Heterogeneous photocatalysis that employs photo-excited semiconductor materials to reduce water and oxidize toxic pollutants upon solar light irradiation holds great prospects for renewable energy substitutes and environmental protection. To utilize solar light effectively, the quest for highly active photocatalysts working under visible light has always been the research focus. Layered BiOX (X = Cl, Br, I) are a kind of newly exploited efficient photocatalysts, and their light response can be tuned from UV to visible light range. The properties of semiconductors are dependent on their morphologies and compositions as well as structures, and this also offers the guidelines for design of highly-efficient photocatalysts. In this review, recent advances and emerging strategies in tailoring BiOX (X = Cl, Br, I) nanostructures to boost their photocatalytic properties are surveyed.

Engineering BiOX (X = Cl, Br, I) nanostructures for highly efficient photocatalytic applications

Dynamic covalent polymer networks (DCPN) have historically attracted attention for their unique roles in chemical recycling and self-healing, which are both relevant for sustainable societal development. Efforts in these directions have intensified in the past decade with notable progress in newly discovered dynamic covalent chemistry, fundamental material concepts, and extension toward emerging applications including energy and electronic devices. Beyond that, the values of DCPN in discovering/designing functional properties not offered by classical thermoplastic and thermoset polymers have recently gained traction. In particular, the dynamic bond exchangeability of DCPN has shown unparalleled design versatility in various areas including shape-shifting materials/devices, artificial muscles, and microfabrication. Going beyond this basic bond exchangeability, various molecular mechanisms to manipulate network topologies (topological transformation) have led to opportunities to program polymers, with notable concepts such as living networks and topological isomerization. In this review, we provide an overview of the above progress with particular focuses on molecular design strategies for the exploitation of functional material properties. Based on this, we point out the remaining issues and offer perspectives on how this class of materials can shape the future in ways that are complementary with classical thermoplastic and thermoset polymers.

Dynamic Covalent Polymer Networks: A Molecular Platform for Designing Functions beyond Chemical Recycling and Self-Healing.

The emergence of methyl-ammonium lead halide (MAPbX3) perovskites motivates the identification of unique properties giving rise to exceptional bulk transport properties, and identifying future materials with similar properties. Here, we propose that this “defect tolerance” emerges from fundamental electronic-structure properties, including the orbital character of the conduction and valence band extrema, the chargecarrier effective masses, and the static dielectric constant. We use MaterialsProject.org searches and detailed electronic-structure calculations to demonstrate these properties in other materials than MAPbX3. This framework of materials discovery may be applied more broadly, to accelerate discovery of new semiconductors based on emerging understanding of recent successes.

Identifying defect-tolerant semiconductors with high minority-carrier lifetimes: beyond hybrid lead halide perovskites

Block polymers have undergone extraordinary evolution since their inception more than 60 years ago, maturing from simple surfactants to an expansive class of macromolecules encoded with exquisite attributes. Contemporary synthetic accessibility coupled with facile characterization and rigorous theoretical advances have conspired to continuously generate fundamental insights and enabling concepts that target applications spanning chemistry, biology, physics, and engineering. Here, we parse the vast literature to examine the forefront of the field and identify exciting themes and challenging opportunities that portend a bracing future trajectory. This Perspective celebrates the visionary role played by Macromolecules in advancing our understanding of this remarkable class of materials.

http://pubs.acs.org/doi/pdf/10.1021/acs.macromol.6b02355

50th Anniversary Perspective: Block Polymers—Pure Potential

The classical division of polymeric materials into thermoplastics and thermosets based on covalent network structure often implies that these categories are distinct and irreconcilable. Yet, the past two decades have seen extensive development of materials that bridge this gap through incorporation of dynamic crosslinks, enabling them to behave as both robust networks and moldable plastics. Although their potential utility is significant, the growth of covalent adaptable networks (CANs) has obscured the line between “thermoplastic” and “thermoset” and erected a conceptual barrier to the growing number of new researchers entering this discipline. This Perspective aims to both outline the fundamental theory of CANs and provide a critical assessment of their current status. We emphasize throughout that the unique properties of CANs emerge from the network chemistry, and particularly highlight the role that the crosslink exchange mechanism (i.e., dissociative exchange or associative exchange) plays in the res...

Adaptable Crosslinks in Polymeric Materials: Resolving the Intersection of Thermoplastics and Thermosets.

