Catalytic Reaction Research Articles

Impact of mixed boundary conditions and nonsmooth data on layer‐originated nonpremixed combustion problems: Higher‐order convergence analysis

AbstractThis work explores the theoretical and computational impacts of mixed‐type flux conditions and nonsmooth data on boundary/interior layer‐originated singularly perturbed semilinear reaction–diffusion problems. Such problems are prevalent in nonpremixed combustion models and catalytic reaction models. The inclusion of arbitrarily small diffusion terms results in boundary layers influenced by specific flux conditions normalized by perturbation parameters. We have demonstrated theoretically that the sharpness of the boundary layer is significantly reduced when this normalization is independent of the diffusion parameter. In addition, the presence of a nonsmooth source function gives rise to an interior layer in the current problem. We show that using upwind discretizations for mixed boundary fluxes achieves nearly second‐order accuracy if the first derivatives are not normalized concerning perturbation parameters. This outcome arises from the bounds of a prior derivative of the continuous solution. Furthermore, it is theoretically shown that nearly second‐order uniform accuracy can be attained for reaction‐dominated semilinear problems using a hybrid scheme at the discontinuity point. To ensure the uniform stability of the discrete solution, a transformation is necessary for the corresponding discrete problem. Theoretical results are supported by various experiments on nonlinear problems, illustrating the pointwise rates and highlighting both linear and higher‐order accuracy at specific points.

Using In situ Transmission Electron Microscopy to Study Strong Metal‐Support Interactions in Heterogeneous Catalysis

AbstractPrecisely controlling the microstructure of supported metal catalysts and regulating metal‐support interactions at the atomic level are essential for achieving highly efficient heterogeneous catalysts. Strong metal‐support interaction (SMSI) not only stabilizes metal nanoparticles and improves their resistance to sintering but also modulates the electrical interaction between metal species and the support, optimizing the catalytic activity and selectivity. Therefore, understating the formation mechanism of SMSI and its dynamic evolution during the chemical reaction at the atomic scale is crucial for guiding the structural design and performance optimization of supported metal catalysts. Recent advancements in in situ transmission electron microscopy (TEM) have shed new light on these complex phenomena, providing deeper insights into the SMSI dynamics. Here, the research progress of in situ TEM investigation on SMSI in heterogeneous catalysis is systematically reviewed, focusing on the formation dynamics, structural evolution during the catalytic reactions, and regulation methods of SMSI. The significant advantages of in situ TEM technologies for SMSI research are also highlighted. Moreover, the challenges and probable development paths of in situ TEM studies on the SMSI are also provided.

Anchoring cobalt dual-atom pairs on open hollow-structured carbon via a facile in-situ synthetic strategy for enhanced advanced oxidation processes

Atomically dispersed catalysts offer unprecedented opportunities for high-efficiency Fenton-like oxidation of organic pollutants in water. However, the hazardous metal leaching of atomically dispersed catalysts hinders their practical application for wastewater treatment, while the inaccessible interior active sites in carbon substrates have been commonly overlooked. Herein, we develop a straightforward approach for tightly anchoring cobalt dual-atom pairs on nitrogen-doped open hollow carbon structure (Co-NOHC) via an in-situ polyelectrolyte nanosphere-guided strategy. The unique open hollow carbon structure benefits the electron/mass transfer and maximizes the exposure of active sites. As a result, the as-synthesized Co-NOHC exhibits outstanding peroxymonosulfate activation activity and Fenton-like performance in oxidation by taking rhodamine B degradation as an example. Remarkably, the turnover frequency of the Co-NOHC is 6.5, 26.5, and 9.3 times higher than that of the Co2+, cobalt, and its oxides, respectively, and its catalytic activity also greatly outperforms the pristine zeolitic-imidazole frameworks derived Co-based atomically dispersed catalysts. More importantly, benefitted from the stable anchoring of cobalt dual atoms, the Co2+ leaching from the Co-NOHC is greatly alleviated, as low as 0.1 mg/L after the catalytic reaction, showing outstanding stability as compared to most atomically dispersed catalysts. Furthermore, the reactive active species, including SO4−, OH and O2− radicals, and electron-transfer mechanism are demonstrated to dominate the rhodamine B removal. This work offers a new consideration for promoting the development of the advanced catalysts and their potential applications in advanced oxidation process.

