Switch in Relative Stability between cis and trans 2-Butene on Pt(111) as a Function of Experimental Conditions: A Density Functional Theory Study
Switch in Relative Stability between cis and trans 2-Butene on Pt(111) as a Function of Experimental Conditions: A Density Functional Theory Study
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DOI：
10.1021/acscatal.8b00544
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发表时间：
2018-03
期刊：
影响因子：
12.9
通讯作者：
Jinyu Li;P. Fleurat‐Lessard;F. Zaera;F. Delbecq
中科院分区：
文献类型：
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作者：
Jinyu Li;P. Fleurat‐Lessard;F. Zaera;F. Delbecq
通过基于包含色散力的密度泛函理论 (DFT) 的计算，研究了顺式和反式 2-丁烯在 Pt(111) 上的吸附与氢覆盖度 θH 的函数关系。所有氢覆盖范围均已考虑，从 0 到 1.00 单层 (ML)。对于每种情况，在 θC4H8 = 0.11 ML 的表面覆盖度下比较了烯烃的 di-σ 和 π 吸附几何形状。对这些系统的吉布斯自由能的计算确定了最稳定的 2-丁烯异构体（顺式或反式）作为覆盖率、温度和压力的函数。特别是，重点放在两组条件上，即一组条件为压力为 10-7 Torr、温度为 80 K、气体比（PH2/P丁烯）为 25，类似于表面科学研究中使用的条件；第二组条件为压力为 1 bar、温度范围为 300-400 K、气体比（PH2/P丁烯）为 10，类似于催化氢化条件。具有所有选定的功能（PW91、PBE-TS 和 o...
The adsorption of cis and trans 2-butenes on Pt(111) has been studied as a function of hydrogen coverage θH by means of calculations based on density functional theory (DFT) with the inclusion of dispersion forces. All hydrogen coverages have been considered, from 0 to 1.00 monolayer (ML). For each case, the di-σ and π adsorption geometries of the olefins have been compared at a surface coverage of θC4H8 = 0.11 ML. Calculations of the Gibbs free energies of these systems have identified the most stable 2-butene isomer (cis or trans) as a function of coverage, temperature, and pressure. In particular, focus was placed on two sets of conditions, namely, one with a pressure of 10–7 Torr, a temperature of 80 K, and a gas ratio (PH2/Pbutene) of 25, similar to the conditions used in surface-science studies, and a second with a pressure of 1 bar, a temperature range of 300–400 K, and a gas ratio (PH2/Pbutene) of 10, similar to catalytic hydrogenation conditions. With all selected functionals (PW91, PBE-TS, and o...