Temperature-programmed Desorption Mass Spectrometry Research Articles

Polyurethane-based thin-film composites with carbon micro- to nanoscale fillers and their microwave properties

Polyurethane-based thin-film composites (PUR-based TFCs) with different carbon fillers, namely, carbon flocs formed by carbon dots (CDs) containing O, N, and F heteroatoms and carbon nanotubes (CNTs), were prepared by hot pressing. The morphology and composition of the carbon fillers were investigated by SEM/EDX. Temperature-programmed desorption mass spectrometry and thermogravimetric analysis revealed that the CNTs have the highest thermostability among the fillers. Microwave studies in the X-band showed that the PUR-based TFCs with the CNTs were characterized by higher reflection losses and lower transmission losses than the PUR-based TFCs with the flocs formed by the studied CDs.

Sublimation of volatiles from H2O:CO2 bulk ices in the context of comet 67P/Churyumov–Gerasimenko. II. Noble gases

The ROSINA instrument on board the Rosetta spacecraft measured, among others, the outgassing of noble gases from comet 67P/Churyumov–Gerasimenko. The interpretation of this dataset and unravelling underlying desorption mechanisms requires detailed laboratory studies. We aim to improve our understanding of the desorption patterns, trapping, and fractionation of noble gases released from the H$_ $O:CO$_ $-dominated ice of comet 67P. In the laboratory, ice films of neon, argon, krypton, or xenon (Ne, Ar, Kr, and Xe) mixed in CO$_ $:H$_ $O were prepared at 15 K. Temperature-programmed desorption mass spectrometry is employed to analyse the desorption behaviour of the noble gases. Mass spectrometric ROSINA data of 67P were analysed to determine the fraction of argon associated with CO$_ $ and H$_ $O, respectively. CO$_ $ has a significant effect on noble gas desorption behaviour, resulting in the co-release of noble gases with CO$_ $, decreasing the amount of noble gas trapped within water, shifting the pure phase noble gas peak desorption temperature to lower temperatures, and prolonging the trapping of neon. These effects are linked to competition for binding sites in the water ice and the formation of crystalline CO$_ $. Desorption energies of the pure phase noble gas release were determined and found to be higher than those previously reported in the literature. Enhancement of the Ar/Kr and Ar/Xe ratios are at best 40<!PCT!> and not significantly influenced by the addition of CO$_ $. Analysis of ROSINA mass spectrometric data shows that the fraction of argon associated with H$_ $O is 0.53 pm 0.30, which cannot be explained by our laboratory results. Multicomponent ice mixtures affect the desorption behaviour of volatiles compared to simple binary mixtures and experiments on realistic cometary ice analogues are vital to understanding comet outgassing.

Sublimation of volatiles from H2O:CO2 bulk ices in the context ofcomet 67P/Churyumov–Gerasimenko. I. N2 and CO

Comets are considered to be remnants from the formation of the Solar System. ESA's Rosetta mission targeted comet 67P/Churyumov-Gerasimenko and was able to record high-quality data on its chemical composition and outgassing behaviour, including low abundances of N$_ $ that are observed to be correlated with H$_ $O and CO$_ $ in approximately a 63:37 ratio. In this work, the thermal desorption behaviour of N$_2$ in H$_2$O:CO$_2$ ices was studied in the laboratory to investigate the co-desorption behaviour of N$_2$ within the two most abundant cometary ices in 67P and to derive desorbing fractions in different temperature regimes. H$_2$O:CO$_2$:N$_2$ ices of various ratios were prepared in a gas mixing system and co-deposited at 15 K onto a copper sample holder. Sublimation of the ice was measured using temperature programmed desorption mass spectrometry. Quantitative values were derived for the fraction of N$_2$ co-desorbing with CO$_2$ and H$_2$O respectively. To validate the results, H$_2$O:CO$_2$:13CO ices were prepared as well. The experiments show that the co-desorption of N$_2$ with CO$_2$ in H$_2$O:CO$_2$:N$_2$ ices depends on the bulk amount of CO$_2$ present in the ice. The fraction of N$_ $ trapped in H$_ $O reduces as more N$_ $ and CO$_ $ are added to the mixture. CO behaves qualitatively similar to N$_ $, but more CO is found to co-desorb with CO$_ $. To reproduce the ratio of N$_ $ desorbing with H$_ $O over that of CO$_ $ (N$_ $(H$_ $O)/N$_ $(CO$_ $)), our ice analogues need to contain geq 15<!PCT!> CO$_ $, while 67P contains leq 7.5<!PCT!> CO$_ $. Large fractions of N$_ $ can be removed from the ice due to heating up to 70 K, but for ice that most closely resembles that of 67P, the loss fraction of pure phase N$_2$ is expected to be leq 20<!PCT!>. Therefore, N$_2$ is suggested to be a minor carrier of nitrogen in the comet.

