Reaction By-products Research Articles

Preparation of single-phase YbB6 by low-temperature solid-state reaction method using iodine

In this study, low-temperature solid-state synthesis of pure nanocrystalline ytterbium hexaboride (YbB6) employing iodine-based reduction method has been discussed. For the reduction reaction, the mechanically activated powder mixture of ytterbium oxide, boron oxide, magnesium, and iodine was heated up under Ar in a quartz tube to 85 °C. All reaction byproducts, viz. MgO, Mg3(BO3)2, and YbI2, were removed by hot acid leaching with 3 M HCl solution to form pure YbB6. The morphological and phase structure of the synthesized YbB6 powder were analyzed by X-ray diffractometry (XRD), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. The crystalline phases obtained were refined by multi-phase Rietveld refinement. XRD and Raman spectroscopy showed a contrast between the nano-YbB6 formed by the present low-temperature iodine-based reduction method versus mechanochemical method. The YbB6 produced by the low-temperature iodine reduction method is highly crystalline in nature, whereas YbB6 produced by mechanochemical method is less crystalline or conversely more amorphous in nature. The iodine-based reduction method indeed played a definitive role to allow the reaction to take place at a lower temperature enabling the formation of nanocrystalline YbB6.

In situ fabrication of robust three dimensional ordered macroporous γ-MnO2/LaMnO3.15 catalyst for chlorobenzene efficient destruction

Catalytic activity of perovskite oxides as LaMnO3+δ is greatly limited by their low surface area and deficient active site density though they are thought to be one category of desired candidates for noble metal-based catalysts. Here, a robust three dimensional ordered macroporous (3DOM) γ-MnO2/LaMnO3.15 (Mn/3DLM) was in situ fabricated by the strategy of selectively dealloyed surface La cations. Mn/3DLM displayed excellent activity with 90% of chlorobenzene destructed at 207 °C (apparent activation energy of 45.4 kJ/mol), obviously lower than those of γ-MnO2 (244 °C; 51.9 kJ/mol) and bulk LaMnO3.15 (311 °C; 70.2 kJ/mol) owing to large surface area, excellent reducibility, and improved surface active oxygen concentration. Nucleophilic substitution was the main process for active oxygen attacking, while electrophilic substitution mainly contributed to chlorinated byproducts formation. Remarkably, reaction byproducts as phenol, o-dichlorobenzene, trichloroethylene, and bichloroethylene over Mn/3DLM can be efficiently inhibited during the long-term operations via weakened the electrophilic substitution effect.

Mechanistic Insights into Dissolved Organic Sulfur Photomineralization through the Study of Cysteine Sulfinic Acid.

Photochemical reactions convert dissolved organic matter (DOM) into inorganic and low-molecular-weight organic products, contributing to its cycling across environmental compartments. However, knowledge on the formation mechanisms of these products is still scarce. In this work, we investigate the triplet-sensitized photodegradation of cysteine sulfinic acid, a (photo)degradation product of cysteine, to sulfate (SO42-). We use kinetic analysis, targeted experiments, and previous literature from several fields of chemistry to explain the elementary steps that lead to the release of sulfate. Our analysis indicates that triplet sensitizers act as one-electron oxidants on the sulfinate S lone pair. The resulting radical undergoes C-S fragmentation to form SO2, which becomes hydrated to sulfite/bisulfite (S(IV)). S(IV) is further oxidized to SO42- in the presence of triplet sensitizers and oxygen. We point out that the reaction sequence SO2 ⇌ S(IV) → SO42- is valid independently of the chemical structure of the model compound and might represent a sulfate photoproduction mechanism with general validity for DOS. Our mechanistic investigation revealed that amino acids in general might also be photochemical precursors of CO2, ammonia, acetaldehyde, and H2O2 and that reaction byproducts can influence the rate and mechanism of S(IV) (photo)oxidation.

