Elevated temperature-driven coordinative reconstruction of an unsaturated single-Ni-atom structure with low valency on a polymer-derived matrix for the electrolytic oxygen evolution reaction.

A high-temperature pyrolysis-controlled coordination reconstruction resulted in a single-Ni-atom structure with a Ni-Nx-C structural unit (x = N atom coordinated to Ni). Pyrolysis of Ni-phen@ZIF-8-RF at 700 °C resulted in NiNP-NC-700 with predominantly Ni nanoparticles. Upon elevating the pyrolysis temperature from 700 to 900 °C, a coordination reconstruction offers Ni-Nx atomic sites in NiSA-NC-900. A combined investigation with X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and soft X-ray L3-edge spectroscopy suggests the stabilization of low-valent Niδ+ (0 < δ < 2) in the Ni-N-C structural units. The oxygen evolution reaction (OER) is a key process during water splitting in fuel cells. However, OER is a thermodynamically uphill reaction with multi-step proton-coupled electron transfer and sluggish kinetics, due to which there is a need for a catalyst that can lower the OER overpotentials. The adsorption energy of a multi-step reaction on a single metal atom with coordination unsaturation tunes the adsorption of each oxygenated intermediate. The promising OER activity of the NiSA-NC-900/NF anode on nickel foam was followed by the overall water splitting (OWS) using using NiSA-NC-900/NF as anode and Pt coil as the cathodic counterpart, wherein a cell potential of 1.75 V at 10 mA cm-2 was achieved. The cell potential recorded with Pt(-)/(+)NiSA-NC-900/NF was much lower than that obtained for other cells, i.e., Pt(-)/NF and NF(-)/(+)NF, which enhances the potentials of low-valent NiSAs for insightful understanding of the OER. At a constant applied potential of 1.61 V (vs. RHE) for 12 h, an small increase in current for initial 0.6 h followed by a constant current depicts the fair stability of catalyst for 12 h. Our results offer an insightful angle into the OER with a coordinatively reconstructed single-Ni-atom structure at lower valency (<+2).

Metal-organic framework derived inverse opal type 3D graphitic carbon for highly stable lithium-ion batteries.

Graphitic carbon-based anodes for lithium-ion batteries have seen remarkable development and commercial acceptance during the past three decades. Still, the performance of these materials is limited due to the low surface area, stacking of layers, poor porosity, and meager conductivity. To overcome these limitations, we propose using polystyrene as a core and small-sized zeolitic imidazolate framework-67 (ZIF-67) particles as decorators to develop a highly porous three-dimensional graphitic carbon material. The developed material is optimized with the carbonization temperature for the best anodic performance of LIBs. The pyridinic nitrogen content in the material carbonized at 700 °C makes it high performing and more stable than the samples treated at 600, 800, and 900 °C. The packed coin cell exhibited an initial discharge capacity of 775 mA h g-1 at a current density of 50 mA g-1, which increases to 806 mA h g-1 after testing the material at different current densities for 55 cycles. The packed half-cell exhibited a highly stable performance of about 96% even after testing for 2000 cycles at 1 A g-1.

Ionic-Liquid-Assisted Synthesis of Mixed-Phase Manganese Oxide Nanorods for a High-Performance Aqueous Zinc-Ion Battery.

Aqueous zinc-ion batteries (ZIBs) provide a safer and cost-effective energy storage solution by utilizing nonflammable water-based electrolytes. Although many research efforts are focused on optimizing zinc anode materials, developing suitable cathode materials is still challenging. In this study, one-dimensional, mixed-phase MnO2 nanorods are synthesized using ionic liquid (IL). Here, the IL acts as a structure-directing agent that modifies MnO2 morphology and introduces mixed phases, as confirmed by morphological, structural, and X-ray photoelectron spectroscopy (XPS) studies. The MnO2 nanorods developed by this method are utilized as a cathode material for ZIB application in the coin-cell configuration. As expected, Zn//MnO2 nanorods show a significant increase in their capacity to 347 Wh kg-1 at 100 mA g-1, which is better than bare MnO2 nanowires (207.1 Wh kg-1) synthesized by the chemical precipitation method. The battery is highly rechargeable and maintains good retention of 86% of the initial capacity and 99% Coulombic efficiency after 800 cycles at 1000 mA g-1. The ex situ XPS, X-ray diffraction, and in-depth electrochemical analysis confirm that MnO6 octahedra experience insertion/extraction of Zn2+ with high reversibility. This study suggests the potential use of MnO2 nanorods to develop high-performance and durable battery electrode materials suitable for large-scale applications.

