Anhydrous Solution Research Articles

A 1,4-benzoquinone with counteracting inductive donor and acceptor substituents

Investigation of a published route to produce 3,5-di- tert-butylphenol, starting from commercial 3,5-di- tert-butylbenzoic acid via 3,5-di- tert-butylanlinium hydrogen sulfate, unexpectedly yielded 2,6-dintitro-3,5-di- tert-butylphenol. Attempts to increase the yield of the latter resulted, instead, in the previously unreported 2,6-dinitro-3,5-di- tert-butylcyclohexa-2,5-dien-1,4-dione. Single-crystal X-ray diffraction structures are reported for the anilinium salt, the nitrated phenol, and the quinone. Voltammetry of the quinone shows two chemically reversible reductions in anhydrous solution and the radical anion produced from the first reduction step has been characterized by electron paramagnetic resonance spectroscopy. This compound fits well to the middle range of electron-poor quinones, indicating that the inductive effects of the tert-butyl and nitro groups counteract each other. This conclusion is also supported by the infrared spectroscopic data where the ν(C=O) and ν(C=C) bands are of very similar energy to those of 2,3,5,6-tetrachloro-1,4-benzoquinone.

Preparation of eggshell-based materials and their adsorption performance on Fe(III) in water*

Abstract If there is too much trivalent iron in the body, it will disrupt the balance of osmotic pressure inside the body, and its heavy metal properties will denature proteins. Therefore, effective management of industrial pollution source wastewater is very important for environmental protection and human’s health. Calcium carbonate particles have a good ability to adsorb trivalent iron in wastewater. The aim is to prepare porous calcium carbonate by a template method using eggshell powder, hydrochloric acid, sodium stearate, and anhydrous sodium carbonate solution as the raw materials and research the adsorption properties of porous calcium carbonate to trivalent iron. Porous calcium carbonate was prepared by a template method using eggshell powder, hydrochloric acid, sodium stearate, and anhydrous sodium carbonate solution as the raw materials. The morphology and adsorptive properties of Fe (III) of the porous calcium carbonate were analyzed by scanning electron microscope (SEM) and UV-visible spectrophotometer (UV). The best value was found between different temperatures, time, and pH. The results verified that the maximum amount of adsorption was obtained when calcination was 400°C, pH was 5, time was 60 min, and the input amount was 20 mg. The adsorption of porous calcium carbonate to Fe (III) is chemical and has a better adsorption effect.

Investigation of Weathering Resistance and Damage Manifestations of Mortar Formulations for Heritage Structures in Saline Environment

ABSTRACT Salt, moisture, wind, relative humidity, and temperature fluctuations accelerate the deterioration of heritage masonry mortars. The salt entering the structure crystallizes on water evaporation, resulting in efflorescence and cryptoflorescence. As the conservation of built heritage primarily focuses on protecting the structure’s functionality, durability, and compatibility with the materials, salt weathering resistance must be emphasized when choosing a repair material for conservation. This study investigates the resistance of five different mortar compositions to salt exposure. Mortar cubes of size 50 mm were cast using five different binder compositions — dry hydrated lime, lime aged for one month, lime aged for one year, lime mortar with 20% Ordinary Portland Cement by weight and lime mortar with 50% Ordinary Portland Cement by weight. Alternate wetting and drying cycles were simulated by immersing the cubes in a 10% anhydrous sodium sulphate solution followed by drying. Physicomechanical characterization of the mortar was conducted before weathering. X-ray diffraction and Scanning Electron Microscopy provided the mineralogical and morphological alterations of the mortar specimens with weathering, respectively. Along with the microstructural assessment, observations on the mass change during the weathering cycles indicated that the partial replacement of lime with cement improved the weathering resistance of the mortar by changing the pore structure of the matrix. However, salt weathering resistance was unaffected by the changes in the ageing duration of lime. The study provides options for alternative lime-based systems with enhanced salt weathering resistance and investigates the role of the compositional differences and their impact on the pore structure and strength of the matrix, which in turn governs the salt weathering resistance.

