Lewis Acid Research Articles

Modulating the chemical environment of Ni2+ for the oxidative dehydrogenation of ethane: The formation of LAS(Al3+/Ga3+)-Ni-OH site

The oxidative dehydrogenation of ethane to ethylene (ODHE) usually suffers from the issues of ethane conversion-ethylene selectivity seesaw. Herein, a series of alumina-supported Ni and Ga catalysts with different molar ratios of Ni to Ga were synthesized by facile impregnation method constructing the Lewis acid site (LAS) strategy to obtain great ethylene selectivity (97 %). The variation of Ni:Ga ratio adjusted the ionic substitution ability, redox ability and acidity, thus regulate the chemical environment of Ni2+ to the formation of LAS(Al3+/Ga3+)-Ni-OH structure, which was proposed to be the active site for selective oxidation of ethane to ethylene, as proved by H2-TPR, ToF-SIMS, quasi in-situ XPS and in-situ FTIR. Moreover, the probable mechanism of ODHE reaction was proposed that C2H6 molecules were mainly adsorbed on LAS sites and activated on Ni-OH site of the catalyst. The pulse test further suggested that O- was mainly associated with the generation of CO2 and Ni(2-n)+ was connected with the production of CH4. It is highlighted that adjusting the Ni-related species and oxygen species on the catalyst surface are crucial to further improve the ethylene selectivity.

Highly efficient Ru/CeO2 catalyst using colloidal chemical method for propane oxidation

Although supported-Ru catalysts have been widely studied for the light alkane oxidation root in their lower cost compared to Pt and Pd, developing Ru-based catalysts with high efficiency for low-temperature light alkane elimination remains a significant challenge. Herein, Ru/CeO2 catalysts were prepared utilizing the colloidal synthesis (Ru/CeO2-CS) and compared with the catalyst prepared with the traditional impregnation method (Ru/CeO2-IM) in the textural properties and catalytic propane oxidation. It was discovered that Ru/CeO2-CS sample contained a higher concentration of active Ru − O − Ce interface and oxygen vacancies attributed to the strong Ru-CeO2 interaction, which further enhanced the redox capacity. Besides, the lower valence state of Ru species and higher contents of Lewis acid sites on Ru/CeO2-CS sample boosted the adsorption, dissociation, and activation of propane, thus promoting the deep oxidation of propane to CO2 and H2O. The reaction mechanism of propane oxidation was revealed by in-situ DRIFTS, and both the catalysts showed bands related to acrylate species, suggesting that propane underwent an acrylate oxidation pathway on Ru/CeO2-CS and Ru/CeO2-IM samples. The distinct textural properties of these catalysts resulted in Ru/CeO2-CS synthesized by colloidal methods showing a T90 of 170 °C, and Ea of 50.9 ± 1.8 kJ·mol−1, markedly lower than Ru/CeO2-IM prepared with the traditional impregnation method. Apart from the activity, the Ru/CeO2-CS sample obtained superior water resistance, thermal stability, and durability. This comprehensive work provides promising insights into low-temperature propane oxidation.

Unveiling the Role of Filler Characteristics in Enhancing the High-Voltage Performance of Succinonitrile-Based Solid-State Lithium-Metal Batteries.

For exploiting high-energy lithium-metal batteries, it is of utmost importance to develop electrolytes that possess exceptional ionic conductivity and an extensive electrochemical stability range. In this study, 3D PAN nanofibers and polymer electrolytes incorporating various inorganic fillers with different Lewis acid-base properties were fabricated. PAN@Al-SSE exhibits exceptional ionic conductivity (0.48 mS·cm-2 at room temperature), a high Li+ transference number (0.41), and a wide electrochemical window (5.26 V). The device is able to operate stably in Li symmetric cells for more than 1000 h under a potential of 0.03 V under a current density of 0.2 mA·cm-2. Besides, the groundbreaking technology equips high-voltage Li-LiCoO2 solid-state batteries with exceptional cycling performance (91.3% and 82.1% retention after 100 cycles at 0.2 and 1 C, respectively) at room temperature. Mechanistic studies indicate that the Lewis acid-base properties of surface fillers are instrumental and crucial to form a stable solid-electrolyte interphase layer. γ-Al2O3, in particular, with more Lewis acid sites, ensures the dissociation of LiTFSI and induces the excessive decomposition and polymerization of succinonitrile. There exists an equilibrium effect between dissociation and polymerization in a succinonitrile-based solid electrolyte, which plays a critical role in improving the manifestation of succinonitrile-based solid-state lithium cells, especially under high-voltage conditions.

