Intermolecular charge transfer (ICT) effect has been widely studied in both small molecules and linear polymers. Covalently-bonded donor-acceptor pairs with tunable bandgaps and photoelectric properties endow these materials with potential applications in optoelectronics, fluorescent bioimaging, and sensors, etc. However, owing to the lack of charge transfer pathway or effective separation of charge carriers, unfavorable charge recombination gives rise to inevitable energy loss. Covalent organic frameworks (COFs) can be mediated with various geometry-and property-tailored building blocks, where donor (D) and acceptor (A) segments are connected by covalent bonds and can be finely arranged to form highly ordered networks (namely DÀ A COFs). The unique structural features of DÀ A COFs render the formation of segregated DÀ A stacks, thus provides pathways and channels for effective charge carriers transport. This review highlights the significant progress on DÀ A COFs over the past decade with emphasis on design principles, growing structural diversities, and promising application potentials.
Two-dimensional
(2D) covalent organic frameworks (COFs) are an
emerging class of promising 2D materials with high crystallinity and
tunable structures. However, the low electrical conductivity impedes
their applications in electronics and optoelectronics. Integrating
large π-conjugated building blocks into 2D lattices to enhance
efficient π-stacking and chemical doping is an effective way
to improve the conductivity of 2D COFs. Herein, two nonplanar 2D COFs
with kagome (DHP-COF) and rhombus (c-HBC-COF) lattices
have been designed and synthesized from distorted aromatics with different
π-conjugated structures (flexible and rigid structure, respectively).
DHP-COF shows a highly distorted 2D lattice that hampers stacking,
consequently limiting its charge carrier transport properties. Conversely, c-HBC-COF, with distorted although concave–convex
self-complementary nodes, shows a less distorted 2D lattice that does
not interfere with interlayer π-stacking. Employing time- and
frequency-resolved terahertz spectroscopy, we unveil a high charge-carrier
mobility up to 44 cm2 V–1 s–1, among the highest reported for 2D COFs.
Easy preparation,
high stability, prominent activity, and excellent
recyclability are four key elements for high-performance heterogeneous
photocatalysts. Developing covalent organic framework (COF)-based
heterogeneous photocatalysts possessing all of these traits is highly
challenging. In this study, we successfully synthesized an imine-linked
BBO-COF by the “two-in-one” strategy featuring the above
four merits. Highly crystalline and porous BBO-COF can be easily prepared
in at least 11 different simplex solvents independent of their polarity
and boiling points and even under an air atmosphere. Moreover, BBO-COF
exhibits extraordinary chemical stability and photostability in strong
acid (12 M HCl), corrosive base (12 M NaOH), and visible light for
7 days. Furthermore, BBO-COF exhibited prominent photocatalytic activity
toward oxidative hydroxylation reaction of arylboronic acids with
excellent substrates tolerance and reusability. This “two-in-one”
design strategy open a new avenue for facile constructing novel functional
COFs with tailor-made properties.
We report the first organically synthesized sp-sp hybridized porous carbon, OSPC-1. This new carbon shows electron conductivity, high porosity, the highest uptake of lithium ions of any carbon material to-date, and the ability to inhibit dangerous lithium dendrite formation. The new carbon exhibits exceptional potential as anode material for lithium-ion batteries (LIBs) with high capacity, excellent rate capability, long cycle life, and potential for improved safety performance.
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