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红外吸收光谱在多相催化反应表征中的新进展。

New advances in the use of infrared absorption spectroscopy for the characterization of heterogeneous catalytic reactions.

机构信息

Department of Chemistry, University of California, Riverside, CA 92521, USA.

出版信息

Chem Soc Rev. 2014 Nov 21;43(22):7624-63. doi: 10.1039/c3cs60374a.

Abstract

Infrared absorption spectroscopy has proven to be one of the most powerful spectroscopic techniques available for the characterization of catalytic systems. Although the history of IR absorption spectroscopy in catalysis is long, the technique continues to provide key fundamental information about a variety of catalysts and catalytic reactions, and to also offer novel options for the acquisition of new information on both reaction mechanisms and the nature of the solids used as catalysts. In this review, an overview is provided of the main contributions that have been derived from IR absorption spectroscopy studies of catalytic systems, and a discussion is included on new trends and new potential directions of research involving IR in catalysis. We start by briefly describing the power of Fourier-transform IR (FTIR) instruments and the main experimental IR setups available, namely, transmission (TIR), diffuse reflectance (DRIFTS), attenuated total reflection (ATR-IR), and reflection-absorption (RAIRS), for advancing research in catalysis. We then discuss the different environments under which IR characterization of catalysts is carried out, including in situ and operando studies of typical catalytic processes in gas-phase, research with model catalysts in ultrahigh vacuum (UHV) and so-called high-pressure cell instruments, and work involving liquid/solid interfaces. A presentation of the type of information extracted from IR data follows in terms of the identification of adsorbed intermediates, the characterization of the surfaces of the catalysts themselves, the quantitation of IR intensities to extract surface coverages, and the use of probe molecules to identify and titrate specific catalytic sites. Finally, the different options for carrying out kinetic studies with temporal resolution such as rapid-scan FTIR, step-scan FTIR, and the use of tunable lasers or synchrotron sources, and to obtain spatially resolved spectra, by sample rastering or by 2D imaging, are introduced.

摘要

红外吸收光谱已被证明是用于催化体系表征的最强大的光谱技术之一。尽管在催化作用中红外吸收光谱的历史悠久,但该技术仍继续为各种催化剂和催化反应提供关键的基本信息,并为获取有关反应机制和用作催化剂的固体的性质的新信息提供新的选择。在这篇综述中,概述了从催化体系的红外吸收光谱研究中得出的主要贡献,并讨论了涉及催化中的红外的新趋势和新的潜在研究方向。我们首先简要描述傅里叶变换红外(FTIR)仪器的功能以及可用的主要实验红外设置,即透射(TIR)、漫反射(DRIFTS)、衰减全反射(ATR-IR)和反射吸收(RAIRS),用于推进催化研究。然后,我们讨论了对催化剂进行红外表征的不同环境,包括在气相中进行典型催化过程的原位和操作条件研究、在超高真空(UHV)和所谓的高压池仪器中进行模型催化剂的研究,以及涉及液/固界面的研究。接下来,根据从红外数据中提取的信息类型进行介绍,包括吸附中间体的鉴定、催化剂表面的表征、IR 强度的定量以提取表面覆盖率,以及使用探针分子识别和滴定特定的催化位点。最后,介绍了具有时间分辨率的动力学研究的不同选项,例如快速扫描 FTIR、步进扫描 FTIR,以及使用可调谐激光器或同步辐射源,以及通过样品扫描或 2D 成像获得空间分辨光谱的选项。

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