Anchoring of a Carboxyl-Functionalized Norbornadiene Derivative to an Atomically Defined Cobalt Oxide Surface
Anchoring of a Carboxyl-Functionalized Norbornadiene Derivative to an Atomically Defined Cobalt Oxide Surface
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羧基官能化降冰片二烯衍生物锚定至原子定义的氧化钴表面
DOI：
10.1021/acs.jpcc.7b02620
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发表时间：
2017
影响因子：
3.7
通讯作者：
Libuda
中科院分区：
文献类型：
--
作者：
Schwarz;Döpper;Civale;Hirsch;Görling;Libuda
我们研究了分子能量载体降冰片二烯（NBD）锚定到原子定义的氧化物表面。为此，我们合成了一种羧基官能化的NBD衍生物1-（2 ′-norbornadienyl）pentanoic acid（NBDA），并在超高真空（UHV）条件下通过物理气相沉积（PVD）将其沉积到生长在Ir（100）上的有序Co3O4（111）薄膜上。此外，我们在相同条件下使用苯甲酸（BA）进行了比较生长研究，将其用作参比。NBDA和BA与氧化物表面的相互作用和取向进行了监测，在原位薄膜生长过程中，通过等温时间分辨红外反射吸收光谱（TR-IRAS），低于和高于多层脱附温度。利用程序升温红外光谱（TP-IRAS）和密度泛函（DF）计算研究了薄膜的热行为和稳定性。BA与Co3O4（111）结合形成对称螯合羧酸盐，其分子平面取向几乎垂直于表面。在低温（130 K）下，完整的BA物理吸附在饱和单层的顶部上的二聚体的形式。当退火至155 K时，观察到重新排序转变，其中多层膜中的BA采用更平坦的取向。BA多层膜在220 K下脱附，而表面锚定的BA单层膜在400 K以下是稳定的。在较高温度（400 - 550 K）下，观察到脱附和分解。与BA非常相似，NBDA通过形成对称螯合羧酸盐与Co3O4（111）结合。在多层膜中，在240 K下脱附，形成氢键键合的NBDA二聚体。在300 K下对NBDA进行PVD时，只有表面锚定的羧酸盐是稳定的。锚定的NBDA膜显示出作为覆盖函数的特征性重构行为。在低覆盖度的NBDA，采用平躺结构，其中降冰片二烯单元与Co3O4表面相互作用。随着覆盖度的增加，降冰片二烯单元从氧化物中分离，NBDA采用直立取向。与BA类似，锚定膜在高达400 K时是稳定的，并且在400和550 K之间的温度区域中分解，在氧化物表面上留下烃残留物。
We have investigated the anchoring of the molecular energy carrier norbornadiene (NBD) to an atomically defined oxide surface. To this end, we synthesized a carboxyl-functionalized NBD derivative, namely 1-(2′-norbornadienyl)pentanoic acid (NBDA), and deposited it by physical vapor deposition (PVD) under ultrahigh vacuum (UHV) conditions onto a well-ordered Co3O4(111) film grown on Ir(100). In addition, we performed a comparative growth study with benzoic acid (BA) under identical conditions which was used as a reference. The interaction and orientation of NBDA and BA with the oxide surface were monitored in situ during film growth by isothermal time-resolved infrared reflection–absorption spectroscopy (TR-IRAS), both below and above the multilayer desorption temperature. The thermal behavior and stability of the films were investigated by temperature-programmed IRAS (TP-IRAS), with help of density functional (DF) calculations. BA binds to Co3O4(111) under formation of a symmetric chelating carboxylate with the molecular plane oriented nearly perpendicular to the surface. At low temperature (130 K), intact BA physisorbs in form of dimers on top of the saturated monolayer. Upon annealing to 155 K, a reordering transition is observed, in which BA in the multilayer adopts a more flat-lying orientation. The BA multilayer desorbs at 220 K, whereas the surface-anchored BA monolayer is stable up to 400 K. At higher temperature (400–550 K), desorption and decomposition are observed. Very similar to BA, NBDA binds to Co3O4(111) by formation of a symmetric chelating carboxylate. In the multilayer, which desorbs at 240 K, hydrogen-bonded NBDA dimers are formed. Upon PVD of NBDA at 300 K, only a surface anchored carboxylate is stable. The anchored NBDA film shows a characteristic restructuring behavior as a function of coverage. At low coverage the NBDA, adopts a flat-lying structure in which the norbornadiene unit interacts with the Co3O4surface. With increasing coverage, the norbornadiene units detach from the oxide and the NBDA adopts an upright-standing orientation. Similar to BA, the anchored film is stable up to 400 K and decomposes in the temperature region between 400 and 550 K, leaving behind hydrocarbon residues on the oxide surface.
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影响因子：
4.3
作者：
Quant, Maria;Lennartson, Anders;Dreos, Ambra;Kuisma, Mikael;Erhart, Paul;Borjesson, Karl;Moth-Poulsen, Kasper
通讯作者：
Moth-Poulsen, Kasper
DOI：
--
发表时间：
1981
期刊：
影响因子：
--
作者：
K. Maruyama;Kazutoshi Terada;Yoshinori Yamamoto
通讯作者：
Yoshinori Yamamoto
振动光谱探测锐钛矿型 TiO2(1 0 1) 上甲酸的解离
影响因子：
5.3
作者：
Mingchun Xu;H. Noei;Maria Buchholz;M. Muhler;C. Wöll;Yuemin Wang
通讯作者：
Yuemin Wang
影响因子：
2.5
作者：
COLOMBO, L;VOLOVSEK, V;LEPOSTOLLEC, M
通讯作者：
LEPOSTOLLEC, M
影响因子：
7.3
作者：
Desikusumastuti, Aine;Staudt, Thorsten;Libuda, Joerg
通讯作者：
Libuda, Joerg