Reversible solvent interactions with UiO-67 metal-organic frameworks.

The utility of UiO-67 Metal-Organic Frameworks (MOFs) for practical applications requires a comprehensive understanding of intermolecular host-guest MOF-analyte interactions. To investigate intermolecular interactions between UiO-67 MOFs and complex molecules, it is useful to evaluate the interactions with simple polar and non-polar analytes. This problem is approached by investigating the interactions of polar (acetone and isopropanol) and non-polar (n-heptane) molecules with functionalized UiO-67 MOFs via temperature programmed desorption mass spectrometry and temperature programmed Fourier transform infrared spectroscopy. We find that isopropanol, acetone, and n-heptane bind reversibly and non-destructively to UiO-67 MOFs, where MOF and analyte functionality influence relative binding strengths (n-heptane ≈ isopropanol > acetone). During heating, all three analytes diffuse into the internal pore environment and directly interact with the μ3-OH groups located within the tetrahedral pores, evidenced by the IR response of ν(μ3-OH). We observe nonlinear changes in the infrared cross sections of the ν(CH) modes of acetone, isopropanol, and n-heptane following diffusion into UiO-67. Similarly, acetone's ν(C=O) infrared cross section increases dramatically when diffused into UiO-67. Ultimately, this in situ investigation provides insights into how individual molecular functional groups interact with UiO MOFs and enables a foundation where MOF interactions with complex molecular systems can be evaluated.

Multi-Modal Structure and Distribution Analysis of Functional Groups on Carbon Supports for Polymer-Electrolyte Fuel Cells

