Search Results (45)

The continuous tightening of emission regulations and the escalating costs of palladium (Pd) and rhodium (Rh) have renewed interest in platinum (Pt)-based three-way catalysts (TWCs) as cost-effective alternatives for gasoline aftertreatment. However, despite extensive studies on Pt/CeO₂ and Pt/Ba-based formulations, the cooperative roles of Ba and Ce and, in particular, the fundamental influence of the Ba/Ce ratio on oxygen mobility, NO_x storage behavior, and Pt–support interactions remain poorly understood. In this work, we address this gap by systematically tuning the Ba/Ce molar ratio in a series of Pt–Ba–Ce/Al₂O₃ catalysts prepared from Ba(CH₃COO)₂ and CeO₂ precursors, and evaluating their structure–function relationships in both fresh and hydrothermally aged states. Through comprehensive characterization (N₂ physisorption, XRD, XPS, H₂-TPR, NO_x-TPD, SEM, CO pulse adsorption, and dynamic light-off testing), we establish previously unrecognized correlations between Ba/Ce ratio–dependent structural evolution and TWC performance. The results reveal that the Ba/Ce ratio exerts a decisive control over catalyst textural properties, Pt dispersion, and interfacial Pt–CeO₂ oxygen species. Low Ba/Ce ratios uniquely promote Pt–Ce interfacial oxygen and O₂ spillover—providing a new mechanistic basis for enhanced low-temperature oxidation and reduction reactions—while higher Ba loading selectively drives BaCO₃ formation and boosts NO_x storage capacity. A clear volcano-type dependence of NO_x storage on the Ba/Ce ratio is demonstrated for the first time. Hydrothermal aging at 850 °C induces PtO_x decomposition, BaCO₃–Al₂O₃ solid-state reactions forming inactive BaAl₂O₄, and Pt sintering, collectively suppressing Pt–Ce interactions and reducing TWC activity. Importantly, an optimized Ba/Ce ratio is shown to mitigate these degradation pathways, offering a new design principle for thermally durable Pt-based TWCs. Overall, this study provides new mechanistic insight into Ba–Ce cooperative effects, establishes the Ba/Ce ratio as a critical and previously overlooked parameter governing Pt–support interactions and NO_x storage, and presents a rational strategy for designing cost-effective, hydrothermally robust Pt-based alternatives to Pd/Rh commercial TWCs. Full article

Hybrid electric vehicles (HEVs) frequently cycle their internal combustion engines (ICE), potentially cooling the three-way catalyst (TWC). This challenges the use of compressed natural gas (CNG), as methane (CH₄) requires high temperatures for TWC oxidation. This study experimentally investigates the performance, engine-out emissions (CO, NO_x, CH₄, NMHC, CO₂), and catalyst temperatures of a Toyota RAV4 hybrid vehicle on gasoline (G), CNG, and dual fuel (MIX) during the WLTC. Engine-out emissions were measured upstream of the TWC. Results showed similar engine work output (~17.8 kWh/100 km), while CNG significantly reduced fuel mass consumption (−18.7%) and CO₂ emissions (−27.5%) compared to gasoline, driven by both its higher LHV and higher average BTE. CO (−32.3%) and NO_x (−34.0%) emissions were lower with CNG, linked to leaner operation and significantly retarded ignition timing for NO_x control. However, CH₄ emissions drastically increased with CNG. This study reveals a synergy between the same retarded ignition timing strategy used to successfully control engine-out NO_x (−34.0%) and created a positive secondary effect, raising pre-TWC temperatures by 4.5%. Higher thermal condition is essential for the aftertreatment of chemically stable methane, highlighting a direct link between the engine’s NO_x control logic and the potential to mitigate methane slip. Full article

In response to increasingly stringent emission regulations, low-carbon fuels have received significant attention as sustainable energy sources for internal combustion engines. This study investigates four representative low-carbon fuels, methane, methanol, hydrogen, and ammonia, by systematically summarizing their combustion characteristics and emission profiles, along with a review of existing after-treatment technologies tailored to each fuel type. For methane engines, unburned hydrocarbon (UHC) produced during low-temperature combustion exhibits poor oxidation reactivity, necessitating integration of oxidation strategies such as diesel oxidation catalyst (DOC), particulate oxidation catalyst (POC), ozone-assisted oxidation, and zoned catalyst coatings to improve purification efficiency. Methanol combustion under low-temperature conditions tends to produce formaldehyde and other UHCs. Due to the lack of dedicated after-treatment systems, pollutant control currently relies on general-purpose catalysts such as three-way catalyst (TWC), DOC, and POC. Although hydrogen combustion is carbon-free, its high combustion temperature often leads to elevated nitrogen oxide (NO_x) emissions, requiring a combination of optimized hydrogen supply strategies and selective catalytic reduction (SCR)-based denitrification systems. Similarly, while ammonia offers carbon-free combustion and benefits from easier storage and transportation, its practical application is hindered by several challenges, including low ignitability, high toxicity, and notable NO_x emissions compared to conventional fuels. Current exhaust treatment for ammonia-fueled engines primarily depends on SCR, selective catalytic reduction-coated diesel particulate filter (SDPF). Emerging NO_x purification technologies, such as integrated NO_x reduction via hydrogen or ammonia fuel utilization, still face challenges of stability and narrow effective temperatures. Full article

