Todd J. Toops

Low-Temperature CO Oxidation over a Ternary Oxide Catalyst with High Resistance to Hydrocarbon Inhibition.

Platinum group metal (PGM) catalysts are the current standard for control of pollutants in automotive exhaust streams. Aside from their high cost, PGM catalysts struggle with CO oxidation at low temperatures (<200 °C) due to inhibition by hydrocarbons in exhaust streams. Here we present a ternary mixed oxide catalyst composed of copper oxide, cobalt oxide, and ceria (dubbed CCC) that outperforms synthesized and commercial PGM catalysts for CO oxidation in simulated exhaust streams while showing no signs of inhibition by propene. Diffuse reflectance IR (DRIFTS) and light-off data both indicate low interaction between propene and the CO oxidation active site on this catalyst, and a separation of adsorption sites is proposed as the cause of this inhibition resistance. This catalyst shows great potential as a low-cost component for low temperature exhaust streams that are expected to be a characteristic of future automotive systems.

Investigation of thin/well-tunable liquid/gas diffusion layers exhibiting superior multifunctional performance in low-temperature electrolytic water splitting

Liquid/gas diffusion layers (LGDLs), which are located between the catalyst layer (CL) and bipolar plate (BP), play an important role in enhancing the performance of water splitting in proton exchange membrane electrolyzer cells (PEMECs). They are expected to transport electrons, heat, and reactants/products simultaneously with minimum voltage, current, thermal, interfacial, and fluidic losses. In this study, the thin titanium-based LGDLs with straight-through pores and well-defined pore morphologies are comprehensively investigated for the first time. The novel LGDL with a 400 μm pore size and 0.7 porosity achieved a best-ever performance of 1.66 V at 2 A cm−2 and 80 °C, as compared to the published literature. The thin/well-tunable titanium based LGDLs remarkably reduce ohmic and activation losses, and it was found that porosity has a more significant impact on performance than pore size. In addition, an appropriate equivalent electrical circuit model has been established to quantify the effects of pore morphologies. The rapid electrochemical reaction phenomena at the center of the PEMEC are observed by coupling with high-speed and micro-scale visualization systems. The observed reactions contribute reasonable and pioneering data that elucidate the effects of porosity and pore size on the PEMEC performance. This study can be a new guide for future research and development towards high-efficiency and low-cost hydrogen energy.

Discovery of true electrochemical reactions for ultrahigh catalyst mass activity in water splitting

Increase 50-time catalyst mass activity from revealing true reactions in proton exchange membrane electrolysis. Better understanding of true electrochemical reaction behaviors in electrochemical energy devices has long been desired. It has been assumed so far that the reactions occur across the entire catalyst layer (CL), which is designed and fabricated uniformly with catalysts, conductors of protons and electrons, and pathways for reactants and products. By introducing a state-of-the-art characterization system, a thin, highly tunable liquid/gas diffusion layer (LGDL), and an innovative design of electrochemical proton exchange membrane electrolyzer cells (PEMECs), the electrochemical reactions on both microspatial and microtemporal scales are revealed for the first time. Surprisingly, reactions occur only on the CL adjacent to good electrical conductors. On the basis of these findings, new CL fabrications on the novel LGDLs exhibit more than 50 times higher mass activity than conventional catalyst-coated membranes in PEMECs. This discovery presents an opportunity to enhance the multiphase interfacial effects, maximizing the use of the catalysts and significantly reducing the cost of these devices.

Impact of rail pressure and biodiesel fueling on the particulate morphology and soot nanostructures from a common-rail turbocharged direct injection diesel engine

An investigation of the impact of rail pressure and biodiesel fueling on exhaust particulate agglomerate morphology and primary particle (soot) nanostructure was conducted with a common-rail turbocharged direct injection diesel engine. The engine was operated at steady state on a dynamometer running at moderate speed with both low (30%) and medium–high (60%) fixed loads, and exhaust particulate was sampled for analysis. The fuels used were ultra-low sulfur diesel and its 20% v/v blends with soybean methyl ester biodiesel. Fuel injection occurred in a single event around top dead center at three different injection pressures. Exhaust particulate samples were characterized with transmission electronic microscopy imaging, scanning mobility particle sizing, thermogravimetric analysis, Raman spectroscopy, and X-ray diffraction analysis. Particulate morphology and oxidative reactivity were found to vary significantly with both rail pressure and biodiesel blend level. Higher biodiesel content led to an increase in the primary particle size and oxidative reactivity but had no impact on nanoscale disorder in the as-received samples. For particulates generated with higher injection pressures, the initial oxidative reactivity increased, but there was no detectable correlation with primary particle size or nanoscale disorder.

