The catalytic performance, depending on the surface nature, is ubiquitous in photocatalysis. However, surface engineering for organic photocatalysts through structural modulation has long been neglected. Here, we propose a zone crystallization strategy for covalent organic frameworks (COFs) that enhances surface ordering through regulator-induced amorphous-tocrystalline transformation. Dynamic simulations show that attaching monofunctional regulators to the surface of spherical amorphous precursor improves surface dynamic reversibility, increasing crystallinity from the inside out. The resulting COF microspheres display surface-enhanced crystallinity and uniform spherical morphology. The visible photocatalytic hydrogen evolution rate reaches 126 mmol g–1 h–1 for the simplest β-ketoenamine-linked COF and 350 mmol gCOF–1 h–1 for SiO2@COF with minimal Pt cocatalysts. Mechanism studies indicate that surface crystalline domains build the surface electrical fields to accumulate photogenerated electrons and diminish electron transfer barriers between the COF and Pt interface. This work bridges the gap between microscopic molecules and macroscopic properties, allowing tailored design of crystalline organic photocatalysts.

The study of structure−activity relationships is a top priority in the development of nontraditional luminescent materials. In this work, nonconjugated polyurethanes (PUs) with full-color emission (red, green, and blue) are easily obtained by control of the diol monomer structure and the polymerization conditions. Selected diol monomers introduced single, double, or triple bond repeating units into the main chain of the PUs, in order to understand how unsaturated bonds and H-bonds affect their luminescence from a molecular orbital viewpoint. Detailed experimental and theoretical results show that the PUs have different temperature-dependent behaviors related to the interplay of H-bonding, through-space n−π interactions, and aggregation properties. The potential applications of PUs in colorful displays, covert information transmission, and multifunctional bioimaging have been verified. This work provides a new general protocol for the simple preparation of multifunctional nonconventional fluorescent polymers and deepens the understanding of their luminescence mechanisms.

Unlike one-dimensional polymers, the theoretical framework on the behaviors of two-dimensional (2D) polymers is far from completeness. In this study, we model single-layer flexible 2D polymers of different sizes and examine their scaling behaviors in solution, represented by Rg ∼ Lν, where Rg is the radius of gyration and L is the side length of a 2D polymer. We find that the scaling exponent ν is 0.96 for a good solvent and 0.64 for under poor solvent condition. Interestingly, we observe a previously unnoticed phenomenon:under intermediate solvent conditions, the 2D polymer folds to maintain a flat structure, and as L becomes larger, multiple folded structures emerge. We introduce a shape parameter Q to diagram the relationship of folded structures with the polymer size and solvent condition. Theoretically, we explain the folding transitions by the competition between bending and solvophobic free energies.

Nonconventional chromophores are good candidates for preparing luminous gels because their luminescence is usually enhanced in the aggregated state. In this work, a simple one-pot strategy for polymerization-induced gelation of polymer fluorescent gels was developed, and a self physically crosslinked luminous gel PUHG based on a non-conjugated/nonconventional luminous polyurethane derivative was obtained. Detailed experimental and theoretical studies probed the physical properties and luminescence principles of PUHG's aggregated state. Molecular dynamics simulations suggest that abundant non-covalent interactions and physical entanglement between polyurethane chains are the main driving forces of gel formation and the source of luminescence. PUHG displays stable photophysical properties, environmental tolerance, good adhesion properties and processability, leading to the validation of patterning applications of PUHG on different organic/inorganic substrates. This work broadens the application range of nonconventional luminous polymers and provides a simple route for large-scale preparation of fluorescent gel soft materials.

Charge-transfer mechanisms in adaptive multicomponent solutions at liquid–solid interfaces with triboelectric probes are crucial for understanding chemistry dynamics. However, liquid–solid charge transfer becomes unpredictable, due to the components or interactions in solutions, restricting its potential application for precise monitoring of liquid environments. This study utilizes triboelectric probes to investigate the charge transfer of chemicals, applying this approach to real-time coolant state monitoring. Analysis of electrical signal dynamics induced by ethylene glycol and its oxidation byproduct, oxalic acid, in ethylene glycol solutions reveals that hydrogen bond and ion adsorption diminishes the efficiency of electron transfer at the liquid–solid interface. These findings promote the engineering of the triboelectric probe that enhances coolant quality with remarkable sensitivity (detection limit:0.0001%) and a broad freezing point operational range (0 to −49 °C). This work advances the precise control of the charge dynamics and demonstrates the potential of triboelectric probes for interdisciplinary applications.