The wettability of graphene is both
fundamental and crucial for
interfacing in most applications, but a detailed understanding of
its time evolution remains elusive. Here we systematically investigate
the wettability of metal-supported, chemical vapor deposited graphene
films as a function of ambient air exposure time using water and various
other test liquids with widely different surface tensions. The wettability
of graphene is not constant, but varies with substrate interactions
and air exposure time. The substrate interactions affect the initial
graphene wettability, where, for instance, water contact angles of
∼85 and ∼61° were measured for Ni and Cu supported
graphene, respectively, after just minutes of air exposure. Analysis
of the surface free energy components indicates that the substrate
interactions strongly influence the Lewis acid–base component
of supported graphene, which is considerably weaker for Ni supported
graphene than for Cu supported graphene, suggesting that the classical
van der Waals interaction theory alone is insufficient to describe
the wettability of graphene. For prolonged air exposure, the effect
of physisorption of airborne contaminants becomes increasingly dominant,
resulting in an increase of water contact angle that follows a universal
linear-logarithmic relationship with exposure time, until saturating
at a maximum value of 92–98°. The adsorbed contaminants
render all supported graphene samples increasingly nonpolar, although
their total surface free energy decreases only by 10–16% to
about 37–41 mJ/m2. Our finding shows that failure
to account for the air exposure time may lead to widely different
wettability values and contradicting arguments about the wetting transparency
of graphene.
Electrocatalytic reduction of CO2 into alcohols of high economic value offers a promising route to realize resourceful CO2 utilization. In this study, we choose three model bicentric copper complexes based on the expanded and fluorinated porphyrin structure, but different spatial and coordination geometry, to unravel their structure-property-performance correlation in catalyzing electrochemical CO2 reduction reactions. We show that the complexes with higher intramolecular tension and coordination asymmetry manifests a lower electrochemical stability and thus more active Cu centers, which can be reduced during electrolysis to form Cu clusters accompanied by partially-reduced or fragmented ligands. We demonstrate the hybrid structure of Cu cluster and partially reduced O-containing hexaphyrin ligand is highly potent in converting CO2 into alcohols, up to 32.5% ethanol and 18.3% n-propanol in Faradaic efficiencies that have been rarely reported. More importantly, we uncover an interplay between the inorganic and organic phases to synergistically produce alcohols, of which the intermediates are stabilized by a confined space to afford extra O-Cu bonding. This study underlines the exploitation of structure-dependent electrochemical property to steer the CO2 reduction pathway, as well as a potential generic tactic to target alcohol synthesis by constructing organic/inorganic Cu hybrids.
Transition metal carbides/nitrides (MXenes) with metallic electrical conductivity and excellent processability attract increasing attention for assembling multifunctional macrostructures. However, the challenges, involving poor mechanical strength, inferior oxidation stability, and limited scalable manufacturing, impede their wide applications. Herein, the large-area, high-strength, ultra-flexible hybrid films are developed through the multiple physical and chemical cross-linking of MXene/cellulose films facilitated by graphene oxide. The MXene-based films manifest significantly improved hydrophobicity, water/solvent resistance, and oxidation stability, and meanwhile, maintain excellent conductivity and electromagnetic interference shielding performance. The X-band surface-specific shielding effectiveness (SE) of 18,837.5 dB cm 2 g −1 and an SE over 60 dB in an ultra-broadband frequency range are achieved, comparable to the best shields ever reported. Furthermore, the wearable films demonstrate excellent photothermal antibacterial and electrothermal deicing applications. Thus, such high-performance MXene-based films developed through a facile and scalable manufacturing method have substantial application prospects in flexible electronics, thermotherapy, electromagnetic compatibility, and aerospace.
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