Emerging Doped Metal-Organic Frameworks: Recent Progress in Synthesis, Applications, and First-Principles Calculations.

Metal-organic frameworks (MOFs) are crystalline porous materials with a long-range ordered structure and excellent specific surface area and have found a wide range of applications in diverse fields, such as catalysis, energy storage, sensing, and biomedicine. However, their poor electrical conductivity and chemical stability, low capacity, and weak adhesion to substrates have greatly limited their performance. Doping has emerged as a unique strategy to mitigate the issues. In this review, the concept, classification, and characterization methods of doped MOFs are first introduced, and recent progress in the synthesis and applications of doped MOFs, as well as the rapid advancements and applications of first-principles calculations based on the density functional theory (DFT) in unraveling the mechanistic origin of the enhanced performance are summarized. Finally, a perspective is included to highlight the key challenges in doping MOF materials and an outlook is provided on future research directions.

Conformal sulfidation of HKUST-1 for constructing porous Cu2S/CuO octahedrons realizing highly sensitive non-enzymatic glucose detection.

Metal-organic frameworks (MOFs) are believed to be promising precursors for constructing novel and efficient catalysts for glucose sensing. Herein, HKUST-1 precursors are first fabricated using a one-pot hydrothermal approach, and then HKUST-1 is converted into porous Cu2S/CuO octahedrons through conformal sulfidation with the help of OH-ions. The as-obtained Cu2S/CuO composite can provide rich electrochemical active sites and promoted electric transfer kinetics. Benefiting from these combined merits, the as-fabricated Cu2S/CuO composite is confirmed to be a high-performance catalyst, with high sensitivities of 8269.45 and 4140.82µA mM-1cm-2in the corresponding ranges of 0.05 ∼ 0.6 mM and 0.6 ∼ 1.2 mM, respectively. Moreover, the as-prepared electrode materials possess good anti-interference ability, reproducibility and long-term stability. This work opens up new avenues for the design and preparation of transition metal sulfide composites.

Bilayered nanostructured V2O5 nH2O xerogel constructed 2D nano-papers for efficient aqueous zinc/magnesium ion storage.

Aqueous zinc ion batteries (AZIBs) and aqueous magnesium ion batteries (AMIBs) offer powerful alternatives for large-scale energy storage because of their high safety and low cost. Consequently, the design of high-performance cathode materials is essential. In this paper, we present a simple strategy that combines oxygen defect (Od) engineering with a 2D-on-2D homogeneous nanopape-like bilayer V2O5 nH2O xerogel (BL-HVOd NPS). This strategy employs Od to improve Zn2+/Mg2+insertion/extraction kinetics and reduce irreversible processes for high-performance AZIBs/AMIBs. And interlayer water molecules serve as an effective spacer to stabilize the expanded interlayer gap in BL-HVOd NPS, thereby providing extended diffusion channels for Zn2+/Mg2+ during insertion/extraction. The interlayer water molecules help shield the electrostatic interaction between Zn2+/Mg2+ and BL-HVOd NPS lattice, which improves diffusion kinetics during repeated. In addition, electrochemical characterization results indicate that the BL-HVOd NPS can effectively the surface adsorption and internal diffusion of Zn2+/Mg2+. More importantly, the successfully prepared unique 2D-on-2D homogenous nanopaper structure enhances electrolyte/electrode contact and reduces the migration/diffusion path of electrons/Zn2+ and Mg2+, thus greatly improving rate performance. As a result, the BL-HVOd NPS as AZIBs/AMIBs electrodes offer better reversible capacity of 361.8 and 162.8 mA h g-1 (at 0.2 A g-1), while displaying impressively long cycle lifes. This method provides a way to prepare advanced xerogel cathode materials for AZIBs and AMIBs.

Crystal engineering of bimetallic cobalt-based metal-organic framework nanosheets for high-performance aqueous rechargeable cobalt-zinc batteries.

