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Metal-organic framework (MOF) thin films offer exceptional properties for diverse applications, yet the mechanisms underlying MOF crystallization are not fully understood. Knowledge gaps remain regarding the nucleation and growth mechanisms of these highly porous, crystalline materials under dynamic evaporative conditions. Here, an in situ grazing incidence wide-angle X-ray scattering (GIWAXS) combined with a microkinetic model is used to probe the dynamic growth of MOF films. We show that while most high-order oligomers are produced in the solution phase, the key parameters that control thin-film growth are autocatalytic synthesis of secondary building units (SBUs) followed by physisorption on silicon wafer substrate, exponential growth due to evaporation-driven step growth, and transition to the stationary phase due to mass-transfer-limited growth. Importantly, this study demonstrates the applicability of this microkinetic modeling framework to predict film properties across a range of temperatures and reactant concentrations, allowing for rational design of MOF thin films. 

High-entropy metal-organic frameworks (HE-MOFs) offer a promising approach for advanced applications like energy storage, catalysis, and sensing, thanks to their high configurational entropy and synergistic effects from multiple elements. Despite the progress in synthesizing HE-MOFs, primarily through solvothermal methods, little is known about the reticular chemistry governing morphological variations. This work presents a new class of porphyrinic HE-MOFs, offering insights into the lattice transformations by controlling secondary building unit (SBU) topology. The study also explores spatial configuration and dynamic elemental composition, proposing that metal incorporation, spatial variation, and node stability are influenced by metal precursor dissociation and metal-oxygen bond strength, which dictate long-term structural dynamics. 

In-situ characterization techniques, although complex, can provide a wealth of insight into material chemistry and evolution dynamics. Grasping the fundamental kinetics of material synthesis is essential to enhance and streamline these processes and facilitate easier scaleup. Metal–organic frameworks (MOFs), a class of porous crystalline materials discovered three decades ago, have been developed and implemented in various applications at the laboratory scale. However, only a few studies have explored the fundamental mechanisms of their formation that determine their physical structure and chemical properties. Independent experimental and theoretical investigations focusing on chemical kinetics have provided some understanding of the mechanisms governing MOF formation. However, more effort is needed to fully control their formation pathways and properties to enhance stability, optimize performance, and design strategies for scalable production. This Perspective highlights current techniques for studying MOF kinetics, discusses their limitations, and proposes multimodal experimental and theoretical protocols, emphasizing how improved data acquisition and multiscale approaches can advance scalable applications. 

Abstract Electrochemical CO₂reduction reaction (CO₂‐RR) in non‐aqueous electrolytes offers significant advantages over aqueous systems, as it boosts CO₂solubility and limits the formation of HCO₃⁻and CO₃²⁻anions. Metal–organic frameworks (MOFs) in non‐aqueous CO₂‐RR makes an attractive system for CO₂capture and conversion. However, the predominantly organic composition of MOFs limits their electrical conductivity and stability in electrocatalysis, where they suffer from electrolytic decomposition. In this work, electrically conductive and stable Zirconium (Zr)‐based porphyrin MOF, specifically PCN‐222, metalated with a single‐atom Cu has been explored, which serves as an efficient single‐atom catalyst (SAC) for CO₂‐RR. PCN‐ 222(Cu) demonstrates a substantial enhancement in redox activity due to the synergistic effect of the Zr matrix and the single‐atom Cu site, facilitating complete reduction of C₂species under non‐aqueous electrolytic conditions. The current densities achieved (≈100 mA cm⁻²) are 4–5 times higher than previously reported values for MOFs, with a faradaic efficiency of up to 40% for acetate production, along with other multivariate C₂products, which have never been achieved previously in non‐aqueous systems. Characterization using X‐ray and various spectroscopic techniques, reveals critical insights into the role of the Zr matrix and Cu sites in CO₂reduction, benchmarking PCN‐222(Cu) for MOF‐based SAC electrocatalysis. 

The chemical pathway for synthesizing covalent organic frameworks (COFs) involves a complex medley of reaction sequences over a rippling energy landscape that cannot be adequately described using existing theories. Even with the development of state-of-the-art experimental and computational tools, identifying primary mechanisms of nucleation and growth of COFs remains elusive. Other than empirically, little is known about how the catalyst composition and water activity affect the kinetics of the reaction pathway. Here, for the first time, we employ time-resolved in situ Fourier transform infrared spectroscopy (FT-IR) coupled with a six-parameter microkinetic model consisting of ∼10 million reactions and over 20 000 species. The integrated approach elucidates previously unrecognized roles of catalyst p K a on COF yield and water on growth rate and size distribution. COF crystalline yield increases with decreasing p K a of the catalysts, whereas the effect of water is to reduce the growth rate of COF and broaden the size distribution. The microkinetic model reproduces the experimental data and quantitatively predicts the role of synthesis conditions such as temperature, catalyst, and precursor concentration on the nucleation and growth rates. Furthermore, the model also validates the second-order reaction mechanism of COF-5 and predicts the activation barriers for classical and non-classical growth of COF-5 crystals. The microkinetic model developed here is generalizable to different COFs and other multicomponent systems.