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Yan, Chao

Publications and source records attributed to Yan, Chao.

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Global variability in atmospheric new particle formation mechanisms

A key challenge in aerosol pollution studies and climate change assessment is to understand how atmospheric aerosol particles are initially formed. Although new particle formation (NPF) mechanisms have been described at specific sites, in most regions, such mechanisms remain uncertain to a large extent because of the limited ability of atmospheric models to simulate critical NPF processes. Here we synthesize molecular-level experiments to develop comprehensive representations of 11 NPF mechanisms and the complex chemical transformation of precursor gases in a fully coupled global climate model. Combined simulations and observations show that the dominant NPF mechanisms are distinct worldwide and vary with region and altitude. Previously neglected or underrepresented mechanisms involving organics, amines, iodine oxoacids and HNO 3 probably dominate NPF in most regions with high concentrations of aerosols or large aerosol radiative forcing; such regions include oceanic and human-polluted continental boundary layers, as well as the upper troposphere over rainforests and Asian monsoon regions. These underrepresented mechanisms also play notable roles in other areas, such as the upper troposphere of the Pacific and Atlantic oceans. Accordingly, NPF accounts for different fractions (10–80%) of the nuclei on which cloud forms at 0.5% supersaturation over various regions in the lower troposphere. The comprehensive simulation of global NPF mechanisms can help improve estimation and source attribution of the climate effects of aerosols.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Kinetics and Mechanism of the Singlet Oxygen Atom Reaction with Dimethyl Ether

Here, 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, H 2 O, HO 2 , and CH 2 O 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 (CH 3 OOCH 3 ) generated via O-insertion into the C–O bond undergoes subsequent dissociation to CH 3 O + CH 3 O 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

The Significant Role of New Particle Composition and Morphology on the HNO 3 -Driven Growth of Particles down to Sub-10 nm

New particle formation and growth greatly influence air quality and the global climate. Recent CERN Cosmics Leaving OUtdoor Droplets (CLOUD) chamber experiments proposed that in cold urban atmospheres with highly supersaturated HNO 3 and NH 3 , newly formed sub-10 nm nanoparticles can grow rapidly (up to 1000 nm h –1 ). Here, we present direct observational evidence that in winter Beijing with persistent highly supersaturated HNO 3 and NH 3 , nitrate contributed less than ~14% of the 8–40 nm nanoparticle composition, and overall growth rates were only ~0.8–5 nm h –1 . To explain the observed growth rates and particulate nitrate fraction, the effective mass accommodation coefficient of HNO 3 (α HNO 3 ) on the nanoparticles in urban Beijing needs to be 2–4 orders of magnitude lower than those in the CLOUD chamber. We propose that the inefficient uptake of HNO 3 on nanoparticles is mainly due to the much higher particulate organic fraction and lower relative humidity in urban Beijing. To quantitatively reproduce the observed growth, we show that an inhomogeneous “inorganic core–organic shell” nanoparticle morphology might exist for nanoparticles in Beijing. Finally, this study emphasized that growth for nanoparticles down to sub-10 nm was largely influenced by their composition, which was previously ignored and should be considered in future studies on nanoparticle growth.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Progress and Application of Halide Perovskite Materials for Solar Cells and Light Emitting Devices

Halide perovskite materials have attracted worldwide attention in the photovoltaic area due to the rapid improvement in efficiency, from less than 4% in 2009 to 26.1% in 2023 with only a nanometer lever photo-active layer. Meanwhile, this nova star found applications in many other areas, such as light emitting, sensor, etc. This review started with the fundamentals of physics and chemistry behind the excellent performance of halide perovskite materials for photovoltaic/light emitting and the methods for preparing them. Then, it described the basic principles for solar cells and light emitting devices. It summarized the strategies including nanotechnology to improve the performance and the application of halide perovskite materials in these two areas: from structure–property relation to how each component in the devices affects the overall performance. Moreover, this review listed the challenges for the future applications of halide perovskite materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Regime-Dependence of Nocturnal Nitrate Formation via N 2 O 5 Hydrolysis and Its Implication for Mitigating Nitrate Pollution

The heterogeneous hydrolysis of dinitrogen pentoxide (N 2 O 5 ) is an important pathway in nitrate formation; however, its formation rate and relative contribution to total particulate nitrate (pNO 3 - ) are highly variable. Here we report that nocturnal pNO 3 - formation via N 2 O 5 hydrolysis is dependent on the regime defined by the ratio of NO 2 to O 3 . Nocturnal pNO 3 - formation via N 2 O 5 hydrolysis is suppressed in an O 3 -limited regime but enhanced in a NO 2 -limited regime. The results have crucial implications for effective control of nitrate pollution in the future. An exclusive decrease in NO 2 will decrease nocturnal pNO 3 - formation in a NO 2 -limited regime but may be less effective or even increase nocturnal pNO 3 - formation in an O 3 -limited regime.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Studies of Low and Intermediate Temperature Oxidation of Propane up to 100 Atm in a Supercritical-Pressure Jet-Stirred Reactor

