On-line Gas Chromatography Research Articles

H-ZSM-5 Materials Embedded in an Amorphous Silica Matrix: Highly Selective Catalysts for Propylene in Methanol-to-Olefin Process

H-ZSM-5 materials embedded in an amorphous silica were successfully synthesized with three different Si/Al ratios (i.e., 40, 45, and 50). The presence of the MFI structure in the synthesized samples was confirmed by X-ray diffraction (XRD), Fourier transform infra-red (FT-IR), and solid state-nuclear magnetic resonance (SSNMR) techniques. The morphology and textural properties of the samples were investigated by scanning electron microscopy (SEM), TEM, and N2-physisorption measurements. Furthermore, acidic properties of the synthesized catalysts have been studied by NH3-TPD and FT-IR spectroscopy of CO adsorption studies. Variation of the Si/Al ratio affected the crystal morphology, porosity, and particle size, as well as the strength and distribution of acid sites. The synthesized zeolite materials possessed low acid-site density and exhibited high catalytic activity in the methanol-to-olefin (MTO) reaction. To study the intermediate species responsible for catalyst deactivation, the MTO reaction was carried out at high temperature (500 °C) to accelerate catalyst deactivation. Interestingly, the synthesized catalysts offered high selectivity towards the formation of propylene (C3=), in comparison to a commercial microporous crystalline H-ZSM-5 with Si/Al = 40, under the same reaction conditions. The synthesized H-ZSM-5 materials offered a selectivity ratio of C3=/C2= 12, while it is around 2 for the commercial H-ZSM-5 sample. The formation of hydrocarbon species during MTO reaction over zeolite samples has been systematically studied with operando UV-vis spectroscopy and online gas chromatography. It is proposed that the strength and type of acid sites of catalyst play a role in propylene selectivity as well as the fast growing of active intermediate species. The effective conversion of methanol into propylene in the case of synthesized H-ZSM-5 materials was observed due to possession of weak acid sites. This effect is more pronounced in H-ZSM-5 sample with a Si/Al ratio of 45.

Operando DRIFTS and DFT Study of Propane Dehydrogenation over Solid- and Liquid-Supported Ga x Pt y Catalysts.

Supported catalytically active liquid metal solutions (SCALMS) represent a class of catalytic materials that have only recently been developed, but have already proven to be highly active, e.g., for dehydrogenation reactions. Previous studies attributed the catalytic activity to isolated noble metal atoms at the surface of a liquid and inert Ga matrix. In this study, we apply diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) with CO as a probe molecule to Ga/Al2O3, Pt/Al2O3, and Ga37Pt/Al2O3 catalysts, to investigate in detail the nature of the active Pt species. Comparison of CO adsorption on Pt/Al2O3 and Ga37Pt/Al2O3 shows that isolated Pt atoms are, indeed, present at the surface of the liquid SCALMS. Combining DRIFTS with online gas chromatography (GC), we investigated the Ga/Al2O3, Pt/Al2O3, and Ga37Pt/Al2O3 systems under operando conditions during propane dehydrogenation in CO/propane and in Ar/propane. We find that the Pt/Al2O3 sample is rapidly poisoned by CO adsorption and coke, whereas propane dehydrogenation over Ga37Pt/Al2O3 SCALMS leads to higher conversion with no indication of poisoning effects. We show under operando conditions that isolated Pt atoms are present at the surface of SCALMS during the dehydrogenation reaction. IR spectra and density-functional theory (DFT) suggest that both the Ga matrix and the presence of coadsorbates alter the electronic properties of the surface Pt species.

Rapid Online Fischer–Tropsch Reaction Monitoring using a Modified Frontier Tandem Micro‐Reactor GC–MS System