Although structures of the functional groups formed on the surface of the carbon supports and their distribution on/inside supports have crucial impacts on determining performance of the catalyst electrodes, understanding of the relationship between them remains unclear, because of limitation of experimental methods for quantitative analysis of them with high spatial resolution. It is well-known that functional groups of the catalyst supports affect chemical properties of the supports, such as, redox- and acid-base properties, hydrophobicity, and electronic interaction. Thus, they should have a great influence on various aspects those related to the performance of polymer electrolyte fuel cell (PEFC), such as the activity, mass transportability, and durability of the catalysts and catalyst layers, and manufacturing process of catalysts and catalyst layer. 1,2). Furthermore, recently, in addition to various conventional high-surface area carbon supports, such as, Vulcan and Ketjen black, accessible carbon supports with mesopores which can host Pt particles protects them from direct ionomer adsorption and allow proton and O2 to have reasonable access to Pt particles, have been attracting great attention for improving catalyst utilization, activity, mass transportability, and suppression of Pt dissolution 3-5). The relationship between structure variation of functional groups on various supports and electrode performances should be of interest. The major difficulty for analyzing the functional groups on carbon supports come from the structure complexity of carbon surface (as well as inner part of the carbon particles), inhomogeneous distribution of various functional groups produced in various chemical processes, and multi-component structure of catalyst electrodes with catalysts and ionomers. Against such background, in this study, we have developed a new experimental approach utilizing multi-modal analysis method with x-ray photoelectron spectroscopy (XPS), x-ray absorption spectroscopy (XAS), temperature-programmed-desorption mass spectroscopy (TPD-MS), vibrational spectroscopy, electron tomography (3D-TEM), and cryo transmission electron microscopy (cryo-TEM). By combining suitable experimental probes for each structural feature and each component in multi-component structures, and by analyzing in integrated manner, we are able to understand the complex structure of functional groups on and inside carbon supports. Here, we demonstrate an example of the analysis for Vulcan (VULCAN® XC72, Cabot Corporation) and Pt-supported Vulcan (TEC10V30E, Tanaka Kikinnzoku Kogyo K. K. ). Vulcan is a solid carbon support used for polymer electrolyte fuel cell catalysts. The sample was reduced for about 30 minutes in a 100% hydrogen atmosphere at room temperature. Hard x-ray photoelectron spectroscopy (HAXPES) using synchrotron radiation x-rays with x-ray energy of 8 keV (BL46XU at SPring-8) . Also soft X-ray XAS were performed on BL1N2 at Aichi SR . Figure 1 shows the C1s HAXPES spectrum and the C K-edge XANES spectrum acquired by total electron yield (TEY) method. HAXPES was normalized by the signal intensity of the C-C substrate components (sp2, sp3) of the support at 284.5 eV 6), whereas the C K-edge XANES is normalized by the signal intensity of the 2pz (π*) orbital extending perpendicular to the carbon hexagonal network plane of the C–C substrate component of the support at 285.2 eV 7, 8). The functional groups are clearly observed in both spectra and the signal intensity of the functional group of the Pt catalyst increased with respect to the support alone, indicating that the amount of functional group on the support increased due to the Pt loading process. By combining other experimental results and theoretical simulations, the relationship between structure properties and electrode performance can be discussed. Acknowledgement This work was conducted in FC-Platform project supported by the New Energy and Industrial Technology Development Organization (NEDO). References :1) E. Antolini, Applied Catalysis B: Environmental 88, 1 (2009)2) Y.-J. Wang, N. Zhao, B. Fang, H. Li, X. T. Bi, and H. Wang, Chem Rev 115, 3433 (2015)3)V. Yarlagadda, M. K. Carpenter, T. E. Moylan, R. S. Kukreja, R. Koestner, W. Gu, L. Thompson, and A. Kongkanand, ACS Energy Letters 3, 618 (2018)4)S. Ott, A. Orfanidi, H. Schmies, B. Anke, H. N. Nong, J. Hübner, U. Gernert, M. Gliech, M. Lerch and P. Strasser , Nature Mater., 19, 77 (2020)5)A. Kobayash, T. Fujii, C. Harada, E. Yasumoto, K. Takeda, K. Kakinuma, and M. Uchida, Acs Appl. Energy Mater. 4 2307 (2021)6) S. Kundu, Y. Wang, W. Xia, and M. Muhler, J. Phys. Chem. C, 112, 16869 (2008)7) Y. Murakami, Y. Ota, and T. Okada, Anal. Sci., 39, 67 (2023)8) C. L. Guillou, S. Bernard. F. de la Pena, and Y. L. Brech, Anal. Chem., 90, 8379 (2018) Figure 1

Wettability Engineering of Solar Methanol Synthesis.

Engineering the wettability of surfaces with hydrophobic organics has myriad applications in heterogeneous catalysis and the large-scale chemical industry; however, the mechanisms behind may surpass the proverbial hydrophobic kinetic benefits. Herein, the well-studied In2O3 methanol synthesis photocatalyst has been used as an archetype platform for a hydrophobic treatment to enhance its performance. With this strategy, the modified samples facilitated the tuning of a wide range of methanol production rates and selectivity, which were optimized at 1436 μmol gcat-1 h-1 and 61%, respectively. Based on in situ DRIFTS and temperature-programmed desorption-mass spectrometry, the surface-decorated alkylsilane coating on In2O3 not only kinetically enhanced the methanol synthesis by repelling the produced polar molecules but also donated surface active H to facilitate the subsequent hydrogenation reaction. Such a wettability design strategy seems to have universal applicability, judged by its success with other CO2 hydrogenation catalysts, including Fe2O3, CeO2, ZrO2, and Co3O4. Based on the discovered kinetic and mechanistic benefits, the enhanced hydrogenation ability enabled by hydrophobic alkyl groups unleashes the potential of the surface organic chemistry modification strategy for other important catalytic hydrogenation reactions.

