Scanning Tunneling Microscopy of Bimetallic Ni/Co-HITP Metal–Organic Framework Monolayers

IF 3.3 3区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry C Pub Date : 2024-09-27 DOI:10.1021/acs.jpcc.4c06050

Fubiao Gu, Sisheng Shu, Christopher E. Patrick, Martin R. Castell

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Abstract

Metals (Ni, Co) and hexaaminotriphenylene (HATP) molecules are evaporated separately in an ultrahigh vacuum onto the Au(111) surface. During an annealing step, monolayer single metal and bimetallic Ni_xCo_3–x(HITP)₂ metal–organic frameworks (MOFs) are formed via an on-surface reaction of the organic molecules with the metals. The MOFs are characterized by scanning tunneling microscopy (STM), which reveals the hexagonal framework structures and growth processes. The pure Ni₃(HITP)₂ and bimetallic Ni_xCo_3–x(HITP)₂ frameworks have a similar isotropic island morphology, while the Co₃(HITP)₂ islands are ribbon shaped. Individual Ni and Co metal centers can be atomically identified by their different apparent heights in the STM images of the bimetallic framework. Density functional theory (DFT) calculations indicate that the apparent height difference is caused by electronic effects rather than the difference of topography. The STM images further reveal that in the mixed-metal MOFs the Ni and Co centers are distributed randomly.

Abstract Image

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双金属镍/Co-HITP 金属有机框架单层的扫描隧道显微镜研究

金属（镍、钴）和六氨基三亚苯（HATP）分子在超高真空中分别蒸发到金（111）表面。在退火步骤中，通过有机分子与金属的表面反应，形成单层单金属和双金属 NixCo3-x(HITP)2 金属有机框架（MOF）。扫描隧道显微镜（STM）对 MOFs 进行了表征，揭示了六边形框架结构和生长过程。纯 Ni3(HITP)2 和双金属 NixCo3-x(HITP)2 框架具有相似的各向同性岛形态，而 Co3(HITP)2 岛则呈带状。在双金属框架的 STM 图像中，可以通过不同的表观高度从原子上识别出单个的镍和钴金属中心。密度泛函理论（DFT）计算表明，表观高度差异是由电子效应而非形貌差异造成的。STM 图像进一步显示，在混合金属 MOF 中，镍和钴中心是随机分布的。

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来源期刊

The Journal of Physical Chemistry C 化学-材料科学：综合

CiteScore

6.50

自引率

8.10%

发文量

2047

审稿时长

1.8 months

期刊介绍： The Journal of Physical Chemistry A/B/C is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.