Dobrezberger Klaus, Bosters Johannes, Moser Nico, Yigit Nevzat, Nagl Andreas, Föttinger Karin, Lennon David, Rupprechter Günther
Institute of Materials Chemistry, Technische Universität Wien, Getreidemarkt 9/BC, 1060 Wien, Austria.
School of Chemistry, University of Glasgow, Joseph Black Building, University Avenue, Glasgow G12 8QQ, Scotland U.K.
J Phys Chem C Nanomater Interfaces. 2020 Oct 29;124(43):23674-23682. doi: 10.1021/acs.jpcc.0c06636. Epub 2020 Oct 19.
Pd nanoparticles (1 wt %; mean size ∼4 nm) were supported on ∼2 μm sized, but few nanometers thick, graphene nanoplatelets (GNPs) and compared to 1 wt % Pd on activated carbon or γ-alumina. Catalyst morphology, specific surface area, and Pd particle size were characterized by SEM, BET, and TEM, respectively. H-TPD indicated that GNPs intercalated hydrogen, which may provide additional H supply to the Pd nanoparticles during CH hydrogenation. Whereas the two types of Pd/GNPs (NaOH vs calcinated) catalysts were less active than Pd/C and Pd/AlO below 40 °C, at 55 °C they were about 3-4 times more active. As for example Pd/GNPs (NaOH) and Pd/AlO exhibited not too different mean Pd particle size (3.7 vs 2.5 nm, respectively), the higher activity is attributed to the additional hydrogen supply likely by the metal/support interface, as suggested by the varying CH and H orders on the different supports. XANES measurements during CH hydrogenation revealed the presence of Pd hydride. The Pd hydride was more stable for Pd/GNPs (NaOH) than for Pd/C, once more pointing to a better hydrogen supply by graphene nanoplatelets.
将钯纳米颗粒(1重量%;平均尺寸约4纳米)负载在尺寸约为2微米、厚度仅几纳米的石墨烯纳米片(GNP)上,并与负载在活性炭或γ-氧化铝上的1重量%钯进行比较。分别通过扫描电子显微镜(SEM)、比表面积测定法(BET)和透射电子显微镜(TEM)对催化剂的形态、比表面积和钯颗粒尺寸进行了表征。程序升温脱附氢(H-TPD)表明,石墨烯纳米片能够嵌入氢,这可能在甲烷氢化过程中为钯纳米颗粒提供额外的氢供应。在40℃以下,两种类型的钯/石墨烯纳米片(氢氧化钠处理与煅烧处理)催化剂的活性低于钯/碳和钯/氧化铝催化剂,但在55℃时,它们的活性约为钯/碳和钯/氧化铝催化剂的3 - 4倍。例如,钯/石墨烯纳米片(氢氧化钠处理)和钯/氧化铝催化剂的钯平均颗粒尺寸差异不大(分别为3.7纳米和2.5纳米),较高的活性归因于金属/载体界面可能提供的额外氢供应,这一点由不同载体上甲烷和氢的反应级数变化所表明。甲烷氢化过程中的X射线吸收近边结构(XANES)测量揭示了氢化钯的存在。氢化钯在钯/石墨烯纳米片(氢氧化钠处理)催化剂中比在钯/碳催化剂中更稳定,这再次表明石墨烯纳米片具有更好的氢供应能力。