The Role of In Situ/Operando IR Spectroscopy in Unraveling Adsorbate-Induced Structural Changes in Heterogeneous Catalysis.

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.

Switchable Cycloadditions of Mesoionic Dipoles: Refreshing up a Regioselective Approach to Two Distinctive Heterocycles.

Mesoionic rings are among the most versatile 1,3-dipoles, as witnessed recently by their incorporation into bio-orthogonal strategies, and capable of affording unconventional heterocycles beyond the expected scope of Huisgen cycloadditions. Herein, we revisit in detail the reactivity of thiazol-3-ium-4-olates with alkynes, leading to thiophene and/or pyrid-2-one derivatives. A structural variation at the parent mesoionic dipole alters sufficiently the steric outcome, thereby favoring the regioselective formation of a single transient cycloadduct, which undergoes chemoselective fragmentation to either five- or six-membered heterocycles. The synthetic protocol benefits largely from microwave (MW) activation, which enhances reaction rates. The mechanism has been interrogated with the aid of density functional theory (DFT) calculations, which sheds light into the origin of the regioselectivity and points to a predictive formulation of reactivity involving competing pathways of mesoionic cycloadditions.

Zr-MOF-808 as Catalyst for Amide Esterification.

In this work, zirconium-based metal-organic framework Zr-MOF-808-P has been found to be an efficient and versatile catalyst for amide esterification. Comparing with previously reported homogeneous and heterogeneous catalysts, Zr-MOF-808-P can promote the reaction for a wide range of primary, secondary and tertiary amides with n-butanol as nucleophilic agent. Different alcohols have been employed in amide esterification with quantitative yields. Moreover, the catalyst acts as a heterogeneous catalyst and could be reused for at least five consecutive cycles. The amide esterification mechanism has been studied on the Zr-MOF-808 at molecular level by in situ FTIR spectroscopic technique and kinetic study.

Unveiling the Role and Stabilization Mechanism of Cu+ into Defective Ce-MOF Clusters during CO Oxidation.

Copper single-site catalysts supported on Zr-based metal-organic frameworks (MOFs) are well-known systems in which the nature of the active sites has been deeply investigated. Conversely, the redox chemistry of the Ce-counterparts is more limited, because of the often-unclear Cu2+/Cu+ and Ce4+/Ce3+ pairs behavior. Herein, we studied a novel Cu2+ single-site catalyst supported on a defective Ce-MOF, Cu/UiO-67(Ce), as a catalyst for the CO oxidation reaction. Based on a combination of in situ DRIFT and operando XAS spectroscopies, we established that Cu+ sites generated during catalysis play a pivotal role. Moreover, the oxygen vacancies associated with Ce3+ sites and presented in the defective Cu/UiO-67(Ce) material are able to activate the O2 molecules, closing the catalytic cycle. The results presented in this work open a new route for the design of active and stable single-site catalysts supported on defective Ce-MOFs.

MOF-Derived CeO2 and CeZrOx Solid Solutions: Exploring Ce Reduction through FTIR and NEXAFS Spectroscopy.

The development of Ce-based materials is directly dependent on the catalyst surface defects, which is caused by the calcination steps required to increase structural stability. At the same time, the evaluation of cerium's redox properties under reaction conditions is of increasing relevant importance. The synthesis of Ce-UiO-66 and CeZr-UiO-66 and their subsequent calcination are presented here as a simple and inexpensive approach for achieving homogeneous and stable CeO2 and CeZrOx nanocrystals. The resulting materials constitute an ideal case study to thoroughly understand cerium redox properties. The Ce3+/Ce4+ redox properties are investigated by H2-TPR experiments exploited by in situ FT-IR and Ce M5-edge AP-NEXAFS spectroscopy. In the latter case, Ce3+ formation is quantified using the MCR-ALS protocol. FT-IR is then presented as a high potential/easily accessible technique for extracting valuable information about the cerium oxidation state under operating conditions. The dependence of the OH stretching vibration frequency on temperature and Ce reduction is described, providing a novel tool for qualitative monitoring of surface oxygen vacancy formation. Based on the reported results, the molecular absorption coefficient of the Ce3+ characteristic IR transition is tentatively evaluated, thus providing a basis for future Ce3+ quantification through FT-IR spectroscopy. Finally, the FT-IR limitations for Ce3+ quantification are discussed.

Synergic Effect of Isolated Ce3+ and Ptδ+ Species in UiO-66(Ce) for Heterogeneous Catalysis.

