Acetonitrile Adsorption and Adhesion Energies onto the Pt(111) Surface by Calorimetry
Acetonitrile Adsorption and Adhesion Energies onto the Pt(111) Surface by Calorimetry
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通过量热法测定乙腈在 Pt(111) 表面上的吸附和粘附能
DOI：
10.1021/acscatal.1c04622
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发表时间：
2022
期刊：
影响因子：
12.9
通讯作者：
Campbell, Charles T.
中科院分区：
文献类型：
--
作者：
Ruehl, Griffin;Harman, S. Elizabeth;Árnadóttir, Líney;Campbell, Charles T.
乙腈是多相催化和电化学应用的常见溶剂，也是有机腈的最简单例子。了解它与铂(111)相互作用的能量学和性质对于广泛的应用是有意义的，特别是对于估计乙腈作为溶剂对催化和电催化反应中间体在铂族金属上的吸附能的影响。本文用单晶吸附量热法(SCAC)测量了乙腈分子在干净的铂(111)面上的吸附热随覆盖度的变化，并由此估算了液态乙腈在铂(111)面上的吸附能。在180K时，微分吸附热最初为82.9kJ/mol，饱和覆盖度为0.25ML时降至63.2kJ/mol。在饱和覆盖度为0.25ML时，180K时的积分吸附热为74.3kJ/mol。在100K时，吸附热最初为84.5kJ/∼，第一层(0.35ML)完成后降至45kJ/m ol，最后在覆盖度高于0.7m L时达到43.4kJ/m o l的恒定多层热。(所有预热的误差条均为±4%。)100K时的饱和覆盖率高于180K，这是由于100K时由于表面迁移率较低而形成了不太稳定的吸附组态。利用100K至块状多层膜的吸附热，我们估算出液体乙腈在铂表面的吸附能为0.198 J/m2，这可以用来估计乙腈作为溶剂对催化反应物相对于气相的吸附能的影响。这个吸附能比水、苯和苯酚在铂(111)面上的吸附能低得多，但略大于甲醇和甲酸的吸附能。
Acetonitrile is a common solvent for heterogeneous catalysis and electrochemical applications, as well as the simplest example of an organic nitrile. Understanding the energetics and nature of its interactions with Pt(111) is of interest for a wide array of applications, especially for estimating the effect of acetonitrile as a solvent on the adsorption energies of catalytic and electrocatalytic reaction intermediates on Pt-group metals. Here, the heat of adsorption of molecular acetonitrile on clean Pt(111) was measured by single-crystal adsorption calorimetry (SCAC) as a function of coverage, and from that, the adhesion energy of liquid acetonitrile to Pt(111) was estimated. At 180 K, the differential heat of adsorption is initially 82.9 kJ/mol, decreasing to 63.2 kJ/mol by a saturation coverage of 0.25 ML. The integral (average) heat of adsorption at 180 K is 74.3 kJ/mol at a saturation coverage of 0.25 ML. At 100 K, the heat of adsorption is 84.5 kJ/mol initially, decreases to ∼45 kJ/mol after the completion of the first layer (0.35 ML), and finally reaches a constant multilayer heat of 43.4 kJ/mol at coverages higher than 0.7 ML. (Errors bars on all heats are ±4%.) The saturation coverage is higher at 100 K than 180 K, attributed to the formation of a less stable adsorbate configuration at 100 K due to lower surface mobility. Using the heats of adsorption at 100 K up to bulklike multilayer coverages, we estimate the adhesion energy for liquid acetonitrile to Pt(111) to be 0.198 J/m2, which can be used to estimate the effect of acetonitrile as a solvent on the adsorption energies of catalytic reactants relative to the gas phase. This adhesion energy is considerably lower than those for water, benzene, and phenol on Pt(111) but slightly greater than those for methanol and formic acid.
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影响因子：
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作者：
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