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金属/氧化物界面效应对伯醇选择性氧化的影响。

Metal/oxide interfacial effects on the selective oxidation of primary alcohols.

机构信息

Department of Chemistry, Tsinghua University, Beijing 100084, China.

State Key Laboratory of Catalysis, CAS Center for Excellence in Nanoscience, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.

出版信息

Nat Commun. 2017 Jan 18;8:14039. doi: 10.1038/ncomms14039.

Abstract

A main obstacle in the rational development of heterogeneous catalysts is the difficulty in identifying active sites. Here we show metal/oxide interfacial sites are highly active for the oxidation of benzyl alcohol and other industrially important primary alcohols on a range of metals and oxides combinations. Scanning tunnelling microscopy together with density functional theory calculations on FeO/Pt(111) reveals that benzyl alcohol enriches preferentially at the oxygen-terminated FeO/Pt(111) interface and undergoes readily O-H and C-H dissociations with the aid of interfacial oxygen, which is also validated in the model study of CuO/Ag(111). We demonstrate that the interfacial effects are independent of metal or oxide sizes and the way by which the interfaces were constructed. It inspires us to inversely support nano-oxides on micro-metals to make the structure more stable against sintering while the number of active sites is not sacrificed. The catalyst lifetime, by taking the inverse design, is thereby significantly prolonged.

摘要

在合理开发多相催化剂方面,主要的障碍是难以确定活性位。在这里,我们证明金属/氧化物界面位在一系列金属和氧化物组合上对苯甲醇和其他工业上重要的伯醇的氧化具有很高的活性。在 FeO/Pt(111) 上进行的扫描隧道显微镜和密度泛函理论计算表明,苯甲醇优先富集在氧终止的 FeO/Pt(111)界面上,并在界面氧的帮助下容易发生 O-H 和 C-H 解离,这在 CuO/Ag(111) 的模型研究中也得到了验证。我们证明界面效应与金属或氧化物的大小以及形成界面的方式无关。这启发我们在微金属上反向支撑纳米氧化物,以使结构更稳定,不易烧结,同时不牺牲活性位的数量。通过采用反向设计,催化剂的寿命得到了显著延长。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/928c/5253635/6fe1d8e97c87/ncomms14039-f1.jpg

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