PREPARATION AND PHYSICOCHEMICAL CHARACTERISTICS OF AN IODINE AND BISMUTH CONTAINING COMPOSITE MATERIAL BASED ON CHITOSAN

We created composite materials by using a straightforward method, combining chitosan, iodine, and bismuth. We used two chitosan with two different molecular masses. We used iodine in the composites as chitosan iodide and bismuth in the form of tetraiodobismuthanuide. We analysed the resulting materials with scanning electron microscopy, X-ray diffraction, temperature-programmed desorption mass spectrometry, and visible light spectroscopy. We observed that bismuth and iodine were evenly distributed throughout the composites and did not separate into distinct phases. These composite materials have the ability to form organised porous sponges, making them suitable for a wide range of applications in different fields.

Hydrogen addition reactions of a three-membered ring in the solid state: c-C3H2O

Abstract Due to the relatively high abundance of hydrogen radicals in the interstellar medium, the H-addition reaction of unsaturated organic molecules in the solid phase and at very low temperatures is considered to play an important role in the chemical complexity of organic substances in the Universe. However, when interacting with hydrogen atoms, all unsaturated functional groups that may be present in several organic species exhibit different behaviours that can significantly alter the reaction pathways from one species to another. By coupling FTIR spectroscopy and temperature programmed desorption mass spectrometry, we have investigated the H + c-C3H2O (cyclopropenone) solid-state reaction using two different experimental methods. We show that cyclopropenone reacts with hydrogen atoms under interstellar medium conditions, leading to propynal (HCCCHO), propadienone (CH2CCO), and two thermodynamically most stable isomers of c-C3H2O. In excess of H atoms, the hydrogenation of cyclopropenone also leads to propenal (CH2CHCHO), propanal (CH3CH2CHO), c-C3H4O (cyclopropanone), in addition to two alcohols, namely cyclopropanol (c-C3H6O) and propanol (CH3CH2CH2OH).

Existence of Acetaldehyde Clathrate Hydrate and Its Dissociation Leading to Cubic Ice under Ultrahigh Vacuum and Cryogenic Conditions.

Acetaldehyde in a dilute aqueous solution gets hydrated to produce a geminal diol under atmospheric conditions. The acetaldehyde-water ice system under high pressure also converts to a geminal diol, and therefore, its stable clathrate hydrate (CH) phase, which in most systems forms at high pressures, is unknown. In the present study, we showed that acetaldehyde CH exists in ultrahigh vacuum (10-10 mbar) under cryogenic conditions (below 140 K) and continues to exist at 115 K for periods well over 1 day. Decomposition of acetaldehyde CH at 130-135 K produces water ice in its cubic crystalline form. The mechanism and kinetics involved in the process have also been studied. Reflection absorption infrared spectroscopy and temperature-programmed desorption mass spectrometry were utilized to confirm the CH formation. Our study establishes the possibility of a stable CH phase for acetaldehyde in interstellar and cometary environments.

