Yusuf Valentino Kaneti

Nanoarchitectured Design of Porous Materials and Nanocomposites from Metal‐Organic Frameworks

The emergence of metal-organic frameworks (MOFs) as a new class of crystalline porous materials is attracting considerable attention in many fields such as catalysis, energy storage and conversion, sensors, and environmental remediation due to their controllable composition, structure and pore size. MOFs are versatile precursors for the preparation of various forms of nanomaterials as well as new multifunctional nanocomposites/hybrids, which exhibit superior functional properties compared to the individual components assembling the composites. This review provides an overview of recent developments achieved in the fabrication of porous MOF-derived nanostructures including carbons, metal oxides, metal chalcogenides (metal sulfides and selenides), metal carbides, metal phosphides and their composites. Finally, the challenges and future trends and prospects associated with the development of MOF-derived nanomaterials are also examined.

Dendrite‐Free, High‐Rate, Long‐Life Lithium Metal Batteries with a 3D Cross‐Linked Network Polymer Electrolyte

A 3D network gel polymer electrolyte (3D-GPE) is designed for lithium metal batteries and prepared by an initiator-free one-pot ring-opening polymerization technique. This 3D-GPE exhibits an unprecedented combination of mechanical strength, ionic conductivity, and more importantly, effective suppression of Li dendrite growth. The produced lithium-based battery presents long life, high rate, and excellent safety.

Metal-Organic Framework-Derived Nanoporous Metal Oxides toward Supercapacitor Applications: Progress and Prospects

Transition metal oxides (TMOs) have attracted significant attention for energy storage applications such as supercapacitors due to their good electrical conductivity, high electrochemical response (by providing Faradaic reactions), low manufacturing costs, and easy processability. Despite exhibiting these attractive characteristics, the practical applications of TMOs for supercapacitors are still relatively limited. This is largely due to their continuous Faradaic reactions, which can lead to major changes or destruction of their structure as well phase changes (in some cases) during cycling, leading to the degradation in their capacitive performance over time. Hence, there is an immediate need to develop new synthesis methods, which will readily provide stable porous architectures, controlled phase, as well as useful control over dimensions (1-D, 2-D, and 3-D) of the metal oxides for improving their performance in supercapacitor applications. Since its discovery in late 1990s, metal-organic frameworks (MOFs) have influenced many fields of material science. In recent years, they have gained significant attention as precursors or templates for the derivation of porous metal oxide nanostructures and nanocomposites for next-generation supercapacitor applications. Even though these materials have widespread applications and have been widely studied in terms of their structural features and synthesis, it is still not clear how these materials will play an important role in the development of the supercapacitor field. In this review, we will summarize the recent developments in the field of MOF-derived porous metal oxide nanostructures and nanocomposites for supercapacitor applications. Furthermore, the current challenges along with the future trends and prospects in the application of these materials for supercapacitors will also be discussed.

Tailored Design of Bicontinuous Gyroid Mesoporous Carbon and Nitrogen-Doped Carbon from Poly(ethylene oxide-b-caprolactone) Diblock Copolymers

Highly ordered mesoporous resol-type phenolic resin and the corresponding mesoporous carbon materials were synthesized by using poly(ethylene oxide-b-caprolactone) (PEO-b-PCL) diblock copolymer as a soft template. The self-assembled mesoporous phenolic resin was found to form only in a specific resol concentration range of 40-70 wt % due to an intriguing balance of hydrogen-bonding interactions in the resol/PEO-b-PCL mixtures. Furthermore, morphological transitions of the mesostructures from disordered to gyroid to cylindrical and finally to disordered micelle structure were observed with increasing resol concentration. By calcination under nitrogen atmosphere at 800 °C, the bicontinuous mesostructured gyroid phenolic resin could be converted to mesoporous carbon with large pore size without collapse of the original mesostructure. Furthermore, post-treatment of the mesoporous gyroid phenolic resin with melamine gave rise to N-doped mesoporous carbon with unique electronic properties for realizing high CO2 adsorption capacity (6.72 mmol g-1 at 0 °C).

