ABSTRACT
We combine in situ laser spectroscopy, quantum chemistry, and kinetic calculations to study the reaction of a singlet oxygen atom with dimethyl ether. Infrared laser absorption spectroscopy and Faraday rotation spectroscopy are used for the detection and quantification of the reaction products OH, H2O, HO2, and CH2O on submillisecond time scales. Fitting temporal profiles of products with simulations using an in-house reaction mechanism allows product branching to be quantified at 30, 60, and 150 Torr. The experimentally determined product branching agrees well with master equation calculations based on electronic structure data and transition state theory. The calculations demonstrate that the dimethyl peroxide (CH3OOCH3) generated via O-insertion into the C-O bond undergoes subsequent dissociation to CH3O + CH3O through energetically favored reactions without an intrinsic barrier. This O-insertion mechanism can be important for understanding the fate of biofuels leaking into the atmosphere and for plasma-based biofuel processing technologies.
ABSTRACT
Manipulating surface charge, electric field, and plasma afterglow in a non-equilibrium plasma is critical to control plasma-surface interaction for plasma catalysis and manufacturing. Here, we show enhancements of surface charge, electric field during breakdown, and afterglow by ferroelectric barrier discharge. The results show that the ferroelectrics manifest spontaneous electric polarization to increase the surface charge by two orders of magnitude compared to discharge with an alumina barrier. Time-resolved in-situ electric field measurements reveal that the fast polarization of ferroelectrics enhances the electric field during the breakdown in streamer discharge and doubles the electric field compared to the dielectric barrier discharge. Moreover, due to the existence of surface charge, the ferroelectric electrode extends the afterglow time and makes discharge sustained longer when alternating the external electric field polarity. The present results show that ferroelectric barrier discharge offers a promising technique to tune plasma properties for efficient plasma catalysis and electrified manufacturing.
ABSTRACT
Machine learning (ML) provides a great opportunity for the construction of models with improved accuracy in classical molecular dynamics (MD). However, the accuracy of a ML trained model is limited by the quality and quantity of the training data. Generating large sets of accurate ab initio training data can require significant computational resources. Furthermore, inconsistent or incompatible data with different accuracies obtained using different methods may lead to biased or unreliable ML models that do not accurately represent the underlying physics. Recently, transfer learning showed its potential for avoiding these problems as well as for improving the accuracy, efficiency, and generalization of ML models using multifidelity data. In this work, ab initio trained ML-based MD (aML-MD) models are developed through transfer learning using DFT and multireference data from multiple sources with varying accuracy within the Deep Potential MD framework. The accuracy of the force field is demonstrated by calculating rate constants for the H + HO2 â H2 + 3O2 reaction using quasi-classical trajectories. We show that the aML-MD model with transfer learning can accurately predict the rate constants while reducing the computational cost by more than five times compared to the use of more expensive quantum chemistry training data sets. Hence, the aML-MD model with transfer learning shows great potential in using multifidelity data to reduce the computational cost involved in generating the training set for these potentials.
ABSTRACT
Non-equilibrium plasma has been found to have a synergistic effect on catalytic synthesis of NH3. The non-equilibrium plasma and catalyst surface together could affect NH3 synthesis through several mechanisms. Charging of the catalyst surface in the presence of non-equilibrium plasma is one such mechanism. We employed density functional theory (DFT) calculations to understand the effect of surface charge on surface reactivity of γ-Al2O3 supported single metal atom catalysts and a metal cluster. We investigated the effect of surface charge on adsorption energies of common adsorbates involved in NH3 synthesis. It is found that adsorption energy of N, N2, H, H2, NH and NH2 on metal atoms increases by up to â¼1.2 eV, whereas NH3 desorption is increased by up to 0.45 eV upon surface charging. The present results provide a new mechanism of plasma enhanced catalysis potentially explaining why Ni, Pt and Co have better catalytic performance compared to Ru and Fe in ammonia plasma catalysis. Furthermore, we found that the correlations between adsorption energies of adsorbates change significantly with surface charging. These findings suggest that surface charging might play an important role in plasma synthesis of NH3.
