Dongxia Yang

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.

Selective catalytic reduction filter (SDPF) technology constitutes a critical methodology for controlling nitrogen oxide (NOx) and particulate matter emissions from light-duty diesel vehicles. A series of SDPFs with different sulfur poisoning times and concentrations were prepared using the worldwide harmonized light vehicles test cycle (WLTC). Bench testing revealed that sulfur poisoning diminished the catalyst’s NH₃ storage capacity, impaired the transient NOx reduction efficiency, and induced premature ammonia leakage. After multiple sulfur poisoning incidents, the NOx reduction performance stabilized. Higher SO₂ concentrations accelerated catalyst deactivation and hastened the attainment of this equilibrium state. The characterization results for the catalyst indicate that the catalyst accumulated the same sulfur content after tail gas poisoning with different sulfur concentrations and that sulfur existed in the form of SO₄²⁻. The sulfur species in low-sulfur-poisoning-concentration catalysts mainly included sulfur ammonia and sulfur copper species, while high-sulfur-poisoning-concentration catalysts contained a higher proportion of sulfur copper species. Neither species type significantly altered the zeolite coating’s crystalline structure. Sulfur ammonia species could easily lead to a significant decrease in the specific surface area of the catalyst, which could be decomposed at 500 °C to achieve NOx reduction performance regeneration. In contrast, sulfur copper species required higher decomposition temperatures (600 °C), achieving only partial regeneration.

Passive NOx adsorber (PNA) is one of the important means to effectively reduce NOx emission control in the cold start of a diesel engine. A series of Pd/SSZ-13 catalysts with different SiO₂/Al₂O₃ ratios (11, 17, and 25) were prepared using the impregnation method. Furthermore, the effect of the SiO₂/Al₂O₃ ratio on the adsorption performance of Pd/SSZ-13 at low-temperature NOx under realistic exhaust conditions was studied. The results show that the Pd/SSZ-13 catalyst with a low SiO₂/Al₂O₃ ratio after loading Pd has a higher specific surface area and palladium ion content. There is a negative correlation between NOx adsorption performance and the SiO₂/Al₂O₃ ratio. After high-temperature heat treatment, the acid sites closely related to palladium species increase and palladium species will redisperse, producing more palladium ions. The palladium ions coexist in Pd/SSZ-13 in the form of Pd²⁺ and Pd⁺, among which Pd²⁺ is divided into two types: Z⁻Pd²⁺Z⁻ and Z⁻[Pd(II)OH]⁺. The NOx adsorption performance of the Pd/SSZ-13 catalyst was significantly improved, and the higher the SiO₂/Al₂O₃ ratio, the more obviously the advantage of NOx adsorption performance increased after heat treatment. The NOx adsorption kinetic model of the Pd/SSZ-13 catalyst under realistic exhaust conditions was most suitably described by the pseudo-first-order model.

Microscopic analyses of the effects of ash on particulate matter oxidation are rather scarce. In this study, three different lubricating oils with varying ash contents were used to investigate their effects on the nanostructure of diesel particulate matter. The nanostructure and nanostructure parameters, including fringe length, fringe separation distance, and fringe tortuosity, were studied using high-resolution transmission electron microscopy. The results show that all samples obtained from blending with different lubricant oil present typical core–shell structures. The inner cores remain relatively unchanged, whereas the thickness of the outer shells increases with the increasing ash content in the lubricant oil under the same working conditions. The fringe length increases and the fringe separation distance decreases with the rising ash content in the lubricant oil operating in the same working conditions. The fringe tortuosity decreases when the ash content in the lubricant oil increases from 0.92% to 1.21%, but shows little change when the ash content in the lubricant oil increases from 1.21% to 1.92%. Based on the effects of ash on the nanostructure parameters, it can be inferred that the oxidation activity of particles decreases with increasing ash content in the lubricant oil.

Pd/Y-ZrO₂ catalysts were prepared by Y-ZrO₂ with different morphologies (flower-like, spherical, reticulated, and bulk-specific morphology), which were prepared by hydrothermal synthesis. Activity evaluation and characterization results show that the morphology influences the microstructures of Y-ZrO₂ and the chemical states of active Pd species, thus affecting the activity of methane oxidation. Bulk Pd/Y-ZrO₂ exhibits the best CH₄ oxidation activity and thermal stability due to the block shape exposed (101) surface, and the single tetragonal phase structure maintained after high-temperature aging. The relatively large-sized Pd particles and Pd⁰ jointly promote the catalytic oxidation of CH₄.