Dan Li

Hydrogen peroxide (H ₂ O ₂ ) is a green oxidant and potential energy carrier, and the photosynthesis of H ₂ O ₂ from water and oxygen offers a sustainable alternative to the conventional anthraquinone process. Due to the tunable skeletons, adjustable pore microenvironments, and designable active sites, covalent organic frameworks (COFs) and metal‐organic frameworks (MOFs) have emerged as crystalline porous photocatalysts for H ₂ O ₂ production. This review summarizes recent advances in COF/MOF photocatalysts for H ₂ O ₂ production, focusing on density functional theory (DFT)‐based mechanistic insights, descriptor construction, and data‐driven catalyst discovery enabled by artificial intelligence (AI) and machine learning (ML). We first discuss how DFT calculations elucidate active sites, charge‐transfer pathways, and reaction mechanisms by revealing electronic structures, excited‐state charge distributions, adsorption behavior, and reaction free‐energy profiles. We then highlight how DFT‐derived descriptors can bridge mechanistic understanding with materials screening. Finally, we discuss how AI and ML approaches integrate experimental performance, reaction conditions, structural features, and theoretical descriptors to enable candidate screening and design‐rule extraction. Overall, the integration of DFT calculations with AI/ML methods provides a promising route toward mechanism‐guided and data‐driven discovery of COF/MOF photocatalysts for solar‐driven H ₂ O ₂ production.

Li-ion batteries (LIBs) capable of sustaining high-temperature cycling are essential for energy storage; however, building cathode materials with stable cycling for long term at high temperatures remains a significant challenge. Organic cathode materials have significant applied implications for LIBs; however, they are limited by low electronic conductivity, which requires a large amount of inactive conductive carbon for electrode fabrication, leading to a significant decrease in energy density. Herein, we demonstrated that a π-conjugated covalent organic polymer (COP) cathode, coupled with ether-based electrolytes containing 2 wt % LiNO3 additives, could act as an ultra-stable conductive-additive-free organic cathode for lithium storage at room and high temperatures. Typically, at 60 °C, the conductive-additive-free COP cathode could deliver a high initial reversible capacity (374 mAh g–1), an unprecedented cyclability for 5000 cycles (0.01% capacity decay per cycle), and a promising rate capability. The π-conjugated framework of this COP promises enhanced electronic conductivity with high mechanical and chemical stability. The ether-based electrolyte shows favorable compatibility with the cathode and yields a stable cathode–electrolyte interface (CEI) with LiF as an ionic-conductor component to facilitate Li+ transport.

Cu( i )-CMOFs showed acid-triggered ABC-to-AA stacking conversion, where the ABC mode showed enhanced catalytic performance in CO ₂ cycloaddition.

The introduction of polycatenane junctions into dative B←N bond‐linked covalent organic polymers (COPs) poses a significant synthetic challenge for the synergistic optimization of both geometric stabilization and molecular functionality. Herein, we strategically employ tritopic borate ligands bearing terminal –Br substituents, rather than their ditopic counterparts, as precursors to construct a single‐crystalline COP ( JNP‐7 ) featuring polycatenane‐like topological junctions. Specifically, B‐centered Lewis acceptors and N‐donor units initially assemble into 1D nanoribbons via dative B←N linkages. By leveraging inter‐nanoribbon halogen···halogen interactions between the semi‐interlocked Br‐containing motifs, the architecture is further extended into 2D arrays, thereby elevating the geometric dimensionality of JNP‐7 . Critically, the resulting polycatenated halogen‐bonded network imparts exceptional structural rigidity, and the dative B←N motifs are found to concurrently promote visible‐light harvesting and facilitate charge‐carrier migration. Consequently, JNP‐7 enables highly efficient H ₂ O ₂ production via both the oxygen reduction reaction (ORR) and water oxidation reaction (WOR) under ambient sunlight, operating without sacrificial agents, photosensitizers, or metal cocatalysts, and outperforming state‐of‐the‐art covalent organic frameworks (COFs) and metal‐organic frameworks (MOFs) in terms of photocatalytic activity and apparent quantum yield (AQY). By aligning molecular topology with catalytic function, this work establishes a generalizable framework for the rational development of topologically sophisticated, high‐performance COP systems.

