Inert Gas Protection Research Articles

Stable and Recyclable Copper Nanoclusters with Exposed Active Sites for Broad‐Scope Protosilylation in Open Air

Despite recent advances in cluster‐based catalysis for organic synthesis, the substrate scope of reactions catalyzed by metal nanoclusters is typically not superior to previously established catalytic systems. Herein, we develop new atomically precise copper nanoclusters for protosilylation, with scope expanding to alkenes and simple enynes that were not suitable for prior synthetic methodologies with traditional copper complexes. The involvement of a second copper center in the metal kernel during the migratory insertion step is thought to be responsible for the expanded scope. In addition, the reaction is highly compatible with water and can be carried out in open air rather than under inert gas protection. Mechanistic studies suggest that the cluster‐catalyzed protosilylation proceeds in the absence of silyl radicals. The current findings demonstrate the potential of using metal nanoclusters for practical and sustainable chemical synthesis.

Stable and Recyclable Copper Nanoclusters with Exposed Active Sites for Broad-Scope Protosilylation in Open Air.

Despite recent advances in cluster-based catalysis for organic synthesis, the substrate scope of reactions catalyzed by metal nanoclusters is typically not superior to previously established catalytic systems. Herein, we develop new atomically precise copper nanoclusters for protosilylation, with scope expanding to alkenes and simple enynes that were not suitable for prior synthetic methodologies with traditional copper complexes. The involvement of a second copper center in the metal kernel during the migratory insertion step is thought to be responsible for the expanded scope. In addition, the reaction is highly compatible with water and can be carried out in open air rather than under inert gas protection. Mechanistic studies suggest that the cluster-catalyzed protosilylation proceeds in the absence of silyl radicals. The current findings demonstrate the potential of using metal nanoclusters for practical and sustainable chemical synthesis.

High stability and reactivity of porous calcium tartrate supported nano zero-valent iron in aerobic environment and alkaline wastewater

Nano zero-valent iron (nZVI) has remarkable reactivity, but its practical application is severely hindered by its easy aggregation and rapid oxidation after exposure in air. In this study, spherical porous calcium tartrate (CaTr) was synthesized with ultrasound technology and used to support nZVI. It was found that the as-obtained nZVI@CaTr was highly stable and reactive in oxygen-rich water under neutral/alkaline conditions. In the pH range of 4–9, the degradation efficiency of p-nitrophenol (PNP, 50 mg/L) by nZVI@CaTr7 exceeded 98.1 %. Importantly, nZVI@CaTr could be stored in air for a long time without inert gas protection. After 60 days and 120 days of air exposure, the removal efficiency of PNP still reached 83.3 % and 63.3 %, which was 2.8 and 9.7 times that of bare nZVI, respectively. Such an excellent performance could be attributed to two reasons: (i) spherical CaTr effectively inhibited the oxidation and aggregation of nZVI by favorable interactions with nZVI, and (ii) the abundant functional groups on the surface of CaTr acted as electronic mediators to significantly promote charge transfer between nZVI (electron donor) and PNP (electron acceptor). Therefore, cheap, air stable and highly effective nZVI@CaTr7 provided a potential application prospect for the degradation of environmental pollutants in aerobic environment and alkaline wastewater.

Ultrafast Synthesis of Transition Metal Phosphides in Air via Pulsed Laser Shock.

Transition metal phosphide nanoparticles (TMP NPs) represent a promising class of nanomaterials in the field of energy; however, a universal, time-saving, energy-efficient, and scalable synthesis method is currently lacking. Here, a facile synthesis approach is first introduced using a pulsed laser shock (PLS) process mediated by metal-organic frameworks, free of any inert gas protection, enabling the synthesis of diverse TMP NPs. Additionally, through thermodynamic calculations and experimental validation, the phase selection and competition behavior between phosphorus and oxygen have been elucidated, dictated by the redox potential and electronegativity. The resulting composites exhibit a balanced performance and extended durability. When employed as electrocatalysts for overall water splitting, the as-constructed electrolyzer achieves a low cell voltage of 1.54 V at a current density of 10 mA cm-2. This laser method for phosphide synthesis provides clear guidelines and holds potential for the preparation of nanomaterials applicable in catalysis, energy storage, biosensors, and other fields.