Persistent ultraviolet luminescence and photocatalytic properties of SiO2-Zn2SiO4:Ga,Pb nanoparticles

Persistent phosphors possess unique afterglow optical properties. In this paper, a class of ultra-violet (UV) persistent luminescence nanoparticles were developed for catalytic photodegradation applications. UV persistent luminescence nanoparticles of SiO2-Zn2SiO4:Ga and SiO2-Zn2SiO4:Ga,Pb were successfully synthesized by using a mesoporous template method. The UV persistent luminescence intensity of SiO2-Zn2SiO4:Ga at 405 nm was enhanced up to ca. 3.5 times by co-doping with Pb2+ (396 nm), along with longer persistent luminescence duration. The photodegradation results indicate that it is useful to introduce UV persistent luminescence property into SiO2-Zn2SiO4:Ga,Pb to obtain enhanced catalytic activity of SiO2-Zn2SiO4 with a bigger catalytic oxidation reaction kinetic constant (up to ∼4 times). This kind of UV persistent catalysis strategy may become a potential feasible method for better catalytic photodegradation activity. The UV persistent photocatalyst has potential applications in the photooxidation of organic molecules in high chroma and/or turbidity aqueous systems.

Coupling of the catalytic reactions from formate dehydrogenase and hydrogenase in solution: Insights from computations and in situ IR spectroscopy

Sophisticated enzymatic systems have evolved in nature to efficiently couple distinct biochemical reactions in form of cascades. As such they serve as reference models to understand the indirect interactions of catalytic centers. Herein, we studied, in solution, the coupling of the reactions from membrane‐bound [NiFe] hydrogenase (MBH) from Cupriavidus necator (reversible H2 splitting into H+ and e‐) and the molybdenum‐dependent formate dehydrogenase from Rhodobacter capsulatus (reversible formate to CO2 interconversion). To follow their interplay via the characteristic absorptions from the MBH's active site or the respective substrate and product bands of FDH, we utilized in situ IR spectrocopy and GC(‐MS), in the absence or presence of soluble redox mediators. Coarse grained molecular dynamics (cgMD) computations revealed the lack of productive enzyme complexes for direct electron transfer (ET). Thus, the observed minor amounts of H2 or formate were produced from transient interactions between the two enzymes. On the contrary, the significantly increased product formation in the presence of methylene viologen can be related to the putative multiple interaction sites of the redox mediator with FDH identified by cgMD. Our study represents a proof‐of‐concept approach that can be used in future to develop novel coupled biocatalytic systems by identifying potential ET pathways.

Mechanical-vibration-driven piezocatalytic degradation of organic pollutants over microcrystalline SnSe with selenium vacancies

Two-dimensional piezoelectric materials are attractive candidates to trigger piezoelectric catalytic reactions for organics degradation. Microcrystalline structures can endow them with enhanced piezocatalytic activity due totheir large surface area and abundant defect structures. In this work, microcrystalline SnSe with selenium vacancies (mc-SeVs SnSe) was synthesized and employed for piezocatalytic degradation of aqueous organics for the first time. Various instrumental testing results demonstrated that this unique microcrystalline SnSe has strong piezoelectric responses, abundant selenium vacancy defects and large active edges. Compared with crystalline SnSe, mc-SeVs SnSe showed superior piezocatalytic activity for the degradation of various organics in water. More importantly, mc-SeVs SnSe could induce the piezoelectric effect through mild mechanical energy to facilitate the efficient degradation of organic pollutants. The degradation efficiency of Crystal violet, p-nitrophenol, Malachite green, Congo red and Rhodamine B approached 100 % within 60 min reaction time. Superoxide and hydroxyl radicals were detected as the main reactive oxygen species generated in the piezocatalytic process. The degradation pathways of Rhodamine B were proposed based on high performance liquid chromatography-quadrupole-time of flight mass spectrum. The impact of strain on the alterations of dipole moment and electronic structure was investigated using density functional theory. The change in electron band structure induced by the polarized electric field was the underlying reason for the generation of hydroxyl radicals. This work will enrich the piezoelectric materials for organics degradation and provide fresh light on the mechanism of mechanically driven piezoelectric catalytic reactions.