Controlling hydroxyl content of reduced graphene oxide for superior cathode performance of lithium sulfur batteries

Here, the hydroxyl content of reduced graphene oxide (rGO) is controlled by adjusting reduction time with l-ascorbic acid as reduction agent to study the effect on cathode performance of lithium sulfur batteries (LSBs). The results indicate that the hydroxyl content decreases from 35.8% to 17.9% with prolonging reduction time from 6 h to 48 h, and the C/O ratio increases. More importantly, it is demonstrated that the rGO with relatively low hydroxyl content within 36 h of reduction is more beneficial to enhance both the initial capacity and capacity retention as well as rate performance of LSBs, which is ascribed to the higher conductivity, stronger adsorption and relatively few reaction by-products with the decrease of hydroxyl content. However, when the reduction time is further prolonged to 48 h, the cathode performance deteriorates. As a result, rGO-36h/S electrode with the optimum hydroxyl content (19.2%) achieves an initial discharge capacity of 1340.9 mAh g−1, which still maintains 707.8 mAh g−1 over 100 cycles at 0.1C. This work may provide a guide for reducing GO when used as sulfur host material or matrix material of LSBs.

A sensitive liquid chromatography-tandem mass spectrometric method for determination of five β-blockers after labeling with either hydrazonoyl chloride or dansyl chloride reagent

A sensitive liquid chromatography-tandem mass spectrometry (LC-MS) method was developed for the screening of five β-blockers (BBs), including atenolol, metoprolol, bisoprolol, propranolol, and betaxolol, in rabbit plasma. An inhouse prepared hydrazonoyl chloride compound (UOSA54) and dansyl chloride (DNS) were successfully coupled with BBs via the amino functional group and analyzed by LC-MS/MS. The excess hydrazonoyl chloride was characterized by a negligible ionization suppression at the electrospray-ionization (ESI) source, which enables the analysis of BBs at a low concentration level. The relative ESI-MS response of derivatized to underivatized BBs was enhanced 2.3 to 3.7-fold. The developed method could be applied for screening of BBs in samples by searching the most abundant MS product ions, including m/z 169 and 211, in addition to the precursor ion and the cleavage of ether moiety. The method could be applied for trace analysis and screening of BBs abuse. The use of UOSA54 was adventitious over dansylated derivatives because of minimal reaction by-products and the negligible ionization suppression effect. The extraction efficiency of BBs from rabbit plasma was improved to reach 77.5–93.9% using tert-butylamine and Chromabond® C18ec-100 mg column. The optimal reaction conditions were optimized and validated. The linear range of analyzed BBs in rabbit plasma was within the range of 0.1 to 25.0 ng/mL, while the limit of quantification (LO Q) was ranged from 0.10 to 0.25 ng/mL.

Mechanistic Understanding of a Robust and Scalable Synthesis of Per(6-deoxy-6-halo)cyclodextrins, Versatile Intermediates for Cyclodextrin Modification

Cyclodextrin (CD) perfunctionalization reactions are challenging to study because they proceed through a number of regioisomeric intermediates, thus warranting creative approaches to understanding the reaction mechanism. Particularly useful perfunctionalization targets are per(6-deoxy-6-halo)cyclodextrins. Their standard synthesis entails selective SN2 halogenation at their primary alcohols using a Vilsmeier reagent, but this requires a strongly basic quench to unmask the Vilsmeier-capped secondary alcohols. Herein we present an alternative and simple acidic hydrolytic quench that utilizes existing HX in the end-of-reaction solution and requires only the addition of water. We performed a detailed mechanistic investigation of the new quench, and a central feature was the use of proton sponge to develop an 1H NMR titration method for HX in organic solvent. This method was used to both quantify and remove HX in the prequenched reaction solution. The HX-free prequenched solution enabled us to (1) identify sensitive intermediates during the quench, (2) quantify all of the reaction byproducts, and (3) determine that HX is critical for hydrolysis. We then studied the halogenation reaction, wherein the new acidic quench facilitated high-throughput experimentation, using mass spectrometry as well as Design of Experiments with automated reaction profiling. Through this, we were able to establish robustness and understand the complex effects of Vilsmeier equivalents and temperature on the reaction outcome.