Conventional laboratory facilities used for Fischer–Tropsch (FT) catalyst evaluation usually consist of a reactor that is connected to an online gas chromatograph (GS). This arrangement is characterized by longer response times that make it difficult to acquire early reaction dynamics, which are crucial to the understanding of long‐term catalyst performance. This article describes how the modification of a Frontier Single micro‐Reactor, interfaced to a gas chromatograph–mass spectrometer (GC–MS) system, can facilitate rapid evaluation of catalysts for FT synthesis reaction. The study has been performed using an Ru/SBA‐15 catalyst prepared by reduction of RuCl3 using NaBH4 and deposition on a synthesized mesoporous SBA‐15 support and characterized using Brunauer–Emmett–Teller, scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, temperature‐programmed reduction, and X‐ray diffraction techniques. The system was successfully modified to perform catalyst evaluation in batch and real‐time modes. Unlike conventional FT setups, which require extended reaction times to generate the Anderson–Schulz–Flory plot and the chain growth probability (α), the modified system in this study allows the determination of product distribution and alpha value in less than 30 min from the start of the reaction. © 2019 American Institute of Chemical Engineers Environ Prog, 38:e13079, 2019

Assessment of a passive sampling method and two on-line gas chromatographs for the measurement of benzene, toluene, ethylbenzene and xylenes in ambient air at a highway site

Accurate, continuous long-term measurements of aromatic volatile organic compounds with known health impacts are needed for comprehensive assessments of air quality in the vicinity of industrial and vehicular emission sources. Historically, evacuated canister sampling and on-line gas chromatography (GC) have been the most popular approaches applied by government institutions in North America to measure benzene, toluene, ethylbenzene and xylenes (BTEX) in ambient air. Canister sampling is labour-intensive and typically does not provide the continuous data needed for epidemiological studies, while on-line GCs are costly and require shelter and power. In this work, the accuracy and suitability of three techniques for generating long-term ambient BTEX datasets are assessed. The first is a passive sampling method involving sorbent-packed thermal desorption tubes, the second is an on-line miniature gas chromatograph (miniGC) coupled with a photoionization detector (PID) and the third is a more traditional on-line gas chromatograph coupled with a flame ionization detector (GC-FID). These three techniques were deployed at an air quality monitoring station located adjacent to a busy highway for six weeks in summer 2018 to compare method performance and accuracy. Ambient mean concentrations of BTEX determined from the three methods for the entire study period were found to agree within 7% for benzene and within 30% for the other species. Interestingly, a temperature dependent positive bias previously identified for 14-day passive tube sampling for ethylbenzene and xylenes under cold wintertime conditions was found to be negligible under summertime conditions.

Catalytic conversion of glycerol to olefins over Fe, Mo, and Nb catalysts supported on zeolite ZSM-5

The large scale production of biodiesel has increased interest in glycerol transformation into higher value products. This study evaluated catalysts supported on HZSM-5 containing Fe, Mo, and Nb, in the glycerol conversion to olefins. The samples were prepared by wet impregnation and characterized by XRD, SBET, NH3-TPD, and TPO techniques. Catalytic experiments were performed in the range of 450–600 °C in a fixed-bed tubular reactor. The gaseous products were analyzed by online gas chromatography. It was observed that the modification in the acidic properties of ZSM-5 plays an important role in the selectivity to olefins. The highest selectivity for olefins was obtained for the Fe/ZSM-5 catalyst in the 450–500 °C range and for Nb/ZSM-5 in the range of 550–600 °C. Fe/ZSM-5 presented the highest selectivity to propylene at lower temperatures due to the higher acidic strength of the strong acid sites.

Secondary Organic Aerosol Formation from Aromatic Alkene Ozonolysis: Influence of the Precursor Structure on Yield, Chemical Composition, and Mechanism.

