confirmed in rechargeable zinc‐air batteries that are stable for 180 cycles with an overall overpotential of only 0.77 V at 10 mA^?2.     

Association of indigo with zeolites for improved color stabilization

The durability of an organic color and its resistance against external chemical agents and exposure to light can be significantly enhanced by hybridizing the natural dye with a mineral. In search for stable natural pigments, the present work focuses on the association of indigo blue with several zeolitic matrices (LTA zeolite, mordenite, MFI zeolite). The manufacturing of the hybrid pigment is tested under varying oxidizing conditions, using Raman and ultraviolet-visible (UV-Vis) spectrometric techniques. Blending indigo with MFI is shown to yield the most stable composite in all of our artificial indigo pigments. In the absence of defects and substituted cations such as aluminum in the framework of the MFI zeolite matrix, we show that matching the pore size with the dimensions of the guest indigo molecule is the key factor. The evidence for the high color stability of indigo@MFI opens a new path for modeling the stability of indigo in various alumino-silicate substrates such as in the historical Maya Blue pigment.     

Layer-by-layer self-assembled mesoporous PEDOT-PSS and carbon black hybrid films for platinum free dye-sensitized-solar-cell counter electrodes

A thin film of poly(3,4-ethylenedioxythiophene)-poly(4-styrenesulfonic acid) (PEDOT-PSS), which is an alternative cathodic catalyst for Pt in dye-sensitized solar cells, was prepared using the layer-by-layer self-assembly method (LbL). The film is highly adhesive to the substrate and has a controllable thickness. Therefore, the PEDOT-PSS film prepared using LbL is expected have high performance and durability as a counter electrode. Moreover, when carbon black was added to the PEDOT-PSS solution, highly mesoporous PEDOT-PSS and carbon black hybrid films were obtained. These films showed high cathodic activity. In this study, we investigated the change in morphology in the obtained film with increasing carbon black content, and the influence of the porosity and thickness on the performance of the cells. In this study, a Pt-free counter electrode with performance similar to that of Pt-based counter electrodes was successfully fabricated. The achieved efficiency of 4.71% was only a factor of 8% lower than that of the cell using conventional thermally deposited Pt on fluorine-doped tin oxide glass counter electrodes.     

In Situ Transformation of MOFs into Layered Double Hydroxide Embedded Metal Sulfides for Improved Electrocatalytic and Supercapacitive Performance

Direct adoption of metal‐organic frameworks (MOFs) as electrode materials shows impoverished electrochemical performance owing to low electrical conductivity and poor chemical stability. In this study, we demonstrate self‐templated pseudomorphic transformation of MOF into surface chemistry rich hollow framework that delivers highly reactive, durable, and universal electrochemically active energy conversion and storage functionalities. In situ pseudomorphic transformation of MOF‐derived hollow rhombic dodecahedron template and sulfurization of nickel cobalt layered double hydroxides (NiCo‐LDHs) lead to the construction of interlayered metal sulfides (NiCo‐LDH/Co₉S₈) system. The embedment of metal sulfide species (Co₉S₈) at the LDH intergalleries offers optimal interfacing of the hybrid constituent elements and materials stability. The hybrid NiCo‐LDH/Co₉S₈ system collectively presents an ideal porous structure, rich redox chemistry, and high electrical conductivity matrix. This leads to a significant enhancement in its complementary electrocatalytic hydrogen evolution and supercapacitive energy storage properties. This work establishes the potential of MOF derived scaffold for designing of novel class hybrid inorganic–organic functional materials for electrochemical applications and beyond.     

Fracture processes of hybrid fiber-reinforced mortar

Subregion Scanning Computer Vision (SSCV), a digital image based method for measuring surface deformation is used to examine the role of the fibers in the fracture process of mortars reinforced with hybrid blends of microfiber (less than 22 μm in diameter) and macrofiber (500 μm in diameter). Closely-spaced microfibers interact with cracks at the microstructural level and hamper the widening of coalesced microcracks, thus encouraging the growth of multiple cracks. The microfibers improved pre-peak mechanical performance and strength by delaying the formation of a through-specimen macrocrack. Macrofibers were most effective at bridging macrocracks and imparting ductility to the composite due to their geometry and greater length. Compared to mortar reinforced with a single fiber type, an increase in strength and toughness was seen with a blend of steel macrofibers and either steel or PVA microfibers. Finally, based on the crack topography observed, the reduction in water permeability of cracked mortar achieved with hybrid fiber-reinforcement, measured directly in a parallel study, was governed by multiple crack development.     