Technology Focus: Oilfield Chemistry (September 2020)

Anyone who works in the oil and gas industry is aware of hydrogen sulfide (H2S) gas. This is a highly toxic gas that gives rise to “sour” production. H2S is highly corrosive to many common materials used by the industry (e.g., mild steels), and there often are strict fiscal and technical limits placed on upstream oil and gas producers by the midstream and downstream operators. The origin of H2S can be authigenic (i.e., occurs in-situ and naturally in the reservoir, related to the biological origin of the organic matter that produces the crude oil and gas), or it can be caused by biological processes and the action of sulfate-reducing bacteria (e.g., during seawater flooding and contamination of the reservoir). The concentration range of H2S that occurs can vary from a few parts per million (ppm) to many tens of percent of the raw gas production. The range of concentrations that may be treated economically by chemical H2S scavengers is typically up to 5,000 ppm (0.5%). Higher concentrations may be treated by other means such as amine recycling unit sequestering systems. The industry has relied upon the triazine family of chemistry for several decades as the mainstay scavenger for H2S (originally patented in the 1990s), and the understanding of the application parameters and reaction byproducts has grown over the years. There is, however, still much to understand, and, even recently, several significant advancements have occurred, many focusing on some of the understood challenges of using triazine chemistry. The featured papers and suggested further reading summarize the current SPE literature state of the art for H2S scavenger research and development and have been selected to give readers a broad indication from both academia and industry around the world.

Anisotropic Electron Conductance Driven by Reaction Byproducts on a Porous Network of Dibromobenzothiadiazole on Cu(110).

Efficiency in charge-transport is a fundamental but demanding prerequisite to allow better exploitation of molecular functionalities in organic electronics and energy-conversion systems. Here, we report on a mechanism that enables a one-dimensional conductance structure by connecting discrete molecular states at 2.1 eV through the pores of a metal-organic network on Cu(110). Two adjacent, periodic and isoenergetic contributions, namely a molecular resonance and the confined surface-state, add-up leading to anisotropic structures, as channels, observable in real-space conductance images. The adsorption configurations of Br atoms, inorganic byproduct of the redox-reacted 4,7-dibromobenzo[c]-1,2,5-thiadiazole (2Br-BTD) molecules on the copper surface, drive the confinement of the Cu surface state within the pores and critically control the channel continuity. Small displacements of the Br atoms change the local surface potential misaligning the energy levels. This work visualizes the effect of order-disorder transitions caused by the movement of single atoms in the electronic properties of two-dimensional organic networks.

High-Resolution Three-Dimensional Sculpting of Two-Dimensional Graphene Oxide by E-Beam Direct Write.