ABSTRACT
Ammonia (NH3) is an attractive low-carbon fuel and hydrogen carrier. However, losses and inefficiencies across the value chain could result in reactive nitrogen emissions (NH3, NOx, and N2O), negatively impacting air quality, the environment, human health, and climate. A relatively robust ammonia economy (30 EJ/y) could perturb the global nitrogen cycle by up to 65 Mt/y with a 5% nitrogen loss rate, equivalent to 50% of the current global perturbation caused by fertilizers. Moreover, the emission rate of nitrous oxide (N2O), a potent greenhouse gas and ozone-depleting molecule, determines whether ammonia combustion has a greenhouse footprint comparable to renewable energy sources or higher than coal (100 to 1,400 gCO2e/kWh). The success of the ammonia economy hence hinges on adopting optimal practices and technologies that minimize reactive nitrogen emissions. We discuss how this constraint should be included in the ongoing broad engineering research to reduce environmental concerns and prevent the lock-in of high-leakage practices.
ABSTRACT
Plasmas can generate ultra-high-temperature reactive environments that can be used for the synthesis and processing of a wide range of materials1,2. However, the limited volume, instability and non-uniformity of plasmas have made it challenging to scalably manufacture bulk, high-temperature materials3-8. Here we present a plasma set-up consisting of a pair of carbon-fibre-tip-enhanced electrodes that enable the generation of a uniform, ultra-high temperature and stable plasma (up to 8,000 K) at atmospheric pressure using a combination of vertically oriented long and short carbon fibres. The long carbon fibres initiate the plasma by micro-spark discharge at a low breakdown voltage, whereas the short carbon fibres coalesce the discharge into a volumetric and stable ultra-high-temperature plasma. As a proof of concept, we used this process to synthesize various extreme materials in seconds, including ultra-high-temperature ceramics (for example, hafnium carbonitride) and refractory metal alloys. Moreover, the carbon-fibre electrodes are highly flexible and can be shaped for various syntheses. This simple and practical plasma technology may help overcome the challenges in high-temperature synthesis and enable large-scale electrified plasma manufacturing powered by renewable electricity.
ABSTRACT
We present spatially enhanced electric-field-induced second-harmonic (SEEFISH) generation with a chirped femtosecond beam for measurements of electric field in mesoscale confined geometries subject to destructive spurious second-harmonic generation (SHG). Spurious SHG is shown to interfere with the measured E-FISH signal coherently, and thus simple background subtraction is not sufficient for single-beam E-FISH approaches, especially in a confined system with a large surface-to-volume ratio. The results show that a chirped femtosecond beam is effective in preventing higher-order mixing and white light generation in windows near the beam focal point which further contaminates the SEEFISH signal. The successful measurements of electric field of a nanosecond dielectric barrier discharge in a test cell demonstrated that spurious SHG detected with a congruent traditional E-FISH approach can be eliminated using the SEEFISH approach.
ABSTRACT
Depolymerization is a promising strategy for recycling waste plastic into constituent monomers for subsequent repolymerization1. However, many commodity plastics cannot be selectively depolymerized using conventional thermochemical approaches, as it is difficult to control the reaction progress and pathway. Although catalysts can improve the selectivity, they are susceptible to performance degradation2. Here we present a catalyst-free, far-from-equilibrium thermochemical depolymerization method that can generate monomers from commodity plastics (polypropylene (PP) and poly(ethylene terephthalate) (PET)) by means of pyrolysis. This selective depolymerization process is realized by two features: (1) a spatial temperature gradient and (2) a temporal heating profile. The spatial temperature gradient is achieved using a bilayer structure of porous carbon felt, in which the top electrically heated layer generates and conducts heat down to the underlying reactor layer and plastic. The resulting temperature gradient promotes continuous melting, wicking, vaporization and reaction of the plastic as it encounters the increasing temperature traversing the bilayer, enabling a high degree of depolymerization. Meanwhile, pulsing the electrical current through the top heater layer generates a temporal heating profile that features periodic high peak temperatures (for example, about 600 °C) to enable depolymerization, yet the transient heating duration (for example, 0.11 s) can suppress unwanted side reactions. Using this approach, we depolymerized PP and PET to their monomers with yields of about 36% and about 43%, respectively. Overall, this electrified spatiotemporal heating (STH) approach potentially offers a solution to the global plastic waste problem.