Study on the microwave absorbing properties of SiC@Ni powders with core@shell structure

Hybridization of dielectric and magnetic materials is considered a promising option for the preparation of electromagnetic wave absorbing materials with excellent properties. In this paper, SiC@Ni powders were prepared by a surface heat-assisted process, in which SiC was first cleaned sequentially with anhydrous ethanol and NaOH solutions, and the samples were etched into a mixed solution of HF and HCl, the SiC@Ni powders were then mixed at high speed at 120 °C under argon atmosphere. The sample were characterized by Scanning electron microscopy (SEM) and vector network analyzer (VNA). It is found that the absorption characteristics of SiC@Ni in the 2–18 GHz band are significantly enhanced due to the introduction of the ni layer which enhances the loss of the sample to solve the problem of a single absorption mechanism and high impedance of SiC. The reflection loss value of SiC@Ni in the 8.7 GHz band decreases to − 22.45 dB when the material thickness is 2.5 mm, the effective absorption frequency width is 2.5 GHz, which is a significant advantage over the initial SiC. The experimental methodology of this work is simple and easy to follow, and provides some guidance for the large-scale production of SiC-based microwave absorbing materials.

Removal and Reoccurrence of LLZTO Surface Contaminants under Glovebox Conditions.

The reactivity of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) solid electrolytes to form lithio-phobic species such as Li2CO3 on their surface when exposed to trace amounts of H2O and CO2 limits the progress of LLZTO-based solid-state batteries. Various treatments, such as annealing LLZTO within a glovebox or acid etching, aim at removing the surface contaminants, but a comprehensive understanding of the evolving LLZTO surface chemistry during and after these treatments is lacking. Here, glovebox-like H2O and CO2 conditions were recreated in a near ambient pressure X-ray photoelectron spectroscopy chamber to analyze the LLZTO surface under realistic conditions. We find that annealing LLZTO at 600 °C in this atmosphere effectively removes the surface contaminants, but a significant level of contamination reappears upon cooling down. In contrast, HCl(aq) acid etching demonstrates superior Li2CO3 removal and stable surface chemistry post treatment. To avoid air exposure during the acid treatment, an anhydrous HCl solution in diethyl ether was used directly within the glovebox. This novel acid etching strategy delivers the lowest lithium/LLZTO interfacial resistance and the highest critical current density.

Reaction calorimetry and structural crystal properties of non-ideal binary rhabdophane solid solutions (Ce1−xREExPO4·nH2O)

Rhabdophane is a hydrous phosphate that commonly replaces monazite as a weathering product in critical mineral deposits during the alteration of rare earth elements (REE) bearing carbonatites and alkaline igneous complexes. It is an important host to the light (L)REE (i.e., La to Gd) but the stability and structure of binary solid solutions between the Ce and the other LREE endmembers have not yet been determined experimentally. Here we present room temperature calorimetric experiments that were used to measure the enthalpy of precipitation of rhabdophane (Ce1−xREExPO4·nH2O; REE = La, Pr, Nd, Sm, Eu, and Gd). The solids were characterized using X-ray diffraction, scanning electron microscopy, Raman spectroscopy, and the role of water in the rhabdophane structure was further determined using thermogravimetric analysis coupled with differential scanning calorimetry. The calorimetric experiments indicate a non-ideal behavior for all of the binary solid solutions investigated with an excess enthalpy of mixing (ΔHex) described by a 2- to 3-term Guggenheim parameters equation. The solid solutions were categorized into three groups: 1) binary Ce-La and Ce-Pr which display positive ΔHex values with a slight asymmetry; 2) binary Ce-Nd and Ce-Sm which display negative ΔHex values with a nearly symmetric shape; 3) Ce-Eu and Ce-Gd which display both negative and positive ΔHex values with nearly symmetric shape. The excess Gibbs energy (ΔGex) of the solid solutions was further investigated using a thermodynamic analysis approach of aqueous-solid solution equilibria and the optimization programs GEMS and GEMSFITS. The resulting ΔGex values combined with the calorimetric ΔHex values indicate that there is likely an excess entropy contribution implying important short-range structural modifications in the solid solutions dependent on the deviation of the REE ionic radii from the size of Ce3+. These observations corroborate with the trends in the Raman v1 stretching bands of the PO4-site. The excess molar volumes determined from X-ray diffraction analysis further indicate an overall asymmetric behavior in all of the studied binary solid solutions, which becomes increasingly important from La to Gd. The pronounced short-range order–disorder occurring in groups 2 and 3 solid solutions mimics some of the behavior observed from previous studies in anhydrous monazite solid solutions. This study highlights the potential to use the chemistry and the structural modifications of rhabdophane as potential indicators of formation conditions in geologic systems and permits improving our modeling capabilities of REE partitioning in critical minerals systems.

Exploring cluster formation in Zr-MOF synthesis in situ using X-ray absorption spectroscopy.