The influence of the precursor chemical structure on secondary organic aerosol (SOA) formation was investigated through the study of the ozonolysis of two anthropogenic aromatic alkenes: 2-methylstyrene and indene. Experiments were carried out in three different simulation chambers: ICARE 7300L FEP Teflon chamber (ICARE, Orléans, France), EUPHORE FEP Teflon chamber (CEAM, Valencia, Spain), and CESAM evacuable stainless steel chamber (LISA, Créteil, France). For both precursors, SOA yield and growth were studied on a large range of initial concentrations (from ∼60 ppbv to 1.9 ppmv) and the chemical composition of both gaseous and particulate phases was investigated at a molecular level. Gas phase was described using FTIR spectroscopy and online gas chromatography coupled to mass spectrometry, and particulate chemical composition was analyzed (i) online by thermo-desorption coupled to chemical ionization mass spectrometry and (ii) offline by supercritical fluid extraction coupled to gas chromatography and mass spectrometry. The results obtained from a large set of experiments performed in three different chambers and using several complementary analytical techniques were in very good agreement. SOA yield was up to 10 times higher for indene ozonolysis than for 2-methylstyrene ozonolysis at the same reaction advancement. For 2-methylstyrene ozonolysis, formaldehyde and o-tolualdehyde were the two main gaseous phase products while o-toluic acid was the most abundant among six products detected within the particulate phase. For indene ozonolysis, traces of formic and phthalic acids as well as 11 species were detected in the gaseous phase and 11 other products were quantified in the particulate phase, where phthaldialdehyde was the main product. On the basis of the identified products, reaction mechanisms were proposed that highlight specific pathways due to the precursor chemical structure. These mechanisms were finally compared and discussed regarding SOA formation. In the case of 2-methylstyrene ozonolysis, ozone adds mainly on the external and monosubstituted double bond, yielding only one C8- and monofunctionalized Criegee intermediate and hence more volatile products as well as lower SOA mass than indene ozonolysis in similar experimental conditions. In the case of indene, ozone adds mainly on the five-carbon-ring and disubstituted C═C double bond, leading to the formation of two C9- and bifunctionalized Criegee intermediates, which then evolve via different pathways including the hydroperoxide channel and form highly condensable first-generation products.

An On-Line Transient Study on Gassing Mechanism of Lithium Titanate Batteries

Gassing at elevated temperature is the main reason for the performance degradation of lithium titanate (Li4Ti5O12, LTO) batteries. In this study, an in-situ device was developed and used to study on-line the transient gassing of custom-made 4.5Ah LTO/NCM pouch batteries at 1C cycling at 55°C. The gas volume and internal pressure of the batteries were recorded on-line for 1000 h, and the composition of the gas components at different times was also analyzed by on-line gas chromatography. The results show that H2 and CO2 are the main gas components. The H2 percentage decreases, while the CO2 percentage increases gradually during the process of gassing. According to the rate-controlling step of gassing from H2 formation reaction to CO2, a stage-by-stage mixed gassing mechanism is proposed, where the water decomposition is dominant in the initial stage and solvent decomposition is dominant in the subsequent stage. The gassing of LTO batteries aged at 55°C was studied on-line at different states of charge (0%, 50%, 100% SOC). The results show that the volume and composition of the gas are essentially independent of the SOC of batteries and that formation of SEI at LTO interface is the main reason for the gassing rate reduction when aged and cycled (final phase) at 55°C.

High-temperature steam electrolysis combined with methane partial oxidation by solid oxide electrolyzer cells

Solid oxide electrolyzer cells consisting of scandia-stabilized zirconia (ScSZ) electrolyte, Ni-yttria-stabilized zirconia (YSZ), and lanthanum strontium ferrite (LSCF)-gadolinia-doped ceria (GDC) were fabricated, and their performance in high-temperature steam electrolysis combined with methane partial oxidation was investigated. The voltage of the electrolyzer cell operated with methane/steam input was significantly reduced compared to that of the cell with air/steam input. The hydrogen production rates at 1.3 V (850 °C) were 4.53 and 1.74 sccm for the electrolyzer cell with methane/steam and air/steam inputs, respectively. On-line gas chromatography analysis confirmed the production of hydrogen and carbon monoxide in the anode side, indicating that methane partial oxidation occurred at the anode side.

Study on single-fuel reactivity controlled compression ignition combustion through low temperature reforming

