Rahul R. Salunkhe

Thermal Conversion of Core–Shell Metal–Organic Frameworks: A New Method for Selectively Functionalized Nanoporous Hybrid Carbon

Core-shell structured ZIF-8@ZIF-67 crystals are well-designed and prepared through a seed-mediated growth method. After thermal treatment of ZIF-8@ZIF-67 crystals, we obtain selectively functionalized nanoporous hybrid carbon materials consisting of nitrogen-doped carbon (NC) as the cores and highly graphitic carbon (GC) as the shells. This is the first example of the integration of NC and GC in one particle at the nanometer level. Electrochemical data strongly demonstrate that this nanoporous hybrid carbon material integrates the advantageous properties of the individual NC and GC, exhibiting a distinguished specific capacitance (270 F·g(-1)) calculated from the galvanostatic charge-discharge curves at a current density of 2 A·g(-1). Our study not only bridges diverse carbon-based materials with infinite metal-organic frameworks but also opens a new avenue for artificially designed nanoarchitectures with target functionalities.

Asymmetric Supercapacitors Using 3D Nanoporous Carbon and Cobalt Oxide Electrodes Synthesized from a Single Metal–Organic Framework

Nanoporous carbon and nanoporous cobalt oxide (Co3O4) materials have been selectively prepared from a single metal-organic framework (MOF) (zeolitic imidazolate framework, ZIF-67) by optimizing the annealing conditions. The resulting ZIF-derived carbon possesses highly graphitic walls and a high specific surface area of 350 m(2)·g(-1), while the resulting ZIF-derived nanoporous Co3O4 possesses a high specific surface area of 148 m(2)·g(-1) with much less carbon content (1.7 at%). When nanoporous carbon and nanoporous Co3O4 were tested as electrode materials for supercapacitor application, they showed high capacitance values (272 and 504 F·g(-1), respectively, at a scan rate of 5 mV·s(-1)). To further demonstrate the advantages of our ZIF-derived nanoporous materials, symmetric (SSCs) and asymmetric supercapacitors (ASCs) were also fabricated using nanoporous carbon and nanoporous Co3O4 electrodes. Improved capacitance performance was successfully realized for the ASC (Co3O4//carbon), better than those of the SSCs based on nanoporous carbon and nanoporous Co3O4 materials (i.e., carbon//carbon and Co3O4//Co3O4). The developed ASC with an optimal mass loading can be operated within a wide potential window of 0.0-1.6 V, which leads to a high specific energy of 36 W·h·kg(-1). More interestingly, this ASC also exhibits excellent rate capability (with the highest specific power of 8000 W·kg(-1) at a specific energy of 15 W·h·kg(-1)) combined with long-term stability up to 2000 cycles.

Electric Double‐Layer Capacitors Based on Highly Graphitized Nanoporous Carbons Derived from ZIF‐67

Nanoporous carbons (NPCs) have large specific surface areas, good electrical and thermal conductivity, and both chemical and mechanical stability, which facilitate their use in energy storage device applications. In the present study, highly graphitized NPCs are synthesized by one-step direct carbonization of cobalt-containing zeolitic imidazolate framework-67 (ZIF-67). After chemical etching, the deposited Co content can be completely removed to prepare pure NPCs with high specific surface area, large pore volume, and intrinsic electrical conductivity (high content of sp(2) -bonded carbons). A detailed electrochemical study is performed using cyclic voltammetry and galvanostatic charge-discharge measurements. Our NPC is very promising for efficient electrodes for high-performance supercapacitor applications. A maximum specific capacitance of 238 F g(-1) is observed at a scan rate of 20 mV s(-1) . This value is very high compared to previous works on carbon-based electric double layer capacitors.

Fabrication of symmetric supercapacitors based on MOF-derived nanoporous carbons

Nanoporous carbon (NPC) materials with high specific surface area have attracted considerable attention for electrochemical energy storage applications. In the present work, we have designed novel symmetric supercapacitors based on NPC by direct carbonization of Zn-based metal–organic frameworks (MOFs) without using an additional precursor. By controlling the reaction conditions in the present study, we synthesized NPC with two different particle sizes. The effects of particle size and mass loadings on supercapacitor performance have been carefully evaluated. Our NPC materials exhibit excellent electrochemical performance with a maximum specific capacitance of 251 F g−1 in 1 M H2SO4 electrolyte. The symmetric supercapacitor studies show that these efficient electrodes have good capacitance, high stability, and good rate capability.

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.

Nanoarchitectured Graphene-Based Supercapacitors for Next-Generation Energy-Storage Applications

Tremendous development in the field of portable electronics and hybrid electric vehicles has led to urgent and increasing demand in the field of high-energy storage devices. In recent years, many research efforts have been made for the development of more efficient energy-storage devices such as supercapacitors, batteries, and fuel cells. In particular, supercapacitors have great potential to meet the demands of both high energy density and power density in many advanced technologies. For the last half decade, graphene has attracted intense research interest for electrical double-layer capacitor (EDLC) applications. The unique electronic, thermal, mechanical, and chemical characteristics of graphene, along with the intrinsic benefits of a carbon material, make it a promising candidate for supercapacitor applications. This Review focuses on recent research developments in graphene-based supercapacitors, including doped graphene, activated graphene, graphene/metal oxide composites, graphene/polymer composites, and graphene-based asymmetric supercapacitors. The challenges and prospects of graphene-based supercapacitors are also discussed.

Large‐Scale Synthesis of Reduced Graphene Oxides with Uniformly Coated Polyaniline for Supercapacitor Applications

We report an effective route for the preparation of layered reduced graphene oxide (rGO) with uniformly coated polyaniline (PANI) layers. These nanocomposites are synthesized by chemical oxidative polymerization of aniline monomer in the presence of layered rGO. SEM, TEM, X-ray photoelectron spectroscopy (XPS), FTIR, and Raman spectroscopy analysis results demonstrated that reduced graphene oxide-polyaniline (rGO-PANI) nanocomposites are successfully synthesized. Because of synergistic effects, rGO-PANI nanocomposites prepared by this approach exhibit excellent capacitive performance with a high specific capacitance of 286 F g(-1) and high cycle reversibility of 94 % after 2000 cycles.

Aligned nickel-cobalt hydroxide nanorod arrays for electrochemical pseudocapacitor applications

Nanorod arrays were grown directly on a stainless steel substrate by the chemical bath deposition method. Parallel arrays of nanorods show a specific capacitance of 456 F g−1 with an energy density of 12.8 W h kg−1. This approach provides a one-step, seedless and cost-effective route for fabricating pseudocapacitive materials in 3-D form.

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.

Direct Growth of Cobalt Hydroxide Rods on Nickel Foam and Its Application for Energy Storage

The present work reports synthesis of cobalt hydroxide (Co(OH)2) rods on nickel foam and its supercapacitor application. Hierarchical Co(OH)2 rods with length of approximately 3.5 μm and diameter of approximately 400 nm were prepared by one-step, simple, and inexpensive chemical-bath-deposition method. The direct growth of Co(OH)2 rods on the Ni foam gave three dimensional (3D) structure for easy access of electrolyte throughout material surface. Also, well-adhered interface between Co(OH)2 rods and Ni-foam surface gave better conduction channels. Detailed electrochemical study was performed by using cyclic voltammetry and galvanostatic charge/discharge measurements. The results demonstrate that Co(OH)2 rods on Ni foam are efficient electrodes for supercapacitor application.