Here, the low and intermediate temperature oxidation of propane has been investigated by using a novel supercritical pressure jet stirred reactor (SP-JSR) with and without 20% CO 2 additions at fuel lean and rich conditions at 10 and 100 atm and 500–1000 K. The mole fractions of C 3 H 8 , O 2 , CO, CO 2 , CH 2 O, C 2 H 4 , CH 3 CHO, and C 3 H 6 were quantified by using a micro-gas chromatograph (µ-GC). The experiment showed that different from that of 10 atm, at 100 atm only a weak negative temperature coefficient (NTC) behavior was observed because of the significant shift of the intermediate temperature HO 2 chemistry to lower temperature. In addition, at 100 atm, existing models in literatures could successfully capture the onset temperatures of the low and intermediate chemistry, while under-predict the fuel oxidation quantitatively and fail to capture the NTC behavior between 650 and 780 K at both fuel lean and rich conditions. Similar discrepancy was observed in studies of n-butane and dimethyl ether (DME) oxidations in literatures, implying that there existed large uncertainties in hierarchy model development of fuels with low temperature chemistries at extremely high pressures. Reaction pathways and sensitivity analyses showed that RO 2 competing reactions through (P1) RO 2 = QOOH, (P2) RO 2 = C 3 H 6 + HO 2 , (P3) RO 2 + CH 2 O/HO 2 = RO 2 H + HCO / O 2 dominated the low and intermediate temperature chemistries, followed by HO 2 / H 2 O 2 chemistry at 100 atm, which differed from the dominant pathway through QOOH consumption reactions at lower pressures. Especially, P3 is a new pathway of RO 2 consumption at high pressures, which was not observed in importance at low pressures. Special attention should be paid to the accurate computations of n-C 3 H 7 O 2 / i-C 3 H 7 O 2 + CH 2 O and n-C 3 H 7 O 2 / i-C 3 H 7 O 2 + in the P3 pathway and n-C 3 H 7 O 2 / i-C 3 H 7 O 2 decomposition reactions in the P2 pathway at high pressures.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2023

Kinetics and extinction of non-premixed cool and warm flames of dimethyl ether at elevated pressure

Here, the growing demand of clean and efficient propulsion and energy systems has sparked an interest in understanding low-temperature combustion at high pressure. Cool flame transition and extinction limits as well as oxygen concentration dependence at elevated pressures provide insights of the low-temperature and high-pressure fuel reactivity. A new experimental high-pressure counterflow burner platform was designed and developed to achieve the studies of high-pressure cool flames. Dimethyl ether (DME) was chosen to study its non-premixed cool flame in high-pressure counterflow burner at pressure up to 5 atm, perhaps for the first time. This paper investigates the effects of pressure on cool flame structure, extinction and transition limits, and oxygen concentration dependence as well as ozone assisted warm flames of DME in experiments and numerical simulations. The results show that the reignition transition from cool flame to hot flame occurs either with the decrease of the strain rate at a given fuel concentration and pressure or with the increase of fuel mole fraction or pressure at a given strain rate. Furthermore, it is shown that the higher pressure shifts the cool flame to higher strain rates and results in higher cool flame extinction strain rates. However, the existing kinetic model of DME fails in predicting the cool flame extinction limit at elevated pressures. Besides, the cool flame extinction limits are proportional to nth power of the oxygen concentration, [O 2 ] n , and the increase of pressure leads to stronger extinction limit dependence (larger n) on oxygen concentration. The present experiment and detailed kinetic analysis show clearly that increasing pressure promotes the low-temperature chemistry including the oxygen addition reactions. In addition, stable warm flame was first experimentally observed by using DME at elevated pressure with ozone sensitization.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2022

Methanol oxidation up to 100 atm in a supercritical pressure jet-stirred reactor

Methanol (CH 3 OH) has attracted considerable attention as a renewable fuel or fuel additive with low greenhouse gas emissions. Methanol oxidation was studied using a recently developed supercritical pressure jet-stirred reactor (SP-JSR) at pressures of 10 and 100 atm, at temperatures from 550 to 950 K, and at equivalence ratios of 0.1, 1.0, and 9.0 in experiments and simulations. Here, the experimental results show that the onset temperature of CH 3 OH oxidation at 100 atm is around 700 K, which is more than 100 K lower than the onset at 10 atm and this trend cannot be predicted by the existing kinetics models. Furthermore, a negative temperature coefficient (NTC) behavior was clearly observed at 100 atm at fuel rich conditions for methanol for the first time. To understand the observed temperature shift in the reactivity and the NTC effect, we updated some key elementary reaction rates of relevance to high pressure CH 3 OH oxidation from the literature and added some new low-temperature reaction pathways such as CH 2 O + HO 2 = HOCH 2 O 2 (RO 2 ), RO 2 + RO 2 = HOCH 2 O (RO) + HOCH 2 O (RO) + O 2 , and CH 3 OH + RO 2 = CH 2 OH + HOCH 2 O 2 H (ROOH). Although the model with these updates improves the prediction somewhat for the experimental data at 100 atm and reproduces well high-temperature ignition delay times and laminar flame speed data in the literature, discrepancies still exist for some aspects of the 100 atm low-temperature oxidation data. In addition, it was found that the pressure-dependent HO 2 chemistry shifts to lower temperature as the pressure increases such that the NTC effect at fuel-lean conditions is suppressed. Therefore, as shown in the experiments, the NTC phenomenon was only observed at the fuel-rich condition where fuel radicals are abundant and the HO 2 chemistry at high pressure is weakened by the lack of oxygen resulting in comparatively little HO 2 formation.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2022