ABSTRACT
The chemical reaction network of low-temperature plasma-assisted oxidation of methane (CH4) and ethylene (C2H4) with nickel oxide (NiO) was investigated in a heated plasma reactor through time-dependent species measurements by electron-ionization molecular beam mass spectrometry (EI-MBMS). Methane (ethylene) oxidation by NiO was explored in temperature ranges from 300-700 °C (300-500 °C) and 300-800 °C (300-600 °C) for the plasma and nonplasma conditions. Significant enhancement of methane oxidation was observed with plasma between 400 and 500 °C, where no oxidation was observed under nonplasma conditions. For the oxidation of methane at higher temperatures, three different oxidation stages were observed: (I) a period of complete oxidation, (II) a period of incomplete CO oxidation, and (III) a period of carbon buildup. For the C2H4 experiments, and unlike the CH4 experiments, the plasma resulted in a significant amount of new intermediate oxygenated species, such as CH2O, CH3OH, C2H4O, and C2H6O. Carbon deposits were observed under both methane and ethylene conditions and verified by X-ray photoelectron spectroscopy (XPS). ReaxFF (reactive force field) simulations were performed for the oxidation of CH4 and C2H4 in a nonplasma environment. The simulated intermediates and products largely agree with the species measured in the experiments, though the predicted intermediate oxygenated species such as CH2O and C2H6O were not observed in experiments under nonplasma conditions. A reaction pathway analysis for CH4 and C2H4 reacting with NiO was created based on the observed species from the MBMS spectra along with ReaxFF simulations.
ABSTRACT
Growing demand for low-emission and high-efficiency propulsion systems spurs interest in understanding low-temperature and ultra-high-pressure combustion of alternative biofuels like diethyl ether (DEE). In this study, DEE oxidation experiments are performed at 10 and 100 atm, over a temperature range of 400-900 K, at fuel-lean, stoichiometric, and fuel-rich conditions by using a supercritical pressure jet-stirred reactor (SP-JSR). The experimental data show that DEE is very reactive and exhibits an uncommon low-temperature oxidation behavior with two negative temperature coefficient (NTC) zones. The first NTC zone is mainly governed by the competition reactions of QOOH + O2 = O2QOOH and QOOH = 2CH3CHO + OH, while the second one is mainly governed by the competition reactions of R + O2 = RO2 and the ß-scission reaction of fuel radical R. It is shown that the increase of pressure stabilizes RO2 and promotes HO2 chemistry. Moreover, the branching ratios of ß-scission reactions of R and QOOH decrease. As a result, it is shown that, with the increase of pressure, both NTC zones become weaker at 100 atm. In addition, the intermediate-temperature oxidation is shifted considerably to lower temperature at 100 atm. The existing DEE model in the literature well predicts the experimental data at low temperature; however, it underpredicts the fuel consumptions at intermediate temperature. The H2/O2 subset in the existing DEE model is updated in this study based on the Princeton updated HP-Mech, including the singlet/triplet competing channels of HO2 related reactions. The updated model improves the overall predictability of key species, especially at intermediate temperature.