A highly efficient oxygen tolerant visible-light mediated RAFT polymerization

Recently, oxygen-tolerant reversible addition-fragmentation chain transfer (RAFT) polymerization has attracted increasing attention in polymer chemistry. Inspired by the monomers containing glycol ethers group have high polymerization rates and even achieved a desirable oxygen tolerance. Herein, we proposed a simple, effective, low-cost, and eco-friendly strategy to accomplish the oxygen-tolerant visible-light activated RAFT polymerization of acrylates and acrylamides in a mixed solution of glycol ether and water at ambient temperature. This photo-mediated RAFT polymerization does not require additives, prior deoxygenation, or inert gas protection. The acrylates and acrylamides with high conversion under irradiation for 2 h, and the resulting polymers were narrow unimodal and narrow molecular weight distributions (PDI<1.3). In addition, the “living” and well-controlled behaviors of this oxygen-tolerant photo-mediated RAFT polymerization were demonstrated through water content in solvents, headspace, initial concentration of monomers, various monomers, chain lengths, light ON/OFF experiment, and high-end group fidelity of block copolymers. This RAFT polymerization also opens up a wide avenue for the industrial production of functional polymeric materials via an in situ chain extension strategy. These results indicate that the mixed solution of glycol ethers and water are effective green media for promoting photo-mediated RAFT polymerization without additives or tedious degassing processes.

C3-Alkylation of Imidazo[1,2-a]pyridines via Three-Component Aza-Friedel-Crafts Reaction Catalyzed by Y(OTf)3.

As an important class of nitrogen-containing fused heterocyclic compounds, imidazo[1,2-a]pyridines often exhibit significant biological activities, such as analgesic, anticancer, antiosteoporosis, anxiolytic, etc. Using Y(OTf)3 as a Lewis acid catalyst, a simple and efficient method has been developed for the synthesis of C3-alkylated imidazo[1,2-a]pyridines through the three-component aza-Friedel-Crafts reaction of imidazo[1,2-a]pyridines, aldehydes, and amines in the normal air atmosphere without the protection of inert gas and special requirements for anhydrous and anaerobic conditions. A series of imidazo[1,2-a]pyridine derivatives were obtained with moderate to good yields, and their structures were confirmed by 1H NMR, 13C NMR, and HRMS. Furthermore, this conversion has the advantages of simple operation, excellent functional group tolerance, high atomic economy, broad substrate scope, and can achieve gram-level reactions. Notably, this methodology may be conveniently applied to the further design and rapid synthesis of potential biologically active imidazo[1,2-a]pyridines with multifunctional groups.

Pd(II)/N,N'-Disulfonyl Bisimidazoline-Catalyzed Enantioselective Synthesis of Cyclic Quaternary Centers and Mechanistic Investigations.

A Pd(II)/N,N'-disulfonyl bisimidazoline-catalyzed asymmetric 1,4-conjugate addition reaction of low-cost arylboronic acids with readily available β-substituted cyclic enones is described, providing a straightforward way of constructing cyclic all-carbon quaternary stereocenters with high enantioselectivity, in which ≥96% ee was obtained in most cases. The reaction proceeded without the protection of inert gas, making the operation process simple. Theoretical calculations have been applied to understand the origins of enantioselectivity.

Perfluorooctanoic acid interface modification enabling efficient true-blue perovskite light-emitting diodes and air-processing compatibility

The pure-bromide quasi-2D perovskite has shown advantages in fabrication of blue perovskite light-emitting diodes (PeLEDs) due to its relatively good color stability and capability of moisture resistance. However, the performances of efficiency and luminance of pure-bromide quasi-2D PeLEDs with true-blue (470 nm−480 nm) emission are still inferior. Here, we show a interfacial modification strategy of involving perfluorooctanoic acid (PFOA) to a hole transport layer of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), to improve the performances of the true-blue PeLEDs. The PFOA regulates the molecular conformation of PEDOT:PSS, forming ordered PEDOT domains that improves the carrier transport and a more favorable band alignment with the perovskite emissive layers. The achieved true-blue PeLEDs show peak EQE of 6.86 % and maximum luminance of 854.10 cd/m2 at wavelength of 478 nm, which are the record values for the pure-bromide quasi-2D PeLEDs in true-blue region. Moreover, owing to the hydrophobic fluorine-carbon (C-F) chains of PFOA, we successfully fabricate the blue PeLEDs in air condition without inert gas protection. This work paves the way for commercial applications in next-generation display technologies.

