Dehydrogenation Products Research Articles

Ensemble Model Approach for Predicting the Yield of Dehydrogenation Products during the Oxidative Dehydrogenation of n-Butane.

Efficient and selective oxidative dehydrogenation (ODH) catalysts are crucial to advance the production of valuable petrochemicals. In this study, we leverage the power of machine learning to predict dehydrogenation (DH) product yield and unravel the factors influencing the product distribution. A comprehensive data set obtained from experiments conducted in a fixed-bed reactor under varying temperatures, feed ratios (O2/n-butane), and metal oxide loadings (Ni, Fe, Co, Bi, Mo, W, Zn, and Mn) on an aluminum oxide support served as the basis for model development. Three supervised machine learning models, Boosted Tree (BT), Extreme Gradient Boosting Linear (XGBL), and Support Vector Machine Radial (SVMR), were evaluated. The ensemble technique of the three models showed remarkable accuracy, with an RMSE of 1.65 and MAE of 1.14 on the test data set, and it demonstrated robust generalization capabilities by capturing 87% of the variation in DH yield. In the feature importance analysis of the selected models, Mo, Co, Ni, and W emerged as critical factors influencing the DH yield. The practical significance of these findings lies in their potential to revolutionize catalysis research and industrial applications. The ability of the ensemble model to predict DH yields opens new avenues for optimizing DH products and designing more advanced catalysts. By providing essential insights into the influential variables governing the ODH reactions, researchers can make informed decisions to achieve higher yields and efficiencies.

CO2-Mediated Hydrogen Energy Release-Storage Enabled by High-Dispersion Gold-Palladium Alloy Nanodots.

Developing and fabricating a heterogeneous catalyst for efficient formic acid (FA) dehydrogenation coupled with CO2 hydrogenation back to FA is a promising approach to constructing a complete CO2-mediated hydrogen release-storage system, which remains challenging. Herein, a facile two-step strategy involving high-temperature pyrolysis and wet chemical reduction processes can synthesize efficient pyridinic-nitrogen-modified carbon-loaded gold-palladium alloy nanodots (AuPd alloy NDs). These NDs exhibit a prominent electron synergistic effect between Au and Pd components and tunable alloy-support interactions. The pyridinic-N dosage in carbon substrate improves the surface electron density of the alloy catalyst, thus regulating the chemical adsorption of FA molecules. Specifically, the engineered Au3Pd7/CN0.25 demonstrates an outstanding room-temperature FA dehydrogenation efficiency, achieving ≈100% conversion and an initial turnover frequency (TOF) of up to 9049h-1. The versatile AuPd alloy NDs also show the ability to convert CO2, one of the products of FA dehydrogenation, into FA (formate) with a 90.8% yield under mild conditions. Moreover, in-depth insights into the unique alloyed microstructure, structure-activity relationship, key intermediates, and the alloy-driven five-step reaction mechanism involving the rate-determining step of C─H bond cleavage from critical *HCOO species via D-labeled isotope, in situ infrared spectroscopy, and theoretical calculations are investigated.

Metabolic pathways, pharmacokinetic, and brain neurochemicals effects of capsaicin: Comprehensively insights from in vivo studies

BackgroundCapsaicin (CAP), a prominent component of chili pepper known for its potent agonistic effects on TRPV1, has attracted significant attention for its diverse physiological effects. Nevertheless, there remains a paucity of data concerning its in vivo distribution, metabolism, pharmacodynamic properties, and influence on the metabolic profile of the brain. MethodsStable isotope tracing, in vitro enzyme incubation, microdialysis coupled with UHPLC-MS/MS techniques were employed to investigate the in vivo metabolic pathways, distribution, and pharmacokinetic properties of CAP, and the potential biases in metabolic pathways was elucidate through molecular docking. Furthermore, the effect of CAP on brain metabolic profiles was assessed using untargeted metabolomics, and spatial visualization analysis was conducted through mass spectrometry imaging. ResultsCAP was distributed predominantly in the kidneys, with lower content in the liver, heart, lungs, brain, and spleen following peripheral administration, and the absorption half-life in the body was about 20 min. CAP primarily underwent alkyl terminal dehydrogenation, hydroxylation, and macrocyclization metabolic pathways under the action of CYP2C9, CYP2C19 and CYP2D6, resulting in at least four metabolites. Among them, the hydroxylation products were main metabolites and the dehydrogenation product 16,17-dihydrocapsaicin could interact with the key binding sites Leu515 and Thr550 of TRPV1 like CAP. CAP quickly diffused to various brain regions and the metabolic characteristics in the striatum were relatively different from that in the blood. The distribution of CAP in the brain primarily triggered the release of neurotransmitters in areas associated with reward, cognition, and memory. Both acute and chronic exposure to CAP elevated amino acid levels in cortical regions, while producing contrasting effects on nucleotide metabolites. ConclusionThis study offers an initial in-depth analysis of the distribution patterns, metabolic pathways and pharmacodynamic properties of CAP in the body and brain. These findings established a basis for further studies on CAP's pharmacology properties and its influence on the central nervous system.