On-demand switchable "additive/subtractive" patterning of two-dimensional (2D) nanomaterials is an essential capability for developing new concepts of functional nanomaterials and their device realizations. Traditionally, this is performed via a multistep process using photoresist coating and patterning by conventional photo or electron beam lithography, which is followed by bulk dry/wet etching or deposition. This limits the range of functionalities and structural topologies that can be achieved as well as increases the complexity, cost, and possibility of contamination, which are significant barriers to device fabrication from highly sensitive 2D materials. Focused electron beam-induced processing (FEBIP) enables a material chemistry/site-specific, high-resolution multimode atomic scale processing and provides unprecedented opportunities for "direct-write", single-step surface patterning of 2D nanomaterials with an in situ imaging capability. It allows for realizing a rapid multiscale/multimode approach, ranging from an atomic scale manipulation (e.g., via targeted defect introduction as an active site) to a large-area surface modification on nano- and microscales, including patterned doping and material removal/deposition with 2D (in-plane)/three-dimensional (3D) (out-of-plane) control. In this work, we report on a new capability of FEBIP for nanoscale patterning of graphene oxide via removal of oxygenated carbon moieties with no use of reactive gas required for etching complemented by carbon atom deposition using a focused electron beam. The mechanism of experimentally observed phenomena is explored using the density functional theory (DFT) calculations, revealing that interactions of e-beam that liberated reactive oxygen radicals with carbon atoms on the graphene basal plane lead to the creation of atomic vacancies in the material. The reaction byproducts are volatile carbon dioxides, which are dissociated and volatilized from the graphene oxide surface functional groups by interactions with an energetic focused electron beam. Along with selective subtractive patterning of graphene oxide, the same electron beam with increased irradiation doses can deposit out-of-plane 3D carbon nanostructures on top of or around the 2D etched pattern, thus forming a hybrid 2D/3D nanocomposite with a feature control down to a few nanometers. This in operando dual nanofabrication capability of FEBIP is unmatched by any other nanopatterning techniques and opens a new design window for forming 2D/3D complex nanostructures and functional nanodevices.

Anisotropic Electron Conductance Driven by Reaction Byproducts on a Porous Network of Dibromobenzothiadiazole on Cu(110)

AbstractEfficiency in charge‐transport is a fundamental but demanding prerequisite to allow better exploitation of molecular functionalities in organic electronics and energy‐conversion systems. Here, we report on a mechanism that enables a one‐dimensional conductance structure by connecting discrete molecular states at 2.1 eV through the pores of a metal–organic network on Cu(110). Two adjacent, periodic and isoenergetic contributions, namely a molecular resonance and the confined surface‐state, add‐up leading to anisotropic structures, as channels, observable in real‐space conductance images. The adsorption configurations of Br atoms, inorganic byproduct of the redox‐reacted 4,7‐dibromobenzo[c]‐1,2,5‐thiadiazole (2Br‐BTD) molecules on the copper surface, drive the confinement of the Cu surface state within the pores and critically control the channel continuity. Small displacements of the Br atoms change the local surface potential misaligning the energy levels. This work visualizes the effect of order‐disorder transitions caused by the movement of single atoms in the electronic properties of two‐dimensional organic networks.

Degradation of Acid Orange 7 Azo Dye in Aqueous Solution by a Catalytic-Assisted, Non-Thermal Plasma Process

The aim of this work was the optimization of the performance of the cold plasma technology coupled with a structured catalyst for the discoloration and mineralization of “acid orange 7” (AO7) azo dye. The structured catalyst consists of Fe2O3 immobilized on glass spheres, and it was prepared by the “dip coating” method and characterized by different chemico-physical techniques. The experiments were carried out in a dielectric barrier discharge (DBD) reactor. Thanks to the presence of the catalytic packed material, the complete discoloration and mineralization of the dye was achieved with voltage equal to 12 kV, lower than those generally used with this technology (approximately 20–40 kV). The best result in terms of discoloration and mineralization (80% after only 5 min both for discoloration and mineralization) was obtained with 0.25 wt% of Fe2O3 immobilized on the glass spheres, without formation of reaction by-products, as shown by the HPLC analysis. The optimized catalyst was reused for several reuse cycles without any substantial decrease of performances. Moreover, tests with radical scavengers evidenced that the most responsible oxidizing species for the degradation of AO7 dye was O2•−.

Evolutionary conservation and post-translational control of S-adenosyl-L-homocysteine hydrolase in land plants.

