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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.

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Pd/Al2O3 catalyst of the "crust" type with Pd loading of 0.03 wt.% was prepared by the deposition of 2 nm Pd particles on the outer surface of the alumina support using laser electrodispersion (LED). This technique differs from a standard laser ablation into a liquid in that the formation of monodisperse nanoparticles occurs in the laser torch plasma in a vacuum. As is found, the LED-prepared catalyst surpasses Pd-containing three-way catalysts, obtained by conventional chemical synthesis, in activity and stability in CO oxidation under prompt thermal aging conditions. Thus, the LED-prepared Pd/Al2O3 catalyst showed the best thermal stability up to 1000 °C. The present research is focused on the study of the high-temperature evolution of the Pd/Al2O3 catalyst in two reaction mixtures by a set of physicochemical methods (transmission electron microscopy, X-ray photoelectron spectroscopy, and diffuse reflectance UV-vis spectroscopy). In order to follow the dispersion of the Pd nanoparticles during the thermal aging procedure, the testing reaction of ethane hydrogenolysis was also applied. The possible reasons for the high stability of LED-prepared catalysts are suggested.

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The interactions between metals and oxide supports, so-called metal-support interactions (MSI), are of great importance in heterogeneous catalysis. Pd-based automotive exhaust control catalysts, especially Pd-based three-way catalysts (TWCs), have received considerable research attention owing to its prominent oxidation activity of HCs/CO, as well as excellent thermal stability. For Pd-based TWCs, the dispersion, chemical state and thermal stability of Pd species, which are crucial to the catalytic performance, are closely associated with interactions between metal nanoparticles and their supporting matrix. Progress on the research about MSI and utilization of MSI in advanced Pd-based three-way catalysts are reviewed here. Along with the development of advanced synthesis approaches and engine control technology, the study on MSI would play a notable role in further development of catalysts for automobile exhaust control.

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The global trend in restrictions on pollutant emissions requires the use of catalytic converters in the automotive industry. Noble metals belonging to the platinum group metals (PGMs, platinum, palladium, and rhodium) are currently used for autocatalysts. However, recent efforts focus on the development of new catalytic converters that combine high activity and reduced cost, attracting the interest of the automotive industry. Among them, the partial substitution of PGMs by abundant non-PGMs (transition metals such as copper) seems to be a promising alternative. The PROMETHEUS catalyst (PROM100) is a polymetallic nanosized copper-based catalyst for automotives prepared by a wet impregnation method, using as a carrier an inorganic mixed oxide (CeO2-ZrO2) exhibiting elevated oxygen storage capacity. On the other hand, catalyst deactivation or ageing is defined as the process in which the structure and state of the catalyst change, leading to the loss of the catalyst's active sites with a subsequent decrease in the catalyst's performance, significantly affecting the emissions of the catalyst. The main scope of this research is to investigate in detail the effect of ageing on this low-cost, effective catalyst. To that end, a detailed characterization has been performed with a train of methods, such as SEM, Raman, XRD, XRF, BET and XPS, to both ceria-zirconia mixed inorganic oxide support (CZ-fresh and -aged) and to the copper-based catalyst (PROM100-fresh and -aged), revealing the impact of ageing on catalytic efficiency. It was found that ageing affects the Ce-Zr mixed oxide structure by initiating the formation of distinct ZrO2 and CeO2 structures monitored by Raman and XRD. In addition, it crucially affects the morphology of the sample by reducing the surface area by a factor of nearly two orders of magnitude and increasing particle size as indicated by BET and SEM due to sintering. Finally, the Pd concentration was found to be considerably reduced from the material's surface as suggested by XPS data. The above-mentioned alterations observed after ageing increased the light-off temperatures by more than 175 °C, compared to the fresh sample, without affecting the overall efficiency of the catalyst for CO and CH4 oxidation reactions. Metal particle and CeZr carrier sintering, washcoat loss as well as partial metal encapsulation by Cu and/or CeZrO4 are identified as the main causes for the deactivation after hydrothermal ageing.