NO reduction over La2O3 using methanol

Nitric oxide (NO) reduction by methanol was studied over La2O3 in the presence and absence of oxygen. In the absence of O2, CH3OH reduced NO to both N2O and N2, with selectivity to dinitrogen formation decreasing from around 85% at 623 K to 50–70% at 723 K. With 1% O2 in the feed, rates were 4–8 times higher, but the selectivity to N2 dropped from 50% at 623 K to 10% at 723 K. The specific activities with La2O3 for this reaction were higher than those for other reductants; for example, at 773 K with hydrogen a specific activity of 35 μmol NO/s m2 was obtained whereas that for methanol was 600 μmol NO/s m2. The Arrhenius plots were linear under differential reaction conditions, and the apparent activation energy was consistently near 14 kcal/mol with CH3OH. Linear partial pressure dependencies based on a power rate law were obtained and showed a near‐zero order in CH3OH and a near‐first order in H2. In the absence of O2, a Langmuir–Hinshelwood type model assuming a surface reaction between adsorbed CH3OH and adsorbed NO as the slow step satisfactorily fitted the data, and the model invoking two types of sites provided the best fit and gave thermodynamically consistent rate constants. In the presence of O2 a homogeneous gas‐phase reaction between O2, NO, and CH3OH occurred to yield methyl nitrite. This reaction converted more than 30% of the methanol at 300 K and continued to occur up to temperatures where methanol was fully oxidized. Quantitative kinetic studies of the heterogeneous reaction with O2 present were significantly complicated by this homogeneous reaction.

In situ investigation on ultrafast oxygen evolution reactions of water splitting in proton exchange membrane electrolyzer cells

The oxygen evolution reaction (OER) is a half reaction in electrochemical devices, including low-temperature water electrolysis, which is considered as one of the most promising methods to generate hydrogen/oxygen for the storage of energy. It is affected by many factors, and its mechanism is still not completely understood. A proton exchange membrane electrolyzer cell (PEMEC) with optical access to the surface of anode catalyst layer (CL) coupled with a distinguished high-speed and micro-scale visualization system (HMVS) was developed to in situ investigate OERs. It was revealed in real time that OERs only occur on the anode CL adjacent to liquid/gas diffusion layer (LGDL). The CL electrical conductivity plays a crucial role in OERs on CLs. The large in-plane electrical resistance of CLs becomes a threshold of OERs over the entire CL, and causes a lot of catalyst waste in the middle of LGDL pores. Moreover, the oxygen bubble nucleation, growth, and detachment and the effect of current density on those processes were also characterized. This study proposes a new approach for better understanding the mechanisms of OERs and optimizing the design and fabrication of membrane electrode assemblies.

NO2 Oxidation Reactivity and Burning Mode of Diesel Particulates

The NO2 oxidation kinetics and burning mode for diesel particulate from light-duty and medium-duty engines fueled with either ultra low sulfur diesel or soy methyl ester biodiesel blends have been investigated and are shown to be significantly different from oxidation by O2. Oxidation kinetics were measured using a flow-through packed bed microreactor for temperature programmed reactions and isothermal differential pulsed oxidation reactions. The burning mode was evaluated using the same reactor system for flowing BET specific surface area measurements and HR-TEM with fringe analysis to evaluate the nanostructure of the nascent and partially oxidized particulates. The low activation energy measured, specific surface area progression with extent of oxidation, HR-TEM images and difference plots of fringe length and tortuosity paint a consistent picture of higher reactivity for NO2, which reacts indiscriminately immediately upon contact with the surface, leading to the Zone I or shrinking core type oxidation. In comparison, O2 oxidation is shown to have relatively lower reactivity, preferentially attacking highly curved lamella, which are more reactive due to bond strain, and short lamella, which have a higher proportion of more reactive edge sites. This preferential oxidation leads to Zone II type oxidation, where solid phase diffusion of oxygen via pores contributes significantly to slowing the overall oxidation rate, by comparison.

