Self-Organized Overlayers Formed by Alanine on Cu{311} Surfaces

Self-Organized Overlayers Formed by Alanine on Cu{311} Surfaces
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Cu{311} 表面上丙氨酸形成的自组织覆盖层

DOI:
10.1021/jp505636v
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发表时间:
2014
期刊:
The Journal of Physical Chemistry C
影响因子:
--
通讯作者:
Madden D
Madden D
中科院分区:
--
文献类型:
--
作者:
Madden D

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当分子吸附在金属表面时,手性可以以不同的方式表现出来。如果要将金属表面用于对映体选择性多相催化或对映体识别传感器,清楚地了解分子手性、“足迹手性”和远程自组织中的手性之间的相互作用是至关重要的。我们用反射吸收红外光谱结合第一性原理计算研究了L-丙氨酸以丙氨酸酯形式吸附在铜{311}上的自组织行为,并用低能电子衍射和扫描隧道显微镜研究了结构特征。观察到三种有序结构。一种具有对称晶格和三点吸附键合(“对称晶格”或SL相);另一种出现在较高覆盖率时,具有手性晶格,还涉及两点键合(“手性晶格”或CL相)。讨论了这些结构的可能模型,以及足迹手性和长程手性在自组织中的作用。这些结果将在铜{110}和{100}表面丙氨酸盐覆盖层中看到的手性形式置于更广泛的背景下。共同的基本原理应该有助于建立一个理解手性吸附物在低对称性金属表面上的行为的一般框架。
Chirality can manifest itself in diverse ways when a molecule adsorbs on a metal surface. A clear understanding of the interplay between molecular chirality, “footprint chirality”, and chirality in the long-range self-organization is crucial if metal surfaces are to be exploited for enantioselective heterogeneous catalysis or enantio-discriminating sensors. We have investigated the self-organization ofl-alanine adsorbed as alaninate on Cu{311}, using reflection–absorption infrared spectroscopy in conjunction with first-principles calculations to determine bonding configurations, and low-energy electron diffraction and scanning tunnelling microscopy to elucidate structural features. Three ordered structures are seen. One has a symmetric lattice and 3-point adsorbate bonding (the “symmetric lattice” or SL phase); the others, occurring at higher coverage, have chiral lattices and also involve 2-point bonding (the “chiral lattice” or CL phase). Possible models for these structures are discussed, together with the roles of footprint chirality and of long-range chirality in the self-organization. These results set the forms of chirality seen in alaninate overlayers on Cu{110} and {100} surfaces into a wider context. The common underlying principles should help in establishing a general framework for understanding the behavior of chiral adsorbates on low-symmetry metal surfaces.
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