• Energy Research

AbstractHybrid metal–organic frameworks (MOFs) demonstrate great promise as ideal electrode materials for energy‐related applications. Herein, a well‐organized interleaved composite of graphene‐like nanosheets embedded with MnO2 nanoparticles (MnO2@C‐NS) using a manganese‐based MOF and employed as a promising anode material for Li‐ion hybrid capacitor (LIHC) is engineered. This unique hybrid architecture shows intriguing electrochemical properties including high reversible specific capacity 1054 mAh g−1 (close to the theoretical capacity of MnO2, 1232 mAh g−1) at 0.1 A g−1 with remarkable rate capability and cyclic stability (90% over 1000 cycles). Such a remarkable performance may be assigned to the hierarchical porous ultrathin carbon nanosheets and tightly attached MnO2 nanoparticles, which provide structural stability and low contact resistance during repetitive lithiation/delithiation processes. Moreover, a novel LIHC is assembled using a MnO2@C‐NS anode and MOF derived ultrathin nanoporous carbon nanosheets (derived from other potassium‐based MOFs) cathode materials. The LIHC full‐cell delivers an ultrahigh specific energy of 166 Wh kg−1 at 550 W kg−1 and maintained to 49.2 Wh kg−1 even at high specific power of 3.5 kW kg−1 as well as long cycling stability (91% over 5000 cycles). This work opens new opportunities for designing advanced MOF derived electrodes for next‐generation energy storage devices.

AbstractOur dependence on finite fossil fuels and the insecure energy supply chains have stimulated intensive research for sustainable technologies. Upcycling glycerol, produced from biomass fermentation and as a biodiesel formation byproduct, can substantially contribute in circular carbon economy. Here, we report glycerol’s solvent-free and room-temperature conversion to high-added-value chemicals via a reusable graphene catalyst (G-ASA), functionalized with a natural amino acid (taurine). Theoretical studies unveil that the superior performance of the catalyst (surpassing even homogeneous, industrial catalysts) is associated with the dual role of the covalently linked taurine, boosting the catalyst’s acidity and affinity for the reactants. Unlike previous catalysts, G-ASA exhibits excellent activity (7508 mmol g−1 h−1) and selectivity (99.9%) for glycerol conversion to solketal, an additive for improving fuels’ quality and a precursor of commodity and fine chemicals. Notably, the catalyst is also particularly active in converting oils to biodiesel, demonstrating its general applicability.

Abstract Two-dimensional (2D) conducting metal-organic frameworks (MOFs) is an emerging family of porous materials that have attracted a great attention due to their outstanding inherent properties such as hierarchical porosity, diverse architectures with high surface area and excellent electrical conductivity. These unique features make them ideal candidates for electrochemical energy storage technologies. This review highlights the key innovations on 2D conducting MOFs with emphasis on the design and synthesis strategies, and their potential applications in energy storage systems. Several recent breakthrough examples of 2D conducting MOFs with enhanced electrochemical performances are outlined. The review further extends the discussion on the significance of Nuclear Magnetic Resonance Spectroscopy (NMR) to understand the charge storage kinetics and their impact on structural implications of the materials. The elucidation of structure-property-performance relationship will further guide the development of new architectures of 2D conducting MOFs for the high-performance energy storage devices.

Potassium‐ion batteries (KIBs) have attracted enormous attention as a next‐generation energy storage system due to their low cost, fast ionic conductivity within electrolytes, and high operating voltage. However, developing suitable electrode materials to guarantee high‐energy output and structural stability to ensure long cycling performance remains a critical challenge. Herein, anatase TiO2 nanoparticles are encapsulated in nitrogen‐rich graphitic carbon (TiO2@NGC) with hierarchical pores and high surface area (250 m2 g−1) using the Ti‐based metal–organic framework NH2‐MIL‐125 (Ti8O8(OH)4(NH2‐bdc)6 with NH2‐bdc2− = 2‐amino‐1,4‐benzenedicarboxylate) as a sacrificial template. Serving as the anode material in a K‐ion half‐cell, TiO2@NGC delivers a high capacity of 228 mA h g−1 with remarkable cycling performance (negligible loss over 2000 cycles with more than 98% Coulombic efficiency). The charge‐storing mechanism is underpinned using ex situ characterization techniques such as ex situ X‐ray diffraction (XRD) and scanning electron microscopy (SEM) analysis. It is revealed that the original TiO2 phase gets transformed to the anorthic Ti7O13 and monoclinic K2Ti4O9 phase after the first charge/discharge cycle, which further initiates the charge storage process via the conversion reactions.

