Nick J. Brownbill

Visible‐Light‐Driven Hydrogen Evolution Using Planarized Conjugated Polymer Photocatalysts

Abstract Linear poly(p‐phenylene)s are modestly active UV photocatalysts for hydrogen production in the presence of a sacrificial electron donor. Introduction of planarized fluorene, carbazole, dibenzo[b,d]thiophene or dibenzo[b,d]thiophene sulfone units greatly enhances the H2 evolution rate. The most active dibenzo[b,d]thiophene sulfone co‐polymer has a UV photocatalytic activity that rivals TiO2, but is much more active under visible light. The dibenzo[b,d]thiophene sulfone co‐polymer has an apparent quantum yield of 2.3 % at 420 nm, as compared to 0.1 % for platinized commercial pristine carbon nitride.

Influence of Functionalization of Nanocontainers on Self-Healing Anticorrosive Coatings

Feedback coating based on pH-induced release of inhibitor from organosilyl-functionalized containers is considered as a compelling candidate to achieve smart self-healing corrosion protection. Four key factors that determine the overall coating performance include (1) the uptake and release capacity of containers, (2) prevention of the premature leakage, (3) compatibility of containers in coating matrix, and (4) cost and procedure simplicity consideration. The critical influence introduced by organosilyl-functionalization of containers is systematically demonstrated by investigating MCM-41 silica nanoparticles modified with ethylenediamine (en), en-4-oxobutanoic acid salt (en-COO(-)), and en-triacetate (en-(COO(-))3) with higher and lower organic contents. The properties of the modified silica nanoparticles as containers were mainly characterized by solid-state (13)C nuclear magnetic resonance, scanning and transmission electron microscopy, N2 sorption, thermogravimetric analysis, small-angle X-ray scattering, dynamic light scattering, and UV-vis spectroscopy. Finally, the self-healing ability and anticorrosive performances of hybrid coatings were examined through scanning vibrating electrode technique (SVET) and electrochemical impedance spectroscopy (EIS). We found that en-(COO(-))3-type functionalization with content of only 0.23 mmol/g performed the best as a candidate for establishing pH-induced release system because the resulting capped and loaded (C-L) functionalized silica nanocontainers (FSNs) exhibit high loading (26 wt %) and release (80%) capacities for inhibitor, prevention of premature leakage (less than 2%), good dispersibility in coating matrix, and cost effectiveness.

Ultra-Fast Molecular Rotors within Porous Organic Cages

Abstract Using variable temperature 2H static NMR spectra and 13C spin‐lattice relaxation times (T1), we show that two different porous organic cages with tubular architectures are ultra‐fast molecular rotors. The central para‐phenylene rings that frame the “windows” to the cage voids display very rapid rotational rates of the order of 1.2–8×106 Hz at 230 K with low activation energy barriers in the 12–18 kJ mol−1 range. These cages act as hosts to iodine guest molecules, which dramatically slows down the rotational rates of the phenylene groups (5–10×104 Hz at 230 K), demonstrating potential use in applications that require molecular capture and release.

Publisher Correction: Liquid phase blending of metal-organic frameworks

The original version of this Article contained an error in Figure 1b, where the blue ‘(ZIF-4-Zn)0.5 (ZIF-62)0.5 blend’ data curve was omitted from the enthalpy response plot. This has now been corrected in both the PDF and HTML versions of the Article.

Berichtigung: Visible-Light-Driven Hydrogen Evolution Using Planarized Conjugated Polymer Photocatalysts

Linear poly(p-phenylene)s are modestly active UV photocatalysts for hydrogen production in the presence of a sacrificial electron donor. Introduction of planarized fluorene, carbazole, dibenzo[b,d]thiophene or dibenzo[b,d]thiophene sulfone units greatly enhances the H2 evolution rate. The most active dibenzo[b,d]thiophene sulfone co-polymer has a UV photocatalytic activity that rivals TiO2, but is much more active under visible light. The dibenzo[b,d]thiophene sulfone co-polymer has an apparent quantum yield of 2.3 % at 420 nm, as compared to 0.1 % for platinized commercial pristine carbon nitride.