Unraveling the Interplay between Stability and Flexibility in the Design of Polyethylene Terephthalate (PET) Hydrolases.

The accumulation of polyethylene terephthalate (PET), a widely used polyester plastic in packaging and textiles, has led to a global environmental crisis. Biodegradation presents a promising strategy for PET recycling, with PET hydrolases (PETase) undertaking the task at the molecular level. Unfortunately, PETase operates only at ambient temperatures with low efficiency, limiting its industrial application. Current engineering efforts focus on enhancing the thermostability of PETase, but increased stability can reduce the structural dynamics needed for substrate binding, potentially slowing enzymatic activity. To elucidate the balance between stability and flexibility in optimizing PETase catalytic activity, we performed theoretical investigations on both wild-type PETase (WT-PETase) and a thermophilic variant (Thermo-PETase) using molecular dynamics simulations and frustration analysis. Despite being initially designed to stabilize the native structure of the enzyme, our findings reveal that Thermo-PETase exhibits an unprecedented increase in structural flexibility at the PET-binding and catalytic sites, beneficial for substrate recruitment and product release, compared to WT-PETase. Upon PET binding, we observed that the structural dynamics of Thermo-PETase is largely quenched, favoring the proximity between the catalytic residues and the carbonyl of the PET substrate. This may potentially contribute to a higher probability of a catalytic reaction occurring in Thermo-PETase compared to WT-PETase. We suggest that Thermo-PETase can exhibit higher PET-degradation performance than WT-PETase across a broad temperature range by leveraging stability and flexibility at high and low temperatures, respectively. Our findings provide valuable insights into how PETase optimizes its enzymatic performance by balancing stability and flexibility, which may contribute to future PETase design strategies.

NiFe2O4 in MoSe2 Exhibits Bifunctional Water Oxidation and Oxygen Reduction (OER and ORR) Catalytic Reactions for Energy Applications

NiFe₂O₄ in MoSe₂ Exhibits Bifunctional Water Oxidation and Oxygen Reduction (OER and ORR) Catalytic Reactions for Energy Applications

Kinetic Studies of CO2 Insertion into Metal-Element σ-Bonds.

ConspectusDespite the plethora of metal catalyzed reactions for CO2 utilization that have been developed in academic laboratories, practical systems remain elusive. The understanding of the elementary steps in catalysis is a proven method to improve catalytic performance. In many catalytic cycles for CO2 utilization, the insertion of CO2 into a metal-element σ-bond, such as hydrides, alkyls, amides, or hydroxides, is a crucial step. However, despite the many demonstrations of CO2 insertion, there are a paucity of kinetic studies, and information about the reaction mechanism has been predominantly elucidated from computational investigations. In this Account, kinetic studies on CO2 insertion into late transition metal-element σ-bonds performed by my group are summarized, along with their implications for catalysis.A common pathway for CO2 insertion into a metal hydride involves a two-step mechanism. The first step is nucleophilic attack on CO2 by the hydride to generate an H-bound formate, followed by rearrangement to form an O-bound formate product. Kinetic studies on systems in which both the first and second steps are proposed to be rate-determining, known as inner-sphere and outer-sphere processes, respectively, show that insertion rates increase as (i) the ligand trans to the hydride becomes a stronger donor, (ii) the ancillary ligand becomes more electron-donating, and (iii) the Dimroth-Reichardt parameter of the solvent increases. However, the magnitude of these effects is generally smaller for inner-sphere processes because there is less buildup of charge in the key transition state. For similar reasons, the presence of Lewis acids only increases the rate of outer-sphere processes. These results suggest it may be possible to experimentally differentiate between inner- and outer-sphere processes.The insertion of CO2 into a metal-alkyl bond results in the formation of a C-C bond, which is important for the generation of fuels from CO2. For square planar Group 10 complexes, the presence of a strong donor ligand trans to the alkyl group is critical for kinetically promoting insertion. Further, the nucleophilicity of the alkyl ligand directly impacts the rate of CO2 insertion via an SE2 mechanism, as does the steric bulk of the complex, and the reaction solvent. In contrast to the relatively slow rates of insertion observed for metal alkyls, CO2 insertion is rapid for metal hydroxides and amides. Although kinetics trends could be determined for hydroxides, reactions with amides are too fast for quantitative studies.Overall, the rates of insertion correlate with the nucleophilicity of the element in the metal-element σ-bond, so amide > hydroxide > hydride > alkyl. Due to the related pathways for insertion, similar trends in ligand and solvent effects are observed for insertion into different metal-element σ-bonds. Thus, the same strategies can be used to control the rates of insertion across systems. Differences in the magnitude of solvent and ligand effects are caused by variation in the amount of charge build-up on the metal in the rate-determining transition state. Likely, given that CO2 is related to organic molecules such as aldehydes, ketones, and amides, the results described in this Account are general to a wider range of substrates.