DEVELOPMENT OF AN ANTIMICROBIAL LIPID COATING TO PREVENT INFECTIONS IN UNCEMENTED JOINT REPLACEMENTS

Preventing infections in joint replacements is a major ongoing challenge, with limited effective clinical technologies currently available for uncemented knee and hip prostheses. This research aims to develop a coating for titanium implants, consisting of a supported lipid bilayer (SLB) encapsulating an antimicrobial agent. The SLB will be robustly tethered to the titanium using self-assembled monolayers (SAMs) of octadecylphosphonic acid (ODPA). The chosen antimicrobial is Novobiocin, a coumarin-derived antibiotic known to be effective against resistant strains of Staphylococcus aureus.ODPA SAMs were deposited on TiO2-coated quartz crystal microbalance (QCM) sensors using two environmentally friendly non-polar solvents (anisole and cyclopentyl methyl ether, CPME), two concentrations of ODPA (0.5mM and 1mM) and two processing temperatures (21°C and 60°C). QCM, water contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and temperature-programmed desorption mass spectrometry (TPD-MS) were used to characterise the ODPA SAM. A SLB with encapsulated Novobiocin was subsequently developed on the surface of the ODPA SAM using fluorescent lipids and a solvent assisted method. The prototype implant surface was tested for antimicrobial activity against S. aureus.A well-ordered, uniform ODPA SAM was rapidly formed using 0.5 mM ODPA in CPME at 21°C during 10 min, as confirmed by high Sauerbrey mass (≍285-290 ng/cm2), high atomic percentage phosphorus (detected using XPS) and high water contact angles (117.6±2.5°). QCM measurements combined with fluorescence microscopy provided evidence of complete planar lipid bilayer formation on the titanium surface using a solvent assisted method. Incorporation of Novobiocin into the SLB resulted in reduced attachment and viability of S. aureus.Key parameters were established for the rapid, robust and uniform formation of an ODPA SAM on titanium (solvent, temperature and concentration). This allowed the successful formation of an antimicrobial SLB, which demonstrated potential for reducing attachment and viability of pathogens associated with joint replacement infections.

Insights into chemical reactions of graphitic carbon nitride with alkali halides

The calcination of nitrogen-rich molecules, such as melamine and urea, with inorganic salts, results in chemical modifications of graphitic carbon nitride (g-CN), a polymeric photocatalyst driven by visible-light illumination. Alkali halides are abundant and low-cost additives for that purpose and enhance photocatalytic activity. The precursors or condensed carbon nitride polymer react with the salts, even below their melting point; however, the mechanistic understanding of the reaction of g-CN with alkali halides is still unknown. In this study, we investigated reactions of melon, a linear polymer of heptazine monomers, with NaCl, employing Fourier-transform infrared (IR) spectroscopy in solid and gas phases, solid-state nuclear magnetic resonance spectroscopy, temperature-programmed desorption mass spectrometry (TPD-MS), and thermogravimetry. The reaction of melon with NaCl at 500 °C substitutes a fraction of amino groups with cyanamide moiety and deprotonates NH groups bridging heptazine monomers. The formation of NH4Cl during the calcination implied that NaCl reacted with NH3 that had evolved as a result of the condensation of melon molecules. TPD-MS and gas-phase IR confirmed the presence of NH3 as well as H2O and CO2 above 400 °C. These gaseous molecules and NaCl lead to NaHCO3 via the Solvay process reactions. NaHCO3 is decomposed into Na2CO3 at the calcination temperature. The base and gaseous H2O finally cause OH−. The resultant hydroxyl anion introduces cyanamide groups into the melon, deprotonates the NH groups, and decomposes a fraction of the polymer into isocyanic acid via the formation of sodium cyamelurate as an intermediate. The reaction mechanisms proposed in this study will promote the molecular understanding of the roles of additives in the modification of the chemical structure of g-CN photocatalysts.

Adsorption and thermal transformation of lignin model compound (ferulic acid) over HY zeolite surface studied by temperature programmed desorption mass-spectrometry, FTIR and UV–Vis spectroscopy

The adsorption of an aqueous solution of ferulic acid (FA) on protonic zeolites was studied. Three different types of zeolites and adsorption parameters (time, solid/liquid ratio, temperature and pH) were analyzed and optimized. The HY zeolite (SiO2/Al2O3 = 12) showed an adsorption percentage of 90% at 30 °C, 5 min, 10 g L−1 and pH ≤ 3. The adsorption complexes structures on the molecular adsorbates were determined by UV–Vis DRS and FTIR spectroscopies. The FA molecule interacted through phenol and carboxyl group forming monodentate and bidentate surfaces complexes (bridge and chelate). Temperature programmed desorption mass-spectrometry (TPD MS) has been used to study the decarboxylation, demethoxylation, and transalkylation processes during pyrolysis of FA surface complexes with the formation of carbon dioxide, 4-vinylguaiacol, methanol, methane, polyaromatic hydrocarbons, phenols and others.

