Lewis Acid Research Articles

Efficient Cascade Reactions involving Esterification, Hydrogen transfer, and Lactonization for Biomass Conversion Using MOF/Metal Oxide Composites as Heterogeneous Catalysts

Development of heterogeneous catalysts with both Brønsted and Lewis acid properties has proved to be promising and useful because they offer an efficient way to cascade reactions. In this study, we present the synthesis pathway and efficacy evaluation of new composites which combined by sulfonic acid functional group modified TiO2 and MIL-101, analyzing their structure-performance correlation as heterogeneous catalysts in cascade reactions involving esterification, hydrogen transfer, and lactonization. These composites possess an open porous structure (MOF and porous TiO2), as well as active sites including Lewis acid (unsaturated coordination metal), Lewis base (Ti-OH), and Brønsted acid (-SO3H). The role of these active sites and the synergies between them were investigated through the esterification of levulinic acid and the direct synthesis of γ-valerolactone from levulinic acid and furfural under cascade reactions. The composites exhibit a 100% ethyl levulinate (EL) yield at 120°C for 6 hours, with γ-valerolactone yields reaching up to 94.5% (160 °C, 9 h) and 89.5% (160 °C, 16 h) from levulinic acid and furfural, respectively. This synergistic effect of Lewis acid/base and Brønsted acid ensures efficient esterification. The presence of a sulfonic acid group promotes the lactonization reaction, while the Meerwein-Ponndorf-Verley reduction is facilitated by the dual Cr sites located adjacent to each other in the secondary building unit of MIL-101(Cr). Moreover, the double-porous structure of porous TiO2 and MIL-101(Cr) effectively guarantees the efficient mass transfer of reactants and intermediates, leading to enhanced synergistic effects that promote more efficient reaction conversion.

Selenylated Analogs of Tacrine: Synthesis, In Silico and In Vitro Studies of Toxicology and Antioxidant Properties.

We present our results on the synthesis and preliminary in silico and in vitro studies of the toxicology and antioxidant properties of selenylated analogs of Tacrine. Initially, we synthesized 2-aminobenzonitriles containing an organic selenium moiety, resulting in sixteen compounds with various substituents linked to the portion derived from diorganyl diselenide. These compounds were then used as substrates in reactions with cyclic ketones, in the presence of 1.4 equivalents of trifluoroboroetherate as a Lewis acid, to synthesize selenylated analogs of Tacrine with yields ranging from 20 % to 87 %. In silico studies explored computational parameters related to antioxidant activity and hepatotoxicity. In vitro studies elucidated the antioxidant effects of Tacrine and its selenium hybrid (TSe) in neutralizing ABTS radicals, scavenging DPPH radicals, and reducing iron ions. Additionally, the acute oral toxicity of one synthesized compound was evaluated.

Methanol-Mediated Hydrogen Transfer Reactions at Surface Lewis Acid Sites of H-SSZ-13

Methanol-Mediated Hydrogen Transfer Reactions at Surface Lewis Acid Sites of H-SSZ-13

Photothermal Effect and Fenton‐Like Oxidation for Synergistic Removal of Fluoroquinolones Antibiotics under Near‐Neutral Conditions

AbstractDefect‐enriched mesoporous CuO nanosheets (NSs) were constructed to investigate the cooperative photo‐Fenton and photothermal‐Fenton catalysis on degradation of fluoroquinolones (FQ) antibiotics. The oxygen vacancies provide abundant active sites to bind the substrates and inhibit charge recombination, by all means to enhance Fenton‐like activity. Two disparate spectral selective functions of photoexcitation and photothermal conversion were achieved on CuO NS, which to promote the Fenton activity synergistically. Visible light induced photoexcitation to facilitate the generation of Cu+ and ⋅OH, while near‐infrared light converted into heat to promote charge separation and accelerate medium transport. Ultimately, as a unitary catalyst system, the CuO NS integrated the Lewis acid catalysis, Fenton‐like catalysis and photothermal catalysis that rapidly and sustainably degraded antibiotics under near‐neutral conditions.