Metal-Free Synthesis of Trifluoromethyl Carbinol-Containing Imidazo[1,2-a]pyridines via Dehydrative Coupling of Imidazo[1,2-a]pyridines with Trifluoroacetaldehyde

AbstractA facile and efficient method for the synthesis of trifluoromethylated carbinols has been developed from imidazo[1,2-a]pyridines and trifluoroacetaldehyde. The direct C(sp2)–H hydroxytrifluoromethylation is successfully implemented at room temperature using HFIP as solvent through dehydrative cross-coupling process, which displays a broad substrate scope and functional group tolerance. Furthermore, gram-scale and synthetic transformation experiments have also been demonstrated, which indicate its potential applicable values in organic synthesis. This green protocol features operational simplicity, atom economy, mild reaction conditions (e.g., at room temperature, transition-metal- and oxidant-free, without inert gas protection), wide substrate scope, and excellent practicality.

Mechanochemical C-H Arylation and Alkylation of Indoles Using 3 d Transition Metal and Zero-Valent Magnesium.

Although the 3 d transition-metal catalyzed C-H functionalization have been extensively employed to promote the formation of valuable carbon-carbon bonds, the persistent problems, including the use of sensitive Grignard reagents and the rigorous operations (solvent-drying, inert gas protection, metal pre-activation and RMgX addition rate control), still leave great room for further development of sustainable methodologies. Herein, we report a mechanochemical technology toward in-situ preparation of highly sensitive organomagnesium reagents, and thus building two general 3 d transition-metal catalytic platforms that enables regioselective arylation and alkylation of indoles with a wide variety of halides (including those containing post transformable functionalities and heteroaromatic rings). This mechanochemical strategy also brings unique reactivity and high step-economy in producing functionalized N-free indole products.

Corrosion of Pure Magnesium and Binary Magnesium Alloy in Ringer's Solution

The work presents monitoring of the corrosion rate for pure magnesium and the binary magnesium alloy Mg72Zn28. Alloying elements with a purity of 99.9% were used. The melting was performed under the protection of inert gas - argon in an induction furnace. The liquid alloy was poured into a copper mold. In order to make amorphous ribbons, the obtained samples in the form of rods were re-melted on a melt spinner machine. The next step was to perform corrosion tests in Ringer's solution. Corrosion tests were carried out at a temperature of 37°C and pH 7.2. The purpose of using Ringer's solution was to recreate the conditions for the body fluids of the human body. The use of the following research methods, such as: OCP (open circuit potential), LSV (linear sweep voltammetry) and EIS (electrochemical impedance spectroscopy), was aimed at determining the corrosion resistance of the tested materials. Tests carried out in Ringer's solution showed that pure magnesium has significantly worse corrosion resistance than the binary Mg72Zn28 alloy. The conducted research also confirmed that the cathodic reaction takes place faster on the surface of amorphous ribbons. It was also confirmed that for both crystalline materials there is diffusion of chloride ions through the corrosion product layer. SEM-EDS tests were performed on the surface of an amorphous ribbon of the Mg72Zn28 alloy after corrosion in Ringer's solution.

Microwave‐Assisted Rapid Synthesis of MOF‐Based Single‐Atom Ni Catalyst for CO2 Electroreduction at Ampere‐Level Current

AbstractCarbon‐based single‐atom catalysts (SACs) have attracted tremendous interest in heterogeneous catalysis. However, the common electric heating techniques to produce carbon‐based SACs usually suffer from prolonged heating time and tedious operations. Herein, a general and facile microwave‐assisted rapid pyrolysis method is developed to afford carbon‐based SACs within 3 min without inert gas protection. The obtained carbon‐based SACs present high porosity and comparable carbonization degree to those obtained by electric heating techniques. Specifically, the single‐atom Ni implanted N‐doped carbon (Ni1−N−C) derived from a Ni‐doped metal–organic framework (Ni‐ZIF‐8) exhibits remarkable CO Faradaic efficiency (96 %) with a substantial CO partial current density (jCO) up to 1.06 A/cm2 in CO2 electroreduction, far superior to the counterpart obtained by traditional pyrolysis with electric heating. Mechanism investigations reveal that the resulting Ni1−N−C presents abundant defective sites and mesoporous structure, greatly facilitating CO2 adsorption and mass transfer. This work establishes a versatile approach to rapid and large‐scale synthesis of SACs as well as other carbon‐based materials for efficient catalysis.

Microwave-Assisted Rapid Synthesis of MOF-Based Single-Atom Ni Catalyst for CO2 Electroreduction at Ampere-Level Current.