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In response to growing levels of air pollution and emission regulations, novel three-way catalysts (TWCs) with high efficiency are highly coveted. Herein, a multi-step heating strategy to fabricate a unique dual-site catalyst composed of strongly coupled Pt and Pd atoms located in neighboring positions on the surface of CeO2 is demonstrated. Outstanding three-way catalytic performance is demonstrated, especially for NO elimination. Based on comprehensive investigations, the enhancement is attributed to the strong interactions between the neighboring Pt and Pd atoms, which can separately serve as active sites for CO and NO adsorption, efficiently reducing the energy barrier and accelerating the reaction rate. These findings not only contribute to designing and constructing next-generation catalysts, but also provide a promising opportunity to improve fuel efficiency and control emissions.

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Platinum group metals (PGMs), especially platinum (Pt), palladium (Pd), and rhodium (Rh), are widely used in automotive three-way catalysts (TWCs). PGM resources are scarce and unevenly distributed, with global reserves of 69,000 t in 2020, of which more than 99% are concentrated in South Africa, Russia, Zambia, and the United States. However, the demand for PGMs worldwide is growing continually, especially in China. The recovery of PGMs from spent TWCs not only can alleviate the contradiction between supply and demand but also have good economic and environmental benefits. This paper briefly analyzes the market demand for Pt, Pd, and Rh in the global automotive industry in recent years, emphasizing the importance of waste TWC recycling. It also presents the current status of waste TWC management in some countries, especially China, and critically reviews the main recycling strategies for waste TWCs. On this basis, suggestions for strengthening the management of waste TWCs in China are put forward, and the future development trend of recycling technology is foreseen. The purpose of this paper is to provide some valuable references for the decision-makers of waste TWC management, and hopefully to provide inspiration for related scholars on the future research direction of waste TWC recycling technology.

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The cerium density and valence in micrometer-size platinum-supported cerium-zirconium oxide Pt/Ce2 Zr2 Ox (x=7-8) three-way catalyst particles were successfully mapped by hard X-ray spectro-ptychography (ptychographic-X-ray absorption fine structure, XAFS). The analysis of correlation between the Ce density and valence in ptychographic-XAFS images suggested the existence of several oxidation behaviors in the oxygen storage process in the Ce2 Zr2 Ox particles. Ptychographic-XAFS will open up the nanoscale chemical imaging and structural analysis of heterogeneous catalysts.

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A CeO2-ZrO2 compound with mixed phase composition (CZ4) was prepared by modified co-precipitation method, and for comparison, single-phase Ce(0.2)Zr(0.8)O2, Ce(0.5)Zr(0.5)O2 and Ce(0.8)Zr(0.2)O2 were synthesized via simultaneous co-precipitation method. The textural, structural and redox properties, together with the catalytic performance of the supported Pd-only three-way catalysts were investigated systematically. The results revealed that the generation of numerous interface sites in Pd/CZ4 due to its mixed phase composition (as confirmed by TEM observation) had a positive influence on modifying its structural, redox properties and thermal stability. The XRD and Raman results revealed that the highest structural stability was obtained by Pd/CZ4 with negligible lattice variation and slightest grain growth after aging treatment. The XPS analysis demonstrated that the compositional heterogeneity of Pd/CZ4 could facilitate the formation of Ce(3+), and was beneficial to preserve high dispersion of Pd as well as maintain Pd at a more oxidized state. The H2-TPR and oxygen storage capacity measurements indicated that Pd/CZ4 possessed highest reduction ability as well as largest oxygen storage capacity regardless of thermal aging treatment. And consequently Pd/CZ4 exhibited improved three-way catalytic activity compared with the catalysts supported on single-phase Ce(x)Zr(1-x)O2 both before and after thermal aging treatment.

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The catalytic activity of Pd catalysts supported on Ce0.73Tb0.27Ox/SiO2, Ce0.6Zr0.4Ox/SiO2, Ce0.73Tb0.27Ox/La2O3-Al2O3 and Ce0.6Zr0.4Ox/La2O3-Al2O3 was studied using the reduction of NO by CO. The catalysts were characterized by X-ray fluorescence, surface area, X-ray diffraction, temperature-programmed reduction, CO chemisorption and oxygen storage capacity. Temperature-programmed reduction results indicated that Tb or Zr incorporation improves the reducibility and oxygen storage capacity. CO chemisorption data suggested the presence of large PdO particles due to the low CO/Pd ratio. No significant differences were obtained in light off temperatures (TLight off) for all Pd catalysts and the most active was 1.5%Pd/Ce0.6Zr0.4Ox/SiO2.

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