Metal-organic frameworks (MOFs) with a Zr-oxo cluster [(Zr6O4(OH)4)]12- are exceptionally stable and offer vast potential for a wide range of applications. Synthesis parameters strongly affect the quality, stability, morphology, etc., of the MOFs. In this study, we present an experimental set-up that allows following in situ element-specific chemical transformations during synthesis and the effect of various reaction parameters on the reaction products. Zr-fumarate formation was monitored using X-ray absorption spectroscopy (XAS) in ZrCl4-DMF-based solutions. We have studied (i) the local (∼2-5 Å) environment around Zr4+ ions in the early stages of the Zr-oxo cluster formation and MOF-synthesis reaction, (ii) kinetics of the synthesis reaction and its dependence on water and modulator concentrations, and (iii) the effect of the reaction parameters on MOF product quality. XAS data have provided direct evidence that the increased amounts of water and modulator accelerate the reaction. It has also confirmed that water is essential for MOF formation in DMF. Zr-cluster formation and the synthesis reaction were not observed in the absence of water in ZrCl4-DMF and ZrCl4-DMF-linker-modulator solutions. According to the EXAFS data, Zr4+ ions are octahedrally coordinated by chlorine atoms in anhydrous solutions with and without the linker. In contrast, the Zr-oxo clusters and MOFs were formed only in the presence of water. The results of the in situ experiments were correlated with post-synthetic characterization of the resultant MOF products.

Осаждение металлов в пористую структуру оксида алюминия

Introduction. Nanostructured porous anodic aluminum oxide is used as a matrix, where it is often necessary to introduce impurities of various metals into its structure. In this case, an effective solution is the electrochemical deposition of metals into the pores of anodic aluminum oxide. However, metals can be deposited on the cathode from aqueous solutions of salts in which the electrode potential is electronegative and less than the potential for hydrogen evolution in solutions. Materials and methods. The anodizing process takes place in two stages: preliminary anodizing and anodizing itself. Before preliminary anodization, experimental samples were coated with a chemically resistant varnish for separation between the electrolyte and air. Then the samples prepared in this way were dried for 4–6 hours, after which the second stage of anodization was carried out. Results. It has been revealed that substrate inhomogeneities can be reduced by slowing down the oxide growth process or by using pore blanks. Using similar methods, a highly ordered structure can be achieved. A more dense arrangement of pores can be achieved through the use of strong acids, forming a barrier layer of thinner thickness with more penetration paths. It is worth noting that when using such acids, the number of inhomogeneities becomes not such an important parameter. Discussion. Films were obtained with greater chemical strength and a thickness of 84-100 microns, a pore diameter of 0.15-0.3 microns. By carrying out additional etching, the pore diameter was increased to 0.6 µm. Etching of PHA can be carried out in an alkali solution in an anhydrous solution of ethyl alcohol. Also, pores can be dissolved by reanodizing in a solution of phosphoric acid. The barrier layer grows to 100 A, removal is carried out with dilute hydrofluoric acid. The resulting PHAs have a fairly porous, homogeneous structure with an average effective pore size of 0.45-0.65 μm. Conclusion. Conditions have been developed for the joint deposition of two metals from aqueous solutions at close values of their electrode potentials, such as iron and cobalt. The conditions for the deposition of copper from copper sulfate into the pores of porous aluminum oxide have been established at 25 – 70 t/l of sulfate and 7÷12% sulfuric acid. Resume. The research results can be useful in obtaining films of porous anodic aluminum oxide, which can be used as substrates for creating solar-electric energy converters based on materials with a perovskite structure. This is especially true for the Republic of North Ossetia-Alania and for the mountainous territories of the North Caucasus. The use of solar energy converters will make it possible to more efficiently electrify populated areas in mountainous areas.

Formation of well-ordered surfaces of Bi2-xSbxTe3-ySey topological insulators using wet chemical treatment

The surface preparation of topological insulators (TIs) is a critical task in order to realize their efficient applications. A chemical treatment in an anhydrous solution of hydrogen chloride in isopropanol (HCl-iPA) and a subsequent annealing at relatively low temperature in ultrahigh vacuum (UHV) was successfully used for the surface preparation of bulk 3D (0001) TIs Bi2Te3, Sb2Te3, Bi2Se3 and an MBE - grown Bi2-xSbxTe3-ySey (BSTS) thin films. The surface treatment showed a significant modification of the initial TI surfaces, which was free from the structural disorder, oxidation and chemical impurities determined by X-ray photoelectron spectroscopy and low-energy electron diffraction. The insulating nontrivial bulk gap and well resolved gapless surface states with a linear dispersion of a massless Dirac cone were observed by angle-resolved photoelectron spectroscopy (ARPES). In the BSTS film, the Fermi level is located within the bulk band gap. The negative magnetoconductance corresponding to weak antilocalization demonstrated the contribution of the surface states of BSTS, that promise to be protected from backscattering. The surface treatment method proposed in this work is highly efficient for both bulk and thin TI films that can be useful for the deposition of an insulators/metals to fabricate transistor and spin valve systems.