Stability study of nanopigment dispersions

The use of organic pigments rather than dyes for printing ink applications in aqueous systems gives an adequate response in terms of image durability. The main issue with pigments for printing applications is the low stability of their suspensions. Due to the hydrophobic character or high surface energy of the particles, they tend to aggregate into bigger particles with eventual settling. In this paper we present a study of particles size, zeta potential (ζ), absorbance and other properties of suspensions prepared with hybrid (intercalated dye-clay) pigment. A stability study was carried out by an encapsulation with anionic PSS [poly (sodium 4-styrenesulfonate)] and cationic PDADMAC [Poly (diallyldimethylammonium-chloride)] polyelectrolytes to improve the stability of the pigment particle suspensions. Preliminary studies indicate the ionic characteristic of the pigment particle, and the stability of their suspension in aqueous media can be improved by the coating with PDADMAC.     

Single Cobalt Sites Dispersed in Hierarchically Porous Nanofiber Networks for Durable and High-Power PGM-Free Cathodes in Fuel Cells

Increasing catalytic activity and durability of atomically dispersed metal–nitrogen–carbon (M–N–C) catalysts for the oxygen reduction reaction (ORR) cathode in proton-exchange-membrane fuel cells remains a grand challenge. Here, a high-power and durable Co–N–C nanofiber catalyst synthesized through electrospinning cobalt-doped zeolitic imidazolate frameworks into selected polyacrylonitrile and poly(vinylpyrrolidone) polymers is reported. The distinct porous fibrous morphology and hierarchical structures play a vital role in boosting electrode performance by exposing more accessible active sites, providing facile electron conductivity, and facilitating the mass transport of reactant. The enhanced intrinsic activity is attributed to the extra graphitic N dopants surrounding the CoN₄ moieties. The highly graphitized carbon matrix in the catalyst is beneficial for enhancing the carbon corrosion resistance, thereby promoting catalyst stability. The unique nanoscale X-ray computed tomography verifies the well-distributed ionomer coverage throughout the fibrous carbon network in the catalyst. The membrane electrode assembly achieves a power density of 0.40 W cm⁻² in a practical H₂/air cell (1.0 bar) and demonstrates significantly enhanced durability under accelerated stability tests. The combination of the intrinsic activity and stability of single Co sites, along with unique catalyst architecture, provide new insight into designing efficient PGM-free electrodes with improved performance and durability.     

Highly Adsorptive,MOF‐Functionalized Nonwoven Fiber Mats for Hazardous Gas Capture Enabled by Atomic Layer Deposition

While metal‐organic frameworks (MOFs) show great potential for gas adsorption and storage, their powder form limits deployment opportunities. Integration of MOFs on polymeric fibrous scaffolds will enable new applications in gas adsorption, membrane separation, catalysis, and toxic gas sensing. Here, we demonstrate a new synthesis route for growing MOFs on fibrous materials that achieves high MOF loadings, large surface areas and high adsorptive capacities. We find that a nanoscale coating of Al₂O₃ formed by atomic layer deposition (ALD) on the surface of nonwoven fiber mats facilitates nucleation of MOFs on the fibers throughout the mat. Functionality of MOFs is fully maintained after integration, and MOF crystals are well attached to the fibers. Breakthrough tests for HKUST‐1 MOFs [Cu₃(BTC)₂] on ALD‐coated polypropylene fibers reveal NH₃ dynamic loadings up to 5.93 ± 0.20 mol/kg_(MOF+fiber). Most importantly, this synthetic approach is generally applicable to a wide range of polymer fibers (e.g., PP, PET, cotton) and MOFs (e.g., HKUST‐1, MOF‐74, and UiO‐66).     

Spider-Web-Inspired PM0.3 Filters Based on Self-Sustained Electrostatic Nanostructured Networks

Particulate matter (PM) pollution has become a serious public health issue, especially with outbreaks of emerging infectious diseases. However, most present filters are bulky, opaque, and show low-efficiency PM_0.3/pathogen interception and inevitable trade-off between PM removal and air permeability. Here, a unique electrospraying–netting technique is used to create spider-web-inspired network generator (SWING) air filters. Manipulation of the dynamic of the Taylor cone and phase separation of its ejected droplets enable the generation of 2D self-charging nanostructured networks on a large scale. The resultant SWING filters show exceptional long-range electrostatic property driven by aeolian vibration, enabling self-sustained PM adhesion. Combined with their Steiner-tree-structured pores (size 200–300 nm) consisting of nanowires (diameter 12 nm), the SWING filters exhibit high efficiency (>99.995% PM_0.3 removal), low air resistance (<0.09% atmosphere pressure), high transparency (>82%), and remarkable bioprotective activity for biohazard pathogens. This work may shed light on designing new fibrous materials for environmental and energy applications.