Copéret Christophe, Chabanas Mathieu, Petroff Saint-Arroman Romain, Basset Jean-Marie
Laboratoire de Chimie Organométallique de Surface, UMR 9986 CNRS/CPE Lyon, 43 Bd du 11 Novembre 1918, 69616 Villeurbanne Cedex, France.
Angew Chem Int Ed Engl. 2003 Jan 13;42(2):156-81. doi: 10.1002/anie.200390072.
Surface organometallic chemistry is an area of heterogeneous catalysis which has recently emerged as a result of a comparative analysis of homogeneous and heterogeneous catalysis. The chemical industry has often favored heterogeneous catalysis, but the development of better catalysts has been hindered by the presence of numerous kinds of active sites and also by the low concentration of active sites. These factors have precluded a rational improvement of these systems, hence the empirical nature of heterogeneous catalysis. Catalysis is primarily a molecular phenomenon, and it must involve well-defined surface organometallic intermediates and/or transition states. Thus, one must be able to construct a well-defined active site, test its catalytic performance, and assess a structure-activity relationship, which will be used, in turn-as in homogeneous catalysis-to design better catalysts. By the transfer of the concepts and tools of molecular organometallic chemistry to surfaces, surface organometallic chemistry can generate well-defined surface species by understanding the reaction of organometallic complexes with the support, which can be considered as a rigid ligand. This new approach to heterogeneous catalysis can bring molecular insight to the design of new catalysts and even allow the discovery of new reactions (Ziegler-Natta depolymerization and alkane metathesis). After more than a century of existence, heterogeneous catalysis can still be improved and will play a crucial role in solving current problems. It offers an answer to economical and environmental problems faced by industry in the production of molecules (agrochemicals, petrochemicals, pharmaceuticals, polymers, basic chemicals).
表面有机金属化学是多相催化领域中因对均相催化和多相催化进行比较分析而新近出现的一个领域。化学工业一直青睐多相催化,但由于存在多种活性位点以及活性位点浓度较低,更好催化剂的开发受到了阻碍。这些因素妨碍了对这些体系进行合理改进,因此多相催化具有经验性。催化主要是一种分子现象,它必须涉及明确界定的表面有机金属中间体和/或过渡态。因此,必须能够构建一个明确界定的活性位点,测试其催化性能,并评估结构-活性关系,进而像在均相催化中那样利用该关系来设计更好的催化剂。通过将分子有机金属化学的概念和工具转移到表面,表面有机金属化学可以通过了解有机金属配合物与载体(可视为刚性配体)的反应来生成明确界定的表面物种。这种多相催化的新方法能够为新型催化剂的设计带来分子层面的认识,甚至能够发现新的反应(齐格勒-纳塔解聚和烷烃复分解反应)。经过一个多世纪的发展,多相催化仍有改进空间,并且在解决当前问题中将发挥关键作用。它为工业生产分子(农用化学品、石油化学品、药品、聚合物、基础化学品)时面临的经济和环境问题提供了一个解决方案。