Preparation and properties of PTFE@TiO2/epoxy superhydrophobic coating

The problem of bacterial adhesion has been a challenge in everyday life and industry for decades. In this paper, polytetrafluoroethylene(PTFE) micropowder, titanium dioxide(TiO2) nanopowder, ethyl acetate and epoxy resin were sequentially added to a beaker and stirred well, then the nanoparticles were modified using perfluorooctyltriethoxysilane (POTS), and finally superhydrophobic coatings were fabricated on the surface of an aluminium sheet by spraying process. Characterisation was carried out using scanning electron microscopy and contact angle measurement, and the coating wettability, chemical stability and mechanical stability properties were investigated, and finally the coating was tested for antimicrobial properties. The study suggests that the hydrophobicity of the sample was optimal at a contact angle of 163.3° and a rolling angle of 3.2° when the ratio of PTFE micropowder to nano-TiO2 by mass was 1:4 and the ration between POTS and nanoparticles by mass was 12%. The contact angles were 137.8° and 143.6° after 25 and 32 hours of soaked in an anhydrous solution with a pH of 14 and 1, respectively. Most importantly, it exhibits good antimicrobial properties.

Simulation of ammonia injection system for a compression ignition engine

Ammonia in anhydrous and aqueous forms, are attractive carbonless fuels for future marine diesel engines. The aim of this study was to determine if these fuels could be injected into a two-stroke marine diesel engine using a unit injector system. In this study, existing in service injector hardware was used to develop a dynamic numerical injector model. The results of the simulation were then validated against injector performance literature obtained for an engine, using conventional diesel fuel oil. Using the developed numerical model, the injection performance of anhydrous and aqueous ammonia solutions could then be investigated. The study found good correspondence between the model and the pressure trace found in literature. In terms of fuel injection performances, it was found that both fuels were injectable with a unit injector, however the correct volume and mass required were not achieved. Furthermore, injection timing and duration were affected marginally. For aqueous ammonia, with the higher bulk modulus, injection was advanced by 0.21 CA degrees and for anhydrous ammonia with a lower bulk modulus; it was delayed by 0.21 CA degrees. Overall proper operation of the injection system was observed. This outcome is promising, especially in shifting the maritime industry towards zero carbon ammonia engines.

Evaporation of Saline Droplets on a Superhydrophobic Substrate: Formation of Crystal Shell and "Legs".

We studied the evaporation-driven crystallization in the droplets of sodium acetate anhydrous (CH3COONa) aqueous solution, which were deposited on superhydrophobic substrates. The results reveal distinct crystallization behaviors between saturated and unsaturated droplets under identical experimental conditions. Specifically, unsaturated droplets could form a quasi-spherical crystal shell on the superhydrophobic substrate, while saturated droplets could develop crystal legs between the droplet and substrate when the crystal shell formed. Subsequently, the saturated droplet was lifted off the substrate by the growing crystal legs. The formation of crystal shell was closely associated with the evaporation from the droplet surface and the internal convection inside the droplet. The formation of crystal legs was induced by the heterogeneous nucleation effect caused by the substrate of SiO2 nanoparticles. These findings provide valuable insights into regulating the morphology of salt crystallization through adjustments in salt solution concentration and substrate surface structure.

Crystal Growth and Crystal Structures of Gold(V) Compounds: Cu(AuF6)2, Ag(AuF6)2, and O2(CuF)3(AuF6)4 ⋅ HF

AbstractCrystal growth from anhydrous hydrogen fluoride solutions of M2+(M=Cu, Ag) and [AuF6]−gave M(AuF6)2salts (M=Cu, Ag). Similar attempts to prepare single crystals of the corresponding nickel, zinc and magnesium salts failed. The crystal structure of Cu(AuF6)2consists of layers of Cu2+cations connected by [AuF6]−anions, thus forming slabs. Only van der Waals interactions exist between adjacent slabs. The crystal structure of Ag(AuF6)2consists of a three‐dimensional framework in which Ag+cations are linked by [AuF6]−anions. Both structures are members of the MII(XVF6)2family, in which seven different structure types have been observed to date. In the crystal structure of O2(CuF)3(AuF6)4 ⋅ HF, the bridging AuF6units connect [−Cu−F−Cu−F−]∞chains to form stacks between which O2+cations and HF molecules are located.