Parameters controlling octadecyl phosphonic acid self-assembled monolayers on titanium dioxide for anti-fouling biomedical applications

Octadecylphosphonic acid (ODPA) self-assembled monolayers (SAMs) have demonstrated potential for deterring bacterial attachment to titanium, however the coating process is time consuming and uses toxic solvents. In this study, ODPA SAM quantity, quality, and structure were evaluated on titanium quartz crystal microbalance (QCM) sensors by varying solvent type (anisole or cyclopentyl methyl ether (CPME), environmentally friendly non-polar solvents); ODPA concentration (0.5 mM or 1 mM); and temperature (21 °C or 60 °C). Surfaces were characterised using QCM frequency and dissipation measurements and Sauerbrey mass calculations; X-ray photoelectron spectroscopy; water contact angle measurements; and temperature-programmed desorption mass spectrometry (TPD-MS). Anti-fouling ability was established against Staphylococcus aureus. Incubation in 0.5 mM ODPA in CPME at 21 °C rapidly formed uniform rigid ODPA SAMs as demonstrated by high Sauerbrey mass (≈285-290 ng/cm2), viscoelastic modelling, high atomic percentage surface phosphorus (1.1%) and high water contact angles (117.6 ± 2.5°), consistent across the entire sample surface. High temperatures or the use of anisole resulted in suspected multilayer formation, which reduced bacterial attachment. TPD-MS confirmed covalent bonding of ODPA SAMs on TiO2 at ≈ 110–120 °C and thermal stability below 300 °C. This study demonstrates the key parameters that control ODPA SAM formation on titanium and their future potential for biomedical applications.

Detection of the synergetic influence of chemical and microbiological factors on the properties of concrete constructions at chemical plants during the long-term service

Long-term operation of reinforced concrete structures in the conditions of chemical enterprises has a powerful negative impact on the physical and chemical properties of concrete, which leads to its destruction. The aim of this research is to determine the effect of biological and chemical corrosion on concrete structures in the workshop for the production of titanium dioxide by the sulphate method and the storage of finished products. In particular, chemical production for the synthesis of titanium dioxide by the sulfate method causes the rapid course of chemical (acid and sulfate) and microbiological (thionic bacteria and microscopic fungi) corrosion processes. These corrosion processes reinforce each other according to a synergistic principle. As a result, temperature-programmed desorption mass spectrometry (TPD MS) and scanning electron microscopy have experimentally proven the presence and spatial localization of colonies of thionic bacteria and microscopic fungi in concrete structures. Correlations between the intensity of biochemical corrosion and the depth of damage to the microstructures of concrete structures have been established. Moreover, a change in the chemical composition of concrete in the workshop for the production of titanium dioxide (increased SO2 content and reduced CO2) and the formation of gypsum crystals (CaSO4 2H2O) as a result of the dissimilation of microorganisms was established. Also, in the storage room for finished products, calcium citrate crystals and a violation of the formation of calcium carbonate are formed in the surface layers of concrete. In addition, the results of the study can be used to develop antimicrobial and anticorrosive protective agents to stop the biochemical corrosion of concrete in a chemical plant

The high catalytic activity and strong stability of 3%Fe/AC catalysts for catalytic wet peroxide oxidation of m-cresol: The role of surface functional groups and FeO particles