Simultaneous quantification of alkanolamines and their dehydrogenation products in aqueous samples using high-performance liquid chromatography with pre-column derivatization with 2,4-dinitrofluorobenzene

BackgroundDiethanolamine, monoethanolamine, iminodiacetic acid, and glycine are important fine chemical intermediates, often requiring simultaneous quantitative analysis in various applications. This presents the challenge of accurately quantifying multiple substances within a single sample. The catalytic dehydrogenation of diethanolamine and monoethanolamine has garnered significant research interest, yet no analytical method has been reported for the simultaneous quantification of reactants and products in the dehydrogenation reaction mixtures of different alkanolamines. ResultsA high-performance liquid chromatography (HPLC) method has been developed for the simultaneous quantification of diethanolamine (DEA), iminodiacetic acid (IDA), glycine (Gly), and monoethanolamine (MEA) in aqueous solutions using 2,4-dinitrofluorobenzene (DNFB) for pre-column derivatization. The method demonstrated excellent linearity, with correlation coefficients (R2) of 0.9999, 0.9997, and 0.9998 for IDA, DEA, and Gly, respectively. The detection limits (LODs) were 0.02, 0.08, and 0.01 mg L−1, respectively. The quantification limits (LOQs) were 0.06, 0.24, and 0.03 mg L−1, respectively. Spiked recovery rates ranged from 96.99 % to 104.32 %, with relative standard deviations (RSDs) between 0.70 % and 3.03 %. For MEA and Gly, the R2 values were 0.9970 and 0.9990, the LODs were 0.12 and 0.01 mg L−1, the LOQs were 0.36 and 0.03 mg L−1, and spiked recoveries ranged from 96.24 % to 104.82 %, with RSDs between 1.22 % and 3.68 %. Compared to other methods, this HPLC approach offers superior sensitivity, accuracy, and precision. SignificanceThis method provides a robust reference for the individual or simultaneous quantification of alkanolamines, glycine, and iminodiacetic acid in aqueous matrices. It offers new insights into the simultaneous analysis of alkanolamines with multiple organic acids in complex matrices. Additionally, the method can guide the optimization of catalytic dehydrogenation processes for alkanolamines, potentially extending the advantages of dehydrogenation catalysts to other reactions.

Absorption, Metabolism, and Excretion of [14C]-Labeled Anaprazole: A New Proton Pump Inhibitor, After a Single Oral Administration in Healthy Chinese Male Subjects.

Anaprazole is a proton pump inhibitor. This study aims to elucidate absorption, metabolism, and excretion pathways of anaprazole sodium in the human body. A total of 4 healthy Chinese male subjects were administered a single oral dose of 20mg/100µCi of [14C]-anaprazole sodium enteric-coated capsules. The whole blood, plasma, and excreta were analyzed for a total radioactivity (TRA) and metabolite profile. The cumulative radioactivity excretion rate was 93.2%, with 53.3% and 39.9% of the radioactive dose excreted in urine and feces, respectively, and 91.6% of dose recovered within 96hours after dosing. The parent drug, anaprazole, showed good absorption and was extensively metabolized majorly to thioether M8-1 via nonenzymatic metabolism. Overall, 35 metabolites were identified in plasma, urine, and fecal samples. Anaprazole was the most abundant component in plasma followed by the thioether M8-1, accounting for 28.3% and 16.6%, respectively, of the plasma TRA. Thioether carboxylic acid XZP-3409 (26.3% of urine TRA) and XZP-3409 oxidation and dehydrogenation product M417a (15.1% of fecal TRA) were the major metabolites present in urine and feces, respectively. Anaprazole was undetectable in urine, while fecal samples showed traces (0.07% dose). Blood/plasma ratios of the radioactivity (approximately 0.60) remained consistent over time. Anaprazole showed good absorption and was extensively metabolized majorly to thioether M8-1 via nonenzymatic metabolism, and cytochrome P450 3A4 also contributed to its metabolism in healthy individuals.