Dependence of oxygen evolution reaction catalysis at thin cathodically-deposited nickel-iron-selenide on Fe in the alkaline electrolyte vs. codeposited Fe

This study interrogated the role of Fe co-deposited in films versus Fe included from traces in the electrolyte on the electrochemical dynamics and kinetics for the oxygen evolution reaction (OER) in alkaline at a nickel-iron selenide OER pre-catalyst. Iron was co-included in the bulk of nickel selenide (NixSey) during cathodic deposition and is termed bulk-Fe (Febulk), and/or was included on its surface post-deposition by conditioning at anodic bias in alkaline with Fe traces and is termed surface-Fe (Fesurface). The electrochemical dynamics, OER kinetics, and sustainability of catalysis were studied in 1 M KOH stripped of Fe (Fe-free KOH) or containing Fe traces (KOH). The selenides transformed into a selenide/hydroxide with a few monolayers of surface hydroxide during the hours of conditioning and electrokinetic measurements at anodic bias in both solutions. Bulk-Fe did not enhance OER catalysis at nickel selenide, while surface-Fe promoted OER catalysis. Tafel slopes of ca. 40 mV/dec were recorded at (NiFebulk)xSey-Fesurface and NixSey-Fesurface in KOH, while Tafel-slopes of ca. 100 mV/dec were recorded at (NiFebulk)xSey in Fe-free KOH. Tafel slopes of 60–80 mV/dec were recorded in Fe-free KOH at (NiFebulk)xSey-Fesurface and NixSey-Fesurface that had been conditioned in KOH. OER catalysis at Fesurface-activated electrocatalysts was not sustained in alkaline stripped of Fe, neither at anodic bias nor subjected to potential cycling. The electrochemical data is consistent with a mechanism involving a low-coordination surface-Fe in the thin hydroxide layer of not more than few monolayers formed in-situ on the selenide. Surface-Fe is pictured as part of a dynamic catalytic site whose equilibrium density, to ensure sustainable catalysis, requires a greater than a threshold activity of Fe ions and lower than a threshold of activity of Ni, otherwise Fe will be in an inactive high-coordination state.

The effect of pore boundary shape on the performance of catalytic self-pumping membranes and channels