To improve the prediction accuracy of soot load in gasoline particulate filters (GPFs) and the control accuracy during GPF regeneration, this study developed a prediction model to predict the soot mass concentration at the GPF inlet of gasoline direct injection (GDI) engines using advanced machine learning methods. Three machine learning approaches, namely, support vector regression (SVR), deep neural network (DNN), and a Stacking integration model of SVR and DNN, were employed, respectively, to predict the soot mass concentration at the GPF inlet. The input data includes engine speed, torque, ignition timing, throttle valve opening angle, fuel injection pressure, and pulse width. Exhaust gas soot mass concentration at the three-way catalyst (TWC) outlet is obtained by an engine bench test. The results show that the correlation coefficients (R²) of SVR, DNN, and Stacking integration model of SVR and DNN are 0.937, 0.984, and 0.992, respectively, and the prediction ranges of soot mass concentration are 0–0.038 mg/s, 0–0.030 mg/s, and 0–0.07 mg/s, respectively. The distribution, median, and data density of prediction results obtained by the three machine learning approaches fit well with the test results. However, the prediction result of the SVR model is poor when the soot mass concentration exceeds 0.038 mg/s. The median of the prediction result obtained by the DNN model is closer to the test result, specifically for data points in the 25–75% range. However, there are a few negative prediction results in the test dataset due to overfitting. Integrating SVR and DNN models through stacked models extends the predictive range of a single SVR or DNN model while mitigating the overfitting of DNN models. The results of the study can serve as a reference for the development of accurate prediction algorithms to estimate soot loads in GPFs, which in turn can provide some basis for the control of the particulate mass and particle number (PN) emitted from GDI engines. Full article

Strict gaseous emission standards are applied globally to regulate the maximum amounts of pollutant emissions that can be produced from all vehicles. The exhaust aftertreatment systems used by automotive manufacturers rely on the utilization of precious metals (Pt, Pd, Rh). However, much effort has been devoted on the reduction or the replacement of the amount of Platinum Group Metals (PGMs) in three-way catalysts (TWC), both from a cost-effectiveness as well as an environmental point of view. PROMETHEUS catalyst, which was recently homologated for Euro 6 applications, is a low-cost, Cu-based TWC, which consists of a significantly lower quantity of PGMs compared to conventional state-of-the-art catalysts and achieves similar or even better catalytic efficiencies. In this review paper, a complex reaction scheme is proposed for the first time for a catalytic converter utilizing Cu and PGMs, following an extensive literature investigation of the available models. The scheme also accounts for the surface reaction mechanisms of the main processes and the side reactions potentially taking place during the TWC operation in the presence of Cu and at least one of the following PGMs: Pt, Pd or Rh. At a next step, the proposed reaction scheme will be validated based on experimental data, using mathematical modelling of a PROMETHEUS catalytic converter incorporating Cu and PGM nanoparticles. Full article

This study reassesses an overview of the potential of the radio frequency (RF)-based state diagnostics of three-way catalysts (TWC) based on a previous study with an emphasis on the defect chemistry of the catalyst material during reoxidation and reduction. Some data are based on the previous works but are newly processed, and the signal parameters resonant frequency and inverse quality factor are evaluated with respect to applicability. The RF-based method uses electromagnetic resonances in a cavity resonator to provide information on the storage level of the oxygen storage component. The analysis focuses on a holistic investigation and evaluation of the major effects influencing the RF signal during operation. On the one hand, the response to the oxygen storage behavior and the resolution of the measurement method are considered. Therefore, this study merges original data from multiple former publications to provide a comprehensive insight into important measurement effects and their defect chemistry background. On the other hand, the most important cross-sensitivities are discussed and their impact during operation is evaluated. Additionally, the effect of catalyst aging is analyzed. The effects are presented separately for the two resonant parameters: resonant frequency and (unloaded) quality factor. Overall, the data suggest that the quality factor has a way higher signal quality at low temperatures (<400 °C) and the resonant frequency is primarily suitable for high operating temperatures. At most operating points, the quality factor is even more robust against interferences such as exhaust gas stoichiometry and water content. Correctly estimating the catalyst temperature is the most important factor for reliable results, which can be achieved by combining the information of both resonant signals. In the end, the data indicate that microwave-based state diagnosis is a powerful system for evaluating the oxygen storage level over the entire operating range of a TWC. As a research tool and in its application, the system can therefore contribute to the improvement of the emission control of future gasoline vehicles. Full article