Lewis Acidic VOx Engineered PdAu Nanocatalysts for Efficient Formic Acid Dehydrogenation

AbstractThe development of high‐performance catalysts for formic acid (FA) dehydrogenation is of extreme significance to the successful production of hydrogen under ambient conditions. Despite some encouraging progress, their activity is still unsatisfied than needed. In this work, it is presented that Lewis acidic VOx sites engineered ultrafine PdAu nanoclusters (PdAu‐VOx) perform perfectly for hydrogen production from FA dehydrogenation. Strikingly, the best catalyst — PdAu‐VOx embed in amino‐functionalized hollow mesoporous support (PdAu‐VOx/NHMS) discloses an impressive initial turnover frequency of 14155 h−1 and a low activation energy of 31.2 kJ mol−1 without additives at room temperature, and maintains 100% selectivity and conversion in the tenth cycle reaction. Mechanistic investigations illustrate that VOx species can serve as the Lewis acid sites, which not only regulate the adsorption strength of reactant and intermediate on PdAu, but also reinforce the C─H bond activation within FA molecule, thereby promoting the reaction kinetics for efficient hydrogen production. This work thus provides a strategy for the development of new‐style heterogeneous catalysts with Lewis acid‐base sites applied to a variety of energy‐related catalytic reactions.

Tetra-Amido Macrocyclic Ligand (TAML) at Silicon(IV): A Structurally Constrained, Water-Soluble Silicon Lewis Superacid.

Tetracoordinate silicon species are typically tetrahedral, weak Lewis acids, and often sensitive to moisture. In this study, we present a tetra-amido macrocyclic ligand (TAML)-substituted Si(IV), isolated as its bis(pyridine) adduct. Due to structural constraint toward anti van't-Hof/Le Bel geometry, this compound exhibits Lewis superacidity and effectively catalyzes the hydroboration of pyridine. Kinetic and computational analyses of the catalytic cycle reveal that TAML-Si(IV) acts as a hydride transfer agent, and the hydrido silicate key intermediate is isolated. Notably, the Lewis acid is highly soluble (5 g/L) and long-term stable in water. Unlike previously described silicon-H2O adducts, the bound water becomes substantially acidified, reaching the Bro̷nsted superacidity range. A comparison of water affinity versus pKa lowering confirms our previous theory of the strength and the effect of Lewis acids. Overall, the compound's unlimited water compatibility and its mechanistically understood catalytic efficiency mark significant progress in applying structural constraint strategies for p-block element-based catalysis, while the acidification touches critical aspects of zeolite and silica surface chemistry.

Single-Atom Ce-Doped Metal Hydrides with High Phosphatase-like Activity Amplify Oxidative Stress-Induced Tumor Apoptosis.

Phosphates within tumors function as key biomolecules, playing a significant role in sustaining the viability of tumors. To disturb the homeostasis of cancer cells, regulating phosphate within the organism proves to be an effective strategy. Herein, we report single-atom Ce-doped Pt hydrides (Ce/Pt-H) with high phosphatase-like activity for phosphate hydrolysis. The resultant Ce/Pt-H exhibits a 26.90- and 6.25-fold increase in phosphatase-like activity in comparison to Ce/Pt and Pt-H, respectively. Mechanism investigations elucidate that the Ce Lewis acid site facilitates the coordination with phosphate groups, while the surface hydrides enhance the electron density of Pt for promoting catalytic ability in H2O cleavage and subsequent nucleophilic attack of hydroxyl groups. Finally, by leveraging its phosphatase-like activity, Ce/Pt-H can effectively regulate intracellular phosphates to disrupt redox homeostasis and amplify oxidative stress within cancer cells, ultimately leading to tumor apoptosis. This work provides fresh insights into noble-metal-based phosphatase mimics for inducing tumor apoptosis.