Many technologies demand highly controllable membranes, including lab-on-a-chip systems, microfluidic sensors, and electrochemical cells. The pumps for these systems can be scaled down by many orders of magnitude with electrochemical pumps, and more still with recently invented membrane pumps. Such pumps have been demonstrated to independently pump fluid via catalytic reactions that create and consume H+ cations on opposite sides of the membrane. Our prior work showed that the mechanism behind this phenomenon was a self-generated electric field driving the fluid flow caused by the space charge polarization due to the electrochemical reactions. However, that work assumed that the pores inside a membrane were perfectly cylindrical, which is not always true. This work investigates more complicated and realistic structures that deviate from a perfectly cylindrical shape, as is typical of actual track-etched or polymeric membranes. The pore structures were studied using a 2D model, which solved the Poisson-Nernst-Planck-Stokes equations in COMSOL 5.5. Based on our previously validated model, we examine the impact of different parameters on self-pumping flow rates, including pore width, contracting/expanding variation, pore length, and pore inclination angle. According to the results, the self-pumping flow rate is more sensitive to pore width than pore length. Regarding the effects of pore defects, membranes with complicated shapes of contracting/expanding pores and cross-linked connecting pores should follow the same pattern as those membranes with straight pores and similar pore size; likewise, pore inclination does not significantly influence self-pumping flow. Therefore, the conclusions we obtained for cylindrical straight pores are still applicable. The results highlight the potential of utilizing catalytic reactions to manipulate liquid via actual track-etched membranes.

Enhancement of oxygen flux through Nb-doped La0.4Sr0.6FeO3-δ ceramic hollow fiber membranes by Fe exsolution

In recent years, numerous studies have focused on the use of mixed ionic-electronic conducting oxides for coupled oxygen separation and catalytic reactions in membrane reactors. A promising strategy for the efficient fabrication of oxygen separation membranes involves modification of the membrane surface via exsolved metal nanoparticles decoration. Here, we present a detailed characterization of the structural and transport properties of a novel membrane material La0.4Sr0.6Fe0.95Nb0.05O3−δ (LSFNb5). The exsolution of Fe nanoparticles was observed after heating of LSFNb5 in a reducing atmosphere (5 % Н2/Ar) and was confirmed by X-ray diffraction analysis, Mössbauer spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy. The formation of Fe nanoparticles on the surface of LSFNb5 hollow fiber membrane in the reduction process leads to the enhancement of oxygen fluxes and reduces the apparent activation energy. Kinetic parameters for oxygen transport through LSFNb5 hollow fiber membrane estimated using two different models, are in good agreement with the experimental results. Furthermore, LSFNb5 hollow fiber membrane demonstrates stable performance both before and after surface treatment.

Assessment of acid catalytic properties of ferrosilicate MFI zeolite by methanol-to-hydrocarbon conversion.

Four representative synthetic methods were employed to prepare Fe-containing siliceous MFI zeolites. The obtained Fe-MFI zeolites exhibited markedly different catalytic performances in the methanol-to-hydrocarbon (MTH) conversion reaction depending on the type of Fe incorporation within the siliceous framework. The catalytically active Brønsted acid sites were analyzed using pyridine adsorption experiments combined with Fourier transform infrared spectroscopy, providing characteristic signal intensities according to the acid-base interactions. Based on the MTH conversion results and acidity analyses, a suitable synthetic method was identified for the incorporation of Fe within the MFI zeolite framework. However, compared to other catalytic reactions, structural analyses by transmission electron microscopy, ultraviolet-visible spectroscopy, and X-ray absorption spectroscopy were much less conclusive.

Efficient Encapsulation of β-Lapachone into Self-Immolative Polymer Nanoparticles for Cyclic Amplification of Intracellular Reactive Oxygen Species Stress.

The selective upregulation of intracellular oxidative stress in cancer cells presents a promising approach for effective cancer treatment. In this study, we report the integration of enzyme catalytic amplification and chemical amplification reactions in β-lapachone (Lap)-loaded micellar nanoparticles (NPs), which are self-assembled from reactive oxygen species (ROS)-responsive self-immolative polymers (SIPs). This integration enables cyclic amplification of intracellular oxidative stress in cancer cells. Specifically, we have developed ROS-responsive SIPs with phenylboronic ester triggering motifs and hexafluoroisopropanol moieties in the side chains, significantly enhancing Lap loading efficiency (98%) and loading capacity (33%) through multiple noncovalent interactions. Upon ROS activation in tumor cells, the Lap-loaded micellar NPs disassemble, releasing Lap and generating additional ROS via enzyme catalytic amplification. This process elevates intracellular oxidative stress and triggers polymer depolymerization in a positive feedback loop. Furthermore, the degradation of SIPs via chemical amplification produces azaquinone methide intermediates, which consume intracellular thiol-related substrates, disrupt intracellular redox hemostasis, further intensify oxidative stress, and promote cancer cell apoptosis. This work introduces a strategy to enhance intracellular oxidative stress by combining enzymatic and chemical amplification reactions, providing a potential pathway for the development of highly efficient anticancer agents.