Aqueous rechargeable Zn-based batteries (ARZBs) have attracted increasing attention as favorable candidates for energy storage systems due to their high security, environmental friendliness, and abundance of electrode materials. At present, the most widely reported materials used in cobalt-zinc (Co-Zn) batteries are cobalt-based oxides and their derivatives, however, they still exhibit low actual capacities and unsatisfactory cycle lives. Metal-organic frameworks (MOFs), as a new class of porous materials with high specific surface area and adjustable pore size, have attracted considerable attention in the field of energy storage. Currently, pristine MOFs have currently few applications in Co-Zn batteries, and their performance is not ideal. Herein, we report a series of two-dimensional (2D) bimetallic CoM-MOF (M = Ni, Mn, Mg and Cu) nanosheets based on trimesic acid (H3BTC) ligand as cathodes for alkaline Co-Zn batteries via a simple one-pot hydrothermal synthesis. Among the synthesized MOFs, the CoNi-MOF nanosheets have the best performance, exhibiting a high reversible capacity of 344 mA h g-1 and demonstrating a good cycling life with 90 % capacity retention at 20 A g-1 after 1500 cycles. The energy storage mechanism is studied through a series of ex-situ characterizations. This study is of great importance in advancing the application of 2D pristine MOFs for high-performance Co-Zn batteries.

Large scale and oxygen vacancy VO2 porous thin sheets to enable high-performance zinc ion storage.

Herein, we report the first result of large scale and oxygen vacancy VO2 porous thin sheets assembled by a 3D interconnected nanoflake array framework, which is recorded as VOd. The as-prepared VOd was characterized by various methods and Zn2+ intercalation/deintercalation and structural decomposition mechanisms were proposed based on ex situ X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).

Mesoporous copper-doped δ-MnO2 superstructures to enable high-performance aqueous zinc-ion batteries.

Aqueous zinc-ion batteries (AZIBs) are competitive alternatives for large-scale energy-storage devices owing to the abundance of zinc and low cost, high theoretical specific capacity, and high safety of these batteries. High-performance and stable cathode materials in AZIBs are the key to storing Zn2+. Manganese-based cathode materials have attracted considerable attention because of their abundance, low toxicity, low cost, and abundant valence states (Mn2+, Mn3+, Mn4+, and Mn7+). However, as a typical cathode material, birnessite-MnO2 (δ-MnO2) has low conductivity and structural instability. The crystal structure may undergo severe distortion, disorder, and structural damage, leading to severe cyclic instability. In addition, its energy-storage mechanism is still unclear, and most of the reported manganese oxide-based materials do not have excellent electrochemical performance. Herein, we propose a copper-doped Cu0.05K0.11Mn0.84O2·0.54H2O (Cu2-KMO) cathode, which exhibits a large interlayer spacing, a stable structure, and accelerated reaction kinetics. This cathode was prepared using a simple hydrothermal method. The AZIB assembled using Cu2-KMO showed high specific capacity (600 mA h g-1 at 0.1 A g-1 after 75 cycles). The dissolution-deposition energy storage mechanism of Cu-KMO in AZIBs with double electron transfer was revealed using ex situ tests. The good electrochemical performance of the Cu2-KMO cathode fabricated by the doping strategy in this study provides ideas for the subsequent preparation of manganese dioxide using other strategies.

Metal ion and organic ligand disubstituted bimetallic metal-organic framework nanosheets for high-performance alkaline zinc-based batteries.

Herein, a disubstitution strategy of metal ions and organic ligands is employed to synthesize metal-organic framework (MOF) nanosheets with a three-dimensional (3D) porous structure and a highly active metal-sulfur (M-S, M = Co and Ni) region. The obtained MOFs//Zn batteries exhibit excellent electrochemical properties and the electrochemical reaction mechanism was elucidated through a series of ex situ characterizations.

Insights into the cycling stability of manganese-based zinc-ion batteries: from energy storage mechanisms to capacity fluctuation and optimization strategies.

Manganese-based materials are considered as one of the most promising cathodes in zinc-ion batteries (ZIBs) for large-scale energy storage applications owing to their cost-effectiveness, natural availability, low toxicity, multivalent states, high operation voltage, and satisfactory capacity. However, their intricate energy storage mechanisms coupled with unsatisfactory cycling stability hinder their commercial applications. Previous reviews have primarily focused on optimization strategies for achieving high capacity and fast reaction kinetics, while overlooking capacity fluctuation and lacking a systematic discussion on strategies to enhance the cycling stability of these materials. Thus, in this review, the energy storage mechanisms of manganese-based ZIBs with different structures are systematically elucidated and summarized. Next, the capacity fluctuation in manganese-based ZIBs, including capacity activation, degradation, and dynamic evolution in the whole cycle calendar are comprehensively analyzed. Finally, the constructive optimization strategies based on the reaction chemistry of one-electron and two-electron transfers for achieving durable cycling performance in manganese-based ZIBs are proposed.