The introduction of polycatenane junctions into dative B←N bond‐linked covalent organic polymers (COPs) poses a significant synthetic challenge for the synergistic optimization of both geometric stabilization and molecular functionality. Herein, we strategically employ tritopic borate ligands bearing terminal –Br substituents, rather than their ditopic counterparts, as precursors to construct a single‐crystalline COP ( JNP‐7 ) featuring polycatenane‐like topological junctions. Specifically, B‐centered Lewis acceptors and N‐donor units initially assemble into 1D nanoribbons via dative B←N linkages. By leveraging inter‐nanoribbon halogen···halogen interactions between the semi‐interlocked Br‐containing motifs, the architecture is further extended into 2D arrays, thereby elevating the geometric dimensionality of JNP‐7 . Critically, the resulting polycatenated halogen‐bonded network imparts exceptional structural rigidity, and the dative B←N motifs are found to concurrently promote visible‐light harvesting and facilitate charge‐carrier migration. Consequently, JNP‐7 enables highly efficient H ₂ O ₂ production via both the oxygen reduction reaction (ORR) and water oxidation reaction (WOR) under ambient sunlight, operating without sacrificial agents, photosensitizers, or metal cocatalysts, and outperforming state‐of‐the‐art covalent organic frameworks (COFs) and metal‐organic frameworks (MOFs) in terms of photocatalytic activity and apparent quantum yield (AQY). By aligning molecular topology with catalytic function, this work establishes a generalizable framework for the rational development of topologically sophisticated, high‐performance COP systems.

Acidic CO ₂ electroreduction offers a compelling route to mitigate carbonate formation and improve carbon efficiency, yet the high proton concentration intensifies hydrogen evolution reaction (HER), severely suppressing multi‑carbon (C ₂₊ ) production. While covalent organic frameworks (COFs) are explored to modulate the reaction microenvironment, existing studies primarily focus on the confinement of alkali cations, CO ₂ , and CO intermediates, largely overlooking the critical role of proton‑transport. Herein, we demonstrate that an imine‑linked COF (TAPB–BTCA) anchored on Cu electrocatalysts functions as a proton‑regulating interlayer. Combined experimental and molecular dynamics simulation analyses reveal that the reversible protonation of its C═N bonds retards H ⁺ diffusion to the Cu surface, suppressing HER and preserving a locally alkaline environment conducive to C─C coupling. The Cu/TAPB–BTCA electrode achieves 74.0% Faradaic efficiency for C ₂₊ at −250 mA cm ⁻² , a 58% improvement over bare Cu, and outperforms previously reported COF‑based electrocatalysts under similar acidic conditions. Comparison with two other imine‐linked COFs (LZU‑1 and CQN) shows that the protonation capability, dictated by the conjugated framework structure, governs proton‑blocking efficacy, local microenvironment, and consequently CO ₂ RR performance. This work highlights proton‑transport management via rationally designed COF frameworks as a promising strategy to achieve efficient acidic CO ₂ electroreduction.

Acidic CO ₂ electroreduction offers a compelling route to mitigate carbonate formation and improve carbon efficiency, yet the high proton concentration intensifies hydrogen evolution reaction (HER), severely suppressing multi‑carbon (C ₂₊ ) production. While covalent organic frameworks (COFs) are explored to modulate the reaction microenvironment, existing studies primarily focus on the confinement of alkali cations, CO ₂ , and CO intermediates, largely overlooking the critical role of proton‑transport. Herein, we demonstrate that an imine‑linked COF (TAPB–BTCA) anchored on Cu electrocatalysts functions as a proton‑regulating interlayer. Combined experimental and molecular dynamics simulation analyses reveal that the reversible protonation of its C═N bonds retards H ⁺ diffusion to the Cu surface, suppressing HER and preserving a locally alkaline environment conducive to C─C coupling. The Cu/TAPB–BTCA electrode achieves 74.0% Faradaic efficiency for C ₂₊ at −250 mA cm ⁻² , a 58% improvement over bare Cu, and outperforms previously reported COF‑based electrocatalysts under similar acidic conditions. Comparison with two other imine‐linked COFs (LZU‑1 and CQN) shows that the protonation capability, dictated by the conjugated framework structure, governs proton‑blocking efficacy, local microenvironment, and consequently CO ₂ RR performance. This work highlights proton‑transport management via rationally designed COF frameworks as a promising strategy to achieve efficient acidic CO ₂ electroreduction.

Controlling the photophysical properties of metal clusters without altering their intrinsic cores remains challenging because molecular structure and crystal packing are often strongly coupled in such system. Herein, we show that a cyclic trinuclear gold (I) complex (Au3) can serve as a structurally defined precursor for hierarchical assembly, enabling packing-controlled photoluminescence while changing the metal core composition. By varying the feed ratio of Au3 and AgBF4, two polymorphs, Au6Ag-α and Au6Ag-β, were obtained, both featuring distorted trigonal-prismatic Au3–Ag–Au3 sandwich structures. Despite their identical compositions, they exhibit distinct solid-state emission, with Au6Ag-α showing yellow emission and Au6Ag-β displaying red-shift orange emission with a higher quantum yield. Single-crystal structure analysis and theoretical calculations reveal that Au6Ag-α is governed by a ligand-dominated heptanuclear unit, whereas tighter packing in Au6Ag-β induces intersandwich interactions, giving rise to a stacked decanuclear emissive unit with pronounced ligand-to-metal-metal charge transfer (LMMCT) character. These findings demonstrate that the use of an appropriate cluster precursor enables spatial packing control over compositionally identical clusters, providing a viable route to tune photophysical properties without altering the intrinsic metal core.