FeO x supported on activated carbon (AC) has been shown to be an ideal catalyst for catalytic wet peroxide oxidation (CWPO) due to its high CWPO reaction activity and stability. Although there have been some studies on the mechanism of Fe/AC catalysis in CWPO, the specific contribution of each component (surface oxygen groups and FeO x on AC) inside an Fe/AC catalyst and their corresponding reaction mechanism remain unclear, and the reaction stability of CWPO catalysts has rarely been discussed. Then the optimal CWPO catalyst in our laboratory, 3%Fe/AC, was selected. (1) By removing certain components on the AC through heat treatment, its contribution to the reaction and the corresponding reaction mechanism were investigated. With the aid of temperature-programmed desorption-mass spectrometry (TPD-MS) and the CWPO reaction, the normalized catalytic contributions of components were shown to be: 37.3% (carboxylic groups), 5.3% (anhydride), 19.3% (ether/hydroxyl), −71.4% (carbonyl groups) and 100% (FeO x ), respectively. DFT calculation and EPR analysis confirmed that carboxylic groups and Fe 2 O 3 are able to activate the H 2 O 2 to generate ·OH. (2) The catalysts at were characterized at different reaction times (0 h, 450 h, 900 h, 1350 h, and 1800 h) by TPD-MS and Mössbauer spectroscopy. Results suggested that the number of carboxylic goups gradually increased and the size of paramagnetic Fe 2 O 3 particle crystallites gradually increased as the reactions progressed. The occurrence of strong interactions between metal oxides and AC was also confirmed. Due to these effects, the strong stability of 3%Fe/AC was further improved. Therefore, the reasons for the high activity and strong stability of 3%Fe/AC in CWPO were clearly shown. We believe that this work provides an idea of the removal of cresols from wastewater into the introduction to show the potential applications of CWPO.

Development of deconvolution analysis on the temperature programmed desorption mass spectrometry

In the temperature programmed desorption-mass spectrometry (TPD-MS) experiments, the time lag and broadening of the gas evolved from the sample until it is detected by the MS detector can be a problem. The deconvolution method was successfully applied to TPD-MS. The pulse injection of N2, 1-butene, CO2, and H2O gasses in the TPD-MS system showed the same MS intensity-time response. This result suggests the MS signal can be used as an impulse response function of deconvolution analysis. The present TPD-MS method was applied to evaluate the dehydration from zeolites during heating. The shape of differential thermogravimetry (DTG) curves was in good agreement with deconvolved TPD-MS curves. The signal-to-noise ratio of TPD-MS is higher than that of DTG. The present method can be applicable for TG-MS or Fast scanning calorimetry (FSC)-MS in the upcoming study.

Catalytic Pyrolysis of Lignin Model Compound (Ferulic Acid) over Alumina: Surface Complexes, Kinetics, and Mechanisms

Studies of the thermochemical properties of the important model compound of lignin-ferulic acid (FA) and its surface complexes are substantial for developing technologies for catalytic pyrolysis of renewable biomass into biofuels and lignin-derived chemicals as well as for bio-oil upgrading. In this work, the catalytic pyrolysis of ferulic acid over alumina was studied by temperature-programmed desorption mass spectrometry (TPD MS), in situ FT-IR spectroscopy, thermogravimetric analysis, and DFT calculations. We established that both the carboxyl group and the active groups (HO and CH3O) of the aromatic ring interact with the alumina surface. We calculated the kinetic parameters of formation of the main products of catalytic pyrolysis: 4-vinylguaiacol, guaiacol, hydroxybenzene, benzene, toluene, cresol, naphthalene, and PACs. Possible methods of their forming from the related surface complexes of FA are suggested.

Identifying UiO-67 Metal-Organic Framework Defects and Binding Sites through Ammonia Adsorption.