In this work, we have synthesized through an efficient electrostatic deposition a Pt single-atom catalyst (SAC) supported on a Ce-MOF. The basic solution employed in the impregnation process favors the deprotonation of the hydroxyl groups allocated on the clusters that can easily interact with the cationic Pt species. The resulting material, denoted as Pt/UiO-66(Ce), shows an increment of Ce3+ content, as demonstrated by UV-vis and Ce L3-edge XANES spectroscopy. These Ce3+ species and their corresponding oxygen vacancies are able to accommodate very disperse Pt single sites. Moreover, Pt L3-edge XANES and CO-FTIR spectroscopy confirm the cationic nature of the supported Ptδ+ (2+ < δ < 4+). For comparison purpose, we have synthesized and characterized a well-known Pt single-site catalyst supported on nanocrystalline ceria, denoted as Pt/nCeO2. Since the simultaneous presence of Ce3+ and Ptδ+ on the MOF clusters were able to activate the oxygen molecules and the CO molecule, respectively, we tested Pt/UiO-66(Ce) for the CO oxidation reaction. Interestingly, this catalyst showed ∼six-fold increment in activity in comparison with the traditional Pt/nCeO2 material. Finally, the characterization after catalysis reveals that the Pt nature is preserved and that the activity is maintained during 14 h at 100 °C without any evidence of deactivation.

Sustainable Synthesis of Silicon Precursors Coupled with Hydrogen Delivery Based on Circular Economy via Molecular Cobalt-Based Catalysts.

The development of a circular economy is a key target to reduce our dependence on fossil fuels and create more sustainable processes. Concerning hydrogen as an energy vector, the use of liquid organic hydrogen carriers is a promising strategy, but most of them present limitations for hydrogen release, such as harsh reaction conditions, poor recyclability, and low-value byproducts. Herein, we present a novel sustainable methodology to produce value-added silicon precursors and concomitant hydrogen via dehydrogenative coupling by using an air- and water-stable cobalt-based catalyst synthesized from cheap and commercially available starting materials. This methodology is applied to the one-pot synthesis of a wide range of alkoxy-substituted silanes using different hydrosilanes and terminal alkenes as reactants in alcohols as green solvents under mild reaction conditions (room temperature and 0.1 mol % cobalt loading). We also demonstrate that the selectivity toward hydrosilylation/hydroalkoxysilylation can be fully controlled by varying the alcohol/water ratio. This implies the development of a circular approach for hydrosilylation/hydroalkoxysilylation reactions, which is unprecedented in this research field up to date. Kinetic and in situ spectroscopic studies (electron paramagnetic resonance, nuclear magnetic resonance, and electrospray ionization mass spectrometry), together with density functional theory simulations, further provide a detailed mechanistic picture of the dehydrogenative coupling and subsequent hydrosilylation. Finally, we illustrate the application of our catalytic system in the synthesis of an industrially relevant polymer precursor coupled with the production of green hydrogen on demand.

Coordinatively Unsaturated Hf-MOF-808 Prepared via Hydrothermal Synthesis as a Bifunctional Catalyst for the Tandem N-Alkylation of Amines with Benzyl Alcohol.

The modulated hydrothermal (MHT) synthesis of an active and selective Hf-MOF-808 material for the N-alkylation reaction of aniline with benzyl alcohol under base-free mild reaction conditions is reported. Through kinetic experiments and isotopically labeled NMR spectroscopy studies, we have demonstrated that the reaction mechanism occurs via borrowing hydrogen (BH) pathway, in which the alcohol dehydrogenation is the limiting step. The high concentration of defective -OH groups generated on the metallic nodes through MHT synthesis enhances the alcohol activation, while the unsaturated Hf4+, which acts as a Lewis acid site, is able to borrow the hydrogen from the methylene position of benzyl alcohol. This fact makes this material at least 14 times more active for the N-alkylation reaction than the material obtained via solvothermal synthesis. The methodology described in this work could be applied to a wide range of aniline and benzyl alcohol derivates, showing in all cases high selectivity toward the corresponding N-benzylaniline product. Finally, Hf-MOF-808, which acts as a true heterogeneous catalyst, can be reused in at least four consecutive runs without any activity loss.

Metalloenzyme-Inspired Ce-MOF Catalyst for Oxidative Halogenation Reactions.

The structure of UiO-66(Ce) is formed by CeO2-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 CeO2-x defective clusters connected by adequate organic ligands in MOFs offers exciting opportunities in the design of Ce-based redox catalysts.

Tailoring Lewis/Brønsted acid properties of MOF nodes via hydrothermal and solvothermal synthesis: simple approach with exceptional catalytic implications.

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.

Catalytic Transfer Hydrogenation of Biomass-Derived Carbonyls over Hafnium-Based Metal-Organic Frameworks.

A series of highly crystalline, porous, hafnium-based metal-organic frameworks (Hf-MOFs) have been shown to catalyze the transfer hydrogenation reaction of levulinic ester to produce γ-valerolactone by using isopropanol as a hydrogen donor. The results are compared with their zirconium-based counterparts. The role of the metal center in Hf-MOFs has been identified and reaction parameters optimized. NMR studies using isotopically labeled isopropanol provide evidence that the transfer hydrogenation occurs through a direct intermolecular hydrogen transfer route. The catalyst, Hf-MOF-808, can be recycled several times with only a minor decrease in catalytic activity. The generality of the procedure has been demonstrated by accomplishing the transformation with aldehydes, ketones, and α,ß-unsaturated carbonyl compounds. The combination of Hf-MOF-808 with the Brønsted-acidic Al-Beta zeolite gives the four-step one-pot transformation of furfural to γ-valerolactone in good yield of 75 %.