Correction to “Impact of Sn Lewis Acid Sites on the Dehydration of Cyclohexanol”

Correction to “Impact of Sn Lewis Acid Sites on the Dehydration of Cyclohexanol”

Coupling CoIr Nanoalloys with MXene by Lewis Acidic Molten Salt Etching for Wide-pH-Environment Hydrogen Evolution Reaction.

Metal/MXene-based materials show broad prospects in energy conversation through the strong metal-support interaction (SMSI). However, the difficulty and harshness of synthesis heavily limit their further application. Herein, using Lewis acidic molten salt to etch MAX as a precursor of MXene, a more convenient and safer strategy is designed to in situ construct the MXene-supported CoIr nanoalloy (CoIr/MXene) catalyst through Ti─O─M bond. The special layered structure and oxygen-containing functional group of MXene regulate the SMSI upon CoIr nanoalloys. Moreover, the contact angle and in situ Raman test results exhibit good interface hydrophilicity of MXene, enhancing the water adsorption on interfaces, and accelerating the mass transfer process. As a result, CoIr/MXene shows high hydrogen evolution reaction (HER) performance, which only needs overpotentials of 34 and 50mV to drive a current density of 10mA cm-2 in alkaline and acidic media, respectively, with excellent stability. Especially, in alkaline media, CoIr/MXene possesses 6 times higher HER mass activity (4.297 A mgIr -1) than commercial Pt/C catalysts (0.686 A mgPt -1) at the potential of 50mV, indicating larger active site density and intrinsic activity for CoIr/MXene. This work expands the application of the molten salt assist etching strategy and provides new insight for the development of metal/MXene-based catalysts.

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

AbstractUnderstanding the changes in the zeolite framework and catalytic active sites during 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 HLW, Si−O−Si bonds exhibit poorer hydrothermal stability than Si−O−Al bonds, in contrast to steam. Significant Si atom leaching occurs regardless of whether the framework tetrahedral Al atoms (Al(IV)‐1) are removed. Similar to steam, Al(IV)‐1 species in HLW 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 are primarily attacked in steam, whereas the Si−O−Si bond are primarily attacked in HLW.

Selective Hydrogenolysis Conversion of Polyethylene into Alkyl Oil Over Iridium-based Catalyst.

Plastic not only brings convenience but also places a great burden on the environment. Utilizing plastic as a low-cost feed-stock for producing valuable chemicals and fuels is one of the most attractive directions. Among the huge types of plastics, polyolefins (PO), especially polyethylene (PE), were the most abundant type and the most difficult to upgrade. Hydrocracking and hydrogenolysis operate at relatively low reaction temperatures which show promising applications. Herein, Iridium-based catalysts were developed and proved to be effective in PE hydrogenolysis under relatively mild conditions. Catalysts were characterized by TEM, HRTEM, SEM, HAADF-STEM, XPS, CO chemisorption and H2 chemisorption etc. The Ir catalysts showed similar reactivity but better selectivity for liquid products than Ru under similar conditions. A highest 92.7 % percent of liquid products could be obtained under 250 °C, 3 MPa of H2 in 8 hours with Ir/γ-Al2O3 catalyst. The support could also affect the performance, including Lewis acid amount, surface areas, and morphology. And we suppose Iridium catalysts could serve as another choice for plastic hydrogenolysis under mild conditions.

DMAP Catalyzed Ring-Opening/Cycloaddition of Vinyl Oxiranes with Activated Ketone Compounds to Construct the 1,3-Dioxolane Skeletons.

The present work develops a DMAP-catalyzed [3 + 2] cycloaddition of vinyl oxiranes with activated ketone compounds, affording dioxolane derivatives with moderate to excellent yields. This approach represents the first Lewis base (LB)-catalyzed ring-opening reaction of vinyl epoxides, simultaneously providing a rare oxygen-containing active intermediate in this field. The gram-scale preparation and facile derivatization of the cycloadduct highlight the significant synthetic potential of this strategy.