To achieve wider reactivity control, single-fuel reactivity controlled compression ignition (RCCI) through low temperature reforming (LTR) was proposed and experimentally explored. An LTR system was established on an optical compression ignition engine to investigate the impact of LTR on engine performance, where LTR products of the same fuel (n-heptane) as in-cylinder direct injection was routed into the intake port. The quantitative online gas chromatograph (GC) measurements indicate that LTR of n-heptane can produce numerous species with different chemical structures. The higher reforming temperature can lead to the higher fuel conversion rate. Optical engine experiments show that the ignition timing is retarded significantly via LTR. A two-stage low temperature heat release (LTHR) arises at the reforming temperature of 423 K (LTR-423 without LTR). CH2O-PLIF images suggest that the HCCI combustion of unreformed n-heptane cause the first LTHR because of its earlier occurrence time than in-cylinder direct injection and the homogeneous distribution of CH2O fluorescence. Meanwhile, the chemical calculation of CH2O formation manifests that the contributions of each reaction pathway to CH2O formation are different in each stage of LTHR. At the reforming temperature of 523 K (LTR-523 with LTR), prior to LTHR, weak PLIF signals were also captured, emitted by aldehydes and ketones LTR produced in the reformer. In the subsequent LTHR stage, formaldehyde develops at a relatively low speed due to LTR. In the HTHR stage, high-speed images show that LTR leads to a smooth combustion and reduces soot formation. The effect of LTR products on mixture reactivity was analyzed by the constant volume ignition delay model. The calculation results manifest that the reactivity of each LTR product is different, influenced by both thermal dilution effect and chemical effect. The combined impact of LTR products on mixture reactivity depends on both the chemical structure and the concentration in the mixture. The thermal dilution effect of LTR products contributes more for the final decline of mixture reactivity LTR caused. Finally, although the reactivity just decreased under current LTR conditions, it is believed that LTR has the potential to achieve further reactivity control of RCCI combustion to accommodate changes in the operating conditions of engines by changing LTR conditions (temperature, equivalence ratio, residence time, fuel type, feeding water, etc.).

Visible light assisted photocatalytic reduction of CO2 to ethane using CQDs/Cu2O nanocomposite photocatalyst

CO2 reduction through photocatalysis is considered a promising way to mitigate the abundance of this greenhouse gas in the earth's atmosphere. In this work, blue-fluorescent carbon quantum dots (CQDs) were synthesized via a facile top-down hydrothermal method using biochar as the carbon source. The as-synthesized CQDs were incorporated together with commercial copper (I) oxide (Cu2O) nanoparticles to form CQDs/Cu2O nanocomposite. The CQDs, Cu2O and CQDs/Cu2O nanocomposite were then applied for gas phase photocatalytic reduction of CO2. The experiments were performed under visible light irradiation in a self-designated photoreactor which was connected to an online Gas Chromatography (GC). High resolution transmission electron microscopy (HRTEM) confirmed the uniform deposition of CQDs with size ranging from 2.5 to 6.0 nm on the surface of Cu2O nanoparticles. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy further revealed the presence of CQDs on the surface of Cu2O. The CQDs/Cu2O nanocomposite photocatalyst showed a considerable improvement in the CO2 photoreduction with an enhancement of 54% compared to the pure Cu2O. In addition, the band alignment of CQDs/Cu2O, charge carriers transfer and separation as well as possible reaction pathways for CO2 photoreduction was proposed. Finally, the photostability test revealed the CQDs/Cu2O nanocomposite was able to retain its photostability of up to ~90% under five cycles of photoreaction.

On-line liquid chromatography-comprehensive two dimensional gas chromatography with dual detection for the analysis of mineral oil and synthetic hydrocarbons in cosmetic lip care products

An on-line liquid chromatography-comprehensive two-dimensional gas chromatography (LC-GC×GC) separation process, combined with a dual detection system, namely triple quadrupole mass spectrometry (used as a single quadrupole - QMS) and flame ionization detection (FID), was developed for the analysis of cosmetic lip care products. The LC step was carried out by using a fused-core silica column, with this enabling the separation of mineral oil saturated hydrocarbons (MOSH), as well as polyolefin oligomeric saturated hydrocarbons (POSH), from the mineral oil aromatic hydrocarbon (MOAH) families. Each chemical class was then subjected to GC×GC-QMS/FID analysis, using a medium polarity-low polarity column combination. Notwithstanding the utility of the flame ionization detector for quantification purposes, it is obviously also desirable to obtain information on the type of hydrocarbons present (of mineral or synthetic origin), in order to identify a potential contamination source. Following method optimization, various analytical figures of merit (method linearity, intra- and inter-day repeatability, limits of detection and quantification, and injector discrimination) were measured. Specifically, for MOSH and MOAH, linearities were evaluated in the 32.5–2080 and 50–500 mg L−1 range, respectively; furthermore, intra- and inter-day repeatability values were 6.2 and 8.3%, respectively, while limits of detection and quantification were 3.5 and 11.8 mg L−1, respectively.The proposed method, enables for the first time (to the best of the authors’ knowledge), the detailed qualitative and quantitative analysis of saturated and aromatic hydrocarbons, in a single run and in a fully-automated manner. Quantities of MOSH + POSH in the cosmetic products ranged from 8.7 to 44.4% (CV values were in the 1.5–5.4% range) while MOAH contamination was found in four samples, ranging from 386 to 5869 mg kg−1 (CV values were in the 0.5–4.5% range).