ABSTRACT
In many low-temperature plasmas (LTPs), the OH radical and temperature represent key properties of plasma reactivity. However, OH and temperature measurements in weakly ionized LTPs are challenging, due to the low concentration and short lifetime of OH and the abrupt temperature rise caused by fast gas heating. To address such issues, this Letter combined cavity-enhanced absorption spectroscopy (CEAS) with femtosecond (fs) pulses to enable sensitive single-shot broadband measurements of OH and temperature with a time resolution of â¼180 ns in LTPs. Such a combination leveraged several benefits. With the appropriately designed cavity, an absorption gain of â¼66 was achieved, enhancing the actual OH detection limit by â¼55× to the 1011 cm-3 level (sub-ppm in this work) compared with single-pass absorption. Single-shot measurements were enabled while maintaining a time resolution of â¼180â ns, sufficiently short for detecting OH with a lifetime of â¼100 µs. With the broadband fs laser, â¼34,000 cavity modes were matched with â¼95 modes matched on each CCD pixel bandwidth, such that fs-CEAS became immune to the laser-cavity coupling noise and highly robust across the entire spectral range. Also, the broadband fs laser allowed simultaneous sensing of many absorption features to enable simultaneous multi-parameter measurements with enhanced accuracies.
ABSTRACT
Conventional thermochemical syntheses by continuous heating under near-equilibrium conditions face critical challenges in improving the synthesis rate, selectivity, catalyst stability and energy efficiency, owing to the lack of temporal control over the reaction temperature and time, and thus the reaction pathways1-3. As an alternative, we present a non-equilibrium, continuous synthesis technique that uses pulsed heating and quenching (for example, 0.02 s on, 1.08 s off) using a programmable electric current to rapidly switch the reaction between high (for example, up to 2,400 K) and low temperatures. The rapid quenching ensures high selectivity and good catalyst stability, as well as lowers the average temperature to reduce the energy cost. Using CH4 pyrolysis as a model reaction, our programmable heating and quenching technique leads to high selectivity to value-added C2 products (>75% versus <35% by the conventional non-catalytic method and versus <60% by most conventional methods using optimized catalysts). Our technique can be extended to a range of thermochemical reactions, such as NH3 synthesis, for which we achieve a stable and high synthesis rate of about 6,000 µmol gFe-1 h-1 at ambient pressure for >100 h using a non-optimized catalyst. This study establishes a new model towards highly efficient non-equilibrium thermochemical synthesis.
ABSTRACT
We report the development of a simple and sensitive two-beam hybrid femtosecond/picosecond pure rotational coherent anti-Stokes Raman scattering (fs/ps CARS) method to simultaneously measure the rotational and vibrational temperatures of diatomic molecules. Rotation-vibration non-equilibrium plays a key role in the chemistry and thermalization in low-temperature plasmas as well as thermal loading of hypersonic vehicles. This approach uses time-domain interferences between ground state and vibrationally excited N2 molecules to intentionally induce coherence beating that leads to apparent non-Boltzmann distributions in the pure rotational spectra. These distortions enable simultaneous inference of both the rotational and vibrational temperatures. Coherence beating effects were observed in single-shot fs/ps CARS measurements of a 75 Torr N2 DC glow discharge and were successfully modeled for rotational and vibrational temperature extraction. We show that this method can be more sensitive than a pure rotational fs/ps CARS approach using a spectrally narrow probe pulse. Lastly, we experimentally measured the beat frequencies via Fourier transform of the time-domain response and obtained excellent agreement with the model.
ABSTRACT
Faraday rotation spectroscopy (FRS) employs the Faraday effect to detect Zeeman splitting in the presence of a magnetic field. In this article, we present system design and implementation of radical sensing in a photolysis reactor using FRS. High sensitivity (100 ppb) and time resolved in situ HO2 detection is enabled with a digitally balanced acquisition scheme. Specific advantages of employing FRS for sensing in such dynamic environments are examined and rigorously compared to the more established conventional laser absorption spectroscopy (LAS). Experimental results show that FRS enables HO2 detection when LAS is deficient, and FRS compares favorably in terms of precision when LAS is applicable. The immunity of FRS to spectral interferences such as absorption of hydrocarbons and other diamagnetic species absorption and optical fringing are highlighted in comparison to LAS.