Trans-methylation reactions are intrinsic to cellular metabolism in all living organisms. In land plants, a range of substrate-specific methyltransferases catalyze the methylation of DNA, RNA, proteins, cell wall components and numerous species-specific metabolites, thereby providing means for growth and acclimation in various terrestrial habitats. Trans-methylation reactions consume vast amounts of S-adenosyl-L-methionine (SAM) as a methyl donor in several cellular compartments. The inhibitory reaction by-product, S-adenosyl-L-homocysteine (SAH), is continuously removed by SAH hydrolase (SAHH), which essentially maintains trans-methylation reactions in all living cells. Here we report on the evolutionary conservation and post-translational control of SAHH in land plants. We provide evidence suggesting that SAHH forms oligomeric protein complexes in phylogenetically divergent land plants and that the predominant protein complex is composed by a tetramer of the enzyme. Analysis of light-stress-induced adjustments of SAHH in Arabidopsis thaliana and Physcomitrella patens further suggests that regulatory actions may take place on the levels of protein complex formation and phosphorylation of this metabolically central enzyme. Collectively, these data suggest that plant adaptation to terrestrial environments involved evolution of regulatory mechanisms that adjust the trans-methylation machinery in response to environmental cues.

Understanding the depletion of electrons in dusty plasmas at atmospheric pressure

The nucleation and growth of NPs in the gas phase using atmospheric-pressure plasma systems is an important approach to synthesizing novel dimensionally-controlled materials. Here, we investigated the effect of the NPs on a typical type of continuous-flow, substrate-free plasma at atmospheric pressure to understand their potential contribution to electron density changes. A tandem plasma system was set up consisting of one plasma reactor that produced carbonaceous NPs from mixtures of argon and hexane, and another identical plasma reactor where the as-grown particles were injected and non-intrusive electrical and optical measurements were performed. The electron densities obtained from conductivity measurements and a plasma fluid model were found to decrease in the presence of NPs. However, control experiments revealed that the main source of the electron depletion was residual vapor or reaction byproducts in the form of molecular species or nanoclusters and not the particles themselves. These results were validated by constant number Monte Carlo simulations which showed that at the experimentally-measured conditions, the NPs were not of sufficiently high enough concentration to reduce the electron density; however, if molecules or clusters are ionizable, they remain in sufficient concentration to deplete electron densities. Our study shows that at atmospheric pressure, because of their typically larger electron density values, particle-producing plasmas are distinct from those at low pressure, and nanoparticle formation does not have the same impact while molecular-scale species may be a more important consideration.

Simultaneous Electrochemical Generation of Ferrate and Oxygen Radicals to Blue BR Dye Degradation

In this study, electro-oxidation (EOx) and in situ generation of ferrate ions [Fe(VI)] were tested to treat water contaminated with Blue BR dye (BBR) using a boron-doped diamond (BDD) anode. Two electrolytic media (0.1 M HClO4 and 0.05 M Na2SO4) were evaluated for the BDD, which simultaneously produced oxygen radicals (•OH) and [Fe(VI)]. The generation of [Fe(VI)] was characterized by cyclic voltammetry (CV) and the effect of different current intensity values (e.g., 7 mA cm−2, 15 mA cm−2, and 30 mA cm−2) was assessed during BBR degradation tests. The discoloration of BBR was followed by UV-Vis spectrophotometry. When the EOx process was used alone, only 78% BBR discoloration was achieved. The best electrochemical discoloration conditions were found using 0.05 M Na2SO4 and 30 mA cm−2. Using these conditions, overall BBR discoloration values up to 98%, 95%, and 87% with 12 mM, 6 mM, and 1 mM of FeSO4, respectively, were achieved. In the case of chemical oxygen demand (COD) reduction, the EOx process showed only a 37% COD reduction, whereas combining [Fe(VI)] generation using 12 mM of FeSO4 achieved an up to 61% COD reduction after 90 min. The evolution of reaction byproducts (oxalic acid) was performed using liquid chromatography analysis.