Enhanced role of graphitic-N on nitrogen-doped porous carbon ball for direct dehydrogenation of ethylbenzene

Nitrogen doping is an efficient strategy to improve the catalytic activity of carbocatalysts in direct dehydrogenation reactions. The interpretation of enhanced activity is now mainly attributed to the strengthened basicity. On the other side of doping, electronic properties that differed in various nitrogen doping configurations, however, were barely considered. Herein, to elucidate the role of graphitic N, pyridinic N and pyrrolic N, N-doped porous carbon balls with tunable contents of these nitrogen species were used as moulded carbocatalysts for steam-free direct dehydrogenation of ethylbenzene to styrene. Along with CO groups that were commonly certified as active sites on carbocatalysts, graphitic N contributes to the styrene yield. The former serves as active site that directly activates and dissociates C–H bond, while the latter one provides additional electrons into the delocalized π-system and leads to improved chemical reactivity of CO. The loss of CO active sites is not only attributed to the carbon deposition as illustrated by the elevated area ratio of D3 to G band in Raman spectra, but also its failed regeneration from intermediate hydroxyl groups (C–OH), which was proved by the tiny thermal decomposed products of CO and H2O as detected by the on-line mass spectrometry and gas chromatography.

Kinetic Study of the Pyrolysis and Oxidation of Guaiacol.

Guaiacol or 2-methoxy phenol is one of the main primary tars produced during lignin pyrolysis. Tar conversion in the gas phase influences the production of gaseous and condensable products, and is also responsible for PAH and soot formation during biomass and bio-oil gasification or combustion. Guaiacol pyrolysis and oxidation under stoichiometric conditions were studied in a jet stirred reactor between 623 and 923 K for a residence time of 2 s and under a pressure of 800 Torr (106.7 kPa). Speciation was obtained thanks to online gas chromatography using flame ionization detection and mass spectrometry and allowed the quantification of 22 species in pyrolysis and 42 species in oxidation. Decomposition of guaiacol starts at 650 K, and a conversion degree of 50% is obtained at about 785 K in pyrolysis and 765 K in oxidation. The main products of reaction are pyrocatechol o-HOC6H4OH, o-hydroxybenzaldehyde, methylcatechols, and light products, such as methane, carbon monoxide, ethylene, and hydrogen. A detailed kinetic model based on a combustion model for light aromatics and anisole has been extended to guaiacol. Thermochemical data of guaiacol and main products were calculated theoretically at the CBS-QB3 level of theory. The model predicts well the conversion of guaiacol and the formation of the main products. Guaiacol decomposes mainly through a unimolecular O-C bond breaking to hydroxy phenoxy and methyl radicals in both pyrolysis and oxidation, but H atom abstractions are also of importance in the low temperature range of the study. The unimolecular mechanism leads mainly to pyrocatechol and methylcatechols, whereas the chain radical mechanism is responsible for the formation of hydroxybenzaldehyde. As for anisole but in a much lower extent, an early formation of benzene and soot precursors is observed.

A method for the quantitative analysis of gaseous mixtures by online mass spectrometry

Online mass spectrometry is a widely used technique in tracking composition changes of gas mixture during the reaction. This paper reports a quantification analysis method of gas mixtures detected by an online mass spectrometry. In this analysis, a mass spectrum correction coefficient matrix is generated based on the calibration of mass spectrometry intensities of premixed calibration gas mixtures, and then the concentrations of gas components are calculated from this matrix by subtracting the interferences of other components with overlapped peaks. The accuracy of obtained results were verified by online gas chromatography in the meanwhile. The detailed error analysis was supplied in a separate supplement document. This method can be applied on the online detection of gas phase reactions with promising advantages to analysis of online gas chromatography, which is suitable for analysis of spectra overlaps (a given m/z signal contributed from two or multiple components) and kinetic studies.