Compressed natural gas (CNG) taxis represent the most ubiquitous and dynamically active passenger vehicles in urban settings. The pollutant emission characteristics of in-use CNG taxis driving on a typical mountain city before and after three-way catalyst (TWC) replacement was examined using a modular on-board portable emissions measurement system (PEMS), the OBS-ONE developed by Horiba. The results showed that the exhaust NO of CNG taxis equipped with deactivation TWC exceeded the emission limits, even higher than gasoline vehicles. The high emission rate of CNG taxis is mainly concentrated on road slopes between a 2% and 6% gradient and a deceleration rate in the interval of [0.5, 4], respectively, which results in higher emissions from CNG taxis traveling in the mountain city of Chongqing than other cities and vehicles. Moreover, the pollutant emission rates of the in-use CNG taxis were highly correlated with the velocity and the vehicle specific power (VSP). After a new TWC replacement, the emission factors of carbon monoxide (CO), total hydrocarbons (THC), nitrogen oxides (NOx), and particle number (PN) decreased by 85.21–89.11%, 68.71–85.49%, 60.91–81.11%, and 62.26–68.39%, respectively. Our results will provide guidance for urban environments to carry out the comprehensive management of in-use vehicles and emphasize the importance of TWC replacement for CNG taxis. Full article

This study aims to examine the particle number (PN) emissions of a retrofitted heavy-duty spark ignition (HD-SI) engine powered by liquefied petroleum gas (LPG) under both steady-state and transient conditions. The engine was tested under seven steady-state operating points to investigate the PN behavior and particle size distribution (PSD) upstream and downstream of the three-way catalyst (TWC). This analysis intends to assess the impact of including particles with diameters ranging from 10 nm to 23 nm on the total particle count, a consideration for future regulations. The study employed the World Harmonized Transient Cycle (WHTC) for transient conditions to encompass the same engine working region as is used in the steady-state analysis. A Dekati FPS-4000 diluted the exhaust sample to measure the PSD and PN for particle diameters between 5.6 nm and 560 nm using the TSI-Engine Exhaust Particle Sizer (EEPS) 3090. The findings indicate that PN levels tend to increase downstream of the TWC under steady-state conditions in operating points with low exhaust gas temperatures and flows (equal to or less than 500 °C and 120 kg/h). Furthermore, the inclusion of particles with diameters between 10 nm and 23 nm leads to an increase in PN emissions by 17.70% to 40.84% under steady conditions and by an average of 40.06% under transient conditions, compared to measurements that only consider particles larger than 23 nm. Notably, in transient conditions, most PN emissions occur during the final 600 s of the cycle, linked to the most intense phase of the WHTC. Full article

CeO₂-ZrO₂-La₂O₃ supported Pt-Pd bimetallic three-way catalysts (0.6Pt-0.4Pd/CZL) were synthesized through the conventional impregnation method and then subjected to severe thermal aging. Reactivating treatments under different temperatures were then applied to the aged catalysts above. Three-way catalytic performance evaluations and dynamic operation window tests along with detailed physio-chemical characterizations were carried out to explore possible structure–activity evolutions during the reactivating process. Results show that the reactivating process conducted at proper temperatures (500~550 °C) could effectively restore the TWC catalytic performance and widen the operation window width. The suitable reactivating temperature ranges are mainly determined by the decomposing temperature of PMO_x species, the thermal stability of PM-O-Ce species, and the encapsulation temperature of precious metals by CZL support. Reactivating under appropriate temperature helps to restore the interaction between Pt and CZL support to a certain extent and to re-expose part of the encapsulated precious metals. Therefore, the dynamic oxygen storage/release capacity, redox ability, as well as thermal stability of PtOx species, can be improved, thus benefiting the TWC catalytic performances. However, the excessively high reactivating temperature would cause further embedment of Pd by CZL support, thus leading to a further decrease in both dynamic oxygen storage/release capacity and the TWC catalytic performance after reactivating treatment. Full article

