Zhaowei Jia

2D covalent organic frameworks (COFs) have emerged as promising functional materials for catalysis, adsorption, sensing, and energy storage. Their interfacial behavior and surface microenvironment play a decisive role in performance, yet these features are typically considered static or irreversible due to the lack of dynamic structure models. In this study, we report the construction of an ionic COF (iCOF), I‐4, designed through precise tuning of its skeleton and counterions, which uniquely exhibits reversable dynamic exfoliation and aggregation behavior in aqueous environments. This enables bidirectional control over particle size and phase states. Photocatalytic hydrogen evolution (PHE) studies reveal a strong correlation between solution concentration, particle size, and hydrogen production efficiency. Notably, I‐4 achieves a remarkable PHE rate of 190 mmol g ⁻¹ h ⁻¹ at 35°C. Moreover, the material can be fully precipitated and recovered from solution by simple iodide salt addition, enabling closed‐loop material recycling. Mechanistic analysis based on weak‐force interactions and soft‐hard acid‐base theory provides insight into the dynamic exfoliation process, highlighting the synergistic roles of counterion assembly and framework structure. These findings pave the way for the tailored synthesis of next‐generation dynamic COF materials with reversible interfacial adaptability, offering broad application potential in catalysis, ion transport, and molecular separation.

Precise arrangement of multivalent Cu sites for the synchronized activation of CO ₂ and H ₂ in selective methanol synthesis remained challenging. Herein, we designed spatially arrayed Cu ⁺ ‐Cu ⁰ cluster pairs confined within UiO‐66 (U66) to achieve spatiotemporally directed CO ₂ hydrogenation to methanol. This architecture was constructed by creating missing‐linker defects within U66 using L‐ascorbic acid (LA), followed by sequential anchoring of high‐density, adjacent Cu ⁺ ‐Cu ⁰ cluster pairs (≈1:1 ratio) to yield a Cu/U66(LA‐Cu) catalyst. Under reaction conditions of 220°C and 3 MPa, this catalyst achieved a methanol space‐time yield of 688.1 mg·g ⁻¹ ·h ⁻¹ and an ultra‐high methanol selectivity (97.0%). Its unity‐methanol selectivity was 1.06–1.77 times that of high‐stability oxide materials. Meanwhile, catalyst's stability of 200 h was significantly prolonged compared to high‐selectivity MOF‐based catalysts that operated stably for 60–175 h. Mechanistic studies revealed that Cu ⁺ ‐Cu ⁰ cluster pairs within defective U66 not only enabled partitioned synergistic activation of CO ₂ and H ₂ , but established an efficient electron/hydrogen transfer pathway. This facilitated the migration of active hydrogen species to CO ₂ adsorption sites, where adsorbed CO ₂ was converted into CO intermediates and underwent deep hydrogenation. This structural design synergistically enhanced compatibility between H ₂ dissociation and CO ₂ hydrogenation steps, enabling reaction to proceed efficiently along the RWGS + CO‐hydro pathway.

Precise arrangement of multivalent Cu sites for the synchronized activation of CO ₂ and H ₂ in selective methanol synthesis remained challenging. Herein, we designed spatially arrayed Cu ⁺ ‐Cu ⁰ cluster pairs confined within UiO‐66 (U66) to achieve spatiotemporally directed CO ₂ hydrogenation to methanol. This architecture was constructed by creating missing‐linker defects within U66 using L‐ascorbic acid (LA), followed by sequential anchoring of high‐density, adjacent Cu ⁺ ‐Cu ⁰ cluster pairs (≈1:1 ratio) to yield a Cu/U66(LA‐Cu) catalyst. Under reaction conditions of 220°C and 3 MPa, this catalyst achieved a methanol space‐time yield of 688.1 mg·g ⁻¹ ·h ⁻¹ and an ultra‐high methanol selectivity (97.0%). Its unity‐methanol selectivity was 1.06–1.77 times that of high‐stability oxide materials. Meanwhile, catalyst's stability of 200 h was significantly prolonged compared to high‐selectivity MOF‐based catalysts that operated stably for 60–175 h. Mechanistic studies revealed that Cu ⁺ ‐Cu ⁰ cluster pairs within defective U66 not only enabled partitioned synergistic activation of CO ₂ and H ₂ , but established an efficient electron/hydrogen transfer pathway. This facilitated the migration of active hydrogen species to CO ₂ adsorption sites, where adsorbed CO ₂ was converted into CO intermediates and underwent deep hydrogenation. This structural design synergistically enhanced compatibility between H ₂ dissociation and CO ₂ hydrogenation steps, enabling reaction to proceed efficiently along the RWGS + CO‐hydro pathway.

The photosensitive unit and conjugation play a significant role in photocatalytic performance of covalent organic frameworks (COFs). In this work, a series of COFs that introduced the phenyl phenanthridine as photosensitive unit with different planarity of linkages were synthesized and the common regulation between them for photocatalysis hydrogen evolution reaction (HER) was also studied. The results indicate that DHTB‐PPD, with 2/3 planarity linkages (β‐ketoenamine/imine is 2/3) and the phenyl phenanthridine as building blocks, shows the narrowest bandgap and the strongest charge separation efficiency. Therefore, it shows the highest H₂ production rate of 12.13 mmol g⁻¹ h⁻¹. The optimal photocatalytic efficiency of DTHB‐PPD can be attributed to the combined effect of the photosensitive unit and the long‐range ordering of the COF skeleton. According to The Density Functional Theory (DFT), the O site on β‐ketoamine is the most possible H₂ generation site, but the photocatalytic efficiency of TP‐PPD, with the highest skeletal conjugation and the highest proportion of β‐ketoamine is not the most efficient photocatalyst, indicating that the long‐range ordering of COFs is important on photocatalytic performance. Thus, these findings provide valuable guidance for the structural design of COFs photocatalysts.

Sulfur hexafluoride (SF ₆ ) is an artificial inert gas widely used in the power and semiconductor industries and is known to be a significant contributor to the greenhouse effect due to its high global warming potential.

The poly(phenolic ester)s are attracting growing attention due to their essential role in the application as biodegradable plastics. Thus, extensive efforts have been devoted to the development of methodology that allows facile preparation of poly(phenolic ester)s with controlled molecular weights for widespread utilities. However, it is highly challenging to introduce phenolic ester bond structure into polyesters from ring‐opening polymerization (ROP) to yield aromatic/semiaromatic poly(phenolic ester)s due to severe transesterification reactions. To synthesize poly(phenolic ester)s with desired structures and properties, scientists have developed various ring‐opening polymerization systems with distinct advantages. Here, we have summarized basic features and recent progresses of these methods, including the cyclic phenolic lactone polymerization system, the salicylic acid O‐carboxyanhydride polymerization system, and the dissymmetric cyclic phenolic lactide polymerization system, as well as other copolymerization routes. Furthermore, the advantages and unsettled problems in various synthetic ways are discussed for readers to choose fast and controllable ROP systems for poly(phenolic ester)s.