Ligand-functionalized surfaces for chemoselective heterogeneous catalysis

IF 2.1 4区 化学 Q3 CHEMISTRY, PHYSICAL Surface Science Pub Date : 2024-06-19 DOI:10.1016/j.susc.2024.122539
Swetlana Schauermann, Carsten Schröder, Marvin Ch. Schmidt, Philipp A. Haugg, Jan Smyczek
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Abstract

Selectivity of multi-pathway surface reactions depends on subtle differences in the activation barriers of competing reactive processes, which is difficult to control. One of the most promising strategies to overcome this problem is to introduce a specific selective interaction between the reactant and the catalytically active site, directing the chemical transformations towards the desired route. This interaction can be imposed via functionalization of a solid catalyst with organic ligands, promoting the desired pathway via steric constrain and/or electronic effects. The microscopic-level understanding of the underlying surface processes is an important prerequisite for rational design of such new class of ligand-functionalized catalytic materials. In this perspective, we present an overview over our recent mechanistic studies on heterogeneous Pd(111) catalysts functionalized with different types of organic ligands for chemoselective hydrogenation of a,b-unsaturated aldehyde acrolein. Employing a combination of real space microscopic (STM) and in operando spectroscopic (IRAS) surface sensitive techniques, we show that self-ordered active ligand layers are formed under operational conditions and identify their chemical nature and the geometric arrangement on the surface turning over. Deposition of a ligand layer renders Pd highly active and nearly 100 % selective toward propenol formation by promoting acrolein adsorption in a specific adsorption configuration via the O atom of the C = O bond. In this adsorption configuration, acrolein can be hydrogenated first to the desired reaction intermediate propenoxy species followed by formation of the target product propenol. Both the reaction intermediate and the final product propenol as well as their time evolution were identified by IRAS and gas phase analysis via quadrupole mass spectrometry (QMS). Particular focus of these studies was on the role of geometric and electronic effects imposed by specific functional groups purposefully introduced in the ligand layer. Obtained atomistic-level insights into the formation and dynamic evolution of the active ligand layer under operational conditions as well as into the role of geometric vs. electronic effects imposed by the ligand provide important input required for controlling chemoselectivity by purposeful surface functionalization.

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用于化学选择性异相催化的配体功能化表面
多途径表面反应的选择性取决于相互竞争的反应过程活化障碍的细微差别,而这是很难控制的。克服这一问题的最有前途的策略之一是在反应物和催化活性位点之间引入特定的选择性相互作用,将化学转化引向所需的途径。这种相互作用可以通过有机配体对固体催化剂进行官能化来实现,通过立体约束和/或电子效应促进所需的途径。从微观层面了解潜在的表面过程是合理设计这类新型配体功能化催化材料的重要前提。从这个角度出发,我们概述了最近对不同类型有机配体功能化的异质钯(111)催化剂进行的机理研究,这些催化剂用于 a、b-不饱和醛丙烯醛的化学选择性氢化。通过结合使用实空间显微镜(STM)和操作中光谱(IRAS)表面敏感技术,我们发现在操作条件下形成了自有序的活性配体层,并确定了它们的化学性质以及在表面翻转时的几何排列。配体层的沉积通过 C = O 键的 O 原子以特定的吸附构型促进丙烯醛的吸附,从而使钯具有很高的活性,对丙烯醇的形成几乎具有 100% 的选择性。在这种吸附构型中,丙烯醛可以首先氢化为所需的反应中间体丙烯氧基,然后形成目标产物丙烯醇。通过 IRAS 和四极杆质谱(QMS)气相分析,确定了反应中间体和最终产物丙烯醇及其时间演化过程。这些研究的重点是配位层中特意引入的特定官能团所产生的几何和电子效应。这些研究从原子层面深入了解了活性配体层在工作条件下的形成和动态演变,以及配体的几何效应和电子效应的作用,为通过有目的的表面官能化来控制化学选择性提供了重要依据。
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来源期刊
Surface Science
Surface Science 化学-物理:凝聚态物理
CiteScore
3.30
自引率
5.30%
发文量
137
审稿时长
25 days
期刊介绍: Surface Science is devoted to elucidating the fundamental aspects of chemistry and physics occurring at a wide range of surfaces and interfaces and to disseminating this knowledge fast. The journal welcomes a broad spectrum of topics, including but not limited to: • model systems (e.g. in Ultra High Vacuum) under well-controlled reactive conditions • nanoscale science and engineering, including manipulation of matter at the atomic/molecular scale and assembly phenomena • reactivity of surfaces as related to various applied areas including heterogeneous catalysis, chemistry at electrified interfaces, and semiconductors functionalization • phenomena at interfaces relevant to energy storage and conversion, and fuels production and utilization • surface reactivity for environmental protection and pollution remediation • interactions at surfaces of soft matter, including polymers and biomaterials. Both experimental and theoretical work, including modeling, is within the scope of the journal. Work published in Surface Science reaches a wide readership, from chemistry and physics to biology and materials science and engineering, providing an excellent forum for cross-fertilization of ideas and broad dissemination of scientific discoveries.
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