Ammonia is a widely used toxic industrial chemical that can cause severe respiratory ailments. Therefore, understanding and developing materials for its efficient capture and controlled release is necessary. One such class of materials is 3D porous metal-organic frameworks (MOFs) with exceptional surface areas and robust structures, ideal for gas storage/transport applications. Herein, interactions between ammonia and UiO-67-X (X: H, NH2 , CH3 ) zirconium MOFs were studied under cryogenic, ultrahigh vacuum (UHV) conditions using temperature-programmed desorption mass spectrometry (TPD-MS) and in-situ temperature-programmed infrared (TP-IR) spectroscopy. Ammonia was observed to interact with μ3 -OH groups present on the secondary building unit of UiO-67-X MOFs via hydrogen bonding. TP-IR studies revealed that under cryogenic UHV conditions, UiO-67-X MOFs are stable towards ammonia sorption. Interestingly, an increase in the intensity of the C-H stretching mode of the MOF linkers was detected upon ammonia exposure, attributed to NH-π interactions with linkers. These same binding interactions were observed in grand canonical Monte Carlo simulations. Based on TPD-MS, binding strength of ammonia to three MOFs was determined to be approximately 60 kJ mol-1 , suggesting physisorption of ammonia to UiO-67-X. In addition, missing linker defect sites, consisting of H2 O coordinated to Zr4+ sites, were detected through the formation of nNH3 ⋅H2 O clusters, characterized through in-situ IR spectroscopy. Structures consistent with these assignments were identified through density functional theory calculations. Tracking these bands through adsorption on thermally activated MOFs gave insight into the dehydroxylation process of UiO-67 MOFs. This highlights an advantage of using NH3 for the structural analysis of MOFs and developing an understanding of interactions between ammonia and UiO-67-X zirconium MOFs, while also providing directions for the development of stable materials for efficient toxic gas sorption.

Decarboxylation of p-Coumaric Acid during Pyrolysis on the Nanoceria Surface

Temperature-programmed desorption mass spectrometry (TPD MS) was used to study the pyrolysis of p-coumaric acid (pCmA) on the nanoceria surface. The interaction of pCmA with the CeO2 surface was investigated by FT-IR spectroscopy. The obtained data indicated the formation on the nanoceria surface of bidentate carboxylate complexes with chelate (Δν = 62 cm−1) and bridge structure (Δν = 146 cm−1). The thermal decomposition of pCmA over nanoceria occurred in several stages, mainly by decarboxylation. The main decomposition product is 4-vinylphenol (m/z 120). The obtained data can be useful for studying the mechanisms of catalytic thermal transformations of lignin-containing raw materials using catalysts containing cerium oxide and the development of effective technologies for the isolation of pCmA from lignin.

Self-Heating Mechanism of All-Solid-State Battery with Sulfide Electrolyte

All-solid-state batteries (ASSBs) are expected to have less safety concern than Lithium-ion batteries with organic liquid electrolyte (LIBs) because flammable liquid electrolytes are not used in ASSBs. The thermal behaviors in LIBs have widely discussed in many literatures1. However, thermal behaviors of ASSBs have not investigated much.In this study, to clarify the self-heating phenomenon of our prototype ASSB with Argyrodite-type solid electrolyte we have performed calorimetric studies and gas analyses. In the calorimetric measurement, an accelerated rate calorimetry (ARC) was used to compare the starting temperature of self-heating in ASSB to that in LIB. It was found that the self-heating of ASSB takes place at 200-300ºC which was significantly higher than that in LIB.To identify the endothermic and exothermic peaks in the calorimetric profile and to estimate the amount of heat generation in ASSB, a Calvet-type calorimeter (C600) and a differential scanning calorimeter (DSC) were used with a heating rate of 1 ℃/min under Ar atmosphere for a full cell and electrode layers of the ASSB, respectively. The exothermic peaks at 200- 300℃ for charged ASSB (at ca. 4.1 V) mostly corresponded to those for the cathode layer which was extracted from the charged ASSB. The crystal structure change of the cathode layer charged at ca. 4.1 V associated with temperature change was analyzed by X-ray diffraction (XRD) to understand the reaction mechanism. The XRD peaks for the active material and the solid electrolyte in the cathode layer were disappeared at 200-300ºC. It was suggested that the heat generation at 200- 300ºC were mainly caused by the reaction between the cathode active material and the solid electrolyte.We also analyzed the evolved gas during the heating of ASSB using a temperature-programmed desorption-mass spectrometry (TPD-MS). The detailed mechanism will be discussed on-site.AcknowledgmentsThis study was carried out in SOLiD-EV project supported by NEDO (New Energy and Industrial Technology Development Organization).References Xuning Feng, Minggao Ouyang, Xiang Liu, Languang Lu, Yong Xi, Xiangming He, Energy Storage Materials 10 (2018) 246-267.