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A facile strategy has been explored for loading noble metals onto the surface of ferrite nanoparticles with the assistance of phosphine-functionalized linkers. Palladium loading is shown to occur with participation of both the phosphine function and the surface hydroxyl groups. Hybrid nanoparticles containing simultaneously Pd and Au (or Rh) are obtained by successive loading of metals. Similarly, ferrite nanoparticles decorated with Pd, Au, and Rh have also been formed by using the same strategy. The catalytic properties of the new nanoparticles are evidenced in processes such as reduction of 4-nitrophenol or hydrogenation of styrene. Besides, the sequential process involving a cross-coupling reaction followed by reduction of 1-nitrobiphenyl has been successfully achieved by employing Pd/Au decorated nanoferrite particles. [ABSTRACT FROM AUTHOR]

Abstract: A silicon micromonolith of 7mm diameter and 0.2mm length containing 1.5 million regular channels with a diameter of 3.3μm was used for obtaining hydrogen through ethanol or bio-ethanol steam reforming (ESR) and oxidative steam reforming (OSR). The microchannels were coated with RhPd/CeO2 catalyst by a two-step method. First a CeO2 layer of ca. 100nm thickness was deposited from cerium methoxyethoxide over a SiO2 layer, which was previously grown over the silicon microchannels by oxidation. Then, noble metals were grafted over the CeO2 support from chloride precursors. The unit was successfully tested for hydrogen production, achieving hydrogen rates of for the steam reforming of bio-ethanol at 873K, S/C=2 and 0.009s contact time. Reaction yields of 3.8 and 3.7mol hydrogen generated per mol ethanol in feed were measured for ESR and OSR, respectively. A performance comparison was performed with a conventional cordierite monolith with the same catalyst formulation. Results show for the silicon microreactor an outstanding improvement of the specific hydrogen production rate, operating at considerably reduced residence times, due to the increase in contact area per unit volume. [Copyright &y& Elsevier]

Ni-Fe nanocatalysts supported on CeO 2 have been prepared for the catalysis of methane steam reforming (MSR) aiming for coke-resistant noble metal-free catalysts. The catalysts have been synthesized by traditional incipient wetness impregnation as well as dry ball milling, a green and more sustainable preparation method. The impact of the synthesis method on the catalytic performance and the catalysts' nanostructure has been investigated. The influence of Fe addition has been addressed as well. The reducibility and the electronic and crystalline structure of Ni and Ni-Fe mono- and bimetallic catalysts have been characterized by temperature programmed reduction (H 2 -TPR), in situ synchrotron X-ray diffraction (SXRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Their catalytic activity was tested between 700 and 950 °C at 108 L g cat -1 h -1 and with the reactant flow varying between 54 and 415 L g cat -1 h -1 at 700 °C. Hydrogen production rates of 67 mol g met -1 h -1 have been achieved. The performance of the ball-milled Fe 0.1 Ni 0.9 /CeO 2 catalyst was similar to that of Ni/CeO 2 at high temperatures, but Raman spectroscopy revealed a higher amount of highly defective carbon on the surface of Ni-Fe nanocatalysts. The reorganization of the surface under MSR of the ball-milled NiFe/CeO 2 has been monitored by in situ near-ambient pressure XPS experiments, where a strong reorganization of the Ni-Fe nanoparticles with segregation of Fe toward the surface has been observed. Despite the catalytic activity being lower in the low-temperature regime, Fe addition for the milled nanocatalyst increased the coke resistance and could be an efficient alternative to industrial Ni/Al 2 O 3 catalysts., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

The hydrogenation of CO 2 to methanol over Cu/ZnO-based catalysts is highly sensitive to the surface composition and catalyst structure. Thus, its optimization requires a deep understanding of the influence of the pre-catalyst structure on its evolution under realistic reaction conditions, including the formation and stabilization of the most active sites. Here, the role of the pre-catalyst shape (cubic vs spherical) in the activity and selectivity of ZnO-supported Cu nanoparticles was investigated during methanol synthesis. A combination of ex situ , in situ , and operando microscopy, spectroscopy, and diffraction methods revealed drastic changes in the morphology and composition of the shaped pre-catalysts under reaction conditions. In particular, the rounding of the cubes and partial loss of the (100) facets were observed, although such motifs remained in smaller domains. Nonetheless, the initial pre-catalyst structure was found to strongly affect its subsequent transformation in the course of the CO 2 hydrogenation reaction and activity/selectivity trends. In particular, the cubic Cu particles displayed an increased activity for methanol production, although at the cost of a slightly reduced selectivity when compared to similarly sized spherical particles. These findings were rationalized with the help of density functional theory calculations.

Bimetallic Pt-Pd catalysts supported on ceria have been prepared by mechanochemical synthesis and tested for lean methane oxidation in dry and wet atmosphere. Results show that the addition of platinum has a negative effect on transient light-off activity, but for Pd/Pt molar ratios between 1:1 and 8:1 an improvement during time-on-stream experiments in wet conditions is observed. The bimetallic samples undergo a complex restructuring during operation, starting from the alloying of Pt and Pd and resulting in the formation of unprecedented "mushroom-like" structures consisting of PdO bases with Pt heads as revealed by high-resolution transmission electron microscopy (HRTEM) analysis. On milled samples, these structures are well-defined and observed at the interface between palladium and ceria, whereas those on the impregnated catalyst appear less ordered and are located randomly on the surface of ceria and of large PdPt clusters. The milled catalyst prepared by first milling Pd metal and ceria followed by the addition of Pt shows better performances compared to a conventional impregnated sample and also to a sample obtained by inverting the Pd-Pt milling order. This has been ascribed to the intimate contact between Pd and CeO 2 generated at the nanoscale during the milling process.