Secondary Sphere Lewis Acid Activated Heme Superoxo Adducts Mimic Crucial Non‐Covalent Interactions in IDO/TDO Heme Dioxygenases

Heme enzymes play a central role in a medley of reactivities within a wide variety of crucial biological systems. Their active sites are highly decorated with pivotal evolutionarily optimized non‐covalent interactions that precisely choreograph their biological functionalities with specific regio‐, stereo‐, and chemo‐selectivities. Gaining a clear comprehension of how such weak interactions within the active sites control reactivity offers powerful information to be implemented into the design of future therapeutic agents that target these heme enzymes. To shed light on such critical details pertaining to tryptophan dioxygenating heme enzymes, this study investigates the indole dioxygenation reactivities of Lewis acid‐activated heme superoxo model systems, wherein an unprecedented kinetic behavior is revealed. In that, the activated heme superoxo adduct is observed to undergo indole dioxygenation with the intermediacy of a non‐covalently organized precursor complex, which forms prior to the rate‐limiting step of the overall reaction landscape. Spectroscopic and theoretical characterization of this precursor complex draws close parallels to the ternary complex of heme dioxygenases, which has been postulated to be of crucial importance for successful 2,3‐dioxygenative cleavage of indole moieties.

Controllable Crystallization of Perovskite Films during the Blade-Coating Fabrication Process for Efficient and Stable Solar Cells

The scalable production of high-quality perovskite thin films is pivotal for the industrialization of perovskite thin film solar cells. Consequently, the solvent system employed for the fabrication of large-area perovskite films via coating processes has attracted significant attention. In this study, a solvent system utilizing a volatile solvent as the primary reagent has been developed to facilitate the rapid nucleation of volatile compounds. While adding the liquid Lewis base dimethylformamide (DMF) can help to improve the microstructure of perovskite films, its slow volatilization renders the crystal growth process uncontrollable. Based on the solvent system containing DMF and ethanol (EtOH), introducing a small amount of NH4Cl increases the proportion of the intermediate phase in the precursor films. This not only results in a controllable growth process for the perovskite crystals but also contributes to the improvement of the film microstructure. Under the simulated illumination (AM1.5, 1000 W/m2), the photoelectric conversion efficiency (PCE) of the inverted solar cells has been improved to 20.12%. Furthermore, after 500 hours of continuous illumination, the photovoltaic device can retain 95.6 % of the initial, indicating that the solvent system is suitable for the scalable fabrication of high-quality FAPbI3 thin films.

CO2 capture using functionalized MIL-101(Cr) metal–organic frameworks: Functionality nanoarchitectonics of nanospace for CO2 adsorption

In this study, we investigated the effect of functional groups of metal–organic frameworks (MOFs) on CO2 adsorption at low pressure through experimental and computational approaches. We compared the performance of −SO3H, –NO2, aryl –NH2, and alkyl –NH2 groups (in similar molar quantities) in CO2 adsorption under the same conditions. The adsorption efficiency followed in the order: alkyl –NH2 > -SO3H>aryl –NH2 > –NO2 because of the different adsorption mechanisms over the groups. The main mechanism over alkyl –NH2 was the formation of ammonium carbamate via the carbamic acid formation. The adsorption mechanism over −SO3H and aryl –NH2 groups was Lewis acid-base and H-bonding interactions, while that over –NO2 group was solely Lewis acid-base interaction. The alkyl amine exhibited the best performance (in adsorption capacity, selectivity, and adsorption heat) due to its ability to form carbamate readily. On the contrary, aryl amine demonstrated lower performance than −SO3H groups, attributed to their low capability to form carbamate. These findings underscore the importance of amine type in CO2 adsorption, highlighting that aryl amines, different from alkyl amines, perform worse than other functional groups, such as −SO3H.