ABSTRACT
Diethyl carbonate (DEC) oxidation with different levels of O3 addition was performed in an atmospheric laminar flow reactor from 400 to 850 K. Experimental results showed that, without O3 addition, the oxidation of DEC began from 650 K with no low-temperature reactivity, while with O3 addition the low-temperature chemistry of DEC was observed from 450 K. A DEC/O3 kinetic model was developed, and the model predictions agreed with the experimental data reasonably well with a slight overprediction of DEC oxidation between 550 and 750 K. The low-temperature chemistry of DEC with O3 addition was described in the reaction pathway of DEC. It was found that O3 assisted the low-temperature oxidation of DEC mainly through the production of the active O: atom instead of the direct reaction with the fuel molecule. The present work indicated that the Li-ion battery degradation at 400-500 K might result from the low-temperature chemistry of DEC with active oxygen supplies from the cathode metal oxide materials or from singlet O2 during the battery discharge process. This article used O3 to mimic the oxidizing environment in the Li-ion battery by providing active atomic oxygen. It provided insights into the chemically sensitized gas-phase low-temperature chemistry of DEC and explained the mechanism of battery degradation involving the low-temperature oxidation at the electrolyte solvent and the cathode interface from 400 to 500 K.
ABSTRACT
The accelerating chemical effect of ozone addition on the oxidation chemistry of methyl hexanoate [CH3(CH2)4C(âO)OCH3] was investigated over a temperature range from 460 to 940 K. Using an externally heated jet-stirred reactor at p = 700 Torr (residence time τ = 1.3 s, stoichiometry φ = 0.5, 80% argon dilution), we explored the relevant chemical pathways by employing molecular-beam mass spectrometry with electron and single-photon ionization to trace the temperature dependencies of key intermediates, including many hydroperoxides. In the absence of ozone, reactivity is observed in the so-called low-temperature chemistry (LTC) regime between 550 and 700 K, which is governed by hydroperoxides formed from sequential O2 addition and isomerization reactions. At temperatures above 700 K, we observed the negative temperature coefficient (NTC) regime, in which the reactivity decreases with increasing temperatures, until near 800 K, where the reactivity increases again. Upon addition of ozone (1000 ppm), the overall reactivity of the system is dramatically changed due to the time scale of ozone decomposition in comparison to fuel oxidation time scales of the mixtures at different temperatures. While the LTC regime seems to be only slightly affected by the addition of ozone with respect to the identity and quantity of the observed intermediates, we observed an increased reactivity in the intermediate NTC temperature range. Furthermore, we observed experimental evidence for an additional oxidation regime in the range near 500 K, herein referred to as the extreme low-temperature chemistry (ELTC) regime. Experimental evidence and theoretical rate constant calculations indicate that this ELTC regime is likely to be initiated by H abstraction from methyl hexanoate via O atoms, which originate from thermal O3 decomposition. The theoretical calculations show that the rate constants for methyl ester initiation via abstraction by O atoms increase dramatically with the size of the methyl ester, suggesting that ELTC is likely not important for the smaller methyl esters. Experimental evidence is provided indicating that, similar to the LTC regime, the chemistry in the ELTC regime is dominated by hydroperoxide chemistry. However, mass spectra recorded at various reactor temperatures and at different photon energies provide experimental evidence of some differences in chemical species between the ELTC and the LTC temperature ranges.
ABSTRACT
We present one-dimensional (1-D) imaging of rotation-vibration non-equilibrium measured by two-beam pure rotational hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps CARS). Simultaneous measurements of the spatial distribution of molecular rotation-vibration non-equilibrium are critical for understanding molecular energy transfer in low temperature plasmas and hypersonic flows. However, non-equilibrium CARS thermometry until now was limited to point measurements. The red shift of rotational energy levels by vibrational excitation was used to determine the rotational and vibrational temperatures from 1-D images of the pure rotational spectrum. Vibrational temperatures up to 5500 K were detected in a CH4/N2 nanosecond-pulsed pin-to-pin plasma within 2 mm near the cathode. This approach enables study of non-equilibrium systems with 40 µm spatial resolution.
