纳米金催化一氧化碳氧化反应的理论研究

doi:10.1016/S1872-2067(16)62476-2

摘要/Abstract

摘要：

近年来，纳米金催化剂独特的催化性质，特别是其优异的低温催化氧化活性，引起了人们极大的研究热情.除低温选择氧化外，在精细化学品合成、大气污染物消除、氢能的转换和利用等领域也开发出了一系列有广泛应用前景的金催化反应.此外，体相金的化学惰性和纳米金的超高活性之间差异的“鸿沟”也引起了理论工作者浓厚兴趣，试图从原理上理解体相金和纳米金活性差异的根源.CO催化氧化是最具有代表性的研究金催化活性的化学反应，本文主要综述了近十多年来金催化CO氧化反应理论计算方面的研究工作.
一般认为，CO在纳米金表面的吸附是CO氧化反应的初始步骤.密度泛函理论研究表明，CO在金表面的吸附强度主要与被吸附金原子的配位数有关：金配位数越低，CO的吸附能越强，部分研究结果表明两者之间存在近似的线性关系.我们研究发现，CO吸附强度也与被吸附金周围配位金原子的相对位置有关，其中位于正下方的配位金原子加强CO吸附，而位于侧位的配位金原子则弱化CO吸附，这显然削弱了CO吸附与金配位数线性关系的可靠性.理论研究表明，在纯金表面上O₂吸附强度一般很弱，只有在一些特殊结构的金团簇上才有较强的吸附，但在Au/TiO₂界面及CeO₂表面上O₂吸附较强.金表面原子氧的吸附和金的表面结构有关.我们发现，原子氧倾向于在金的表面形成一种线性的O-Au-O结构以增加其稳定性.当金表面的氧覆盖度增大时，会形成一种金氧化物薄膜结构，其结构依赖于氧的化学势和金的表面结构.
纳米金催化CO氧化反应机理可能因体系、载体等的差异而不同.大部分理论计算结果表明，在纯金表面上O₂很难直接解离形成原子氧，因此反应机理可能是吸附的CO先与O₂反应形成了一种CO-O₂中间体，然后解离形成CO₂.在Au/TiO₂和Au/CeO₂催化剂上CO催化氧化机理争议很大，均有计算结果支持LH机理和M-vK机理.另外，根据实验上观察到了负载型纳米金能直接活化分子氧的结果，理论上也提出了分子氧先解离为原子氧再与CO反应的氧解离机理.针对如何解离分子氧问题，人们分别提出了低配位金模型、正方形金结构模型、Ti5c模型及Au/Ti5c模型等.我们也提出了一种独特的双直线O-Au-O模型来理解Au/TiO₂或Au/CeO₂界面解离活化分子氧.
理论计算结果表明，低配位的金，金和载体之间的电荷转移，以及金所表现出的强相对论效应对于纳米金的活性影响很大.需要特别指出的是，金的强相对论效应有助于理解金表面的CO吸附与金配位的关系、金表面原子氧的吸附特性、金氧化物薄膜的结构和分子氧的活化等过程.我们认为，金的强相对论作用导致了体相金的化学惰性以及纳米金的活性，因此相对论效应的深入研究将有助于理解金催化CO氧化反应机理，从而有助于深层次理解纳米金催化活性来源.

关键词: 一氧化碳氧化反应, 金纳米粒子, 反应机理, 理论计算, 相对论效应

Abstract:

It is crucial to understand the mechanism of low temperature CO oxidation reaction catalyzed by gold nanoparticles so as to find out the origin of the high catalytic reactivity and extend the industrialization applications of nano gold catalysts. In this work, some theoretical works on CO adsorption, O₂ adsorption, atomic oxygen adsorption, formation of surface gold oxide films, reaction mechanisms of CO oxidation involving O₂ reaction with CO and O₂ dissociation before reacting with CO on gold surfaces and Au/metal oxide were summarized, and the influences of coordination number, charge transfer and relativity of gold on CO oxidation reaction were briefly reviewed. It was found that CO reaction mechanism depended on the systems with or without oxide and the strong relativistic effects might play an important role in CO oxidation reaction on gold catalysts. In particular, the relativistic effects are related to the unique behav-iors of CO adsorption, O adsorption, O₂ activation on gold surfaces, effects of coordination number and the wide gap between the chemical inertness of bulk gold and high catalytic activity of nano gold. The present work helps us to understand the CO oxidation reaction mechanism on gold catalysts and the influence of relativistic effects on gold catalysis.

Key words: Carbon monoxide oxidation reaction, Gold nanoparticle, Reaction mechanism, Theoretical calculation, Relativistic effect

孙科举. 纳米金催化一氧化碳氧化反应的理论研究[J]. 催化学报, 2016, 37(10): 1608-1618.

Keju Sun. Theoretical investigations on CO oxidation reaction catalyzed by gold nanoparticles[J]. Chinese Journal of Catalysis, 2016, 37(10): 1608-1618.

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