Block copolymer-assisted synthesis of VO2 (B) microflowers for supercapacitor applications.

Nanoporous metal oxides are appealing candidates for energy storage applications as they can interact with guest species from inner and outer surfaces, leading to improved energy and power density performance. We have synthesized VO2 (B) microflowers with a stable phase and tailored porous structures utilizing block copolymers to achieve excellent supercapacitor performance.

High Stability and Long Cycle Life of Rechargeable Sodium-Ion Battery Using Manganese Oxide Cathode: A Combined Density Functional Theory (DFT) and Experimental Study.

Sodium-ion batteries (SIBs) can develop cost-effective and safe energy storage technology for substantial energy storage demands. In this work, we have developed manganese oxide (α-MnO2) nanorods for SIB applications. The crystal structure, which is crucial for high-performance energy storage, is examined systematically for the metal oxide cathode. The intercalation of sodium into the α-MnO2 matrix was studied using the theoretical density functional theory (DFT) studies. The DFT studies predict Na ions' facile diffusion kinetics through the MnO2 lattice with an attractively low diffusion barrier (0.21 eV). When employed as a cathode material for SIBs, MnO2 showed a moderate capacity (109 mAh·g-1 at C/20 current rate) and superior life cyclability (58.6% after 800 cycles) in NaPF6/EC+DMC (5% FEC) electrolyte. It shows a much higher capacity of 181 mAh·g-1 (C/20 current rate) in NaClO4/PC (5% FEC) electrolyte, though it suffers fast capacity fading (11.5% after 800 cycles). Our findings show that high crystallinity and hierarchical nanorod morphology of the MnO2 are responsible for better cycling performance in conjunction with fast and sustained charge-discharge behaviors.

Significant Effect of Pore Sizes on Energy Storage in Nanoporous Carbon Supercapacitors.

Mesoporous carbon can be synthesized with good control of surface area, pore-size distribution, and porous architecture. Although the relationship between porosity and supercapacitor performance is well known, there are no thorough reports that compare the performance of numerous types of carbon samples side by side. In this manuscript, we describe the performance of 13 porous carbon samples in supercapacitor devices. We suggest that there is a "critical pore size" at which guest molecules can pass through the pores effectively. In this context, the specific surface area (SSA) and pore-size distribution (PSD) are used to show the point at which the pore size crosses the threshold of critical size. These measurements provide a guide for the development of new kinds of carbon materials for supercapacitor devices.

Periodically Arranged Arrays of Dendritic Pt Nanospheres Using Cage-Type Mesoporous Silica as a Hard Template.

Dendritic Pt nanospheres of 20 nm diameter are synthesized by using a highly concentrated surfactant assembly within the large-sized cage-type mesopores of mesoporous silica (LP-FDU-12). After diluting the surfactant solution with ethanol, the lower viscosity leads to an improved penetration inside the mesopores. After Pt deposition followed by template removal, the arrangement of the Pt nanospheres is a replication from that of the mesopores in the original LP-FDU-12 template. Although it is well known that ordered LLCs can form on flat substrates, the confined space inside the mesopores hinders surfactant self-organization. Therefore, the Pt nanospheres possess a dendritic porous structure over the entire area. The distortion observed in some nanospheres is attributed to the close proximity existing between neighboring cage-type mesopores. This new type of nanoporous metal with a hierarchical architecture holds potential to enhance substance diffusivity/accessibility for further improvement of catalytic activity.

Porous nanozymes: the peroxidase-mimetic activity of mesoporous iron oxide for the colorimetric and electrochemical detection of global DNA methylation.

Nanomaterials (nanozymes) with peroxidase-mimetic activity have been widely used in biosensing platforms as low-cost, relatively stable and prevailing alternatives to natural enzymes. Herein, we report on the synthesis and application of the peroxidase-mimetic activity of mesoporous iron oxide (MIO) for the detection of global DNA methylation in colorectal cancer cell lines. The target DNA was extracted and denatured to get ssDNA followed by direct adsorption onto the surface of a bare screen-printed gold electrode (SPGE). A 5-methylcytosine antibody (5mC) functionalized nanomaterial (MIO-5mC) was then used to recognise the methylcytosine groups present on the SPGE. The MIO-5mC conjugates catalyse the TMB solution in the presence of hydrogen peroxide to give the colorimetric (i.e., naked-eye observation) and electrochemical detection of DNA methylation. The assay could successfully detect as low as 10% difference in the global DNA methylation level in synthetic samples and cell lines with good reproducibility and specificity (%RSD = <5%, for n = 3). This strategy avoids the use of natural enzyme horseradish peroxidase (HRP), traditional PCR based amplification and bisulfite treatment steps that are generally used in many conventional DNA methylation assays. We envisage that our assay could be a low-cost platform with great potential for genome-wide DNA methylation analysis in point-of-care applications.