ABSTRACT
Development of earth-abundant electrocatalysts for hydrogen evolution and oxidation reactions in strong acids represents a great challenge for developing high efficiency, durable, and cost effective electrolyzers and fuel cells. We report herein that hafnium oxyhydroxide with incorporated nitrogen by treatment using an atmospheric nitrogen plasma demonstrates high catalytic activity and stability for both hydrogen evolution and oxidation reactions in strong acidic media using earth-abundant materials. The observed properties are especially important for unitized regenerative fuel cells using polymer electrolyte membranes. Our results indicate that nitrogen-modified hafnium oxyhydroxide could be a true alternative for platinum as an active and stable electrocatalyst, and furthermore that nitrogen plasma treatment may be useful in activating other non-conductive materials to form new active electrocatalysts.
ABSTRACT
The reaction network of the simplest Criegee intermediate (CI) CH2OO has been studied experimentally during the ozonolysis of ethylene. The results provide valuable information about plasma- and ozone-assisted combustion processes and atmospheric aerosol formation. A network of CI reactions was identified, which can be described best by the sequential addition of CI with ethylene, water, formic acid, and other molecules containing hydroxy, aldehyde, and hydroperoxy functional groups. Species resulting from as many as four sequential CI addition reactions were observed, and these species are highly oxygenated oligomers that are known components of secondary organic aerosols in the atmosphere. Insights into these reaction pathways were obtained from a near-atmospheric pressure jet-stirred reactor coupled to a high-resolution molecular-beam mass spectrometer. The mass spectrometer employs single-photon ionization with synchrotron-generated, tunable vacuum-ultraviolet radiation to minimize fragmentation via near-threshold ionization and to observe mass-selected photoionization efficiency (PIE) curves. Species identification is supported by comparison of the mass-selected, experimentally observed photo-ionization thresholds with theoretical calculations for the ionization energies. A variety of multi-functional peroxide species are identified, including hydroxymethyl hydroperoxide (HOCH2OOH), hydroperoxymethyl formate (HOOCH2OCHO), methoxymethyl hydroperoxide (CH3OCH2OOH), ethoxymethyl hydroperoxide (C2H5OCH2OOH), 2-hydroxyethyl hydroperoxide (HOC2H4OOH), dihydroperoxy methane (HOOCH2OOH), and 1-hydroperoxypropan-2-one [CH3C([double bond, length as m-dash]O)CH2OOH]. A semi-quantitative analysis of the signal intensities as a function of successive CI additions and temperature provides mechanistic insights and valuable information for future modeling work of the associated energy conversion processes and atmospheric chemistry. This work provides further evidence that the CI is a key intermediate in the formation of oligomeric species via the formation of hydroperoxides.
ABSTRACT
Ethylene oxidation initiated by ozone addition (ozonolysis) is carried out in a jet-stirred reactor from 300 to 1000 K to explore the kinetic pathways relevant to low-temperature oxidation. The temperature dependencies of species' mole fractions are quantified using molecular-beam mass spectrometry with electron ionization and single-photon ionization employing tunable synchrotron-generated vacuum-ultraviolet radiation. Upon ozone addition, significant ethylene oxidation is found in the low-temperature regime from 300 to 600 K. Here, we provide new insights into the ethylene ozonolysis reaction network via identification and quantification of previously elusive intermediates by combining experimental photoionization energy scans and ab initio threshold energy calculations for isomer identification. Specifically, the C2H4 + O3 adduct C2H4O3 is identified as a keto-hydroperoxide (hydroperoxy-acetaldehyde, HOOCH2CHO) based on the calculated and experimentally observed ionization energy of 9.80 (±0.05) eV. Quantification using a photoionization cross-section of 5 Mb at 10.5 eV results in 5 ppm at atmospheric conditions, which decreases monotonically with temperature until 550 K. Other hydroperoxide species that contribute in larger amounts to the low-temperature oxidation of C2H4, like H2O2, CH3OOH, and C2H5OOH, are identified and their temperature-dependent mole fractions are reported. The experimental evidence for additional oxygenated species such as methanol, ketene, acetaldehyde, and hydroxy-acetaldehyde suggest multiple active oxidation routes. This experimental investigation closes the gap between ozonolysis at atmospheric and elevated temperature conditions and provides a database for future modeling.