Abstract
ConspectusHeteroatom-doped porous carbon membranes (HPCMMs) with a tailor-made pore architecture, chemical composition, atomic structural order, and surface state represent an exciting family of porous carbon materials for diverse potential applications in catalysis, water treatment, biofiltration, energy conversion/storage, and so forth. Conventional porous carbon membranes possess intrinsic structural integrity, interconnectivity, and chemical purity across the atomic-to-macro world and have been popularly incorporated into devices as separators or chemically inert conductive supports, circumventing otherwise the inevitable complicated processing and structure weakness of their fine powderous counterpart. Motivated by the distinguished heteroatom-doping effect that revolutionizes the chemical and physical nature of carbon materials, the HPCMM research surges very recently, and focuses not only on the eminent conductive supports or separators but also on electro(co)catalysts in energy devices. Synergy of the porous nature, incorporation of heteroatoms, and the membrane state creates a vivid profile pattern and new task-specific usage. It is also noteworthy that the inherent structural merits of HPCMMs plus a high electron conductivity imbue them as a reliable binder-free model electrode to derive the intrinsic structure–property relationship of porous carbons in electrochemical environments, excluding the complex and adverse factors in association with polymer binders in carbon powder-based electrodes. HPCMMs are of both intense academic interest and practical value because of their well-defined properties endowed by controllable structure and porosity at both atomic and macroscopic scales in a membrane form. The sole aim of this article is to bring this group of porous carbon materials to the forefront so their comprehensive properties and functions can be better understood to serve the carbon community to address pressing materials challenges in our society.In this Account, we highlight the latest discovery and proceedings of HPCMMs, particularly the advancements in how to tailor structures and properties of HPCMMs by rational structure design of porous polymer membranes as sacrificial template built up especially from heteroatom-rich poly(ionic liquid)s (PILs). We will also stress the carbonization craft and the state-of-the-art electrochemical applications for HPCMMs. Key factors and thoughts in heteroatom doping and porous systems in HPCMMs are discussed. A future perspective of the challenges and promising potential of HPCMMs is cast on the basis of these achievements.
Highlights
Heteroatom-doped porous carbon membranes (HPCMMs) are a unique group of carbon materials carrying an interconnected porous network in a membrane state, in which some of carbon atoms are selectively replaced by heteroatom such as nitrogen (N), sulfur (S), phosphorus (P), boron (B), and selenium (Se)
poly(ionic liquid)s (PILs) were first used in the presence of FeCl3 to produce mesoporous carbons in 2010 by us;[18] thereafter, we found pyrolysis of a hydrophobic PIL poly(1-cyanomethyl-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide) alone at 1000 °C produced N-coped micro/mesoporous carbons with a Brunauer−Emmett−Teller specific surface area (SBET) of up to 520 m2/g
It is beyond question that HPCMMs are a type of challenging carbon materials in view of their demanding synthesis and a full control of structure parameters in an unusually wide range of dimension and chemical composition
Summary
Heteroatom-doped porous carbon membranes (HPCMMs) are a unique group of carbon materials carrying an interconnected porous network in a membrane state, in which some of carbon atoms are selectively replaced by heteroatom such as nitrogen (N), sulfur (S), phosphorus (P), boron (B), and selenium (Se). In stark contrast to easy-to-make porous carbon powders that dominate the current research of porous carbons, HPCMMs are synthetically more demanding This is due to their hierarchical pores in the entire micro-, meso- to macropore size range, and the covalent doping of heteroatoms, plus a macroscopically visible membrane shape that can be directly used in devices without complicated processing procedures. Other heteroatoms, including B, Se, or more, are rarely found in bio(macro)molecules but can be positioned into synthetic polymers on demand Another issue is the carbonization craft for creating HPCMMs, in which the temperature program, carbonization environment, and inner oncotic pressure of PPMs during pyrolysis have to be aligned with the final usage of HPCMMs. For example, preheating of macromolecules containing cyano groups at 300 °C could form a thermally more robust polytriazine network than ones without cyano groups. This article will present the latest advance in template synthesis, structural control, and electrochemical applications of HPCMMs
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