Energetics of adsorbed benzene on Ni(111) and Pt(111) by calorimetry
Energetics of adsorbed benzene on Ni(111) and Pt(111) by calorimetry
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DOI：
10.1016/j.susc.2018.02.014
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发表时间：
2018-10-01
期刊：
影响因子：
1.9
通讯作者：
Campbell, Charles T.
中科院分区：
文献类型：
--
作者：
Carey, Spencer J.;Zhao, Wei;Campbell, Charles T.
用单晶吸附量热法(SCAC)测定了90K下苯在Ni(111)和Pt(111)上的吸附热和粘附率。苯在Ni(111)上的低覆盖范围内以208kJ/mol的热吸附在阶地上，在1/9ML的覆盖度下的标准生成热(H-f(0))为C6H6，ADS为-251kJ/mol。将这些结果与在铂(111)面上的量热结果进行了比较，在1/9ML的覆盖度下，C6H6，ADS的标准生成热(H-f(0))为-244kJ/mol。与Ni的成键略强归因于较强的C-Ni共价键，部分补偿了对Ni的较弱的范德华(VDW)引力。将测得的苯的能量学与以前文献中的密度泛函理论(DFT)计算进行了比较，表明不包含VDW相互作用修正的泛函严重低估了苯与Ni(111)和Pt(111)的键能，而许多修正VDW相互作用的泛函要精确得多。
The heat of adsorption and sticking probability of benzene were measured on Ni(111) and Pt(111) at 90 K using single crystal adsorption calorimetry (SCAC). Benzene adsorbs molecularly with a heat of 208 kJ/mol on terrace sites in the low-coverage limit on Ni(111) and has a standard enthalpy of formation (Delta H-f(0)) of C6H6,ads of -251 kJ/mol at a coverage of 1/9 ML. These results are compared to calorimetric results on Pt(111), where the standard enthalpy of formation (Delta H-f(0)) of C6H6,ads was found to be - 244 kJ/mol at a coverage of 1/9 ML. The slightly stronger bonding to Ni is attributed to stronger C-Ni covalent bonding partially compensated by weaker van der Waals (vdW) attractions to Ni compared to Pt. The measured energetics for benzene are compared to Density Functional Theory (DFT) calculations from previous literature, showing that functionals that do not contain corrections for vdW interactions badly underestimate the bond energies of benzene to both Ni(111) and Pt(111), while many of those that correct for vdW interactions are much more accurate.