Synthesis of MOF-525 Derived Nanoporous Carbons with Different Particle Sizes for Supercapacitor Application.

Nanoporous carbon (NC) materials have attracted great research interest for supercapacitor applications, because of their excellent electrochemical and mechanical stability, good electrical conductivity, and high surface area. Although there are many reports on metal-organic framework (MOF)-derived carbon materials, previous synthetic studies have been hindered by imperfect control of particle sizes and shapes. Here, we show precise control of the particle sizes of MOF-525 from 100 nm to 750 nm. After conversion of MOF-525 to NC, the effects of variation of the particle size on the electrochemical performance have been carefully investigated. The results demonstrate that our NC is a potential candidate for practical supercapacitor applications.

Correction: Zeolitic imidazolate framework (ZIF-8) derived nanoporous carbon: the effect of carbonization temperature on the supercapacitor performance in an aqueous electrolyte.

Correction for 'Zeolitic imidazolate framework (ZIF-8) derived nanoporous carbon: the effect of carbonization temperature on the supercapacitor performance in an aqueous electrolyte' by Christine Young et al., Phys. Chem. Chem. Phys., 2016, 18, 29308-29315.

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.

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.

Nanoarchitectures for Metal-Organic Framework-Derived Nanoporous Carbons toward Supercapacitor Applications.

The future advances of supercapacitors depend on the development of novel carbon materials with optimized porous structures, high surface area, high conductivity, and high electrochemical stability. Traditionally, nanoporous carbons (NPCs) have been prepared by a variety of methods, such as templated synthesis, carbonization of polymer precursors, physical and chemical activation, etc. Inorganic solid materials such as mesoporous silica and zeolites have been successfully utilized as templates to prepare NPCs. However, the hard-templating methods typically involve several synthetic steps, such as preparation of the original templates, formation of carbon frameworks, and removal of the original templates. Therefore, these methods are not favorable for large-scale production. Metal-organic frameworks (MOFs) with high surface areas and large pore volumes have been studied over the years, and recently, enormous efforts have been made to utilize MOFs for electrochemical applications. However, their low conductivity and poor stability still present major challenges toward their practical applications in supercapacitors. MOFs can be used as precursors for the preparation of NPCs with high porosity. Their parent MOFs can be prepared with endless combinations of organic and inorganic constituents by simple coordination chemistry, and it is possible to control their porous architectures, pore volumes, surface areas, etc. These unique properties of MOF-derived NPCs make them highly attractive for many technological applications. Compared with carbonaceous materials prepared using conventional precursors, MOF-derived carbons have significant advantages in terms of a simple synthesis with inherent diversity affording precise control over porous architectures, pore volumes, and surface areas. In this Account, we will summarize our recent research developments on the preparation of three-dimensional (3-D) MOF-derived carbons for supercapacitor applications. This Account will be divided into three main sections: (1) useful background on carbon materials for supercapacitor applications, (2) the importance of MOF-derived carbons, and (3) potential future developments of MOF-derived carbons for supercapacitors. This Account focuses mostly on carbons derived from two types of MOFs, namely, zeolite imidazolate framework-8 (ZIF-8) and ZIF-67. By using examples from our previous works, we will show the uniqueness of these carbons for achieving high performance by control of the chemical reactions/conditions as well proper utilization in asymmetric/symmetric supercapacitor configurations. This Account will promote further developments of MOF-derived multifunctional carbon materials with controlled porous architectures for optimization of their electrochemical performance toward supercapacitor applications.

Hollow carbon nanospheres using an asymmetric triblock copolymer structure directing agent.

We introduce a simple method to prepare hollow carbon nanospheres (HCNs) by using triblock copolymer poly(styrene-b-2-vinylpyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) micelles as a new class of soft-templates. Simply by changing the solvent we can prepare ultra-small sized micelles of the triblock copolymer PS-b-P2VP-b-PEO soft template to obtain HCNs with ultra-small diameters (43 nm) and hollow cores (19 nm). Furthermore, we use these HCNs to make electric double-layer capacitors (EDLCs) that exhibit superior performance.

Correction: A high-performance supercapacitor cell based on ZIF-8-derived nanoporous carbon using an organic electrolyte.

Correction for 'A high-performance supercapacitor cell based on ZIF-8-derived nanoporous carbon using an organic electrolyte' by Rahul R. Salunkhe et al., Chem. Commun., 2016, 52, 4764-4767.