Carbon-based single-atom catalysts (SACs) have attracted tremendous interest in heterogeneous catalysis. However, the common electric heating techniques to produce carbon-based SACs usually suffer from prolonged heating time and tedious operations. Herein, a general and facile microwave-assisted rapid pyrolysis method is developed to afford carbon-based SACs within 3 min without inert gas protection. The obtained carbon-based SACs present high porosity and comparable carbonization degree to those obtained by electric heating techniques. Specifically, the single-atom Ni implanted N-doped carbon (Ni1 -N-C) derived from a Ni-doped metal-organic framework (Ni-ZIF-8) exhibits remarkable CO Faradaic efficiency (96 %) with a substantial CO partial current density (jCO ) up to 1.06 A/cm2 in CO2 electroreduction, far superior to the counterpart obtained by traditional pyrolysis with electric heating. Mechanism investigations reveal that the resulting Ni1 -N-C presents abundant defective sites and mesoporous structure, greatly facilitating CO2 adsorption and mass transfer. This work establishes a versatile approach to rapid and large-scale synthesis of SACs as well as other carbon-based materials for efficient catalysis.

Radical-Smiles Rearrangement by a Vitamin B2-Derived Photocatalyst in Water.

Herein, we report a catalytic radical-Smiles rearrangement system of arene migration from ether to carboxylic acid with riboflavin tetraacetate (RFT), a readily available ester of natural vitamin B2, as the photocatalyst and water as a green solvent, being free of external oxidant, base, metal, inert gas protection, and lengthy reaction time. Not only the known substituted 2-phenyloxybenzoic acids substrates but also a group of naphthalene- and heterocycle-based analogues was converted to the corresponding aryl salicylates for the first time. Mechanistic studies, especially a couple of kinetic isotope effect (KIE) experiments, suggested a sequential electron transfer-proton transfer processes enabled by the bifunctional flavin photocatalyst.

Room-temperature synthesis of full-component APbX3 perovskite nanocrystal inks for optoelectronic applications

Lead halide perovskite nanocrystals (PNCs) have received great research interests due to their excellent optoelectronic properties. However, high temperature, inert gas protection and insulating long-chain ligands are used during the conventional hot-injection synthesis of PNCs, which limits their practical applications. In this work, we first develop a simple and scalable polar-solvent-free method for the preparation of full-component APbX3 (A = Cs, methylammonium (MA), formamidinium (FA), X = Cl, Br, I) PNCs under ambient condition. Through an exothermic reaction between butylamine (BA) and propionic acid (PA) short ligands, the PbX2 precursors could be well dissolved without use of any polar solvent. Meanwhile, the relatively lower growth rate of PNCs in our room-temperature reaction enables us to modulate the synthetic procedure to enhance the scalability (40-fold) and achieve large-scale synthesis. The resultant short ligands passivated PNC inks are compatible with varying solution depositing technique like spray coating for large-area film. Finally, we showcase that adopting the as-prepared MAPbI3 PNC inks, a self-powered photodetector is fabricated and shows a high photoresponsivity. These results demonstrate that our ambient-condition synthetic approach can accelerate the preparation of tunable and ready-to-use PNCs towards commercial optoelectronic applications.

High-velocity impact damage by projectile and tension after impact behavior at 1300 ℃ for SiC/SiC with environment barrier coating

The research on the high-speed & low-energy impact under millimetre sized projectile and residual strength under high temperature are rare for SiC/SiC with Environmental Barrier Coatings (EBC). The impact of 2 mm steel projectiles at the speed of 177.5 m/s–252.7 m/s was studied for EBC(Si/Yb2Si2O7/Yb2SiO5)-SiC/SiC with Chemical Vapor Infiltration (CVI) process. The tensile test at 1300 ℃ was conducted on an inert gas protection testing machine. The optical microscope, Scanning Electronic Microscope(SEM), μCT were used to observe the impact and tension after impact(TAI) damage. The results shows that projectile impact has strong effect on EBC peeling, SiC/SiC damage and fracture, and residual-tension strength at 1300 ℃. And the threshold values of impact velocity or energy are different for them. Furthermore, an analysis method for damage evolution by the attachment quantity of oxide was found for EBC-SiC/SiC composites.

Modular Synthesis of Fluoro-Substituted Furan Compounds via Controllable Fluorination of Biomass-Based 5-HMF and Its Derivatives.

