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在h-BN载体上形成单相Rh O纳米颗粒用于高度可控的甲烷部分氧化制合成气

Single-Phase Formation of Rh O Nanoparticles on h-BN Support for Highly Controlled Methane Partial Oxidation to Syngas.

作者信息

Kim Younhwa, Kang Sungsu, Kang Dohun, Lee Kyung Rok, Song Chyan Kyung, Sung Jongbaek, Kim Ji Soo, Lee Hyunjoo, Park Jungwon, Yi Jongheop

机构信息

School of Chemical and Biological Engineering, and Institute of Chemical Processes, Seoul National University, Seoul, 08826, Republic of Korea.

Center for Nanoparticle Research, Institute of Basic Science (IBS), Seoul, 08826, Republic of Korea.

出版信息

Angew Chem Int Ed Engl. 2021 Nov 22;60(48):25411-25418. doi: 10.1002/anie.202110292. Epub 2021 Oct 21.

Abstract

Single-phase formation of active metal oxides on supports has been vigorously pursued in many catalytic applications to suppress undesired reactions and to determine direct structure-property relationships. However, this is difficult to achieve in nanoscale range because the effect of non-uniform metal-support interfaces becomes dominant in the overall catalyst growth, leading to the nucleation of various metastable oxides. Herein, we develop a supported single-phase corundum-Rh O (I) nanocatalyst by utilizing controlled interaction between metal oxide and h-BN support. Atomic-resolution electron microscopy and first-principle calculation reveal that single-phase formation occurs via uniform and preferential attachment of Rh O (I) (110) seed planes on well-defined h-BN surface after decomposition of rhodium precursor. By utilizing the Rh/h-BN catalyst in methane partial oxidation, syngas is successfully produced solely following the direct route with keeping a H /CO ratio of 2, which makes it ideal for most downstream chemical processes.

摘要

在许多催化应用中,人们一直在大力追求在载体上形成单相活性金属氧化物,以抑制不希望发生的反应并确定直接的结构-性能关系。然而,这在纳米尺度范围内很难实现,因为不均匀的金属-载体界面效应在整个催化剂生长过程中占主导地位,导致各种亚稳氧化物的成核。在此,我们通过利用金属氧化物与h-BN载体之间的可控相互作用,开发了一种负载型单相刚玉-RhO(I)纳米催化剂。原子分辨率电子显微镜和第一性原理计算表明,在铑前驱体分解后,单相形成是通过RhO(I)(110)籽晶面在明确的h-BN表面上均匀且优先附着而发生的。通过在甲烷部分氧化中使用Rh/h-BN催化剂,合成气仅通过直接路线成功生产,且H/CO比保持为2,这使其成为大多数下游化学过程的理想选择。

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