Catalytic Asymmetric Cycloadditions of Cyclic Sulfamidate Imines: Straightforward Access to Chiral N‐Heterocycles

AbstractChiral N‐heterocyclic compounds are key structures in natural compounds and pharmaceuticals, and they serve as essential building blocks of functional materials. Catalytic asymmetric cycloaddition reactions represent one of the most efficient synthetic strategies for constructing optically active heterocycles. Cyclic sulfamidate imines have recently come to be extensively studied and widely utilized in both organocatalytic and transition metal‐catalyzed asymmetric cycloadditions, where they have been shown to provide various N‐fused‐heterocycles and spiro‐cycles exhibiting high efficiencies with excellent stereoselectivities. This review highlights recent advancements in catalytic asymmetric cycloadditions of cyclic sulfamidate imines for the stereoselective synthesis of biologically active sulfamidate‐containing heterocycles since 2012 while focusing on the diverse reactivities of cyclic sulfamidate imines and the mechanisms of chiral induction in catalysis.

Zr‐MOF Nanosheets Featuring Benzothiadiazoles Enable Efficient Visible Light Driven Photooxidation of Sulfides and Amines

AbstractUltrathin zirconium‐based metal−organic framework (MOF) nanosheets, embedded with photochromic units, are expected to be highly efficient heterogeneous photocatalysts, thanks to their rich catalytic sites, short diffusion paths, and effective separation of photogenerated charge carriers. Herein, we reported the synthesis of novel Zr‐MOF nanosheets (Zr‐BTDB) through a solvothermal synthesis that integrates benzothiadiazole (BTz) as a photochromic moiety within the framework of MOF. The Zr‐BTDB nanosheets processes a [Zr12(μ3‐O)8(μ3‐OH)8(μ2‐OH)6] cluster with hcp topology. Importantly, Zr‐BTDB nanosheets exhibit excellent photocatalytic activity for the photooxidation of sulfides and amines at room temperature under blue light irradiation. Notably, these nanosheets maintain their photocatalytic activity and selectivity for up to five cycles without significant loss of activity and crystallinity. Systematical catalytic reactions revealed that the Zr‐BTDB nanosheets enable the generation of singlet oxygen (1O2) and superoxide radical (O2⋅−) under visible light irradiation, which is critical reactive oxygen species for the photooxidation of sulfides and benzylamines. Our work represents a straightforward route for the preparation of ultrathin, water stable, and visible‐light‐activated Zr‐MOF nanosheets, offering new potentials for the selective photooxidation of sulfides and amines in an eco‐friendly way.

Electrochemical detection of quercetin at a Pt nanoaggregate-decorated Ti3C2-modified electrode

The surface chemical state of the electrode modification material, particularly crystal defects, significantly affects electrochemical detection properties. In this study, Ti3C2 decorated by Pt nanoaggregates (Pt NAs-Ti3C2) with enhanced crystal defect was developed for quercetin detection, where Pt nanoaggregates on Ti3C2 exhibit improved dispersibility and smaller particle size, generating a more favorable environment for interfacial catalytic reactions. A large specific surface area, the Pt NAs-Ti3C2 composite is beneficial for the adsorption and transfer of quercetin on the electrode surface. In comparison to Pt nanoaggregates with complete crystals, the Pt NA-Ti3C2-modified glassy carbon electrode (Pt NA-Ti3C2/GCE) demonstrates superior quercetin detection capabilities, achieving a detection sensitivity of 72.3 μA μM−1 and an outstanding detection linear region of 0.1–1500 nM. Besides, the electrode showcases excellent reproducibility with RSD of 2.41 %, repeatability with RSD of 1.08 %, and long-term stability with 92.3 % of the original signal retained, and resistance to interference, achieving accurately and selectively quercetin detection even in the presence of other ions and compounds. In addition, the Pt NA-Ti3C2/GCE allows for precise quercetin detection in real-life samples. Our findings establish a theoretical guideline and furnish the material foundation for the development of high-performance electrochemical sensors.