Role of the in situ formed LiAl(NH)2 and LiNH2 in significantly improving the hydrogen storage properties of the Mg(NH2)2-2LiH systems with Li3AlH6 addition

The Mg(NH2)2-2LiH system has attracted considerable interest due to its high hydrogen capacity and low theoretical dehydrogenation enthalpy. However, its practical application is limited by sluggish kinetics due to the slow mass transfer rate and the stable N-H bond. In response to these problems, this study introduced Li3AlH6 into the Mg(NH2)2-2LiH system, leveraging the mutual destabilization effects between lithium alanates and metal amides to attenuate the stability of the N-H bond in Mg(NH2)2. The results show that the Mg(NH2)2-2LiH-0.1Li3AlH6 composite can reversibly desorb/absorb hydrogen up to 4.33 wt% at 140 °C with an initial dehydrogenation temperature of 90 °C. This represents a significant improvement over the pristine sample's capacity of 1.23 wt% under the same conditions. Phase structure analyses reveal that the in situ formed LiAl(NH)2 and LiNH2 particles during ball milling play a crucial role in decreasing the energy required for cleaving the N-H bond, transferring mass, and initiating nucleation. Dehydrogenation curves suggest that the dehydrogenation process follows the Avrami-Erofe'ev equation, signifying that the process is controlled by both nucleation and diffusion processes. A pronounced correlation exists between dehydrogenation kinetic energy barriers and nucleation energy barriers of the dehydrogenation products. This finding implies that future reductions in operating temperature and enhancements of the dehydrogenation rate in the Mg(NH2)2-2LiH system can be achieved by decreasing the nucleation energy barriers of the dehydrogenation products.

Active and stable Pt-Ga2O3/Al2O3 catalyst for dehydrogenation of methylcyclohexane

Methylcyclohexane (MCH) is considered as one of the most promising liquid organic hydrogen carriers (LOHCs) in terms of hydrogen storage and delivery. However, the dehydrogenation process of MCH is relatively difficult, which requires catalyst having high activity and stability. In this work, a catalyst of Pt/Al2O3 by doping Ga2O3 was prepared and tested in the dehydrogenation of MCH, resulting in both high activity and stability. After 176 h of the reaction, the conversion of MCH is no significant decrease, and the toluene (TOL) selectivity was greater than 99%. The characterization results of the catalyst evidenced that the excellent performance of the catalyst is due to the introduction of Ga2O3, which prevents the growth of Pt species and results more positively charged Pt species. These Pt species can weaken the strength of the adsorption between Pt and dehydrogenation products, making dehydrogenation products more easily to be desorbed, which achieving high activity and stability. The catalyst shows great potential for industrial application in the future. This work provides theoretical guidance for designing highly stable dehydrogenation catalysts.

Biomimetic Dehydrogenation of Non-Conventional Lignin Monomers on Cellulose Ferulate Interfaces.

Cellulose ferulate, synthesized by Mitsunobu reaction, is shaped into thin films and also used as an aqueous dispersion to perform artificial lignin polymerization on anchor groups. This biomimetic approach is carried out in a Quartz crystal microbalance with a dissipation monitoring (QCM-D) device to enable online monitoring of the dehydrogenation, applying H2O2 and adsorbed horseradish peroxidase (HRP). The systematic use of phenylpropanoids with different oxidation states, i.e., ferulic acid, coniferyl aldehyde, coniferyl alcohol, and eugenol allowed to conclude structure-property relationships. Both the deposited material, as well as the surface roughness increased with the hydrophobicity of the monomers. Beyond surface characterizations, py-GC-MS, HSQC NMR spectroscopy and Size exclusion chromatography (SEC) measurements revealed the linkage types β-β, β-5, 5-5, and β-O-4, as well as the oligomeric character of the dehydrogenation products. All samples possessed an antibacterial activity against B. subtilis and can be used in the field of antimicrobialbiomaterials.