Gold supported on Bi2MoO6 based on oxygen vacancy structure: Enhanced adsorption activation for efficient photocatalytic selective oxidation of benzyl alcohol

In this work, ethylene glycol was used as a mild reducing agent to prepare Bi2MoO6 support with oxygen vacancies. By introducing Au active species, an Au/BMO-Ov (Bi2MoO6 support with oxygen vacancies) photocatalyst was synthesized, which was co-modified with oxygen vacancies and Au NPs (nanoparticles), and significantly improved the capability of Bi2MoO6 for visible light-driven BA (benzyl alcohol) conversion. The 1wt% Au/BMO-Ov exhibited the highest conversion (98.8%) of BA and excellent selectivity (97.4%) of BAD (benzaldehyde) under visible light. Oxygen vacancies have an inhibitory effect on the recombination of photogenerated carriers. Au NPs acted as both photosensitizers (LSPR effect captures light and generates electrons and holes) and active species (used as Lewis acids). The results of photoelectrochemistry (PEC) tests confirmed that the synergistic interaction of Au and oxygen vacancies enhanced the photoactivity of bismuth molybdate. Meanwhile, density functional theory (DFT) calculations indicated that oxygen vacancies and Au synergistically reduced the bandgap energy of Bi2MoO6 and enhanced the adsorption of BA. Au served as the Lewis acid site for adsorption of BA, and improved the reactivity of light-driven BA conversion. The corresponding mechanism was proposed based on the experimental results and DFT calculations.

A Benchmark Study of DFT-Computed p-Block Element Lewis Pair Formation Enthalpies against Experimental Calorimetric Data.

The quantification of Lewis acidity is of fundamental and applied importance in chemistry. While the computed fluoride ion affinity (FIA) is the most widely accepted thermodynamic metric, only sparse experimental values exist. Accordingly, a benchmark of methods for computing Lewis pair formation enthalpies, also with a broader set of Lewis bases against experimental data, is missing. Herein, we evaluate different density functionals against a set of 112 experimentally determined Lewis acid/base binding enthalpies and gauge influences such as solvation correction in structure optimization. From that, we can recommend r2SCAN-3c for robust quantification of this omnipresent interaction.

Mg-modified layered erbium hydroxides promoting glucose transformation to lactic acid

Layered rare earth hydroxides (LREHs) with unique layer structure and tunable properties have shown attractive potentials as heterogeneous catalyst, but is still challenging in biomass valorization towards valuable chemical production due to the poor catalytic activity. Herein, Mg-modified erbium hydroxides (Mg-LErHs) with well-constructed layered structure have been first fabricated, where the properties and structure of Mg-LErHs significantly depend on the proportion of Mg. The results of catalyst characterizations reveal that Mg introduction increases the interlayer spacing and the content of Er(III)-O. Mg modification also hinders the desorption of crystallized H2O and dehydroxylation, thereby increasing the degree of crystallinity and promoting the stability of the catalyst. The activity test indicate that Mg modification greatly promotes the production of lactic acid from monosaccharides, where Mg(5.8)-LErHs affords the highest lactic acid yield of 60.9%. Mg-LErHs also outperform other Mg-LREHs catalysts for the production of lactic acid. The highest catalytic activity of Mg(5.8)-LErHs are possibly attributed to its highest degree of crystallinity, and the increased layer spacing after Mg modification might have an advantage in facilitating the entry of substrate. The increased Er(III)-O content with high Lewis acidity might facilitate the combination with electronic-rich carbonyl oxygen in substrate. This research may provide a novel strategy to design the layered rare earth catalysts with tunable catalytic activity for biomass valorization.