Solvothermal synthesis of ZnO-decorated α-Fe2O3 nanorods with highly enhanced gas-sensing performance toward n-butanol

This paper reports a newly developed solvothermal strategy for the synthesis of ZnO-decorated α-Fe2O3 nanorods based on the reaction of α-Fe2O3 nanorods with zinc sulfate and urea in autoclaves at 180 °C. The resulting nanocomposites consist of porous α-Fe2O3 nanorods with diameters of 100–200 nm and a surface decorated with small ZnO nanoparticles (10–20 nm). The ZnO NPs are found to grow epitaxially on {110} planes of α-Fe2O3, forming an interfacial orientation relationship of (100)ZnO/(110)α-Fe2O3. The addition of ZnO is found to shift the Fe 2p peak position in the α-Fe2O3/ZnO nanocomposites to higher binding energies due to the formation of the α-Fe2O3/ZnO heterojunction interface. The gas-sensing results show that the ZnO-decorated α-Fe2O3 nanorods exhibit excellent sensitivity, selectivity, and stability toward n-butanol gas at a low optimum temperature of 225 °C. In particular, they show higher sensitivity compared to pure α-Fe2O3 (4 times higher) and ZnO nanorods (2.5 times higher), respectively, along with faster response times. The significant enhancement in sensitivity may be attributed to the chemical and electronic sensitization induced by the ZnO nanoparticles deposited on the surfaces of the α-Fe2O3 nanorods. The findings reported in this study will be useful for the design and construction of surface modified-metal oxide nanostructures with enhanced gas-sensing performance.

Spontaneous Weaving of Graphitic Carbon Networks Synthesized by Pyrolysis of ZIF-67 Crystals

Three-dimensional (3D) networks of graphitic carbon are promising materials for energy storage and conversion devices because of their high electrical conductivity, which is promoted by the good interconnection between the carbon particles. However, it is still difficult to directly synthesize such carbon networks. Herein, we report the novel synthesis of 3D graphitic carbon networks through the pyrolysis of nanosized ZIF-67 crystals. Interestingly, the unusual effect of downsizing the ZIF-67 crystals and the incorporation of catalytic Co nanoparticles was the spontaneous formation of graphitic networks. The obtained graphitic carbon networks show excellent electrochemical performance for the insertion and extraction of potassium ions.

Strategies for Improving the Functionality of Zeolitic Imidazolate Frameworks: Tailoring Nanoarchitectures for Functional Applications

Zeolitic imidazolate frameworks (ZIFs), a subclass of metal-organic frameworks (MOFs) built with tetrahedral metal ions and imidazolates, offer permanent porosity and high thermal and chemical stabilities. While ZIFs possess some attractive physical and chemical properties, it remains important to enhance their functionality for practical application. Here, an overview of the extensive strategies which have been developed to improve the functionality of ZIFs is provided, including linker modifications, functional hybridization of ZIFs via the encapsulation of guest species (such as metal and metal oxide nanoparticles and biomolecules) into ZIFs, and hybridization with polymeric matrices to form mixed matrix membranes for industrial gas and liquid separations. Furthermore, the developed strategies for achieving size and shape control of ZIF nanocrystals are considered, which are important for optimizing the textural characteristics as well as the functional performance of ZIFs and their derived materials/hybrids. Moreover, the recent trends of using ZIFs as templates for the derivation of nanoporous hybrid materials, including carbon/metal, carbon/oxide, carbon/sulfide, and carbon/phosphide hybrids, are discussed. Finally, some perspectives on the potential future research directions and applications for ZIFs and ZIF-derived materials are offered.

Carbon-Coated Gold Nanorods: A Facile Route to Biocompatible Materials for Photothermal Applications