Development of novel on-line capillary gas chromatography-based analysis method for volatile organic compounds produced by aerobic fermentation

Many volatile compounds, such as isoprene, a precursor used in the synthesis of natural rubber, have been produced through fermentation using genetically engineered microorganisms. Despite this biotechnological success, measuring the concentrations of volatile compounds during fermentation is difficult because of their high volatility. In current systems, off-line analytical methods usually lead to product loss, whereas on-line methods raise the production cost due to the requirement of complex devices. Here, we developed a novel on-line gas chromatography (GC)-based system for analyzing the concentration of isoprene with the aim to minimize the cost and requirement for devices as compared to current strategies. In this system, a programmable logic controller is used to combine conventional GC with a syringe pump module (SPM) directly connected to the exhaust pipe of the fermentor, and isoprene-containing samples are continuously pumped from the SPM into the GC using an air cylinder recycle stream. We showed that this novel system enables isoprene analysis during fermentation with convenient equipment and without the requirement of an expensive desorption tube. Furthermore, this system may be extended to the detection of other volatile organic compounds in fermentation or chemical processes.

Low-temperature gas-phase oxidation of diethyl ether: Fuel reactivity and fuel-specific products

Diethyl ether (DEE) has been recently suggested as a potential biofuel for compression-ignition engines that are known to be significantly controlled by low-temperature (LT) chemistry. However, the LT oxidation of DEE has not fully been understood in term of the formation of LT fuel-specific products. We have thus studied the oxidation of DEE by examining detailed profiles of its oxidation products under LT conditions (400–1100 K). To this end, we have used a dedicated experimental setup including a nearly-atmospheric jet-stirred reactor (JSR) coupled to online gas chromatography (GC). The experiments were complemented by measurements made with a JSR coupled to tunable synchrotron vacuum ultraviolet (SVUV) photoionization (PI) molecular-beam mass spectrometry (MBMS) for a cross-validation of the identification of important LT species.Experimental results indicate that DEE is very reactive; it starts to react around 425 K. DEE exhibits an unusual oxidation behavior with two negative temperature coefficient (NTC) zones in the JSR study. Because of this two-NTC observation, additional experiments were performed with a plug flow reactor (PFR) combined with electron ionization (EI)-MBMS, confirming this behavior in the two types of reactor. Moreover, about 20 oxidation species in C1C4 range were detected with several intermediates containing 2-3 O-atoms. Acetic acid is found to peak at 525 K with a very large amount, suggesting that it is a key species in the early stage of DEE's LT oxidation. Possible DEE-consumption paths leading to acetic acid formation could play an important role in the oxidation mechanism of DEE. A new model is proposed based on the present experimental observations to include new primary LT reaction paths. The model reproduces the experimental phenomena quite well and enhances the understanding of the two-NTC-zone occurrence and of intermediates containing 2-3 O-atoms during the LT oxidation of DEE.

Characteristics and Source Apportionment of Volatile Organic Compounds in the Rainy Season of Guangzhou City

Atmospheric volatile organic compounds (VOCs) were measured in an urban area of Guangzhou on July 2016 using an on-line gas chromatography mass spectrometry/fire ion detector. Seventy-three VOCs were detected with an average concentration of (118.83±79.40) μg·m-3, a maximum concentration of 492.42 μg·m-3, and a minimum concentration of 10.54 μg·m-3 during the period. The peak value of the TVOC concentration appeared at about 07:00 in the morning, indicating that motor vehicle pollution had a significant contribution at the site. The minimum value appeared at about 14:00 in the afternoon, related to photochemical losses. High concentrations were also observed from 21:00 to 24:00, which was probably related to pollution emissions and boundary layer compression. Source analysis by PMF showed that the site was mainly affected by five VOC sources: vehicle exhaust, solvent use, fuel loss at fuel stations, plant emissions, and cooking exhaust, the contributions of which were 29.79%, 26.61%, 24.86%, 9.91%, and 8.84%, respectively. Vehicle exhaust was the largest source of VOCs during the daytime, while the contribution of plant emissions increased significantly at noon. The contribution of solvent uses and fuel loss at fuel stations rose during the night and became the main source of VOCs until early morning.