Tantalum Catalyzed Hydroaminoalkylation Enables a Telescoping Catalytic Reaction Sequence for the Synthesis of Benzoannulated Indolizidines and Quinolizidines

Tantalum Catalyzed Hydroaminoalkylation Enables a Telescoping Catalytic Reaction Sequence for the Synthesis of Benzoannulated Indolizidines and Quinolizidines

Efficient epoxidation of styrene over single-atomic copper-doped ordered mesoporous alumina (Cu-OMA) composited with carbon nitride

The present study assessed the catalytic performance in epoxidation of styrene using tert‑butyl hydroperoxide (TBHP) as an oxidant over single-atomic copper-doped Ordered mesoporous alumina (Cu-OMA) composited with g-C3N4 (CN). The thermal treatment at three temperatures (300, 500, 700 °C) provided a facile mean to modify the texture and electronic structure of the Cu-OMA@CN composite. The X-Ray absorption spectroscopy proved the single-atomic Cu-O-Al and Cu-O-C in Cu-OMA@CN-500 catalyst. Catalytic reaction parameters, namely temperature (60–80 °C), catalyst amount (10–70 mg), substrate/oxidant ratio (1:1–1:3), and solvents (acetone, ethanol, acetonitrile, N, N-dimethylacetamide) were optimized to obtain high conversion of styrene and selectivity to styrene epoxide. Under the optimized reaction conditions (75 °C, 30 mg of catalyst, 1:2 of styrene/TBHP and acetonitrile as solvent), the conversion decreased in the order of Cu-OMA@CN-500 > Cu-OMA@CN-300 > Cu-OMA@CN-700. This sequence was related to the formation of electron-rich single-atom copper sites, high surface area, medium alkaline environment and high content of graphic nitrogen species in Cu-OMA@CN-500. This structure differed from the blocky structure of C3N4 in Cu-OMA@CN-300 and the destroyed tri-s-triazine ring in Cu-OMA@CN-700. The most active Cu-OMA@CN-500 catalyst displayed a high styrene conversion (87.2 %) and striking selectivity to styrene oxide (90.0 %). Its catalytic activity was retained after five recyclability tests. The possible catalytic mechanism for epoxidation of styrene over this catalyst was tentatively proposed.

A Cascade C(sp3)−H Annulation Involving C(alkyl),C(alkyl)‐Palladacycle Intermediates

AbstractC−H bond functionalization involving C,C‐palladacycle intermediates provides a unique platform for developing novel reactions. However, the vast majority of studies have been limited to the transformations of C(aryl),C‐palladacycles. In sharp contrast, catalytic reactions involving C(alkyl),C(alkyl)‐palladacycles have rarely been reported. Herein, we disclose an unprecedented cascade C(sp3)−H annulation involving C(alkyl),C(alkyl)‐palladacycles. In this protocol, alkene‐tethered cycloalkenyl bromides undergo intramolecular Heck/C(sp3)−H activation to generate C(alkyl),C(alkyl)‐palladacycles, which can be captured by α‐bromoacrylic acids to afford tricyclic fused pyridinediones. In addition, this strategy can also be applied to indole‐tethered cycloalkenyl bromides to construct pentacyclic fused pyridinediones via suquential Heck dearomatization/C(sp3)−H activation/decarboxylative cyclization. Notably, the removal of α‐bromoacrylic acids in the reaction of alkene‐tethered cycloalkenyl bromides can build an interesting tricyclic skeleton containing a four‐membered ring. Preliminary mechanistic experiments indicate that five‐membered C(alkyl),C(alkyl)‐palladacycles serve as the key intermediates. Meanwhile, density functional theory (DFT) calculations have provided insights into the reaction pathway.