AbstractHerein, a novel polymer‐templated strategy is described to obtain 2D nickel‐based MOF nanosheets using Ni(OH)2, squaric acid, and polyvinylpyrrolidone (PVP), where PVP has a dual role as a structure‐directing agent, as well as preventing agglomeration of the MOF nanosheets. Furthermore, a scalable method is developed to transform the 2D MOF sheets to Ni7S6/graphene nanosheet (GNS) heterobilayers by in situ sulfidation using thiourea as a sulfur source. The Ni7S6/GNS composite shows an excellent reversible capacity of 1010 mAh g−1 at 0.12 A g−1 with a Coulombic efficiency of 98% capacity retention. The electrochemical performance of the Ni7S6/GNS composite is superior not only to nickel sulfide/graphene‐based composites but also to other metal disulfide–based composite electrodes. Moreover, the Ni7S6/GNS anode exhibits excellent cycle stability (≈95% capacity retention after 2000 cycles). This outstanding electrochemical performance can be attributed to the synergistic effects of Ni7S6 and GNS, where GNS serves as a conducting matrix to support Ni7S6 nanosheets while Ni7S6 prevents restacking of GNS. This work opens up new opportunities in the design of novel functional heterostructures by hybridizing 2D MOF nanosheets with other 2D nanomaterials for electrochemical energy storage/conversion applications.

AbstractThe development of pseudocapacitive materials for energy‐oriented applications has stimulated considerable interest in recent years due to their high energy‐storing capacity with high power outputs. Nevertheless, the utilization of nanosized active materials in batteries leads to fast redox kinetics due to the improved surface area and short diffusion pathways, which shifts their electrochemical signatures from battery‐like to the pseudocapacitive‐like behavior. As a result, it becomes challenging to distinguish “pseudocapacitive” and “battery” materials. Such misconceptions have further impacted on the final device configurations. This Review is an earnest effort to clarify the confusion between the battery and pseudocapacitive materials by providing their true meanings and correct performance metrics. A method to distinguish battery‐type and pseudocapacitive materials using the electrochemical signatures and quantitative kinetics analysis is outlined. Taking solid‐state supercapacitors (SSCs, only polymer gel electrolytes) as an example, the distinction between asymmetric and hybrid supercapacitors is discussed. The state‐of‐the‐art progress in the engineering of active materials is summarized, which will guide for the development of real‐pseudocapacitive energy storage systems.

Rapid progress on developing smart materials and design of hybrids is motivated by pressing challenges associated with energy crisis and environmental remediation. While emergence of versatile classes of nanomaterials has been fascinating, the real excitement lies in the design of hybrid materials with tunable properties. Metal-organic frameworks (MOFs) are the key materials for gas sorption and electrochemical applications, but their sustainability is challenged by limited chemical stability, poor electrical conductivity, and intricate, inaccessible pores. Despite tremendous efforts towards improving the stability of MOF materials, little progress has made researchers inclined toward developing hybrid materials. MXenes, a family of two-dimensional transition-metal carbides, nitrides and carbonitrides, are known for their compositional versatility and formation of a range of structures with rich surface chemistry. Hybridization of MOFs with functional layered MXene materials may be beneficial if the host structure provides appropriate interactions for stabilizing and improving the desired properties. Recent efforts have focused on integrating Ti3C2Tx and V2CTx MXenes with MOFs to result in hybrid materials with augmented electrochemical and physicochemical properties, widening the scope for emerging applications. This review discusses the potential design strategies of MXene@MOF hybrids, attributes of tunable properties in the resulting hybrids, and their applications in water treatment, sensing, electrochemical energy storage, smart textiles, and electrocatalysis. Comprehensive discussions on the recent efforts on rapidly evolving MXene@MOF materials for various applications and potential future directions are highlighted.