Hollow Carbon-Based Nanoarchitectures Based on ZIF: Inward/Outward Contraction Mechanism and Beyond.

Hollow carbon-based nanoarchitectures (HCAs) derived from zeolitic imidazolate frameworks (ZIFs), by virtue of their controllable morphology and dimension, high specific surface area and nitrogen content, richness of metal/metal compounds active sites, and hierarchical pore structure and easy exposure of active sites, have attracted great interests in many fields of applications, especially in heterogeneous catalysis, and electrochemical energy storage and conversion. Despite various approaches that have been developed to prepare ZIF-derived HCAs, the hollowing mechanism has not been clearly disclosed. Herein, a specialized overview of the recent progress of ZIF-derived HCAs is introduced to provide an insight into their preparation strategy and the corresponding hollowing mechanisms. Based on the fundamental understanding of the structural evolution of ZIF nanocrystals during the high-temperature pyrolysis process, the hollowing mechanisms of ZIF-derived HCAs are classified into four categories: i) inward contraction of core-shell template@ZIF composites or hollow ZIFs, ii) outward contraction of ZIF@shell composites, iii) special outward contraction of ZIF arrays, and iv) mechanism beyond inward/outward contraction of pure ZIF nanocrystals. Finally, an outlook on the development prospects and challenges of HCAs based on ZIF precursors, especially in terms of controlled synthesis and future electrochemical application, is further discussed.

MOF-derived nanoporous carbons with diverse tunable nanoarchitectures.

Metal-organic frameworks (MOFs), or porous coordination polymers, are crystalline porous materials formed by coordination bonding between inorganic and organic species on the basis of the self-assembly of the reacting units. The typical characteristics of MOFs, including their large specific surface areas, ultrahigh porosities and excellent thermal and chemical stabilities, as well as their great potential for chemical and structural modifications, make them excellent candidates for versatile applications. Their poor electrical conductivity, however, has meant that they have not been useful for electrochemical applications. Fortuitously, the direct carbonization of MOFs results in a rearrangement of the carbon atoms of the organic units into a network of carbon atoms, which means that the products have useful levels of conductivity. The direct carbonization of zeolitic imidazolate framework (ZIF)-type MOFs, particularly ZIF-8, has successfully widened the scope of possible applications of MOFs to include electrochemical reactions that could be used in, for example, energy storage, energy conversion, electrochemical biosensors and capacitive deionization of saline water. Here, we present the first detailed protocols for synthesizing high-quality ZIF-8 and its modified forms of hollow ZIF-8, core-shell ZIF-8@ZIF-67 and ZIF-8@mesostuctured polydopamine. Typically, ZIF-8 synthesis takes 27 h to complete, and subsequent nanoarchitecturing procedures leading to hollow ZIF-8, ZIF-8@ZIF-67 and ZIF-8@mPDA take 6, 14 and 30 h, respectively. The direct-carbonization procedure takes 12 h. The resulting nanoporous carbons are suitable for electrochemical applications, in particular as materials for supercapacitors.

KOH-Activated Hollow ZIF-8 Derived Porous Carbon: Nanoarchitectured Control for Upgraded Capacitive Deionization and Supercapacitor.

Herein, the synergistic effects of hollow nanoarchitecture and high specific surface area of hollow activated carbons (HACs) are reported with the superior supercapacitor (SC) and capacitive deionization (CDI) performance. The center of zeolite imidazolate framework-8 (ZIF-8) is selectively etched to create a hollow cavity as a macropore, and the resulting hollow ZIF-8 (HZIF-8) is carbonized to obtain hollow carbon (HC). The distribution of nanopores is, subsequently, optimized by KOH activation to create more nanopores and significantly increase specific surface area. Indeed, as-prepared hollow activated carbons (HACs) show significant improvement not only in the maximum specific capacitance and desalination capacity but also capacitance retention and mean desalination rates in SC and CDI, respectively. As a result, it is confirmed that well-designed nanoarchitecture and porosity are required to allow efficient diffusion and maximum electrosorption of electrolyte ions.