Sheng Zhang

Covalent organic frameworks (COFs) have emerged as a versatile class of porous materials with promising applications in catalysis, energy storage, and gas adsorption. However, their synthesis remains a major bottleneck primarily due to the widespread reliance on inefficient trial-and-error approaches that waste resources and delay discovery. Herein, we address this challenge by integrating success and failure data: we curated 1822 in-house failed synthesis records and extracted 2603 successful cases from the literature. A random forest machine learning (ML) model, selected for its robustness with complex experimental data sets, achieved 91% accuracy in solvent prediction and demonstrated strong predictive performance for reaction temperature (R2 = 0.9129) and reaction time (R2 = 0.9596), significantly outperforming models trained solely on success-only or trial-and-error data sets. Building on this model, we developed the ML-COF toolkit, which automates the retrieval of known COF synthesis routes and accurately predicts conditions for novel frameworks. Experimental validation, conducted across eight structurally complex and synthetically challenging COFs, including six M(salen)-COFs and two M(Rabson)-COFs, confirmed the toolkit’s high predictive accuracy, with all targets successfully synthesized under predicted conditions. This work establishes a data-driven paradigm for COF synthesis, offering a practical alternative to trial-and-error methods and paving the way for accelerated discovery and future robot-assisted synthesis.

Covalent organic frameworks, with their tunable pore structures, chemical environments, and high stability, are promising candidates for next‐generation solid‐state battery separators. To uncover the fundamental Li ⁺ transport mechanisms and enable rational design, we performed high‐throughput molecular dynamics simulations and data‐driven screening on a library of 628 metallosalen‐based COFs across five representative lithium‐salt systems. Our results demonstrate that efficient Li ⁺ transport depends critically on matching the COF pore chemistry with anion characteristics: weakly coordinated BOB ⁻ anions favor lightweight, moderately confined pores, whereas flexible TFSI ⁻ anions perform better in large‐pore, open‐topology COFs. More importantly, our simulation data suggest a potential anion‐engaged cooperative transport mode. This mode is characterized by the formation of a dynamic coordination network when a significant proportion (> 50%) of anions exhibit spatially confined motion. These confined anions appear to repeatedly coordinate and release Li ⁺ ions, facilitating a relay‐style conduction along the pore channels. Simulation analyses indicate that this mode correlates with high Li ⁺ diffusion coefficients and uniform ionic flux. Based on these observations, we propose two material design guidelines: anion‐adaptive pore matching and confined‐anion dynamics regulation. This work offers a theoretical perspective and a computational screening strategy for the rational design of COF‐based solid electrolytes.

Metal–organic frameworks (MOFs) have attracted significant attention for photocatalytic CO2 reduction due to their tunable pore environments, abundant active sites, and diverse stacking modes. However, the effect of different interlayer stacking, particularly when multiple stacking modes coexist within the same structure, remains underexplored. Here, we report a Copper-Melamine Framework (Cu-Mel-MOF) in which AA-rotated and AA-serrated stacking structures coexist in localized region: the 60° interlayer twist in the AA-rotated stacking induces the formation of a short-range Moiré superlattice, whereas the AA-serrated stacking exhibits staggered zigzag-like interlayer offsets. Under visible light irradiation, Cu-Mel-MOF achieves CO and H2 evolution rates of 6.27 and 3.96 mmol g–1 h–1, respectively, surpassing previously reported copper-based MOF photocatalysts. Grand Canonical Monte Carlo simulations reveal that among six stacking configurations, the serrated AA and AA-rotated stackings exhibit the highest CO2 and H2O adsorption capacities. Molecular dynamics simulations show that AA-rotated stacking reduces the CO2 activation energy (Ea = 0.20 eV), facilitating CO2 molecular transport. Density functional theory calculations further indicate that AA-rotated stacking possesses a higher CO2 adsorption energy (1.17 eV), while the serrated AA stacking exhibits a lower Gibbs free energy change in the *COOH adsorption step, enhancing overall photocatalytic performance. These findings highlight the pivotal role of stacking geometry in regulating the thermodynamics and kinetics of MOF-based photocatalysis, providing insights into molecular transport mechanisms and guiding the rational design of efficient MOF photocatalysts for CO2 conversion.

Among the recent developments in metal–organic frameworks (MOFs), porous two-dimensional (2D) MOFs have garnered attention due to providing key technical supports, important energy-saving measures and precise chemical sensors for the green and sustainable society. Herein, two rare porous 2D Dy³⁺ MOFs, namely [Dy₄L₆(DMA)₂(H₂O)₃]·7DMA (1, DMA = N,N-dimethylacetamide) and [Dy₂L₃(DMF)₂]·DMF (2, DMF = N,N-dimethylformamide), have been successfully synthesized from reaction with 4,4′-(1,2-diphenylethene-1,2-diyl) dibenzoic acid (H₂L) under different solvent systems. The main distinctions between the crystal structures of 1 and 2 arise from the differing solvent molecules residing within the pores which interact with the surrounding frameworks. These effects lead to different sizes of 1D channels. Importantly, different solvents of coordinated/free DMA molecules in 1 and DMF molecules in 2 induce the conversion of magnetic dynamics. Compound 1 exhibits obvious slow magnetic relaxation behavior under 0 Oe dc field, while zero-field out-of-phase signals of 2 exhibit no peaks in the whole temperature range. Compound 1 was magnetically characterized as a new example that the slow magnetic relaxation process can be observed in a 2D Dy³⁺ layer with 1D channels. Theoretical analysis based on ab initio calculation provides interpretations of magnetic observation. Additionally, compounds 1 and 2 have been tested as efficient fluorescent sensors for Fe³⁺ ions with high selectivity and sensitivity. The fluorescence quenching of 1 and 2 was demonstrated by an approximately 90% reduction in the emission intensity upon binding to Fe³⁺ ions. The emission intensities of 1 and 2 at 464 nm and 443 nm have shown linear responses to Fe³⁺ ion concentration with detection limits of 4.51 × 10⁶ ppb and 6.90 × 10⁶ ppb.

Based on the synergistic effect of doped Ti and oxygen vacancies, Ti-doped W ₁₈ O ₄₉ shows excellent visible light photochromic performance, and is extremely valuable in applications in smart windows and rewritable paper.

Based on the bis-β-diketonate-Dy₂ metalloligand, six dinuclear complexes with eight-coordinated geometries were synthesized solvothermally through different capping N-donor coligands or solvent systems.

An iodine-mediated oxidative [4+1] cyclization of enamines with TMSN₃ for the synthesis of 2,5-disubstituted imidazole-4-carboxylic derivatives has been developed. The mechanistic studies revealed that the reaction proceeds through a sequential removal of two nitrogen atoms from TMSN₃. The synthetic utility was further demonstrated with a gram-scale reaction and various derivatization transformations of the products.