Causes of anisotropy in thermal atomic layer etching of nanostructures

In this work, the authors have investigated the dependence of the anisotropy level in an atomic layer etching (ALE) process of Al2O3 on form factor constraints when the ALE process involves etching in non-line-of-sight locations beneath a silicon nitride mask. In the experiments described here, thermal etching of Al2O3 without the use of any direction-inducing plasma components was explored utilizing the well characterized hydrogen fluoride/dimethyl-aluminum-chloride atomic layer etching process. The degree of anisotropy was quantified by measuring the ratio of lateral etch rate of this process in comparison to the vertical etch rate as a function of process step time inside 60 nm holes of aluminum oxide. Inside these holes, the authors determined that the horizontal etch rates slowed to an amount of 19% compared to the vertical rate when short process times were used. For process times operating in the saturation mode of the ALE process, horizontal etch rates per cycle could be sped up to 71% of the vertical rate but never reached parity with the latter. The authors propose a simple mechanism for explaining the anisotropy dependence on process step time and applied a reduced-order algorithm to model it. In this model, the authors introduced fitting parameters for surface modification depths and reaction times to match the experimentally found etch results. Conclusions could be drawn regarding topological hindrance or tortuosity for reactants to reach surfaces in shaded areas under the mask and for reaction by-products to escape from these locations and the impact on etch rate. In addition, the authors recognize that this mechanism could explain the unwanted depth dependence of the etch rate per cycle in high aspect ratio structures.

Catalytic reduction of nitrate with Pd-In2O3.

This work presents a novel catalyst preparation method and the optimization of operation conditions for an effective NO3- conversion with a high selectivity and stability that guarantee water quality for human consumption. Catalytic reduction of NO3- and NO2- was carried out with Pd supported on In2O3 under mild operation conditions (25 °C, 1 atm) with H2 and CO2 as reducing and acidifying agents, respectively. The catalyst was used in batch experiments showing the suppression of NO2- accumulation and low NH4+ selectivity at acid pH. Long-term experiments were carried out with Pd on γ-Al2O3 spheres covered with In2O3. This catalyst presented a high stability during more than 700 h. A concentration of NO3- below 50 mg/L was achieved, producing less than 0.5 mg/L of NH4+ as reaction by-product by a strict limitation of the H2 fed and controlling several operating conditions.

SYNTHESIS OPTIMIZATION OF 6-NITRO-3,4-DIHYDROQUINAZOLINE-4-ONE

A method for the synthesis of the substance 6-nitro-3,4-dihydroquinazolin-4-one has been developed. Quantitative determination of the target product was carried out spectrophotometrically using an SF-46 instrument. As a solvent, 0.1 mol/l HCl was used. A 0.1 mol/l hydrochloric acid solution was used as a comparison solution. The optical density of the standard and test samples was measured at a wavelength of 254 nm. The synthesis conditions of 6-nitro-3,4-dihydro-quinazolin-4-one were studied. The structure of the obtained product was studied by IR, Mass, 1H, 13C NMR spectroscopy, and the structure of the synthesized compound was also established. The main factors that influence the process of producing 6-nitro-3,4-dihydroquinazolin-4-one are identified. The process is optimized by the method of mathematical planning of the experiment. A mathematical model is drawn up. And the regression equation is calculated. A steep ascent along the response surface was carried out and optimal process conditions were found: temperature, time, quantitative ratio of the starting materials. It has been established that the main factor affecting the nitration process of 3,4-dihydroquinazolin-4-one is the temperature of 40 ºC and the reaction time is 4.5 h. Note that at a higher temperature, according to the analysis, a significant amount of dinitro derivative is formed, as a reaction byproduct. 

