NiFe and CoFe nanocatalysts supported on highly dispersed alumina-silica: Structure, surface properties, and performance in CO2 methanation.

The hydrogenation of CO2 to CH4 has gained considerable interest in terms of sustainable energy and environmental mitigation. In this regard, the present work aims to investigate the adsorptive concentration and CO2 methanation performance over CoFe and NiFe bimetallic catalysts supported on fumed alumina-silica SA96 support at 170-450 °C and under atmospheric pressure. The catalysts were prepared by wet impregnation method, subjected to calcination and further reduced with hydrogen, and their performance in CO2 methanation was investigated in a hydrogen-rich 2%CO2-55%H2-43%He gas mixture. In this study, we describe the crystal and mesoporous structures of the prepared catalysts by in-situ XRD and ex-situ nitrogen adsorption, evaluate the NiFe and CoFe metal surface states before and after catalysis by XPS, visualize the surface morphology by SEM, estimate the catalytic activity by gas chromatography, and investigate the adsorbed surface species, showing the presence of *HCOO/*HCO and *CO intermediates, determine two possible pathways of CH4 formation on the studied catalysts by temperature-programmed desorption mass spectrometry, and correlate the structural and surface properties with high CO2 conversions up to 100% and methanation selectivities up to 72%. The latter is related to changes in the elemental chemical states and surface composition of CoFe and NiFe nanocatalysts induced by treatment under reaction conditions, and the surface reconstruction during catalysis transfers the part of active 3d transition metals into the pores of the SA96 support. Our thorough characterization study with complementary techniques allowed us to conclude that this high activity is related to the formation of catalytically active Ni/Ni3Fe and Co/CoFeOx nanoscale crystallites under H2 reduction and their maintenance under CO2 methanation conditions. The successfully applied combination of CO2 chemisorption and thermodesorption techniques demonstrates the ability to adsorb the CO2 molecules by supported NiFe and CoFe nanocatalysts and the pure alumina-silica SA96 support.

Heteroaggregation of virions and microplastics reduces the number of active bacteriophages in aqueous environments.

The objective of this study is to explore the effects of microplastics on the viability of the bacteriophages in an aqueous environment. Bacteriophages (phages), that is, viruses of bacteria, are essential in homeostasis. It is estimated that phages cause up to 40% of the death of all bacteria daily. Any factor affecting phage activity is vital for the whole food chain and the ecology of numerous niches. We hypothesize that the number of active phages decreases due to the virions' adsorption on microplastic particles or by the released leachables from additives used in the production of plastic, for example, stabilizers, plasticizers, colorants, and reinforcements. We exposed three diverse phages, namely, T4 (tailed), MS2 (icosahedral), and M13 (filamentous), to 1 mg/mL suspension of 12 industrial-grade plastics [acrylonitrile butadiene styrene, high-impact polystyrene, poly-ε-caproamide, polycarbonate, polyethylene, polyethylene terephthalate, poly(methyl methacrylate), polypropylene, polystyrene, polytetrafluoroethylene, polyurethane, and polyvinyl chloride] shredded to obtain microparticles of radius ranging from 2 to 50 µm. The effect of leachables was measured upon exposure of phages not to particles themselves but to the buffer preincubated with microplastics. A double-overlay plaque counting method was used to assess phage titers. We employed a classical linear regression model to verify which physicochemical parameters (65 variables were tested) govern the decrease of phage titers. The key finding is that adsorption mechanisms result in up to complete scavenging of virions, whereas leachables deactivate up to 50% of phages. This study reveals microplastic pollution's plausible and unforeseen ecotoxicological effect causing phage deactivation. Moreover, phage transmission through adsorption can alter the balance of the food chain in the new environment. The effect depends mainly on the zeta potentials of the polymers and the phage type.

Application of silica-supported Ir and Ir-M (M = Pt, Pd, Au) catalysts for low-temperature hydrodechlorination of tetrachloromethane.

Herein, it is presented a catalytic system for gas-phase hydrodechlorination of tetrachloromethane at low temperature and atmospheric pressure, using iridium supported on silica as parent catalyst. Iridium electronic configuration is suitable to catalyse the hydrodechlorination reactions, however, it has been rarely used in this reaction to date. The catalytic abilities were significantly improved when a second transition metal was added. Catalysts' stability and selectivity to the desired products (i.e. C1-C4 hydrocarbons) improved compared to conventional activation in hydrogen when catalysts were activated shortly with microwave irradiation. Microwave irradiation of catalysts favourably influences the homogeneity of the metallic active phase, both in terms of the size of metal crystals and the homogeneity of bimetallic systems. Addition of platinum to the 'parent' iridium catalyst improved its catalytic properties and decreased deactivation. Fresh and spent catalysts were comprehensively characterized using several techniques (BET, CO-chemisorption, XRD, XPS, electron microscopy and mass spectrometry) to determine structure-activity relationships and potential causes for catalyst deactivation. No significant changes in crystalline size or bimetallic phase composition were observed for spent catalysts (with the exception of Ir-Pd catalysts which underwent bulk carbide during the reaction).

Hydrodechlorination of Tetrachloromethane over Palladium Catalysts Supported on Mixed MgF2-MgO Carriers.

Pd/MgO, Pd/MgF2 and Pd/MgO-MgF2 catalysts were investigated in the reaction of CCl4 hydrodechlorination. All the catalysts deactivated in time on stream, but the degree of deactivation varied from catalyst to catalyst. The MgF2-supported palladium with relatively large metal particles appeared the best catalyst, characterized by good activity and selectivity to C2-C5 hydrocarbons. Investigation of post-reaction catalyst samples allowed to find several details associated with the working state of hydrodechlorination catalysts. The role of support acidity was quite complex. On the one hand, a definite, although not very high Lewis acidity of MgF2 is beneficial for shaping high activity of palladium catalysts. The MgO-MgF2 support characterized by stronger Lewis acidity than MgF2 contributes to very good catalytic activity for a relatively long reaction period (~5 h) but subsequent neutralization of stronger acid centers (by coking) eliminates them from the catalyst. On the other hand, the role of acidity evolution, which takes place when basic supports (like MgO) are chlorided during HdCl reactions, is difficult to assess because different events associated with distribution of chlorided support species, leading to partial or even full blocking of the surface of palladium, which plays the role of active component in HdCl reactions.