Mo-modified Pd/Al2O3 catalysts for benzene catalytic combustion

Mo-modified Pd/Al2O3catalysts were prepared by an impregnation method and tested for the catalytic combustion of benzene. The catalysts were characterized by N2 isothermal adsorption, X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, temperatureprogrammed desorption of NH3（NH3-TPD）, H2temperature-programmed reduction（H2-TPR）, and high-angle annular dark-field scanning transmission electron microscopy（HAADF-STEM）. The results showed that the addition of Mo effectively improved the activity and stability of the Pd/Al2O3catalyst by increasing the dispersion of Pd active components, changing the partial oxidation state of palladium and increasing the oxygen species concentration on the surface of catalyst. In the case of the Pd-Mo/Al2O3catalyst,benzene conversion of 90% was obtained at temperatures as low as 190°C, which was 45°C lower than that for similar performance with the Pd/Al2O3catalyst. Moreover, the 1.0% Pd-5% Mo/Al2O3catalyst was more active than the 2.0% Pd/Al2O3catalyst. It was concluded that Pd and Mo have a synergistic effect in benzene catalytic combustion.     

Biogenic palladium prepared by activated sludge microbes for the hexavalent chromium catalytic reduction: Impact of relative biomass

• Pd nanoparticles could be reduced and supported by activated sludge microbes. • The effect of biomass on Pd adsorption by microbes is greater than Pd reduction. • More biomass reduces Pd particle size, which is more dispersed on the cell surface. • When the biomass/Pd add to 6, the catalytic reduction rate of Cr(VI) reaches stable. Palladium, a kind of platinum group metal, owns catalytic capacity for a variety of hydrogenations. In this study, Pd nanoparticles (PdNPs) were generated through enzymatic recovery by microbes of activated sludge at various biomass/Pd, and further used for the Cr(VI) reduction. The results show that biomass had a strong adsorption capacity for Pd(II), which was 17.25 mg Pd/g sludge. The XRD and TEM-EDX results confirmed the existence of PdNPs associated with microbes (bio-Pd). The increase of biomass had little effect on the reduction rate of Pd(II), but it could cause decreasing particle size and shifting location of Pd(0) with the better dispersion degree on the cell surface. In the Cr(VI) reduction experiments, Cr(VI) was first adsorbed on bio-Pd with hydrogen and then reduced using active hydrogen as electron donor. Biomass improved the catalytic activity of PdNPs. When the biomass/Pd (w/w) ratio increased to six or higher, Cr(VI) reduction achieved maximum rate that 50 mg/L of Cr(VI) could be rapidly reduced in one minute.     

Degradation of pentachlorobiphenyl by a sequential treatment using Pd coated iron and an aerobic bacterium (H1)

The reductive dechlorination and biodegradation of 2,2^′4,5,5^′-pentachlorobiphenyl (PCB#101) was investigated in a laboratory-scale. Palladium coated iron (Pd/Fe) was used as a catalytic reductant for the chemical degradation of 2,2^′4,5,5^′-pentachlorobiphenyl, and an aerobic bacteria was used for biodegradation following the chemical reaction in this study. Dechlorination was affected by several factors such as Pd loading, initial soil pH and the amount of Pd/Fe used. The results showed that higher Pd loading, higher dosage of Pd/Fe and slightly acid condition were beneficial to the catalytic dechlorination of 2,2^′,4,5,5^′-pentachlorobiphenyl. In laboratory batch experiments, 2,2^′4,5,5^′-pentachlorobiphenyl was reduced in the presence of Pd/Fe bimetal, which was not further degraded by aerobic bacteria. 2,2^′,4-trichlorobiphenyl (PCB#17), a reduction product from 2,2^′4,5,5^′-pentachlorobiphenyl, was readily biodegraded in the presence of a aerobic bacterial strain. It is suggested that an integrated Pd/Fe catalytic reduction-aerobic biodegradation process may be a feasible option for treating PCB-contaminated soil.     

Pd-nanoparticles cause increased toxicity to kiwifruit pollen compared to soluble Pd(II)

In the present study, endpoints including in vitro pollen performance (i.e., germination and tube growth) and lethality were used as assessments of nanotoxicity. Pollen was treated with 5-10 nm-sized Pd particles, similar to those released into the environment by catalytic car exhaust converters. Results showed Pd-nanoparticles altered kiwifruit pollen morphology and entered the grains more rapidly and to a greater extent than soluble Pd(II). At particulate Pd concentrations well below those of soluble Pd(II), pollen grains experienced rapid losses in endogenous calcium and pollen plasma membrane damage was induced. This resulted in severe inhibition and subsequent cessation of pollen tube emergence and elongation at particulate Pd concentrations as low as 0.4 mg L⁻¹. Particulate Pd emissions related to automobile traffic have been increasing and are accumulating in the environment. This could seriously jeopardize in vivo pollen function, with impacts at an ecosystem level.     