Gold nanorods and their core-shell nanocomposites have been widely studied because of their well-defined anisotropy and unique optical properties and applications. This study demonstrates a facile hydrothermal synthesis strategy for generating carbon coating on gold nanorods (AuNRs@C) under mild conditions (<200 °C), where the carbon shell is composed of polymerized sugar molecules (glucose). The structure and composition of the produced core-shell nanocomposites were characterized using advanced microscopic and spectroscopic techniques. The functional properties, particularly the photothermal and biocompatibility properties of the produced AuNRs@C, were quantified to assess their potential in photothermal hyperthermia. These AuNRs@C were tested in vitro (under representative treatment conditions) using near-infrared (NIR) light irradiation. It was found that the AuNRs produced here exhibit exemplary heat generation capability. Temperature changes of 10.5, 9, and 8 °C for AuNRs@C were observed with carbon shell thicknesses of 10, 17, and 25 nm, respectively, at a concentration of 50 μM, after 600 s of irradiation with a laser power of 0.17 W/cm(2). In addition, the synthesized AuNRs@C also exhibit good biocompatibility toward two soft tissue sarcoma cell lines (HT1080, a fibrosarcoma; and GCT, a fibrous histiocytoma). The cell viability study shows that AuNRs@C (at a concentration of <0.1 mg/mL) core-shell particles induce significantly lower cytotoxicity on both HT1080 and GCT cell lines, as compared with cetyltrimethylammonium bromide (CTAB)-capped AuNRs. Furthermore, similar to PEG-modified AuNRs, they are also safe to both HT1080 and GCT cell lines. This biocompatibility results from a surface full of -OH or -COH groups, which are suitable for linking and are nontoxic Therefore, the AuNRs@C represent a viable alternative to PEG-coated AuNRs for facile synthesis and improved photothermal conversion. Overall, these findings open up a new class of carbon-coated nanostructures that are biocompatible and could potentially be employed in a wide range of biomedical applications.

Fabrication of an MOF-derived heteroatom-doped Co/CoO/carbon hybrid with superior sodium storage performance for sodium-ion batteries

Metal–organic frameworks (MOFs) have gained significant attention as precursors for the fabrication of porous hybrid materials due to their highly controllable composition, structure and pore size. However, at present, MOF-derived materials have rarely been investigated as anode materials for sodium-ion batteries. In this work, we report the fabrication of a Ni-doped Co/CoO/N-doped carbon (NC) hybrid using bimetallic Ni–Co-ZIF as the starting precursor. The resulting Ni-doped Co/CoO/NC hybrid is highly microporous with a high specific surface area of 552 m2 g−1. When employed as an anode material for sodium-ion batteries, the Ni-doped Co/CoO/NC hybrid exhibited both good rate performance with a high discharge capacity of 218 mA h g−1 at a high current density of 500 mA g−1 and good cycling stability, as a high discharge capacity of 218.7 mA h g−1 can be retained after 100 cycles at 500 mA g−1, corresponding to a high capacity retention of 87.5%. The excellent electrochemical performance of the Ni-doped Co/CoO/NC hybrid for SIBs may be attributed to the synergistic effects of various factors, including: (i) the presence of a carbon matrix which provides protection against aggregation and pulverization during sodiation/desodiation; (ii) the highly microporous nature along with the presence of a few mesopores which facilitates better insertion/de-insertion of Na+ ions; (iii) the Ni-doping which introduces defect sites into the atomic structure of CoO via partial substitution, thus enhancing the conductivity of the cobalt oxide (CoO) component and hence, the overall hybrid material, and (iv) the N-doping which promotes a faster migration speed of sodium ions (Na+) across the carbon layer by creating defect sites, thereby improving the conductivity of the carbon frameworks in the hybrid material.

Li-ion and Na-ion transportation and storage properties in various sized TiO2 spheres with hierarchical pores and high tap density

Titanium oxide (TiO2) has attracted great interest as a promising anode material for lithium (Li) ion batteries (LIBs) and sodium (Na) ion batteries (SIBs). However, the key factors that dictate the Li-ion and Na-ion storage and transportation in TiO2 remain unclear. Herein, we report a facile hydrolysis route to crafting a variety of high tap-density TiO2 spheres with controllable size and hierarchical pores. The Li-ion and Na-ion storage properties based on these TiO2 spheres were systematically investigated. The pore distribution and the size of TiO2 spheres were found to exert profound influence on the Li-ion and Na-ion storage and transportation. The Li-ion storage and transportation in dense TiO2 spheres was dependent mainly upon the micropore distribution and volume and independent of the size of spheres. In contrast, the excellent Na-ion storage and transportation in TiO2 spheres was enabled by the loose structure with a large macroscopic pore volume and shortened Na-ion diffusion length. High tap-density TiO2 spheres (1.06 g cm−3) with superior Li-ion and Na-ion storage properties were produced, exhibiting a Li-ion storage specific capacity of 189 mA h g−1 at 1C and a high capacity retention of 88.1% after 100 cycles, and a Na-ion storage specific capacity of 184 mA h g−1 at 1C and capacity retention of 90.5% after 200 cycles. The ability to understand the critical factors controlling the Li-ion and Na-ion storage in high tap-density TiO2 spheres enables their implementation for practical applications in Li-ion and Na-ion batteries.