Gas‐phase rate coefficients for a series of alkyl cyclohexanes with OH radicals and Cl atoms

AbstractThe rate coefficients of the reactions of OH radicals and Cl atoms with three alkylcyclohexanes compounds, methylcyclohexane (MCH), trans‐1,4‐dimethylcyclohexane (DCH), and ethylcyclohexane (ECH) have been investigated at (293 ± 1) K and 1000 mbar of air using relative rate methods. A majority of the experiments were performed in the Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC), a stainless steel chamber using in situ FTIR analysis and online gas chromatography with flame ionization detection (GC‐FID) detection to monitor the decay of the alkylcyclohexanes and the reference compounds. The studies were undertaken to provide kinetic data for calibrations of radical detection techniques in HIRAC. The following rate coefficients (in cm3 molecule−1 s−1) were obtained for Cl reactions: k(Cl+MCH) = (3.51 ± 0.37) × 10–10, k(Cl+DCH) = (3.63 ± 0.38) × 10−10, k(Cl+ECH) = (3.88 ± 0.41) × 10−10, and for the reactions with OH radicals: k(OH+MCH) = (9.5 ± 1.3) × 10–12, k(OH+DCH) = (12.1 ± 2.2) × 10−12, k(OH+ECH) = (11.8 ± 2.0) × 10−12. Errors are a combination of statistical errors in the relative rate ratio (2σ) and the error in the reference rate coefficient. Checks for possible systematic errors were made by the use of two reference compounds, two different measurement techniques, and also three different sources of OH were employed in this study: photolysis of CH3ONO with black lamps, photolysis of H2O2 at 254 nm, and nonphotolytic trans‐2‐butene ozonolysis. For DCH, some direct laser flash photolysis studies were also undertaken, producing results in good agreement with the relative rate measurements. Additionally, temperature‐dependent rate coefficient investigations were performed for the reaction of methylcyclohexane with the OH radical over the range 273‐343 K using the relative rate method; the resulting recommended Arrhenius expression is k(OH + MCH) = (1.85 ± 0.27) × 10–11 exp((–1.62 ± 0.16) kJ mol−1/RT) cm3 molecule−1 s−1. The kinetic data are discussed in terms of OH and Cl reactivity trends, and comparisons are made with the existing literature values and with rate coefficients from structure‐activity relationship methods. This is the first study on the rate coefficient determination of the reaction of ECH with OH radicals and chlorine atoms, respectively.

Pd/TiO2-WO3 photocatalysts for hydrogen generation from water-methanol mixtures

Solar light is inexhaustible, and therefore to take advantage of this energy it is necessary to develop materials capable of absorbing energy in the widest range of the solar spectra. Although TiO2 is one of the most studied photocatalysts, it only absorbs in the UV range. With the aim of increasing this light absorption towards the visible range, in this study Pd and WO3 were supported on bare TiO2 to determine their photocatalytic properties for generating hydrogen from water-methanol mixtures under UVA and solar irradiation. Several parameters for the hydrogen production, such as the amount of Pd and the catalyst as well as the influence of the water matrix were studied. These catalytic materials were characterized by means of inductively coupled plasma with an optical emission spectrophotometer, nitrogen adsorption-desorption isotherms, X-ray diffraction, high resolution – transmission electron microscopy, X-ray photoelectron spectroscopy and diffuse reflectance UV–Vis spectroscopy. The hydrogen evolution was monitored by online gas chromatography. The incorporation of a small amount of Pd (lower than 0.01 wt%) produced a large increase in the hydrogen production. Furthermore, adding WO3 on the bare titania also increased hydrogen generation. The highest quantum efficiency obtained in this work under solar radiation was 7.7% by the catalyst based on palladium supported on nanotubes of titanium dioxide and tungsten trioxide (Pd/NT-WO3) using an aqueous solution of methanol (50 vol%).

Co-synthesis of large-area graphene and syngas via CVD method from greenhouse gases

In this study, we report a novel and efficient way to produce large-area graphene and syngas simultaneously from CH4 and CO2 via CVD. The successful synthesis of syngas was confirmed by online gas chromatography characterization whereas the graphene produced within the same process was verified using Raman spectroscopy, Raman mapping and HRTEM. This work helps to better understand graphene growth from CH4 and CO2 and improve the CVD method by providing a novel pathway for the synthesis of large-area graphene with a valued by-product. With our derived CVD approach, graphene was grown while producing syngas and consuming green-house gases which is of great importance in this current climate change phenomenon.