Catalytic decomposition of hydrocarbon into hydrogen and carbon in a spouted-bed reactor as the second-stage reactor of a plastic recycling process

A two-stage process for the chemical recycling of plastics is proposed. In this process, which consists of two reactors, plastics are converted into hydrogen and carbon. In the first reactor, plastic chips are thermally decomposed into hydrocarbons. In the second reactor, the hydrocarbons formed in the first reactor are catalytically decomposed into carbon and hydrogen. In this study, in order to obtain basic data for the second reactor, propene was catalytically decomposed in a laboratory-scale spouted-bed reactor (600mm high, 21.6mm internal diameter, made of SUS304). The effect of the type of spouting medium used on the decomposition behavior of propene was investigated using four types of spouting medium (nickel-plated -alumina, palladium-plated -alumina, nickel-impregnated -alumina, and -alumina). The nickel-impregnated -alumina gave the best propene conversion and hydrogen yield.     

Kinetics and pathways for the debromination of polybrominated diphenyl ethers by bimetallic and nanoscale zerovalent iron: effects of particle properties and catalyst

Polybrominated diphenyl ethers (PBDEs) are recognized as a new class of widely-distributed and persistent contaminants for which effective treatment and remediation technologies are needed. In this study, two kinds of commercially available nanoscale Fe⁰ slurries (Nanofer N25 and N25S), a freeze-dried laboratory-synthesized Fe⁰ nanoparticle (nZVI), and their palladized forms were used to investigate the effect of particle properties and catalyst on PBDE debromination kinetics and pathways. Nanofers and their palladized forms were found to debrominate PBDEs effectively. The laboratory-synthesized Fe⁰ nanoparticles also debrominated PBDEs, but were slower due to deactivation by the freeze-drying and stabilization processes in the laboratory synthesis. An organic modifier, polyacrylic acid (PAA), bound on N25S slowed PBDE debromination by a factor of three to four compared to N25. The activity of palladized nZVI (nZVI/Pd) was optimized at 0.3 Pd/Fe wt% in our system. N25 could debrominate selected environmentally-abundant PBDEs, including BDE 209, 183, 153, 99, and 47, to end products di-BDEs, mono-BDEs and diphenyl ether (DE) in one week, while nZVI/Pd (0.3 Pd/Fe wt%) mainly resulted in DE as a final product. Step-wise major PBDE debromination pathways by unamended and palladized Fe⁰ are described and compared. Surface precursor complex formation is an important limiting factor for palladized Fe⁰ reduction as demonstrated by PBDE pathways where steric hindrance and rapid sequential debromination of adjacent bromines play an important role.     

Catalytic reduction of vat and sulfur dyes with hydrogen

Vat and sulfur dyes must be reduced to their leuco forms before application. Since this process is currently carried out using irreversible reducing chemicals, it involves high economic and environmental costs. Here we show that reduction can alternatively be performed in an alkaline bath at room temperature by using H₂ activated by a Pd catalyst. Sulfur dyes are thus directly reduced, whereas vat dyes require an electron transfer mediator. This alternative reaction can also be driven using H₂ at sub-atmospheric pressures. It further avoids all drawbacks raised by electrolytic reductions, so far suggested as alternative green processes.     

Influence of NOx on the activity of Pd/θ-Al2O3 catalyst for methane oxidation: Alleviation of transient deactivation

Alumina supported Pd catalyst（Pd/Al₂O₃） is active for complete oxidation of methane, while often suffers transient deactivation during the cold down process. Herein, heating and cooling cycle tests between 200 and 900 °C and isothermal experiments at 650 °C were conducted to investigate the influence of NO_x on transient deactivation of Pd/θ-Al₂O₃ catalyst during the methane oxidation. It was found that the co-fed of NO alleviated transient d...     

Progress on metal-support interactions in Pd-based catalysts for automobile emission control

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.     

Material flow and industrial demand for palladium in Korea

Material flow analysis (MFA) requires the use of reliable data. In intermediate or the end industries that lack field survey data or actual statistical data, the integrated material flow analysis methodology uses bottom–up flow analysis for primary and secondary resources, and top–down flow analysis for the distribution structure. By combining the advantages of the top–down and bottom–up methods, the Integrated Material flow Analysis Methodology (IMFAM) can overcome the limitations of each methodology. Using the IMFAM, this study surveyed the material flow of palladium, and a platinoid element used in Korea. Palladium is produced as a byproduct in the copper refining process in Korea, and about 80% of used palladium as a three-way catalyst (TWC), i.e., an exhaust gas purifying system for automobiles. As automobile production in Korea is expected to continually increase, the usage of palladium is also expected to increase. Moreover, the increase in the use of printed circuit board (PCB) plating solutions is expected to further increase the use of palladium.This MFA results well represent the flow of palladium in Korea and give a strategy to secure palladium steadily.