Lean NOx Trap Chemistry Under Lean-Gasoline Exhaust Conditions: Impact of High NOx Concentrations and High Temperature

The primary technical barrier to deployment of fuel saving lean gasoline engines is NOx emissions control. We conducted automated flow reactor experiments on a commercial LNT catalyst to identify opportunities and challenges associated with the higher temperatures and higher NOx concentrations expected in lean gasoline applications. Overall NOx conversion was quite high at low to moderate temperatures, but dropped off at high temperatures. The decrease in NOx conversion with temperature was worse for higher inlet NOx concentrations. As expected from equilibrium considerations, the catalyst stored more NOx under higher gas phase NOx concentrations, but that NOx was rapidly released during the rich phase and slipped out of the catalyst before it could be converted to N2 by incoming reductant. This rich phase NOx release was the primary factor limiting performance of the catalyst at high temperatures, and resulted in significant spikes of NOx that would likely exceed any not-to-exceed regulated emissions levels. N2O production was also significant, and increased with NOx concentration. The catalyst made very little NH3 at high temperatures. NH3 yield was significant at the lowest operating temperature studied, but it decreased with increasing NOx concentration.

Nondestructive X-ray Inspection of Thermal Damage, Soot and Ash Distributions in Diesel Particulate Filters

We describe novel results of ongoing research at 3DX-RAY Ltd and Oak Ridge National Laboratory using new, commercially available, nondestructive x-ray techniques to make engineering measurements of diesel particulate filters (DPF). Nondestructive x-ray imaging and data-analysis techniques were developed to detect and visualize the small density changes corresponding to the addition of substances such as soot and ash to DPF monoliths. The usefulness of this technique was explored through the analysis of field-aged samples, accelerated-aged samples, and the synthetic addition of ash and soot to clean DPF samples. We demonstrate the ability to visualize and measure flaws in substrates and quantify the distribution of ash and soot within the DPF. We also show that the technology is sensitive enough for evaluations of soot and ash distribution and thermal damage without removing the DPF from its metal casing.

Nanostructure and burning mode of light-duty diesel particulate with conventional diesel, biodiesel, and intermediate blends

The nanostructure of diesel particulates has been shown to impact its oxidation rate and burnout trajectory. Additionally, this nanostructure can evolve during the oxidation process, furthering its influence on the burnout process. For this study, exhaust particulates were generated on a light-duty diesel engine with conventional diesel fuel, biodiesel, and intermediate blends of the two at a single load-speed point. Despite the singular engine platform and operating point, the different fuels created particulates with varied nanostructure, thereby greatly expanding the window for observing nanostructure evolution and oxidation. The physical and chemical properties of the particulates in the nascent state and at partial oxidation states were measured in a laboratory reactor and by high-resolution transmission electron microscopy as a function of the degree of oxidation in O2. X-ray photoacoustic spectroscopy analysis, thermal desorption, and solvent extraction of the nascent particulate samples reveal a significant organic content in the biodiesel-derived particulates, likely accounting for differences in the nanostructure. This study reports the nanoscale structural changes in the particulate with biofuel blend level and during O2 oxidation as observed by high-resolution transmission electron microscopy and quantitated by fringe analysis and Brunnauer–Emmet–Teller total surface area measurements. It was observed that initial fuel-related differences in the lamella lengths, spacing, and curvature disappear when the particulate reaches approximately 50% burnout. Specifically, the initial ordered, fullerenic, and amorphous nanostructures converge during the oxidation process and the surface areas of these particulates appear to grow through these complex changes in internal particle structure. The specific surface area, measured at several points along the burnout trajectory, did not match the shrinking core projection and in contrast suggested that internal porosity was increasing. Thus, the appropriate burnout model for these particulates is significantly different from the standard shrinking core assumption, which does not account for any internal structure. An alternative burnout model is supported by high-resolution transmission electron microscopy image analysis.