5-Hydroxymethylfurfural (5-HMF) is regarded as one of the most promising platform feedstocks for producing valuable chemicals, fuels, and materials. In this study, we present a controllable fluorination technique for biomass-based 5-HMF and its oxygenated derivatives. This technique allows us to synthesize mono-fluoromethyl, difluoromethyl, and acylfluoro-substituted furan compounds by adjusting experimental conditions such as different fluorine sources and mole ratio. To gain a deeper understanding the reactivity order, we conducted intermolecular and intramolecular competition experiments. The results revealed that the hydroxyl group exhibited the highest reactivity, followed by the aldehyde group. This finding provides important theoretical support and opens up the possibility of selective fluorination. The reaction offers several advantages, including mild conditions, no need for inert gas protection, and easy operation. Furthermore, the fluoro-substituted furan compounds can be further transformed for the preparation of drug analogs, offering a new route for the high-value utilization of biomass molecules.

Synthesis of Polymers with Narrow Molecular Mass Distribution through Interface-Initiated Room-Temperature Polymerization in Emulsion Gels.

Homopolymers of n-butyl acrylate, methyl methacrylate, styrene, and their random copolymers were prepared via interface-initiated polymerization of emulsion gels at 20 °C. The polymerization was conducted in a free radical polymerization manner without inert gas protection. Compared with the polymers synthesized at 60 °C, the polymerization of emulsion gels at 20 °C produced homo- and copolymers with a higher molecular mass and a narrower molecular mass distribution. The polydispersity indices for the polymers synthesized at 20 °C were found to be between 1.12 and 1.37. The glass transition temperatures for the as-synthesized butyl acrylate copolymers agree well with the prediction from the Gordon-Taylor equation. Interface-initiated room-temperature polymerization is a robust, energy-saving polymerization technique for synthesizing polymers with a narrow molecular mass distribution.

The Synergistic Effect of Trace Ag and Hot Extruding on the Microstructure and Properties of a Biodegradable Mg-Zn-Sr-Ag Alloy.

To further improve the mechanical properties and corrosion resistance of the biodegradable magnesium (Mg) alloy, the Mg-4Zn-0.5Sr-xAg alloy (x = 0.2 wt.%, 0.5 wt.%, 1.0 wt.%, and 2.0 wt.%) was smelted in vacuum under the protection of inert gas. The effect of the Ag content on the microstructure and mechanical properties of Mg-4Zn-0.5Sr was tested. The results show that the comprehensive properties of Mg-4Zn-0.5Sr-0.5Ag are best. The grain size of the Mg-4Zn-0.5Sr-0.5Ag alloy is minimal, that is, 83.28 μm. The average tensile strength (σb), yield strength (σs), elongation (ε), and hardness for the Mg-4Zn-0.5Sr-0.5Ag alloy is 168.00 MPa, 88.00 MPa, 12.20%, and 59.90 HV, respectively. To further improve the properties of cast Mg-4Zn-0.5Sr-0.5Ag alloy, extruding treatment was conducted. After extrusion deformation, the grain size of the alloy was significantly refined to 9 μm; at the same time, fine second phases were formed and evenly distributed in the matrix. And then, the mechanical properties of the alloy are significantly enhanced due to the effect of fine crystal strengthening and dispersion strengthening. The σb, σs, ε, and hardness value for the extruded Mg-4Zn-0.5Sr-0.5Ag alloy are 236.00 MPa, 212.00 MPa, 18.97%, and 65.42 HV, respectively. Under the synergistic action of adding the Ag element and extrusion treatment, the grain size of the alloy was significantly refined and the coarse second phase in the alloy became refined to disperse in the matrix, which benefits the formation of electric couples characterized as small cathode-large anode between the second phase and Mg matrix. During full immersion, corrosion products covered on the large anode surface could reduce the galvanic corrosion tendency.

Construction of urchin-like core-shell Fe/Fe2O3@UiO-66 hybrid for effective tetracycline reduction and photocatalytic oxidation

Although Fe/Fe2O3 has potential application compared with nanoscale zero-valent iron (nZVI), its smooth structure largely limits the catalytic performance. To address this challenge, we innovatively constructed highly efficient composite Fe/Fe2O3@UiO-66 via employing an urchin-like core-shell structure of Fe/Fe2O3 onto UiO-66 through a facile ion exchange precipitation method without inert gas protection. The characterization results show the urchin-like core-shell configuration can extend the life span of Fe0 and produce more active sites. Besides, the absorption spectrum is broadened by Fe2O3 which has narrow band gap and the high-efficiency separation of photogenerated electron-hole pairs is obtained with the load of Fe/Fe2O3. Moreover, Two-parameter pseudo-first-order decay model fits well with the reduction and adsorption of composites in the dark reaction, and a plausible pathway for tetracycline (TC) degradation is also proposed. The findings of this research provide a promising method for promoting the catalytic properties of MOF-based materials and Fe/Fe2O3.