Improved Charge‐Transfer Doping in Crystalline Polymer for Efficient and Stable Perovskite Solar Cells

AbstractPerovskite solar cells (PSCs) have significant potential for next‐generation photovoltaic technology applications. However, the instability of hole transport layers (HTLs) becomes the major obstacle to long‐term operational devices, which are affected by the intrinsic thermal instability and loose structure of hole transport materials, as well as the hygroscopicity and migration of dopants. Here, poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) is used as a model crystalline polymer to thoroughly investigate effective p‐type doping strategies and the underlying mechanism. According to Hard–Soft‐Acid–Base theory, the soft base P3HT is more likely to form a stable Lewis acid–base adduct with the reactive soft acid radical, resulting in a strong charge‐transfer interaction, thereby enhancing conductivity and regulating the energy band of the HTL. Meanwhile, the radical cation salt can promote pre‐nucleation to optimize the crystallization orientation of P3HT. The resulting PSCs exhibited the efficiency of 25.16%, which is the highest efficiency reported so far based on doped P3HT. In addition, the resulting devices demonstrated excellent stability, maintaining 96.5%, 96%, and 91% of their initial efficiency after aging under continuous illumination for 2028 h, at 85 °C for 1080 h, and at maximum power point (MPP) tracking under continuous 1 Sun illumination at 85 °C for 528 h, respectively.

Lewis Acid-Catalyzed Unusual (4+3) Annulation of para-Quinone Methides with Bicyclobutanes: Access to Oxabicyclo[4.1.1]Octanes.

Over the past few years, there has been a surge of interest in the chemistry of bicyclobutanes (BCBs). Although BCBs have been used to synthesize bicyclo[2.1.1]hexanes and bicyclo[3.1.1]heptanes, the synthesis of bicyclo[4.1.1]octanes has remained elusive. Herein, we report the first Lewis acid-catalyzed unexpected (4+3) annulation of para-quinonemethides (p-QMs) with BCBs allowing the synthesis of oxabicyclo[4.1.1]octanes proceeding under mild conditions. With 5 mol % of Bi(OTf)3, the reaction afforded the (4+3) annulated product in high regioselectivity and good functional group compatibility via a simultaneous Lewis acid activation of BCBs and p-QMs. The reaction is likely initiated by the 1,6-addition of Lewis acid activated BCBs to p-QMs followed by the C2-selective intramolecular addition of the phenol moiety to the generated cyclobutyl cation intermediate. Moreover, detailed mechanistic studies provided insight into the mechanism of the reaction.

Lewis Acid‐Catalyzed Unusual (4+3) Annulation of para‐Quinone Methides with Bicyclobutanes: Access to Oxabicyclo[4.1.1]Octanes

AbstractOver the past few years, there has been a surge of interest in the chemistry of bicyclobutanes (BCBs). Although BCBs have been used to synthesize bicyclo[2.1.1]hexanes and bicyclo[3.1.1]heptanes, the synthesis of bicyclo[4.1.1]octanes has remained elusive. Herein, we report the first Lewis acid‐catalyzed unexpected (4+3) annulation of para‐quinonemethides (p‐QMs) with BCBs allowing the synthesis of oxabicyclo[4.1.1]octanes proceeding under mild conditions. With 5 mol % of Bi(OTf)3, the reaction afforded the (4+3) annulated product in high regioselectivity and good functional group compatibility via a simultaneous Lewis acid activation of BCBs and p‐QMs. The reaction is likely initiated by the 1,6‐addition of Lewis acid activated BCBs to p‐QMs followed by the C2‐selective intramolecular addition of the phenol moiety to the generated cyclobutyl cation intermediate. Moreover, detailed mechanistic studies provided insight into the mechanism of the reaction.

Multisite Crosslinked Poly(ether-urethane)-Based Polymer Electrolytes for High-Voltage Solid-State Lithium Metal Batteries.

Utilizing solid-state polymer electrolytes (SPEs) in high-voltage Li-metal batteries is a promising strategy for achieving high energy density and safety. However, the SPEs face the challenges such as undesirable mechanical strength, low ionic conductivity and incompatible high-voltage interface. Here, a novel crosslinked poly(ether-urethane)-based SPE with a molecular cross-linked structure is fabricated to create high-throughput Li+ transport pathway. The amino-modified Zr-porphyrin-based metal-organic frameworks (ZrMOF) are introduced as multisite cross-linking nodes and polymer chain extenders. The abundant ether/ketonic-oxygen and Lewis acid sites in the SPE achieve high Li+ conductivity (5.7 × 10-4 S cm-1 at 30°C) and Li+ transference number (0.84). The interpenetrating cross-linked structure of SPE with robust mechanical strength results in a record cycle life of 8000h in Li||Li symmetric cell. The high structural stability of ZrMOF and abundant electron-withdrawing urethane/ureido groups in the SPE with high oxidation potential (5.1V) enables a discharge capacity of 182 mAh g-1 at 0.3 C over 500 cycles in a LiNi0.8Co0.1Mn0.1O2||Li cell. Remarkably, a high energy density of 446Wh kg-1 in a 1.5-Ah pouch cell is obtained with high loading cathode (≈4 mAh cm-2), demonstrating a great prospect of the current SPE for practical application in solid-state, high-voltage Li-metal batteries.

