Multiphasic titanium dioxide (TiO2) possessing abundant heterophase junctions have been widely used for various photocatalytic applications. Current synthesis of multiphasic TiO2 mainly involves the process of thermal treatment and multiple steps of rigorous reactions, which is adverse to controlling the crystal phases and phase ratios of multiphasic TiO2. Meanwhile, the resulting products have relatively low surface area and nonporous structure. Here, a facile polymer‐assisted coordination‐mediated self‐assembly method to synthesize mesoporous TiO2 polymorphs with controllable heterophase junctions and large surface area by using polyethylenimine as the porogen in an acidic aqueous synthesis system is reported. Using this approach, the crystal phases (triphase, biphase, and monophase) and phase compositions (0–100%) are easily tailored by selecting the suitable acidic media. Furthermore, the specific surface areas (77–228 m2 g−1) and pore sizes (2.9–10.1 nm) are readily tailored by changing the reaction temperature. The photocatalytic activity of mesoporous TiO2 polymorphs is evaluated by photocatalytic hydrogen evolution. The triphasic TiO2 exhibits an excellent photocatalytic H2 generation rate of 3.57 mmol h−1 g−1 as compared to other polymorphs, which is attributed to the synergistic effects of heterophase junctions and mesostructure. The band diagram of possible electron transfer pathway for triphasic TiO2 is also elucidated.

Porous polymers with well‐orchestrated nanomorphologies are useful in many fields, but high surface area, hierarchical structure, and ordered pores are difficult to be satisfied in one polymer simultaneously. Herein, a solvent‐induced self‐assembly strategy to synthesize hierarchical porous polymers with tunable morphology, mesoporous structure, and microporous pore wall is reported. The poly(ethylene oxide)‐b‐polystyrene (PEO‐b‐PS) diblock copolymer micelles are cross‐linked via Friedel–Crafts reaction, which is a new way to anchor micelles into porous polymers with well‐defined structure. Varying the polarity of the solvent has a dramatic effect upon the oleophobic/oleophylic interaction, and the self‐assembly structure of PEO‐b‐PS can be tailored from aggregated nanoparticles to hollow spheres even mesoporous bulk. A morphological phase diagram is accomplished to systematically evaluate the influence of the composition of PEO‐b‐PS and the mixed solvent component on the pore structure and morphology of products. The hypercrosslinked hollow polymer spheres provide a confined microenvironment for the in situ reduction of K2PdCl4 to ultrasmall Pd nanoparticles, which exhibit excellent catalytic performance in solvent‐free catalytic oxidation of hydrocarbons and alcohols.

HIGHLIGHTS • Highly crystalline Mn 2 O 3 materials with tunable pore sizes are obtained and employed as high-performance cathode materials for reversible aqueous Zn-ion battery. • The Zn/Mn 2 O 3 battery exhibits significantly improved rate capability and remarkable cycling durability due to the introduction of nanoporous architecture. • The Zn 2+ /H + intercalations mechanism is put forward for the Zn/Mn 2 O 3 battery.

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