Muir Mark, Molina David L, Islam Arephin, Abdel-Rahman Mohammed K, Trenary Michael
Department of Chemistry, University of Illinois at Chicago, 845 W. Taylor St., Chicago, Illinois 60607, USA.
Phys Chem Chem Phys. 2020 Nov 21;22(43):25011-25020. doi: 10.1039/d0cp04634e. Epub 2020 Oct 28.
Reflection absorption infrared spectroscopy and temperature programmed desorption were used to study the adsorption of acrolein, its partial hydrogenation products, propanal and 2-propenol, and its full hydrogenation product, 1-propanol on the Ag(111) surface. Each molecule adsorbs weakly to the surface and desorbs without reaction at temperatures below 220 K. For acrolein, the out-of plane bending modes are more intense than the C[double bond, length as m-dash]O stretch at all coverages, indicating that the molecular plane is mainly parallel to the surface. The two alcohols, 2-propenol and 1-propanol, have notably higher desorption temperatures than acrolein and display strong hydrogen bonding in the multilayers as revealed by a broadened and redshifted O-H stretch. For 1-propanol, annealing the surface to 180 K disrupts the hydrogen-bonding to produce unusally narrow peaks, including one at 1015 cm with a full width at half maximum of 1.1 cm. This suggests that 1-propanol forms a highly orderded monolayer and adsorbs as a single conformer. For 2-propenol, hydrogen bonding in the multilayer correlates with observation of the C[double bond, length as m-dash]C stretch at 1646 cm, which is invisible for the monolayer. This suggests that for monolayer coverages, 2-propenol bonds with the C[double bond, length as m-dash]C bond parallel to the surface. Similarly, the C[double bond, length as m-dash]O stretch of propanal is very weak for low coverages but becomes the largest peak for the multilayer, indicating a change in orientation with coverage.
采用反射吸收红外光谱和程序升温脱附技术研究了丙烯醛及其部分氢化产物丙醛和2-丙烯醇以及完全氢化产物1-丙醇在Ag(111)表面的吸附情况。在220 K以下,每个分子都以弱吸附状态吸附在表面且不发生反应而脱附。对于丙烯醛,在所有覆盖度下,面外弯曲振动模式都比C=O伸缩振动更强烈,这表明分子平面主要与表面平行。两种醇,2-丙烯醇和1-丙醇,脱附温度明显高于丙烯醛,并且如通过展宽和红移的O-H伸缩振动所揭示的,在多层中显示出强氢键作用。对于1-丙醇,将表面加热到180 K会破坏氢键,产生异常窄的峰,包括一个在1015 cm处半高宽为1.1 cm的峰。这表明1-丙醇形成了高度有序的单层,并且以单一构象吸附。对于2-丙烯醇,多层中的氢键作用与在1646 cm处C=C伸缩振动的观测相关,而该振动对于单层是不可见的。这表明对于单层覆盖度,2-丙烯醇以C=C键与表面平行的方式键合。同样,丙醛的C=O伸缩振动在低覆盖度时非常弱,但在多层中成为最大的峰,这表明其取向随覆盖度发生了变化。