Three-way catalysts (TWCs) are widely used in vehicles to convert the exhaust emissions from internal combustion engines into less toxic pollutants. After around 8–10 years of use, the declining catalytic activity of TWCs causes them to need replacing, leading to the generation of substantial amounts of spent TWC material containing precious metals, including palladium. It has previously been reported that [NⁿBu₄]₂[Pd₂I₆] is obtained in high yield and purity from model TWC material using a simple, inexpensive and mild reaction based on tetrabutylammonium iodide in the presence of iodine. In this contribution, it is shown that, through a simple ligand exchange reaction, this dimeric recovery complex can be converted into PdI₂(dppf) (dppf = 1,1′-bis(diphenylphosphino)ferrocene), which is a direct analogue of a commonly used catalyst, PdCl₂(dppf). [NⁿBu₄]₂[Pd₂I₆] displayed high catalytic activity in the oxidative functionalisation of benzo[h]quinoline to 10-alkoxybenzo[h]quinoline and 8-methylquinoline to 8-(methoxymethyl)quinoline in the presence of an oxidant, PhI(OAc)₂. Near-quantitative conversions to the desired product were obtained using a catalyst recovered from waste under milder conditions (50 °C, 1–2 mol% Pd loading) and shorter reaction times (2 h) than those typically used in the literature. The [NⁿBu₄]₂[Pd₂I₆] catalyst could also be recovered and re-used multiple times after the reaction, providing additional sustainability benefits. Both [NⁿBu₄]₂[Pd₂I₆] and PdI₂(dppf) were also found to be active in Buchwald–Hartwig amination reactions, and their performance was optimised through a Design of Experiments (DoE) study. The optimised conditions for this waste-derived palladium catalyst (1–2 mol% Pd loading, 3–6 mol% of dppf) in a bioderived solvent, cyclopentyl methyl ether (CPME), offer a more sustainable approach to C-N bond formation than comparable amination protocols. Full article

With the Euro 7 pollutant emission legislation currently under discussion, advanced and more efficient exhaust aftertreatment systems are being developed. The technologies required for these are leading to an increase in the number of components and control systems requiring diagnoses strategies under the on-board diagnostics (OBD) legislation. With concurrent shorter development times and significant reductions in budgets allocated to conventional powertrain development, challenges in the field of OBD calibration and verification are already rising sharply. In response to these challenges, hardware-in-the-loop (HiL) approaches have been successfully introduced to support and replace conventional development methods. The use of complex simulation models significantly improves the quality of calibrations while minimizing the number of required prototype vehicles and test resources, thus reducing development costs. This paper presents a feasibility study for moving OBD-related calibration and validation tasks from the vehicle to a HiL platform. In this context, the calibration and verification process of an active diagnostic for monitoring the condition of the three-way catalyst (TWC) and the oxygen sensors in the exhaust aftertreatment system is presented. It is shown that all relevant signals are simulated with sufficient accuracy to ensure a robust transfer from the vehicle to a HiL test bench. Special attention is given to the simulation of aged components and their influence on the emission behavior of the system. Furthermore, it is discussed that transferring OBD tasks from the vehicle to the HiL test bench could result in significant savings in development time and a reduction in the number of physical prototype vehicles and test resources required. Full article

The rising interest in the use of gaseous fuels, such as bio-methane and hydro-methane, in Heavy-Duty (HD) engines to reduce Greenhouse Gases pushed by the net-zero CO₂ emissions roadmap, introduced the need for appropriate strategies in terms of fuel economy and emissions reduction. The present work hence aims at analysing the potential benefits derived from the application of the cylinder deactivation strategy on a six-cylinder HD Natural Gas Spark Ignition (SI) engine, typically employed in buses and trucks. The activity stems from an extensive experimental characterisation of the engine, which allowed for validating a related 1D model at several Steady-State conditions over the entire engine workplan and during dynamic phases, represented by the World Harmonized Transient Cycle (WHTC) homologation cycle. The validated model was exploited to assess the feasibility of the considered strategy, with specific attention to the engine working areas at partial load and monitoring the main performance parameters. Moreover, the introduction in the model of an additional pipeline and of valves actuated by a dedicated control logic, allowed for embedding the capability of using Exhaust Gas Recirculation (EGR). In the identified operating zones, the EGR strategy has shown significant benefits in terms of fuel consumption, with a reduction of up to 10%. Simultaneously, an appreciable increase in the exhaust gas temperature was detected, which may eventually contribute to enhance the Three-Way Catalyst (TWC) conversion efficiency. Considering that few efforts are to be found in the literature but for the application of the cylinder deactivation strategy to Light-Duty or conventionally fuelled vehicles, the present work lays the foundation for a possible application of such technology in Natural Gas Heavy-Duty engines, providing important insights to maximise the efficiency of the entire system. Full article