Pyridine N-induced intra-pore and interfacial dual-confined Pd0-Pdδ+ synergistic catalysis for ultra-stable dehydrogenation of dodecahydro-N-propylcarbazole

We developed nano Pd catalysts, encapsulated within carbon-nitrogen layers at both intra-pore and interfacial levels on SiO2, via in-situ thermolysis of metal-organic coordination compounds. The catalysts dehydrogenation efficacy is greatly influenced by thermolysis temperature and ligand-to-metal ratio. The Pd-C-N2/SiO2-600 catalyst notably achieved complete dehydrogenation of 12 H-NPCZ within 240 minutes, demonstrating exceptional stability over 10 cycles without significant degradation, highlighting its viability for commercial use. Characterizations revealed that the C-N layer integration improves Pd nanoparticle dispersion and reduces strong acid site formation on catalyst surface. This synergy between the C-N layer and Pd nanoparticles promotes the formation and stabilization of Pdδ+ species, optimizing them as adsorption sites for dehydrogenation with appropriate acid strength. Moreover, this interaction adjusts the electronic states of Pd0 active sites, optimizing adsorption dynamics for intermediates. This cooperative action between Pd0 and Pdδ+ significantly boosts the desorption rate of dehydrogenation products, substantially improving the catalysis performance.

INVESTIGATION OF THE TRANSFORMATION OF MODEL PETROLEUM RAW MATERIALS UNDER CRACKING CONDITIONS OVER A REGENERATED SPENT HYDROTREATMENT CATALYST

The physicochemical properties and catalytic activity of regenerated spent aluminium-cobalt-molybdenum hydrotreatment catalyst have been investigated under cracking conditions in the model systems n-dodecane - toluene and decalin - toluene - n-hexane. A series of experiments to study the catalytic activity of the sample was carried out using a flow-type laboratory installation within the temperature range 430-470 °C, nitrogen pressure 1.6 MPa, liquid hourly space velocity 0.5-3.0 h-1. The directions of transformation were determined for paraffin and naphthenic hydrocarbons by means of gas chromatography - mass spectrometry. Paraffin hydrocarbons enter into cracking, isomerisation and compaction reactions. Naphthenic hydrocarbons are transformed into the products of isomerisation, dehydrogenation and compaction. Predominant dehydrogenation of decalin with the formation of naphthalene and hydrogen is observed in the system under investigation. A positive role of hydrogen in thermodestructive processing of heavy oil residues is observed due to the hydrogenation of nonlinear olefin hydrocarbons and aromatic hydrocarbon intermediates, which decreases the rate of coke formation. The corresponding reaction rate constants were calculated, and the results were analysed. Conclusions are drawn about the prospects of introducing a regenerated spent hydrotreatment catalyst into the procedure of thermodestructive processing of heavy oil residues.

Desorbent swing adsorption process using ethylene to separate propane and propylene under isobaric conditions

The separation of olefin and paraffin using adsorption technology remains a significant challenge. This study proposes a novel desorbent swing adsorption (DSA) process using an olefin desorbent with a weaker adsorption affinity (C2: ethylene) to separate a paraffin/olefin mixture with a higher adsorption affinity (C3s: propane and propylene) under isobaric conditions, which is the reverse concept of using a desorbent with a stronger affinity in conventional DSA systems. The proposed DSA process effectively separates the C3 mixture because the deteriorating effects caused by the desorbent is minimized. Based on sequential breakthrough experiments with zeolite 13X DSA using ethylene, the efficient separation of a propylene dehydrogenation product (propane:propylene = 60:40 vol%) to produce polymer-grade propylene is achieved. It is confirmed that ethylene desorbent stream pushes out the adsorbed propylene and regenerates the adsorption bed without changing the pressure. The desorption step plays a key role in the separation performance of the proposed DSA process because the regenerated bed offers favorable conditions when filled with the weaker desorbent after the desorption step. The flowrate of the desorbent strongly affects the efficiency of propylene desorption. After validating the dynamic mathematical model using the experimental results, a two-bed DSA process using a six-step sequence that includes rinse export/import and idle steps is shown to achieve a propylene purity above 99.999 % (desorbent-free basis) with a recovery of 99.39 %, a productivity of 4.21 mol∙kg−1∙hr−1, and an ethylene usage of 7.59 mol∙kg−1∙hr−1. This study offers important insights into the development of adsorptive separation designs for olefin/paraffin separation.