Zeolitic imidazolate framework (ZIF-8) derived nanoporous carbon: the effect of carbonization temperature on the supercapacitor performance in an aqueous electrolyte.

Nanoporous carbon materials are a versatile source of carbons that would be useful in applications ranging from electronics to electrochemical energy storage. Here, we focus on nanoporous carbon materials prepared by direct carbonization of zeolitic imidazolate frameworks (ZIF-8) towards supercapacitor applications. Several types of nanoporous carbons have been prepared by varying the applied carbonization temperature. The symmetric devices assembled using nanoporous carbon electrodes were tested for their optimal performance in the electrolyte of sulfuric acid solution. We demonstrate the effects of various factors (e.g., surface area, nitrogen content, degree of graphitization, and relative percentage of micropores) on the performance.

ZIF-8 Derived, Nitrogen-Doped Porous Electrodes of Carbon Polyhedron Particles for High-Performance Electrosorption of Salt Ions.

Three-dimensional (3-D) ZIF-8 derived carbon polyhedrons with high nitrogen (N) content, (denoted as NC-800) are synthesized for their application as high-performance electrodes in electrosorption of salt ions. The results showed a high specific capacitance of 160.8 F·g(-1) in 1 M NaCl at a scan rate of 5 mV·s(-1). Notably, integration of 3-D mesopores and micropores in NC-800 achieves an excellent capacitive deionization (CDI) performance. The electrosorption of salt ions at the electrical double layer is enhanced by N-doping at the edges of a hexagonal lattice of NC-800. As evidenced, when the initial NaCl solution concentration is 1 mM, the resultant NC-800 exhibits a remarkable CDI potential with a promising salt electrosorption capacity of 8.52 mg·g(-1).

Bimetallic Metal-Organic Frameworks for Controlled Catalytic Graphitization of Nanoporous Carbons.

Single metal-organic frameworks (MOFs), constructed from the coordination between one-fold metal ions and organic linkers, show limited functionalities when used as precursors for nanoporous carbon materials. Herein, we propose to merge the advantages of zinc and cobalt metals ions into one single MOF crystal (i.e., bimetallic MOFs). The organic linkers that coordinate with cobalt ions tend to yield graphitic carbons after carbonization, unlike those bridging with zinc ions, due to the controlled catalytic graphitization by the cobalt nanoparticles. In this work, we demonstrate a feasible method to achieve nanoporous carbon materials with tailored properties, including specific surface area, pore size distribution, degree of graphitization, and content of heteroatoms. The bimetallic-MOF-derived nanoporous carbon are systematically characterized, highlighting the importance of precisely controlling the properties of the carbon materials. This can be done by finely tuning the components in the bimetallic MOF precursors, and thus designing optimal carbon materials for specific applications.

A high-performance supercapacitor cell based on ZIF-8-derived nanoporous carbon using an organic electrolyte.

Low-cost supercapacitors have the ability to rapidly store a large amount of charge, which makes them the best alternative to batteries in portable electronics. Here, we demonstrate the fabrication of all-carbon supercapacitors using an organic electrolyte. By using ZIF-derived nanoporous carbon electrodes, we have realized a high-performance supercapacitor cell using 2 M NEt4BF4/PC as the electrolyte. Our device shows good energy storage capacity that is comparable to the other previously reported supercapacitors.

Phosphonate-Derived Nanoporous Metal Phosphates and Their Superior Energy Storage Application.

Nanoporous nickel, aluminum, and zirconium phosphates (hereafter, abbreviated as NiP, AlP, and ZrP, respectively) with high surface areas and controlled morphology and crystallinity have been synthesized through simple calcination of the corresponding phosphonates. For the preparation of phosphonate materials, nitrilotris(methylene)triphosphonic acid (NMPA) is used as phosphorus source. The organic component in the phosphonate materials is thermally removed to form nanoporous structures in the final phosphate materials. The formation mechanism of nanoporous structures, as well as the effect of applied calcination temperatures on the morphology and crystallinity of the final phosphate materials, is carefully discussed. Especially, nanoporous NiP materials have a spherical morphology with a high surface area and can have great applicability as an electrode material for supercapacitors. It has been found that there is a critical effect of particle sizes, surface areas, and the crystallinities of NiP materials toward electrochemical behavior. Our nanoporous NiP material has superior specific capacitance, as compared to various phosphate nanomaterials reported previously. Excellent retention capacity of 97% is realized even after 1000 cycles, which can be ascribed to its high structural stability.