Comparative Study of Si‐O‐Al and Si‐O‐Si Bond Stability in HZSM‐5 Zeolite Under Steam and Hot Liquid Water Environments

Understanding the changes in the zeolite framework and catalytic active sites in zeolite‐based vapor‐phase and aqueous catalytic processes is crucial. Herein, the evolution of framework T atoms (Si and Al) in ammonium hexafluorosilicate (AHFS)‐treated HZSM‐5 zeolite under steam and hot liquid water (HLW) environments was inverstigated using various characterization techniques. In the HLW environment, Si‐O‐Si bonds exhibit poorer hydrothermal stability than Si‐O‐Al bonds, in contrast to the steam environment. Significant Si atom leaching occurs without or with the removal of framework tetrahedral Al atoms (Al(IV)‐1). Similar to steam, Al(IV)‐1 species in the HLW environment sequentially evolve into partially coordinated framework Al species and then into extra‐framework Al (EFAL) species through partial and complete hydrolysis. The generated EFAL species act as Lewis acid sites, but their local structures or chemical environments may differ. These findings reveal the difference in the T‐O‐T bonds attacked by water molecules: the Si‐O‐Al bonds is primarily attacked in steam, whereas the Si‐O‐Si bond is primarily attacked in HLW.

Sn-MFI zeolite nanosponge having high content of Lewis acid sites on external surfaces, exhibiting high activity in Baeyer-Villiger oxidation of bulky ketone

We developed a three-step synthesis strategy to obtain Sn-incorporated MFI-type zeolite nanosponge (Sn-MFI-ns) assembled by ultrathin (∼2.5 nm) zeolite frameworks possessing uniform-sized (∼4 nm) mesopores: 1) synthesis of MFI-type borosilicate nanosponge using a zeolite structure-directing-surfactant, 2) deboronation of the borosilicate using HNO3, and 3) gas-phase incorporation of Sn into the boron-vacant sites via silanol groups using (CH3)2SnCl2 as a precursor. The Sn-MFI-ns shows high crystallinity, consequently high thermal stability, and highly porous structure. The Sn content can be systematically controlled by the amount of the precursor, with Si/Sn ratios ranging from 30 to 200. The Sn species is highly dispersed over entire range of the zeolite surfaces, acting as Lewis acid sites. Due to the highly mesoporous structure, the Sn-MFI-ns has a significant number of Lewis acid sites on the external surfaces and mesopore walls, which are easily accessible to bulky molecules, compared to solely microporous zeolite (Sn-bulk-MFI). Consequently, the Sn-MFI-ns exhibits much higher catalytic activity than the Sn-bulk-MFI with high product selectivity in Baeyer-Villiger oxidation of 2-adamantanone, a molecule larger than the micropore apertures of MFI-type zeolite. The activity of Sn-MFI-ns is comparable to Sn-MCM-41 exposing almost all Sn to mesopore walls, advantageous to the bulky molecules’ reaction.

Highly Efficient Production of Furfural from Corncob by Barley Hull Biochar-Based Solid Acid in Cyclopentyl Methyl Ether–Water System

Furfural, an important biobased compound, can be synthesized through the chemocatalytic conversion of D-xylose and hemicelluloses from lignocellulose. It has widespread applications in the production of valuable furans, additives, resins, rubbers, synthetic fibers, polymers, plastics, biofuels, and pharmaceuticals. By using barley hulls (BHs) as biobased support, a heterogeneous biochar Sn-NUS-BH catalyst was created to transform corncob into furfural in cyclopentyl methyl ether–H2O. Sn-NUS-BH had a fibrous structure with voids, a large comparative area, and a large pore volume, which resulted in more catalytic active sites. Through the characterization of the physical and chemical properties of Sn-NUS-BH, it was observed that the Sn-NUS-BH had tin dioxide (Lewis acid sites) and a sulfonic acid group (Brønsted acid sites). This chemocatalyst had good thermostability. At 170 °C for 20 min, Sn-NUS-BH (3.6 wt%) was applied to transform 75 g/L of corncob with ZnCl2 (50 mM) to generate furfural (80.5% yield) in cyclopentyl methyl ether–H2O (2:1, v/v). This sustainable catalytic process shows great promise in the transformation of lignocellulose to furfural using biochar-based chemical catalysts.