Three-way catalyst (TWC) is the mainstream technology for stoichiometric natural gas vehicle gas emission purification to meet the China VI emission standard for heavy-duty vehicles. Due to the high price of Pd-Rh TWC widely used at present, it is of great significance to develop cheaper Pt-only catalysts as substitutes. However, there are few studies on Pt-only TWC, especially for natural gas vehicles. It remains a formidable challenge to develop Pt-only TWC with excellent activity and stability. In this study, we significantly improved the catalytic performance of Pt/CeO₂ TWC through thermal treatment, especially steam treatment at 800 °C, and used XRD, TEM, H₂-TPR, and XPS techniques to investigate how Pt/CeO₂ can be activated via these treatments. Our results suggested that after these treatments, CeO₂ crystallites sintered slightly, while platinum particles remained highly dispersed. Moreover, these treatments also weakened the Pt-CeO₂ interaction, promoted the formation of oxygen vacancies in CeO₂ support, and generated a new type of active surface oxygen in the vicinity of Pt^δ+, thus improving the activity of the catalyst. After 800 °C steam treatment, the T₅₀ of CH₄ and NO decreased by 31 and 36 °C, respectively. The results obtained in this study provide implications for the synthesis of efficient Pt-based catalysts. Full article

This study explores an eco-friendly method for recovering platinum group metals from a synthetic automotive three-way catalyst (TWC). Bioleaching of palladium (Pd) using the thiosulfate-copper-ammonia leaching processes, with biogenic thiosulfate sourced from a bioreactor used for biogas biodesulfurization, is proposed as a sustainable alternative to conventional methods. Biogenic thiosulfate production was optimized in a gas-lift bioreactor by studying the pH (8–10) and operation modes (batch and continuous) under anoxic and microaerobic conditions for 35 d. The maximum concentration of 4.9 g S₂O₃²⁻ L⁻¹ of biogenic thiosulfate was reached under optimal conditions (batch mode, pH = 10, and airflow rate 0.033 vvm). To optimize Pd bioleaching from a ground TWC, screening through a Plackett–Burman design determined that oxygen and temperature significantly affected the leaching yield negatively and positively, respectively. Based on these results, an optimization through an experimental design was performed, indicating the optimal conditions to be Na₂S₂O₃ 1.2 M, CuSO₄ 0.03 M, (NH₄)₂SO₄ 1.5 M, Na₂SO₃ 0.2 M, pH 8, and 60 °C. A remarkable 96.2 and 93.2% of the total Pd was successfully extracted from the solid at 5% pulp density using both commercially available and biogenic thiosulfate, highlighting the method’s versatility for Pd bioleaching from both thiosulfate sources. Full article

With increasing concerns about global warming, the push for sustainable and eco-friendly fuels is accelerating. Propane, recognized as liquefied petroleum gas or LPG, has garnered research interest as an alternative fuel due to its notable advantages, including a high-octane rating, reduced greenhouse gas emissions, and potential cost-effectiveness. However, to realize its full potential as an alternative fuel it is essential to develop catalysts that efficiently handle emissions at low temperatures. In our research, we investigated three distinct palladium (Pd)-based three-way catalyst (TWC) formulations (PdRh, Pd-only, and Pd-OSC) to investigate the influence of typical TWC components rhodium (Rh) and oxygen storage components (OSC) in exhaust scenarios relevant to propane-fueled engines. Among these, the formulation containing oxygen storage components (Pd-OSC) showed the highest reactivity for both NO and C₃H₈ while minimizing performance degradation from hydrothermal aging (HTA). Notably, the temperature of 50% conversion (T₅₀) for propane in the Pd-OSC fresh and HTA sample was lower by 30 °C and 13 °C, respectively, compared to the Pd-only sample, highlighting the role of oxygen storage materials in enhancing catalyst performance, even without dithering. Additionally, N₂ physisorption showed that the Pd-OSC sample has a higher surface area and increased pore volume. This underscores the idea that OSC materials not only augment the catalyst’s porosity but also optimize reactant accessibility to active sites, thus elevating catalytic efficiency. In addition to evaluating performance, we further explored the performance and characteristics of the catalysts using catalytic probe reactions, such as water–gas shift and steam reforming reactions. Full article