Nanoscale Cobalt-Manganese Oxide Catalyst Supported on Shape-Controlled Cerium Oxide: Effect of Nanointerface Configuration on Structural, Redox, and Catalytic Properties.

Title Nanoscale Cobalt-Manganese Oxide Catalyst Supported on Shape-Controlled Cerium Oxide: Effect of Nanointerface Configuration on Structural, Redox, and Catalytic Properties.
Authors B. Hillary; P. Sudarsanam; M.Hassan Amin; S.K. Bhargava
Journal Langmuir
DOI 10.1021/acs.langmuir.6b03445
Abstract

Understanding the role of nanointerface structures in supported bimetallic nanoparticles is vital for the rational design of novel high-performance catalysts. This study reports the synthesis, characterization, and the catalytic application of Co-Mn oxide nanoparticles supported on CeO2 nanocubes with the specific aim of investigating the effect of nanointerfaces in tuning structure-activity properties. High-resolution transmission electron microscopy analysis reveals the formation of different types of Co-Mn nanoalloys with a range of 6 ± 0.5 to 14 ± 0.5 nm on the surface of CeO2 nanocubes, which are in the range of 15 ± 1.5 to 25 ± 1.5 nm. High concentration of Ce(3+) species are found in Co-Mn/CeO2 (23.34%) compared with that in Mn/CeO2 (21.41%), Co/CeO2 (15.63%), and CeO2 (11.06%), as evidenced by X-ray photoelectron spectroscopy (XPS) analysis. Nanoscale electron energy loss spectroscopy analysis in combination with XPS studies shows the transformation of Co(2+) to Co(3+) and simultaneously Mn(4+/3+) to Mn(2+). The Co-Mn/CeO2 catalyst exhibits the best performance in solvent-free oxidation of benzylamine (89.7% benzylamine conversion) compared with the Co/CeO2 (29.2% benzylamine conversion) and Mn/CeO2 (82.6% benzylamine conversion) catalysts for 3 h at 120 °C using air as the oxidant. Irrespective of the catalysts employed, a high selectivity toward the dibenzylimine product (97-98%) was found compared with the benzonitrile product (2-3%). The interplay of redox chemistry of Mn and Co at the nanointerface sites between Co-Mn nanoparticles and CeO2 nanocubes as well as the abundant structural defects in cerium oxide plays a key role in the efficiency of the Co-Mn/CeO2 catalyst for the aerobic oxidation of benzylamine.

Citation B. Hillary; P. Sudarsanam; M.Hassan Amin; S.K. Bhargava.Nanoscale Cobalt-Manganese Oxide Catalyst Supported on Shape-Controlled Cerium Oxide: Effect of Nanointerface Configuration on Structural, Redox, and Catalytic Properties.. Langmuir. 2017;33(8):17431750. doi:10.1021/acs.langmuir.6b03445

Related Elements

Cerium

See more Cerium products. Cerium (atomic symbol: Ce, atomic number: 58) is a Block F, Group 3, Period 6 element with an atomic weight of 140.116. The number of electrons in each of cerium's shells is 2, 8, 18, 19, 9, 2 and its electron configuration is [Xe]4f2 6s2. Cerium Bohr ModelThe cerium atom has a radius of 182.5 pm and a Van der Waals radius of 235 pm. In its elemental form, cerium has a silvery white appearance. Cerium is the most abundant of the rare earth metals. It is characterized chemically by having two valence states, the +3 cerous and +4 ceric states. The ceric state is the only non-trivalent rare earth ion stable in aqueous solutions. Elemental CeriumIt is therefore strongly acidic and oxidizing, in addition to being moderately toxic.The cerous state closely resembles the other trivalent rare earths. Cerium is found in the minerals allanite, bastnasite, hydroxylbastnasite, monazite, rhabdophane, synchysite and zircon. Cerium was discovered by Martin Heinrich Klaproth, Jöns Jakob Berzelius, and Wilhelm Hisinger in 1803 and first isolated by Carl Gustaf Mosander in 1839. The element was named after the asteroid Ceres, which itself was named after the Roman god of agriculture.

Cobalt

See more Cobalt products. Cobalt (atomic symbol: Co, atomic number: 27) is a Block D, Group 9, Period 4 element with an atomic weight of 58.933195. Cobalt Bohr ModelThe number of electrons in each of cobalt's shells is 2, 8, 15, 2 and its electron configuration is [Ar]3d7 4s2. The cobalt atom has a radius of 125 pm and a Van der Waals radius of 192 pm. Cobalt was first discovered by George Brandt in 1732. In its elemental form, cobalt has a lustrous gray appearance. Cobalt is found in cobaltite, erythrite, glaucodot and skutterudite ores. Elemental CobaltCobalt produces brilliant blue pigments which have been used since ancient times to color paint and glass. Cobalt is a ferromagnetic metal and is used primarily in the production of magnetic and high-strength superalloys. Co-60, a commercially important radioisotope, is useful as a radioactive tracer and gamma ray source. The origin of the word Cobalt comes from the German word "Kobalt" or "Kobold," which translates as "goblin," "elf" or "evil spirit.

Manganese

See more Manganese products. Manganese (atomic symbol: Mn, atomic number: 25) is a Block D, Group 7, Period 4 element with an atomic weight of 54.938045. Manganese Bohr ModelThe number of electrons in each of Manganese's shells is [2, 8, 13, 2] and its electron configuration is [Ar] 3d5 4s2. The manganese atom has a radius of 127 pm and a Van der Waals radius of 197 pm. Manganese was first discovered by Torbern Olof Bergman in 1770 and first isolated by Johann Gottlieb Gahn in 1774. In its elemental form, manganese has a silvery metallic appearance. Elemental ManganeseIt is a paramagnetic metal that oxidizes easily in addition to being very hard and brittle. Manganese is found as a free element in nature and also in the minerals pyrolusite, braunite, psilomelane, and rhodochrosite. The name Manganese originates from the Latin word mangnes, meaning "magnet."

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