Bismuth oxy-iodide is a potentially interesting visible-light-active photocatalyst; yet there is little research regarding its photoelectrochemical properties. Herein we report the synthesis of BiOI nanoplatelet photoelectrodes by spray pyrolysis on fluorine-doped tin oxide substrates at various temperatures. The films exhibited n-type conductivity, most likely due to the presence of anion vacancies, and optimized films possessed incident photon conversion efficiencies of over 20% in the visible range for the oxidation of I– to I3– at 0.4 V vs Ag/AgCl in acetonitrile. Visible-light photons (λ > 420 nm) contributed approximately 75% of the overall photocurrent under AM1.5G illumination, illustrating their usefulness under solar light illumination. A deposition temperature of 260 °C was found to result in the best performance due to the balance of morphology, crystallinity, impurity levels, and optical absorption, leading to photocurrents of roughly 0.9 mA/cm2 at 0.4 V vs Ag/AgCl. Although the films perform...

Spray pyrolysis deposition and photoelectrochemical properties of n-type BiOI nanoplatelet thin films

The effect of catalyst strength on polyester–alcohol dynamic covalent exchange was systematically studied using Bronsted acids and a low-Tg poly(4-methylcaprolactone) vitrimer formulation. Relaxation times, activation energies, and Arrhenius prefactors are correlated with pKa. Strong protic acids induce facile network relaxation at 25 °C on the order of 104–105 s, significantly faster than Lewis acid alternatives that function only above 100 °C. Activation energies span 49–67 kJ/mol and increase as pKa decreases. The opposite trend is observed with the Arrhenius prefactor. We anticipate that the quantitative understanding of Bronsted acid effects disclosed herein will be of utility in future studies that exploit acid-catalyzed dynamic covalent bond exchange.

/pdf/bronsted-acid-catalyzed-exchange-in-polyester-dynamic-19q3llqnbg.pdf

Brønsted-Acid-Catalyzed Exchange in Polyester Dynamic Covalent Networks

We introduce a design strategy to expand the range of accessible mechanical properties in covalent adaptable networks (CANs) using bottlebrush polymer building blocks. Well-defined bottlebrush polymers with rubbery poly(4-methylcaprolactone) side chains were cross-linked in formulations that include a bislactone and strong Lewis acid (tin ethylhexanoate). The resulting materials exhibit tunable stress-relaxation rates at elevated temperatures (160-180 °C) due to dynamic ester cross-links that undergo transesterification with residual hydroxy groups. Varying the cross-linker loading or bottlebrush backbone degree of polymerization yields predictable low-frequency shear moduli ca. 10-100 kPa, well below values typical of linear polymer CANs (1 MPa). These extensible networks can be stretched to strains as large as 350% before failure and undergo efficient self-healing to recover >85% of their original toughness upon repeated fracture and melt processing. In summary, molecular architecture creates new opportunities to tailor the mechanical properties of CANs in ways that are otherwise difficult to achieve.

Dynamic Bottlebrush Polymer Networks: Self-Healing in Super-Soft Materials.

We introduce a novel grafting-through polymerization strategy to synthesize dynamic bottlebrush polymers and elastomers in one step using light to construct a disulfide-containing backbone. The key starting material-α-lipoic acid (LA)-is commercially available, inexpensive, and biocompatible. When installed on the chain end(s) of poly(dimethylsiloxane) (PDMS), the cyclic disulfide unit derived from LA polymerizes under ultraviolet (UV) light in ambient conditions. Significantly, no additives such as initiator, solvent, or catalyst are required for efficient gelation. Formulations that include bis-LA-functionalized cross-linker yield bottlebrush elastomers with high gel fractions (83-98%) and tunable, supersoft shear moduli in the ∼20-200 kPa range. An added advantage of these materials is the dynamic disulfide bonds along each bottlebrush backbone, which allow for light-mediated self-healing and on-demand chemical degradation. These results highlight the potential of simple and scalable synthetic routes to generate unique bottlebrush polymers and elastomers based on PDMS.

Light-Mediated Synthesis and Reprocessing of Dynamic Bottlebrush Elastomers under Ambient Conditions

/pdf/multiaddressable-photochromic-architectures-from-molecules-1lkfemfc7q.pdf

Multiaddressable Photochromic Architectures: From Molecules to Materials

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