Ordered Macro–Microporous Metal–Organic Framework Single Crystals and Their Derivatives for Rechargeable Aluminum-Ion Batteries

Abstract

Constructing ordered hierarchical porous structures while maintaining their overall crystalline order is highly desirable but remains an arduous challenge. Herein, we successfully achieve the growth of single-crystalline metal–organic frameworks (MOFs) in three-dimensional (3D) ordered macroporous template voids by a saturated solution-based double-solvent-assisted strategy with precise control over the nucleation process. The as-prepared single-crystalline ordered macro–microporous Co-based MOFs (SOM ZIF-67) exhibit an ordered macro–microporous structure with robust single-crystalline nature. Moreover, SOM ZIF-67 can serve as a precursor to derive 3D-ordered macroporous cobalt diselenide@carbon (3DOM CoSe2@C) through a facile carbonization–selenization treatment. The as-derived 3DOM CoSe2@C can well preserve the 3D-ordered macroporous structure of the precursor. More importantly, CoSe2 nanoparticles could be uniformly confined in the conductive ordered macroporous carbon framework, affording regularly interconnected macroporous channels and large surface area. As a result, when evaluated as a cathode material for aluminum-ion batteries, the ordered macroporous structure could not only effectively facilitate the diffusion of large-sized chloroaluminate anions but also increase the contact area with electrolyte and provide more exposed active sites, thereby exhibiting superior reversible rate capacity (86 mA h g–1 at 5.0 A g–1) and remarkable cycling performance (125 mA h g–1 after 1000 cycles at 2.0 A g–1).

Keggin‐Type Polyoxometalate‐Based ZIF‐67 for Enhanced Photocatalytic Nitrogen Fixation

“…MOFs have been recognized as a spotlightw ith outstanding efficiencies in both environmental and energy applications, such as gas and energy storage,c onversion, and catalysis owing to periodic and porous structures, high specific surface area,a nd versatility. [18][19][20][21] As ar epresentative of typical MOF materials, zeolitic imidazolate framework-67 (ZIF-67) with network tetrahedral topologies has attracted wide attention as adsorbents, resulting from their fascinating characteristic of well-defined morphology, rich structurald iversity,r emarkable thermal and chemical stability, and uniform pore size. The reticular materials with large specific surface area provide abundant catalytically active sites to adsorb N 2 , and the porouss tructures effectively promotee lectron delivery,s imultaneously.…”

Unveiling the Advances of Nanostructure Design for Alloy‐Type Potassium‐Ion Battery Anodes via In Situ TEM

“…[19] It is assumed that the pyrolysis of N-containing PA Np olymer in ar eductive atmosphere could result in the successful doping of Nelement in the Sb@CNFs.T his can be confirmed by the high-resolution spectrum of N1s ( Figure 2f), which can be divided into three peaks located at 398.4, 400.0, and 401.1 eV, implying the presence of pyridinic-N,p yrrolic-N,a nd graphitic-N,r espectively. [44] Thed oped Nc ould induce numerous extrinsic defects in the carbon framework and effectively increase the chemical activity of material, which is beneficial for enhancing the electrochemical performance. Thee lectrochemical properties of the Sb@CNFs as an anode for PIBs were further investigated in the voltage window of 0.01-2.0 V( vs.K + /K).…”

“…[26,[41][42][43] Based on these basic theories, we have reported ar ange of groundbreaking works.F or instance,weused the thermal instability of MOFs to convert MOFs precursors into hollow transition-metal oxides and ordered macroporous structure transition metal selenides through thermal treatment. [25,44] We also prepared complex hollow boxes by ion-exchanging with different target substrates owing to the chemical instability of MOFs. [26] These previous reports indicated that MOFs as multifunctional precursors/templates have greatly promoted the structural design of electrode materials.H erein, aM OFs-engaged electrospinning coupled with confined ion exchange and subsequent thermal reduction strategy is proposed to prepare hybrid structure with Sb nanoparticles as the yolk confined in carbon shell (Sb@C nanoboxes) embedded in carbon nanofibers (denoted as Sb@CNFs).…”

Hierarchically Ordered Porous Carbon with Atomically Dispersed FeN4 for Ultraefficient Oxygen Reduction Reaction in Proton‐Exchange Membrane Fuel Cells

“…Therefore, it is extremely attractive to construct the hierarchically ordered macro/meso/microporous structure via a traditional ZIF‐8 to meet the dual requirements of rapid mass transfer and efficient utilization of active centers. Previous studies have demonstrated that the macropores and mesopores contribute to the transport of macromolecules, so that reactants can reach the active sites throughout the entire catalytic layer, and the active sites released from encapsulation inside the carbon particles will substantially promote the ORR catalytic efficiency . Besides, abundant defect sites will be formed due to the introduction of macropores and mesopores, and they can effectively prevent the migration and accumulation of metals during the pyrolysis process to produce a uniform distribution of Fe …”