Effect of Residence Time and Carrier Gas on the Dehydrogenation of n-Hexane over Alumina-supported Chromium Catalyst

CrOx/γ-Al2O3 catalyst was prepared by incipient wetness impregnation method, and the influence of residence time and carrier gas on the dehydrogenation of n-hexane were studied. It is found that n-hexane dehydrogenation over CrOx/γ-Al2O3 catalyst with H2 as carrier gas exhibits totally different catalytic behaviors with that of diluting n-hexane with N2. When diluting feed with N2, the selectivity to dehydrogenation product is promoted while the cracking reaction is exhibited with reducing residence time. However, the selectivity to dehydrogenation product is significantly decreased while the isomerization of n-hexane is promoted when using H2 as carrier gas. It is proposed that H2 undergoes dissociation on the dehydrogenation active site, and further facilitates the olefinic dehydrogenation products to form carbocation, which performing isomerization reaction on the acid site on the γ-Al2O3 surface. Therefore, the isomerization of n-hexane is promoted in cost of the selectivity to dehydrogenation product when using H2 as carrier gas.

Shatianyu dietary fiber (Citrus grandis L. Osbeck) promotes the production of active metabolites from its flavonoids during in vitro colonic fermentation.

Recent studies reveal that dietary fiber (DF) might play a critical role in the metabolism and bioactivity of flavonoids by regulating gut microbiota. We previously found that Shatianyu (Citrus grandis L. Osbeck) pulp was rich in flavonoids and DF, and Shatianyu pulp flavonoid extracts (SPFEs) were dominated by melitidin, obviously different from other citrus flavonoids dominated by naringin. The effects of Shatianyu pulp DF (SPDF) on the microbial metabolism and bioactivity of SPFEs is unknown. An in vitro colonic fermentation model was used to explore the effects of SPDF on the microbial metabolism and antioxidant activity of SPFEs in the present study. At the beginning of fermentation, SPDF promoted the microbial degradation of SPFEs. After 24 h-fermentation, the supplemented SPFEs were almost all degraded in SPFEs group, and the main metabolites detected were the dehydrogenation, hydroxylation and acetylation products of naringenin, the aglycone of the major SPFEs components. However, when SPFEs fermented with SPDF for 24 h, 60.7% of flavonoid compounds were retained, and SPFEs were mainly transformed to the ring fission metabolites, such as 3-(4-hydroxyphenyl) propionic acid, 3-phenylpropionic acid and 3-(3-hydroxy-phenyl) propionic acid. The fermentation metabolites of SPFEs showed stronger antioxidant activity than the original ones, with a further increase in SPDF supplemented group. Furthermore, SPFEs enriched microbiota participating in the deglycosylation and dehydrogenation of flavonoids, while co-supplementation of SPDF and SPFEs witnessed the bloom of Lactobacillaceae and Lactobacillus, contributing to the deglycosylation and ring fission of flavonoids. SDPF promote SPFEs to transform to active metabolites probably by regulating gut microbiota. © 2023 Society of Chemical Industry.

ВЛИЯНИЕ ФАЗОВОГО СОСТАВА И УСЛОВИЙ ТЕРМООБРАБОТКИ ЖЕЛЕЗООКСИДНОГО КАТАЛИЗАТОРА НА ЕГО ХИМИЧЕСКИЕ СВОЙСТВА В ПРОЦЕССЕ ДЕГИДРИРОВАНИЯ МЕТИЛБУТЕНОВ