Surface Thermodynamic Properties of Styrene–Divinylbenzene Copolymer Modified by Supramolecular Structure of Melamine Using Inverse Gas Chromatography

The surface thermodynamic properties of polymers and copolymers modified by supramolecular structures are used in several industrial processes, such as selective adsorption, paints, coatings, colloids, and adhesion applications. Background: Inverse gas chromatography at infinite dilution was proved to be the best technique to determine the surface properties of solid surfaces by studying the adsorption of some model polar and non-polar organic molecules adsorbed on solid surfaces at different temperatures. Methods: The retention volume of adsorbed solvents is a valuable parameter that was used to obtain the London dispersive and polar free energies and the London dispersive surface energy of styrene–divinylbenzene copolymer modified by supramolecular structure of melamine using both the Hamieh thermal model and our new methodology consisting of the separation of the two polar molecules and the dispersive free energy of their interaction. This led to the determination of the polar acid and base surface energy, and the Lewis acid–base constants of the various solid materials. Results: Following our new methodology, all surface energetic properties of styrene–divinylbenzene copolymer modified by melamine at different percentages were determined as a function of temperature. Conclusions: It was observed that the styrene–divinylbenzene copolymer exhibited the highest London dispersive surface energy, which decreased when the melamine percentage increased. All materials presented higher Lewis basicity and this Lewis basicity increased with the percentage of melamine.

Effect of NH2-functionalization of MIL-125 on photocatalytic degradation of o-xylene and acetaldehyde

Ligand functionalization of metal organic framework (MOF) is a great important strategy to enhance the various properties of pristine materials. In this study, MIL-125 with different extents of NH2-functionalization were synthesized by solvothermal method. The photocatalytic degradation efficiency of the optimal sample for o-xylene and acetaldehyde were 88 % and 49 %, respectively, which were much improved compared to pristine MIL-125 (56 % for o-xylene and 3 % for acetaldehyde). Compared to pristine MIL-125, NH2-functionlized MIL-125 were more easily photoexcited to form photogenerated carriers, which facilitated the formation of more OH and O2− radicals under visible light irradiation. In addition, NH2 groups as the adsorption site interacted with o-xylene and acetaldehyde by the H-bonding and the Lewis acid-base effect, respectively. The above results contribute to a deep understanding of the influence of ligand functionalization of MOF on the photocatalytic degradation of VOCs.

Synthesis of pyrrolo[1,2-a]quinoline and pyrrolo[1,2-b]isoquinoline derivatives via intramolecular acylation

A methanesulfonic acid mediated intramolecular acylation approach for the synthesis of pyrrolo[1,2-a]quinoline and the isomeric pyrrolo[1,2-b]isoquinoline frameworks has been developed. The reaction is carried out at ambient temperature and no Lewis acid catalyst is required. The product yields are generally good to excellent.

A Robust Synthesis of Co2P and Ni2P Nanocatalysts from Hexaethylaminophosphine and Phosphine-Enhanced Phenylacetylene Hydrogenation.

Metal-rich phases of general formula M2P have demonstrated interesting catalytic activity, e.g., for hydrogen evolution reaction and for hydrogenations in colloidal suspension. The production of well-crystallized nanoparticles of the M2P phase from commercial precursors on a large enough scale is not trivial as the existing routes generally require fairly high reaction temperatures and a large excess of the phosphorus source. Here, we selected a commercial aminophosphine, P(NEt2)3, as the phosphorus precursor (3 equiv or less) to develop a robust synthesis from CoCl2 (respectively NiCl2) that provided crystalline Co2P (respectively Ni2P) nanoparticles with high yields on a 9 mmol scale. Moreover, modification of the M2P nanoparticles via the addition of a molecular Lewis base is a promising route to trigger catalytic activity of the colloidal suspension at a lower temperature. For the hydrogenation of phenylacetylene catalyzed by Co2P and Ni2P nanoparticles, we showed that catalytic amounts of adequate phosphines, such as PnBu3 and also, in some instances, oleylamine, triggered a full conversion at lower temperatures than with the nanoparticles alone. We delineated the most efficient phosphines in the case of a Ni2P catalyst, using a stereoelectronic map of 13 phosphines.