Understanding the roles of Brønsted/Lewis acid sites on manganese oxide-zeolite hybrid catalysts for low-temperature NH3-SCR

Although metal oxide-zeolite hybrid materials have long been known to achieve enhanced catalytic activity and selectivity in NOx removal reactions through the inter-particle diffusion of intermediate species, their subsequent reaction mechanism on acid sites is still unclear and requires investigation. In this study, the distribution of Brønsted/Lewis acid sites in the hybrid materials was precisely adjusted by introducing potassium ions, which not only selectively bind to Brønsted acid sites but also potentially affect the formation and diffusion of activated NO species. Systematic in situ diffuse reflectance infrared Fourier transform spectroscopy analyses coupled with selective catalytic reduction of NOx with NH3 (NH3-SCR) reaction demonstrate that the Lewis acid sites over MnOx are more active for NO reduction but have lower selectivity to N2 than Brønsted acids sites. Brønsted acid sites primarily produce N2, whereas Lewis acid sites primarily produce N2O, contributing to unfavorable N2 selectivity. The Brønsted acid sites present in Y zeolite, which are stronger than those on MnOx, accelerate the NH3-SCR reaction in which the nitrite/nitrate species diffused from the MnOx particles rapidly convert into the N2. Therefore, it is important to design the catalyst so that the activated NO species formed in MnOx diffuse to and are selectively decomposed on the Brønsted acid sites of H-Y zeolite rather than that of MnOx particle. For the physically mixed H-MnOx+H-Y sample, the abundant Brønsted/Lewis acid sites in H-MnOx give rise to significant consumption of activated NO species before their inter-particle diffusion, thereby hindering the enhancement of the synergistic effects. Furthermore, we found that the intercalated K+ in K-MnOx has an unexpected favorable role in the NO reduction rate, probably owing to faster diffusion of the activated NO species on K-MnOx than H-MnOx. This study will help to design promising metal oxide-zeolite hybrid catalysts by identifying the role of the acid sites in two different constituents.

Comparison of Brønsted Acidic Silanol Nests and Lewis Acidic Metal Sites in Ti-Beta Zeolites for Conversion of Butenes

The Lewis acidic framework Ti sites in Ti-Beta and Si-Beta catalysts were compared by FT-IR and NMR characterization methods before they were applied to the conversion of four butenes. The results showed that Si-Beta has fewer Lewis acid sites and abundant weak Brønsted acidic silanol nests, which play an important role in conversions between n-butene, cis-2-butene, and trans-2-butene. The conversions for these butenes over Si-Beta were always higher than those over a series of Ti-Beta catalysts with gradient-varied Lewis acidic framework Ti sites and silanols. This is because isobutene can only oligomerize, which requires stronger acidity, so its conversion over Si-Beta was lower than those over Ti-Beta zeolites. For a series of Ti-Beta catalysts with different abundances of Lewis acidic Ti sites, the more Lewis acid sites it had, the higher the conversions for the four butenes.

Selective C-N Bond Cleavage in Unstrained Pyrrolidines Enabled by Lewis Acid and Photoredox Catalysis.

Cleavage of inert C-N bonds in unstrained azacycles such as pyrrolidine remains a formidable challenge in synthetic chemistry. To address this, we introduce an effective strategy for the reductive cleavage of the C-N bond in N-benzoyl pyrrolidine, leveraging a combination of Lewis acid and photoredox catalysis. This method involves single-electron transfer to the amide, followed by site-selective cleavage at the C2-N bond. Cyclic voltammetry and NMR studies demonstrated that the Lewis acid is crucial for promoting the single-electron transfer from the photoredox catalyst to the amide carbonyl group. This protocol is widely applicable to various pyrrolidine-containing molecules and enables inert C-N bond cleavage including C-C bond formation via intermolecular radical addition. Furthermore, the current protocol successfully converts pyrrolidines to aziridines, γ-lactones, and tetrahydrofurans, showcasing its potential of the inert C-N bond cleavage for expanding synthetic strategies.

Air and Water Stable Bicyclic (Alkyl)(Amino)Carbene Stabilized Phosphenium Cation: Reactivity and Selective Fluoride Ion Affinity.