The present work is devoted to assessing the effect of heat treatment of iron oxide catalysts promoted by potassium and cerium on their activity, which is expressed quantitatively in the form of methylbutenes conversion, and selectivity in the process of methylbutenes dehydrogenation to isoprene, and interpreting the results obtained using kinetic modeling. Iron oxide catalysts were prepared by heat treatment of iron (II) hydroxide Fe(OH)2. The concentrations of the components of the reaction mixture, the conversion of methylbutenes and selectivity were experimentally determined during methylbutenes dehydrogenation in the presence of heat-treated iron oxide catalysts. It has been shown that an increase of α-Fe2O3 hematite phase in the iron oxide catalyst helps to reduce the concentration of carbon dioxide and cracking products in the products of the methylbutenes dehydrogenation, which contributes to increased selectivity. The increase of α-Fe2O3 hematite phase is observed with increasing heat treatment temperature from 298 K to 873 K. In all iron oxide catalysts promoted by potassium and cerium, after the methylbutenes dehydrogenation, the main phase is magnetite Fe3O4 (62.17% by wt.) and a more reduced form of iron oxide wustite FeO (13.81% by wt.) was identified. It can be assumed that the reduction of iron oxides in the iron oxide catalyst during the methylbutenes dehydrogenation is associated with the activity of the catalyst. The higher the activity of the iron oxide catalyst, the higher the concentration of hydrogen in the reaction mixture, which leads to a deeper reduction of iron oxide. As a result of kinetic modeling, it was demonstrated that the kinetic scheme, consisting of the reactions of methylbutene isomers dehydrogenation, isomerization of methylbutenes, cracking of methylbutene isomers and isoprene, interaction of coke with water, is complete enough to adequately describe the experimental data of the methylbutenes dehydrogenation.

Size-dependent reactivity of VnO+ (n = 1-9) clusters with ethane.

Cost-effective and readily accessible 3d transition metals (TMs) have been considered as promising candidates for alkane activation while 3d TMs especially the early TMs are usually not very reactive with light alkanes. In this study, the reactivity of Vn+ and VnO+ (n = 1-9) cluster cations towards ethane under thermal collision conditions has been investigated using mass spectrometry and density functional theory calculations. Among Vn+ (n = 1-9) clusters, only V3-5+ can react with C2H6 to generate dehydrogenation products and the reaction rate constants are below 10-13 cm3 molecule-1 s-1. In contrast, the reaction rate constants for all VnO+ (n = 1-9) with C2H6 significantly increase by about 2-4 orders of magnitude. Theoretical analysis evidences that the addition of ligand O affects the charge distribution of the metal centers, resulting in a significant increase in the cluster reactivity. The analysis of frontier orbitals indicates that the agostic interaction determines the size-dependent reactivity of VnO+ cluster cations. This study provides a novel approach for improving the reactivity of early 3d TMs.

Dehydrogenation of diborane on small Nbn+ clusters.

The reactivity of Nbn+ (1 ≤ n ≤ 21) clusters with B2H6 is studied by using a self-developed multiple-ion laminar flow tube reactor combined with a triple quadrupole mass spectrometer (MIFT-TQMS). The Nbn+ clusters were generated by a magnetron sputtering source and reacted with the B2H6 gas under fully thermalized conditions in the downstream flow tube where the reaction time was accurately controlled and adjustable. The complete and partial dehydrogenation products NbnB1-4+ and NbnB1-4H1,2,4+ were detected, indicative of the removal of H2 and likely BHx moieties. Interestingly, these NbnB1-4+ and NbnB1-4H1,2,4+ products are limited to 3 ≤ n ≤ 6, suggesting that the small Nbn+ clusters are relatively more reactive than the larger Nbn>6+ clusters under the same conditions. By varying the B2H6 gas concentrations and the reactant doses introduced into the flow tube, and by changing the reaction time, we performed a detailed analysis of the reaction dynamics in combination with the DFT-calculated thermodynamics. It is demonstrated that the lack of cooperative active sites on the Nb1+ cations accounts for the weakened dehydrogenation efficiency. Nb2+ forms partial dehydrogenation products at a faster rate. In contrast, the Nbn>6+ clusters are subject to more flexible vibrational relaxation which disperse the energy gain of B2H6-adsorption and thus are unable to overcome the energy barriers for subsequent hydrogen atom transfer and H2 release.

Rhodium-Mediated Dehydrogenation of Hydroboranes and Group 14 Compounds: Base-Stabilized Silylene and Germylene Complexes vs. Transmetalation.