The missing base molecules in atmospheric acid–base nucleation

Abstract Transformation of low-volatility gaseous precursors to new particles affects aerosol number concentration, cloud formation and hence the climate. The clustering of acid and base molecules is a major mechanism driving fast nucleation and initial growth of new particles in the atmosphere. However, the acid–base cluster composition, measured using state-of-the-art mass spectrometers, cannot explain the measured high formation rate of new particles. Here we present strong evidence for the existence of base molecules such as amines in the smallest atmospheric sulfuric acid clusters prior to their detection by mass spectrometers. We demonstrate that forming (H2SO4)1(amine)1 is the rate-limiting step in atmospheric H2SO4-amine nucleation and the uptake of (H2SO4)1(amine)1 is a major pathway for the initial growth of H2SO4 clusters. The proposed mechanism is very consistent with measured new particle formation in urban Beijing, in which dimethylamine is the key base for H2SO4 nucleation while other bases such as ammonia may contribute to the growth of larger clusters. Our findings further underline the fact that strong amines, even at low concentrations and when undetected in the smallest clusters, can be crucial to particle formation in the planetary boundary layer.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

A Macroalgal Cultivation Modeling System (MACMODS): Evaluating the Role of Physical-Biological Coupling on Nutrients and Farm Yield

Offshore aquaculture has the potential to expand the macroalgal industry. However, moving into deeper waters requires suspended structures that will present novel farm-environment interactions. Here, we present a computational modeling framework, the Macroalgal Cultivation Modeling System (MACMODS), to explore within-farm modifications to light, seawater flow, and nutrient fields across time and space scales relevant to macroalgae. A regional ocean model informs the site-specific setting, the Santa Barbara Channel in the Southern California Bight. A fine-scale hydrodynamic model predicts modified flows and turbulent mixing within the farm. A spatially resolved macroalgal growth model, parameterized for giant kelp, Macrocystis pyrifera , predicts kelp biomass. Key findings from model integration are that regional ocean conditions set overall farm performance, while fine-scale within-farm circulation and nutrient delivery are important to resolve variation in within-farm macroalgal performance. Therefore, we conclude that models resolving within-farm dynamics can provide benefit to farmers with insight on how farm design and regional ocean conditions interact to influence overall yield. Here, the presence of repeating longlines aligned with the mean current generate flow diversions around the farm as well as attached Langmuir circulations and increased turbulence intensity. These flow-induced phenomena lead to less biomass in the interior portion of the farm relative to the edges. We also find that there is an effluent “footprint” that extends as much as 20 km beyond the farm. In this regard, MACMODS can be used to not only evaluate farm design and cultivation practices that maximize yield but also explore interactions between the farm and ecosystem in order to minimize impacts.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Low- and intermediate-temperature oxidation of dimethyl ether up to 100 atm in a supercritical pressure jet-stirred reactor

Understanding the low- and intermediate-temperature oxidation chemistry of oxygenated fuels like dimethyl ether (DME) at high pressure is paramount to the development of advanced engines with low carbon emissions. The supercritical pressure jet-stirred reactor (SP-JSR) recently developed at Princeton provides a new platform for conducting kinetic studies at low and intermediate temperatures at extremely high pressures with a uniform temperature distribution and a short flow residence time. This paper uses the SP-JSR to investigate DME oxidation at equivalence ratios of 0.175, 1.0, and 1.72, for pressures of 10 and 100 atm, and temperatures ranging from 400 to 900 K. The results demonstrate weakened NTC behavior at 100 atm relative to 10 atm due to increased flux through QOOH + O 2 = O 2 QOOH relative to QOOH = 2 CH 2 O + OH at 100 atm. Furthermore, the intermediate-temperature oxidation window is shifted to lower temperatures at 100 atm. The experimental data are compared with several chemical kinetic models from the literature. The existing models are seen to agree quite well with the experimental data at 10 atm. However, the models fail to properly capture the NTC behavior at 100 atm. Reaction pathway analyses indicate that both the low- and intermediate-temperature chemistries are controlled by RO 2 consumption pathways. The reaction rates for several of the important reactions, such as DME + OH = CH 3 OCH 2 + H 2 O, H 2 O 2 (+M) = 2 OH (+M), and 2 HO 2 = 2 OH + O 2 are updated in this work. Furthermore, the updated model improves the predictability for all key species compared to the original model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