Optimising the Performance of CO2-Cured Alkali-Activated Aluminosilicate Industrial By-Products as Precursors

Three industrial aluminosilicate wastes were studied as precursors to produce alkali-activated concrete: (i) electric arc furnace slag, (ii) municipal solid waste incineration bottom ashes, and (iii) waste glass rejects. These were characterized via X-ray diffraction and fluorescence, laser particle size distribution, thermogravimetric, and Fourier-transform infrared analyses. Distinctive combinations of anhydrous sodium hydroxide and sodium silicate solution were tried by varying the Na2O/binder ratio (8%, 10%, 12%, 14%) and SiO2/Na2O ratio (0, 0.5, 1.0, 1.5) to find the optimum solution for maximized mechanical performance. Specimens were produced and subjected to a three-step curing process: (1) 24 h thermal curing (70 °C), (2) followed by 21 days of dry curing in a climatic chamber (~21 °C, 65% RH), and (3) ending with a 7-day carbonation curing stage (5 ± 0.2% CO2; 65 ± 10% RH). Compressive and flexural strength tests were performed, to ascertain the mix with the best mechanical performance. The precursors showed reasonable bonding capabilities, thus suggesting some reactivity when alkali-activated due to the presence of amorphous phases. Mixes with slag and glass showed compressive strengths of almost 40 MPa. Most mixes required a higher Na2O/binder ratio for maximized performance, even though, contrary to expectations, the opposite was observed for the SiO2/Na2O ratio.

Immobilization of silver nanoparticles on cellulose nanofibrils incorporated into nanofiltration membrane for enhanced desalination performance

Nanofiltration (NF) membranes circumventing global water scarcity with excellent separation and antibacterial performances are highly desirable for efficient water treatment but remain a great challenge. Herein, a nanofiltration membrane was fabricated by in situ immobilizing silver nanoparticles (AgNPs) on sulfated cellulose nanofibril incorporated during interfacial polymerization. AgNPs were confirmed to be uniformly distributed and in situ grown on sulfated cellulose nanofibril (SCNF) due to its abundant sulfate and hydroxyl groups by mixing them with anhydrous piperazine solution as inorganic phase and homophenyl chloride n-hexane solution as the organic phase on the surface of a polyethersulfone microporous membrane. The attributes of SCNF, excellent hydrophilicity, and highly negative charges enhanced both the rejection and water permeability. As the SCNF charge increased, the roughness of SCNF increased and the contact angle decreased, and the maximum values were 203 nm and 17.67°, respectively. Among all the composite NF membranes, H-SCNF/Ag-0.01 had better rejection of Na2SO4 and NaCl, with a maximum rejection of 97.11% and 32.55%, respectively. Meanwhile, it also maintained high water permeability. Antibacterial experiments indicated that the composite NF membrane had effective inhibition against Escherichia coli and exhibited an expected slow-release capability of Ag+, which made it have long-term antibacterial properties. It was estimated that the antibacterial effect could last for 90 days. This work demonstrated that AgNPs in situ immobilization on SCNF could be used as promising nanofillers for designing advanced functional NF membranes.

Characterization and ohmic contact of hydrothermally synthesized vertical ZnO and Ag/ZnO nanowires

Vertically aligned ZnO nanowire arrays were synthesized by two-step hydrothermal method. ZnO seed layers were prepared on substrate by using anhydrous ethanol and zinc acetate dihydrate solution, followed by the generation of ZnO nanowire arrays by low-temperature liquid-phase hydrothermal methods. The ZnO nanowire arrays were prepared under different conditions to compare the effects of growth conditions on the morphology of ZnO nanowires, in order to explore the optimal growth conditions for ZnO nanowire arrays used in semiconductor device. The morphological changes of ZnO nanowire arrays grown under different conditions were systematically analyzed by SEM, XRD and other characterization means. The results show that the seed solution concentration, growth solution concentration, doping concentration and growth time all have certain effects on the morphology of ZnO nanowire arrays. Besides, the Ag/ZnO ohmic contact were investigated, the optimal annealing temperatures of 450 °C was obtained.

