Heterogeneous catalysts undergo thermal- and/or adsorbate-induced dynamic changes under reaction conditions, which consequently modify their catalytic behavior. Hence, it is increasingly crucial to characterize the properties of a catalyst under reaction conditions through the so-called "operando" approach. Operando IR spectroscopy is probably one of the most ubiquitous and versatile characterization methods in the field of heterogeneous catalysis, but its potential in identifying adsorbate- and thermal-induced phenomena is often overlooked in favor of other less accessible methods, such as XAS spectroscopy and high-resolution microscopy. Without detracting from these techniques, and while aware of the enormous value of a multitechnique approach, the purpose of this Review is to show that IR spectroscopy alone can provide relevant information in this field. This is done by discussing a few selected case studies from our own research experience, which belong to the categories of both "single-site"- and nanoparticle-based catalysts.

The Lewis/Brønsted catalytic properties of the Metal–Organic Framework (MOF) nodes can be tuned by simply controlling the solvent employed in the synthetic procedure. In this work, we demonstrate that Hf-MOF-808 can be prepared from a material with a higher amount of Brønsted acid sites, via modulated hydrothermal synthesis, to a material with a higher proportion of unsaturated Hf Lewis acid sites, via modulated solvothermal synthesis. The Lewis/Brønsted acid properties of the resultant metallic clusters have been studied by different characterization techniques, including XAS, FTIR and NMR spectroscopies, combined with a DFT study. The different nature of the Hf-MOF-808 materials allows their application as selective catalysts in different target reactions requiring Lewis, Brønsted or Lewis–Brønsted acid pairs.

Metal–organic frameworks (MOFs) are promising materials for a wide range of applications given their chemical stability and structural tunability. Most traditional MOF synthesis methods use batch reactors with intrinsic inefficiencies during scale-up that negatively impact process productivity. Here, we report a low-cost and energy-efficient continuous manufacturing process for MOF-808—a Zr-MOF widely studied as a catalyst and adsorbent in industrially important processes—using flow-through reactors that increase process yields and minimize solvent use compared to batch processes. The flow platform allowed us to investigate the influence of several synthesis parameters, including residence time, linker concentration, and volumetric ratio of modulator and solvent on the crystallization process. Under optimal conditions, the N,N-dimethylformamide solvent and formic acid modulator volumetric amounts were decreased by 84% and 67%, respectively, and resulted in an increase in productivity (defined in units of kg_MOF m⁻³ day⁻¹) by two orders of magnitude with similar yields, compared to established batch synthesis methods. A process engineering assessment based on laboratory-scale synthesis routes was performed to compare energy and cost savings for flow and batch workflows, indicating that solvent use was the largest contributor to the overall cost. The methodology presented in this work opens new pathways for critical assessment and optimization of continuous manufacturing routes on a lab-scale environment, which serve as a preliminary step for the transition to more efficient MOF synthesis routes at the industrial scale.

Hafnium-based metal–organic frameworks are promising catalysts for upgrading biomass derivatives via an aldol condensation reaction.

The structure of UiO-66(Ce) is formed by CeO_2–x defective nanoclusters connected by terephthalate ligands. The initial presence of accessible Ce³⁺ sites in the as-synthesized UiO-66(Ce) has been determined by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR)-CO analyses. Moreover, linear scan voltammetric measurements reveal a reversible Ce⁴⁺/Ce³⁺ interconversion within the UiO-66(Ce) material, while nanocrystalline ceria shows an irreversible voltammetric response. This suggests that terephthalic acid ligands facilitate charge transfer between subnanometric metallic nodes, explaining the higher oxidase-like activity of UiO-66(Ce) compared to nanoceria for the mild oxidation of organic dyes under aerobic conditions. Based on these results, we propose the use of Ce-based metal–organic frameworks (MOFs) as efficient catalysts for the halogenation of activated arenes, as 1,3,5-trimethoxybenzene (TMB), using oxygen as a green oxidant. Kinetic studies demonstrate that UiO-66(Ce) is at least three times more active than nanoceria under the same reaction conditions. In addition, the UiO-66(Ce) catalyst shows an excellent stability and can be reused after proper washing treatments. Finally, a general mechanism for the oxidative halogenation reaction is proposed when using Ce-MOF as a catalyst, which mimics the mechanistic pathway described for metalloenzymes. The superb control in the generation of subnanometric CeO_2–x defective clusters connected by adequate organic ligands in MOFs offers exciting opportunities in the design of Ce-based redox catalysts.