Cost Analysis of Carbon Capture and Sequestration of Process Emissions from the U.S. Industrial Sector

The industrial sector represents roughly 22% of U.S. emissions. Unlike emissions from fossil-fueled power plants, the carbon footprint of the industrial sector represents a complex mixture of stationary combustion and process emissions produced as a reaction byproduct of cement, iron and steel, glass, and oil production. This study quantifies the potential opportunities for low-cost carbon capture and sequestration (CCS) scenarios with process emissions from the U.S. industrial sector by analyzing the variabilities in point-source capture and geographic proximity to relevant sinks, specifically enhanced oil recovery (EOR) and geologic sequestration opportunities. Using a technology-agnostic cost model developed from mature CO2 capture technologies, costs of CCS are calculated for each of the 656 facilities considered, with application of the U.S. federal tax credit 45Q to qualifying facilities. Capture of these targeted industrial process emission streams leads to the avoidance of 195 MtCO2/yr (188 MtCO2/yr qualifying for 45Q). Further, 123 facilities have the potential to avoid roughly 68.5 MtCO2/yr at costs below $40/tCO2 delivered. This could be competitive for using CO2 for EOR depending on the price of oil. At regional CO2 collection hubs, emissions of 40 MtCO2/yr can be avoided within 100 miles of the existing Louisiana-Mississippi and Texas-New Mexico pipelines.

A comparative study of silver- and palladium-exchanged zeolites in propylene and nitrogen oxide adsorption and desorption for cold-start applications

Silver and palladium ion-exchanged BEA zeolites (Si/Al = 12.5) and silver ion-exchanged ZSM-5 zeolites (Si/Al = 15) were studied for their ability to adsorb and desorb propylene and NO under simulated diesel exhaust conditions. The adsorption experiment results demonstrated the excellent ability of bare BEA zeolites to adsorb propylene, but only a small amount of NO. The presence of H2O inhibited the adsorption of both C3H6 and NO. Ion-exchanging BEA zeolites with Ag (1.2 and 5.1 wt.% Ag/BEA) attenuated the inhibiting effect of H2O on C3H6 adsorption, while NO storage remained inhibited. Adsorption experiments indicated that C3H6 and NO competed with each other for Pd sites with C3H6 showing stronger adsorption compared to NO, whereas Ag sites preferentially adsorbed C3H6. DRIFTS data indicated the formation of nitrate, formate and acetate species on Ag and Pd, while C3H6 and NO adsorption was also observed on the zeolite hydroxyl groups in the absence of H2O. However, the C3H6 and NO adsorption on the zeolite hydroxyl groups was significantly inhibited in the presence of H2O. Additionally, nitrosyl, acrolein and carbonate species were formed over 1.0 wt.% Pd/BEA. The effluent analysis during the temperature-programmed desorption in the DRIFTS reactor revealed that adsorbed C3H6 and NO reacted during the release to form oxidation reaction byproducts. The 1.0 wt.% Pd/BEA zeolite showed the greatest oxidation ability during desorption with the majority of stored C3H6 converted to CO2.

Atomically decorating of MnOx on palladium nanoparticles towards selective oxidation of benzyl alcohol with high yield

Palladium nanoparticles are effective catalysts for selective oxidation of benzyl alcohol, which is a fundamental reaction in fine chemicals production. Herein, an atomic-scale oxide decoration catalytic structure is designed and implemented by atomic layer deposition (ALD). The MnOx/Pd catalysts fabricated by ALD show enhanced conversion and selectivity simultaneously, thus a high yield of benzaldehyde is obtained. Aiming to the difficulty in controlling reaction pathways and byproducts distribution, Pd (1 1 1) facets are selectively passivated by MnOx deposition. It is found that the byproduct toluene formation is completely suppressed. The proposed structure is also beneficial for inhibiting the decarbonylation reaction of benzaldehyde. On the other hand, the addition of MnOx via ALD realizes the modification of Pd electronic structure. The MnOx coated Pd nanoparticles forms reversed catalytic structure, which also creates large amount of highly active Pd-MnOx interfacial perimeters, result in improved catalytic activity and reaction rate. The TOF of MnOx decorated Pd catalyst reaches 31,561 h−1, which is 8.7 times larger than that of the unmodified Pd catalyst. Meanwhile, the maximum conversion of benzyl alcohol and yield of benzaldehyde are improved to 84.7% and 76.5%, respectively.