Monocarbonyl rhodium complex LRh(CO), 1, which is stabilized by a pyrrole-based bis(phosphinimine) pincer ligand (L=κ3 -NNN'=2,5-[i Pr2 P=N(4-i PrC6 H4 )]2 -N'(C4 H2 )- ), serves as a versatile platform for the dehydrogenation of group 14 substrates. Reaction with primary and secondary silanes and germanes (MesSiH3 , Et2 SiH2 , Ph2 GeH2 , t BuGeH3 ; Mes=mesityl) liberates H2 and yields base-stabilized tetrylene compounds of the form κ2 -L(CO)Rh(ER2 ) (E=Si: R=Mes, H, 2; R=Et, 5; E=Ge: R=Ph, 6; R=t Bu, H, 8). The ":ER2 " fragment in these species bridges between the rhodium center and a phosphinimine donor. Preliminary reactions between pinacol (Pin) and κ2 -L(CO)Rh(ER2 ), E=Si, Ge, indicate that such complexes can serve as silylene and germylene synthons, releasing :ER2 and catalytically generating PinER2 . In contrast, combination of complex 1 and MesGeH3 does not yield the anticipated dehydrogenation product, but rather, transmetalation similar to that observed upon reaction between 1 and 3,5-dimethylphenylborane prevails.

Computational exploration on hydroxyl and sulfate radicals-induced aqueous degradation of imipramine

In the present work, hydroxyl (•OH) and sulfate radicals (SO4•−)-induced aqueous degradation of imipramine (IMI) was theoretically probed by carrying out density functional theory (DFT) calculation. Among the initial reactions of •OH (SO4•−) toward IMI, the hydrogen abstraction (HA) reactions occurring on saturated carbon atoms of the alkylamine side chain are the most favorable, followed by the addition (AD) reactions involving unsaturated carbon positions, and the HA reactions related to unsaturated carbon atoms are the most unfavorable. The most favorable subsequent reactions for the initial AD and HA intermediates can afford the hydroxylation, oxidation, dehydrogenation, CN or CC bond cleavage products of IMI, while the corresponding ring-opening reactions occur hard. The stronger oxidizing ability of SO4•− was predicted in comparison with •OH. The cationic form of IMI has lower reactivity than IMI.H2O and O2 molecules may exert a significant influence over aqueous degradation of IMI.

Activation of Cr2O3 for propane dehydrogenation by doping with Pt single-atom promotor

In this work, we evaluate reaction mechanism and kinetics of propane dehydrogenation (PDH) over Pt single-atom-doped Cr2O3 catalyst by combining density functional theory calculations and microkinetic analysis. Pt single-atom-doped Cr2O3 achieves superior propane conversion and propene selectivity to PtSn alloy and pristine Cr2O3 under typical operating conditions. Pt serves as a promoter to activate nearby Cr-O Lewis-Pair sites. The promotion effect of Pt single-atom on activity is attributed to the lowered energy level of conduction band minimum of nearby O Lewis-base site, enhancing its H capture ability and accordingly facilitating first step of dehydrogenation of propane. The Pt single-atom promoter also enhances propene selectivity by adjusting the Cr-O Lewis acid-base interaction with the deep dehydrogenation product, impeding deep dehydrogenation process. This work provides theoretical insights into the feasibility of atom-level dispersion Pt promoter activating CrOx-based catalysts for PDH process, and guidance for future rational design of other oxide-supported single-atom catalysts for PDH.

IR spectroscopic characterization of products of methane and cyclopropane activation by Ru cations

Methane and cyclopropane (c-C3H6) were reacted with Ru+ ions in a room temperature ion trap and the resulting products were identified using a combination of mass spectrometry, IR action spectroscopy, and density functional theory calculations. In the reaction with methane, no products with odd numbers of carbon atoms were located, whereas significant amounts of products with even numbers of carbon atoms were observed. We identified [Ru,2C,4H]+ as the Ru+ ion with an ethene ligand attached, and [Ru,4C,6H]+ as a Ru(η4-cis-1,3-butadiene)+ complex. The barrier toward formation of Ru(C2H4)+ + 2H2 was calculated at the B3LYP/def2-TZVPPD level to be 0.80 eV above the energy of the ground state Ru+ (4F) + 2 CH4 reactants. In the reaction of c-C3H6 with Ru+, we identified the dehydrogenation product [Ru,3C,4H]+ as Ru(η2-propyne)+, [Ru,2C,2H]+ as Ru+ with an ethyne ligand, and [Ru,5C,5H]+ as Ru(η5-c-C5H5)+ having a cyclopentadienyl ligand.