Porphyrin-based metal–organic frameworks (MOFs), exemplified by MOF-525, PCN-221, and PCN-224, are promising systems for catalysis, optoelectronics, and solar energy conversion. However, subtle differences between synthetic protocols for these three MOFs give rise to vast discrepancies in purported product outcomes and description of framework topologies. Here, based on a comprehensive synthetic and structural analysis spanning local and long-range length scales, we show that PCN-221 consists of Zr6O4(OH)4 clusters in four distinct orientations within the unit cell, rather than Zr8O6 clusters as originally published, and linker vacancies at levels of around 50%, which may form in a locally correlated manner. We propose disordered PCN-224 (dPCN-224) as a unified model to understand PCN-221, MOF-525, and PCN-224 by varying the degree of orientational cluster disorder, linker conformation and vacancies, and cluster–linker binding. Our work thus introduces a new perspective on network topology and disorder in Zr-MOFs and pinpoints the structural variables that direct their functional properties.

The deposition of a thin film layer by plasma polymerization enables the surface functionalization of a wide range of substrate materials for biointerfacial interactions. Plasma polymers can surface-bind proteins specifically via covalent linkages or nonspecifically through other irreversible adsorption mechanisms; key questions are whether covalent chemisorption has indeed occurred, and whether the protein retains functionality. Here the mode of surface binding of streptavidin and the biotin binding functionality of the bound streptavidin layer are studied on plasma polymer (pp) surfaces deposited using propionaldehyde and ethanol that were plasma polymerized at different powers (P) to investigate possible mechanisms for protein binding to a range of different surface chemistries. As expected, with pp surfaces composed principally of aldehyde groups, protein conjugation appears to be specific (chemisorption) allowing the immobilization of streptavidin (SAV) molecules retaining the ability to bind biotinylated probes. To contrast with this, we present the first study of protein adsorption to ethanol pp surfaces prepared at different P. This provides an investigation into retention of the hydroxyl functionality in the pp at low P and its effect on protein adsorption. Adsorption of human serum albumin (HSA) to ethanol pp was similar to that on propionaldehyde pp except at low P (5 W) where hydroxyl group retention and hydration presumably has a role in reducing protein adsorption. Although we observed SAV adsorption to ethanol pp surfaces at all P, interestingly, the protein lost its ability to bind biotinylated probes. Thus we suggest that irreversible, nonspecific adsorption of protein on ethanol pp surfaces results in apparent protein denaturation despite the hydrophilic nature of the ethanol pp surface. We conclude by making inferences between the pp structure as measured by X-ray photoelectron spectroscopy (XPS) and the related protein adsorption mechanisms.

The carbon nitride poly(heptazine imide), PHI, has recently emerged as a powerful 2D carbon nitride photocatalyst with intriguing charge storing ability. Yet, insights into how morphology, particle size, and defects influence its photophysical properties are virtually absent. Here, ultrasonication is used to systematically tune the particle size as well as concentration of surface functional groups and study their impact. Enhanced photocatalytic activity correlates with an optimal amount of those defects that create shallow trap states in the optical band gap, promoting charge percolation, as evidenced by time‐resolved photoluminescence spectroscopy, charge transport studies, and quantum‐chemical calculations. Excessive amounts of terminal defects can act as recombination centers and hence, decrease the photocatalytic activity for hydrogen evolution. Re‐agglomeration of small particles can, however, partially restore the photocatalytic activity. The type and amount of trap states at the surface can also influence the deposition of the co‐catalyst Pt, which is used in hydrogen evolution experiments. Optimized conditions entail improved Pt distribution, as well as enhanced wettability and colloidal stability. A description of the interplay between these effects is provided to obtain a holistic picture of the size–property–activity relationship in nanoparticulate PHI‐type carbon nitrides that can likely be generalized to related photocatalytic systems.

The perovskite-related oxynitride SrTaO 2 N is a prospective photoanode candidate with favorable band-edge positions. We have synthesized SrTaO 2 N nanowires with roughened surfaces by a hydrothermal process on a tantalum substrate and nitridation at 1273 K under flowing ammonia and hydrogen. The nanowires were coated with a ferrihydrite holestorage layer for photoelectrochemical water oxidation under AM 1.5G illumination in 0.1 M NaOH electrolyte (pH 13). The nanowires exhibit an electronic band gap of 2.32 eV, and the photocorrosion can be decreased with ferrihydrite coating. In the presence of Na 2 SO 3 as a hole scavenger, the nanowires do not yield higher photocurrent. This indicates that the limiting factors for hole extraction are processes occurring in the bulk instead of at the semiconductor−electrolyte interface. Our work is the first trial of a SrTaO 2 N photoanode based on nanowires and may also be promising for other quaternary oxynitride semiconductors to achieve a one-dimensional morphology.

The development of all-solid-state sodium batteries for scalable energy storage solutions requires fast sodium conducting solid electrolytes. To fast-track their discovery, candidate materials need to be identified that are synthesized...