Wet Etching of Quartz Using a Solution Based on Organic Solvents and Anhydrous Hydrofluoric Acid.

The quartz-crystal resonator is the core device for frequency control in modern communication systems and network technology. At present, in modern resonator blanks manufacturing, BOE solution is usually used as the etching solution, but its etching rate is relatively volatile, and the surface morphology of the blanks is prone to defects after etching, which brings certain difficulties to the deep-etching process of the wafer. To solve the above challenges, this paper systematically compares a BOE solution and anhydrous etching solution in terms of etching rate, surface morphology, and electrical properties of the blanks after etching. Seven groups of blanks were etched using different etching solutions with different etching conditions to verify their effect on the surface morphology and electrical properties of quartz blanks. The experimental results suggest that the application of anhydrous etching solution has achieved better surface morphology and electrical properties and can be more suitable for application in batch manufacturing. In general, when using anhydrous etching solution, it is possible to reduce surface roughness by up to 70% and equivalent resistance by 32%, and the etch rate is almost 10 times lower than BOE solution under the same temperature, which is more conducive to the rate control of wafers in the etching process.

Fast and High-Yield Anhydrous Synthesis of Ti3 C2 Tx MXene with High Electrical Conductivity and Exceptional Mechanical Strength.

2D transition metal carbides or nitrides (MXenes) have attracted considerable attention from materials scientists and engineers owing to their physicochemical properties. Currently, MXenes are synthesized from MAX-phase precursors using aqueous HF. Here, in order to enhance the production of MXenes, an anhydrous etching solution is proposed, consisting of dimethylsulfoxide as solvent with its high boiling point, NH4 HF2 as an etchant, CH3 SO3 H as an acid, and NH4 PF6 as an intercalant. The reaction temperature can be increased up to 100°C to accelerate the etching and delamination of Ti3 AlC2 MAX crystals; in addition, the destructive side reaction of the produced Ti3 C2 Tx MXene is suppressed in the etchant. Consequently, the etching reaction is completed in 4h at 100°C and produces high-quality monolayer Ti3 C2 Tx with an electrical conductivity of 8200 S cm-1 and yield of over 70%. The Ti3 C2 Tx MXene fabricated via this modified synthesis exhibits different surface structures and properties arising from more F-terminations than those of Ti3 C2 Tx synthesized in aqueous HF2 T. The atypical surface structure of Ti3 C2 Tx MXene results in an exceptionally high ultimate tensile strength (167 ± 8MPa), which is five times larger than those of Ti3 C2 Tx MXenes synthesized in aqueous HF solution (31.7 ± 7.8MPa).

On Demand Flow Platform for the Generation of Anhydrous Dinitrogen Trioxide and Its Further Use in N‐Nitrosative Reactions

AbstractDinitrogen trioxide (N2O3) is a powerful and efficient nitrosating agent that comes with an unprecedented atom economy. However, the synthetic application of N2O3 is still underdeveloped mostly due to its inherent instability and the lack of reliable protocols for its preparation. This paper presents an open‐source setup and procedure for the on‐demand generation of anhydrous N2O3 solution (up to 1 M), which can be further used for reactions under batch and flow conditions. The accuracy and stability of N2O3 concentration are guaranteed with the absence of head‐space in the setup and with the synchronization of the gas flows. The reliability of this protocol is demonstrated by >30 worked examples in the nitrosative synthesis of heterocycles—a library of structurally diverse benzotriazoles and sydnones. Kinetic and mechanistic aspects of the N‐nitrosative steps are also explored.

On Demand Flow Platform for the Generation of Anhydrous Dinitrogen Trioxide and Its Further Use in N-Nitrosative Reactions.

Dinitrogen trioxide (N2 O3 ) is a powerful and efficient nitrosating agent that comes with an unprecedented atom economy. However, the synthetic application of N2 O3 is still underdeveloped mostly due to its inherent instability and the lack of reliable protocols for its preparation. This paper presents an open-source setup and procedure for the on-demand generation of anhydrous N2 O3 solution (up to 1 M), which can be further used for reactions under batch and flow conditions. The accuracy and stability of N2 O3 concentration are guaranteed with the absence of head-space in the setup and with the synchronization of the gas flows. The reliability of this protocol is demonstrated by >30 worked examples in the nitrosative synthesis of heterocycles-a library of structurally diverse benzotriazoles and sydnones. Kinetic and mechanistic aspects of the N-nitrosative steps are also explored.