The synthesis and reactivity of an air and water stable Bicyclic (alkyl)(amino)carbene (BICAAC) stabilized phosphenium cation (1) is reported. Air and water stable phosphenium cation are rare in the literature. Compound 1 is obtained by reaction of BICAAC with Ph2PCl in THF followed by anion exchange with LiOTf. The reduction and oxidation of 1 yielded corresponding α-radical phosphine species (2) and BICAAC stabilized phosphenium oxide (3) respectively. All compounds are well characterized by single crystal X-ray diffraction studies. The Lewis acidity of compounds 1 and 3 are determined by conducting fluoride ion affinity experiments using UV-Vis spectrophotometry and multinuclei NMR spectroscopy. Compounds 1 and 3 exhibited selective binding to fluoride anion but did not interact with other halides (Cl- and Br-). Quantum chemical calculations were performed to understand the structure and nature of bonding interactions in these compounds, as well as to comprehend the specific bonding affinity to fluoride over other halide ions.

Achieving Ultra-Low-Sulfur Model Diesel Through Defective Keggin-Type Heteropolyoxometalate Catalysts

Various Keggin-type heteropolyoxometalate catalysts with structural defects and surface acidity were synthesized by immobilizing 12-phosphotungstic acid (HPW) on mesoporous SBA−15, to produce near-zero-sulfur diesel fuel. As the calcination temperature increased, the W=O and the corner-shared W–O–W bonds in the Keggin unit partially broke, creating oxygen defects, as evidenced by the Rietveld refinement and in situ FTIR characterization. All the catalysts contained Lewis (L) and Brønsted (B) acid sites, with L acidity predominant. The relative intensity of the IR band (I980) of W=O bond inversely correlated with the number of L acid sites as the calcination temperature varied, suggesting that oxygen defects contributed to the Lewis acid sites formation. In the oxidation of dibenzothiophene (DBT) in a model diesel within a biphasic system, DBT conversion exceeded 99% under the optimal reaction conditions (reaction temperature 70 °C, reaction time 60 min, H2O2/sulfur molar ratio 8, H2O2/formic acid molar ratio 1.5, catalyst concentration 2 mg/mL). The influence of fuel composition and addition of indole and 4,6-DMDBT on DBT oxidation were also evaluated. Indole and cyclohexene negatively impacted the DBT oxidative removal. Oxygen defects served as active centers for competitive adsorption of sulfur compound and oxidant. Both L and B acid sites were involved in transferring O atom from peroxophosphotungstate complex to sulfur in DBT, resulting in DBTO2 sulfone, which was immediately extracted by polar acetonitrile. This study confirms that structural defects and surface acidity are crucial in the deep oxidative desulfurization (ODS) reaction, and in enabling the simultaneous oxidation and separation of refractory organosulfur compounds in a highly efficient model diesel.

Unified Enantioselective Allylations and Vinylogous Reactions Enabled by Visible Light-Driven Chiral Lewis Acid Catalysis

Unified Enantioselective Allylations and Vinylogous Reactions Enabled by Visible Light-Driven Chiral Lewis Acid Catalysis

Atomically dispersed Ir Lewis acid sites on (111)-oriented CeO2 enable enhanced reaction kinetics for Li-O2 batteries

Non-aqueous lithium-oxygen batteries are widely regarded as one of the most promising electrochemical energy storage systems, with their ultra-high theoretical energy density and environmental friendliness. However, the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics hinder their practical application. In this study, we tailored an atomically dispersed Ir site on a CeO2 support (Ir@CeO2) with {111} facet-dependent activity to enhance cathode reaction kinetics. The charge interaction between Ir and Ce atoms results in the appropriate regulation of the d-band center of Ir sites leaping into the Fermi energy level, demonstrating a stronger Lewis acidity, which enables easier electron injection from the Ir d-orbitals into O 2p-orbitals of LiO2. This facilitates the conversion kinetics, and as a result, the lithium-oxygen battery with Ir@CeO2 catalyst delivers a minimal discharge/charge polarization and long-term cycle stability, outperforming most traditional catalysts reported. Our promising findings offer compelling insights into the precise manipulation of d orbital structures and the optimization of Lewis acidity, paving the way for advanced electrocatalyst design.

Cage-Shaped Borate Catalysts Bearing Precisely Controlled Lewis Acidity and Their Application in Glycosylations.

Cage-shaped borates, whose Lewis acidity can be precisely modulated by the structural attributes of the triphenolic ligands, were employed as catalysts for glycosylation. Each cage-shaped borate displayed distinctive reactivity; thus, screening of the borate catalysts enabled controllable activation of glycosyl fluorides under mild conditions. Practical glycosylation was achieved by fine-tuning the Lewis acidity tailored to the substrate reactivity, thereby providing a versatile method applicable to the synthesis of complex glycans.