Co<sub>3</sub>O<sub>4</sub>纳米晶表面晶格氧催化氧化CO的理论研究

引用本文: 王阳刚, 杨小峰, 李隽. Co₃O₄纳米晶表面晶格氧催化氧化CO的理论研究[J]. 催化学报, 2016, 37(1): 193-198. doi: 10.1016/S1872-2067(15)60969-X shu

Citation: Yang-Gang Wang, Xiao-Feng Yang, Jun Li. Theoretical studies of CO oxidation with lattice oxygen on Co₃O₄ surfaces[J]. Chinese Journal of Catalysis, 2016, 37(1): 193-198. doi: 10.1016/S1872-2067(15)60969-X shu

Co₃O₄纳米晶表面晶格氧催化氧化CO的理论研究

王阳刚 ^a, ,
杨小峰 ^b, ,
李隽 ^{a,
,}

1.
a 清华大学化学系有机光电子与分子工程教育部重点实验室, 北京100084;
2.
b 中国科学院大连化学物理研究所催化基础国家重点实验室, 辽宁大连116023

通讯作者: 李隽

基金项目:
国家重点基础研究发展计划(2011CB932401) (2011CB932401)

国家自然科学基金(21221062). (21221062)

摘要: 近年来,纳米科学技术的迅速发展给催化领域,特别是多相催化带来了新的机遇和挑战.科学家们开始着眼于在纳米尺度上对催化剂结构和催化性能进行表征、控制和设计.Co₃O₄作为一种重要的半导体金属氧化物材料,由于其优异的氧化还原性质,在锂电池、气体传感器以及多相催化领域得到了十分广泛的应用.最近,研究者发现Co₃O₄纳米晶在催化CO低温氧化和CH₄活化等一系列重要反应中表现出显著的反应活性和晶面效应,表明有效设计和合成特定的高活性、高选择性的纳米晶面,对催化领域的发展将具有十分重要的意义.因而,从原子层面对纳米晶所表现出的这种高活性和晶面效应进行深入解释,将为高效催化剂设计提供重要指导.
低温CO氧化作为一种重要的催化反应在燃料电池、空气净化与汽车尾气处理中具有重要的应用价值.本文采用密度泛函理论对Co₃O₄纳米晶催化CO氧化反应的机理、晶面效应以及结构敏感性进行了理论研究.首先,研究了CO在Co₃O₄(001)和(011)表面Co,Co-O°和Co-O^t三种不同位点的吸附扩散行为,发现CO在Co位点表现出较强的吸附行为,但这种吸附构型需要克服很高的能垒(~1eV)才能转变到Co-O离子对位点,在低温下这种转变将不可能发生,因此我们推断CO在Co位点的吸附对Co₃O₄催化CO氧化的晶面效应没有显著影响.接着,对CO在Co-O离子对位点抽提晶格氧生成CO₂的反应机理进行了研究.我们发现,(011)表面Co-O^t位点可以较强地吸附CO(吸附能-1.15eV),并十分容易夺取晶格氧离子(能垒0.26eV),具有很低的势能面,因而其CO氧化活性明显大于(001)面.
为了更清楚地理解这种晶面效应和结构敏感效应的本质,我们提出将CO₂形成步的过渡态在反应路径上的能级作为反应活性指标.这种活性指标兼顾考虑了CO在Co-O氧位点的吸附覆盖度和CO₂形成步的反应能垒,可以近似理解为反应的表观活化能.据此我们得出,Co₃O₄不同表面不同晶格位点催化CO氧化的反应活性顺序为:(011)-Co-O^t>>(001)-Co-O°>(011)-Co-O°>(001)-Co-O^t.由于CO吸附和CO₂形成步都涉及到表面被还原的过程,我们因此发现CO催化氧化活性的高低与表面晶格氧位点的可还原性具有正相关性.这种表面不同位点的还原性可以直接通过对空穴形成能的计算获得,降低表面氧空穴的生成能将有利于提高CO氧化的活性.
催化设计的终极目标是在对催化活性位点的本质及反应机理深入认识的基础上在原子层面上对催化剂进行可控设计,从而实现催化剂材料的高效、经济的利用.本文研究表明离子对活性位点是Co₃O₄纳米晶催化CO氧化反应的活性位点,其中阳离子负责对CO的吸附,阴离子则负责CO₂的形成过程,这种协同作用实现了Co₃O₄纳米晶的高反应活性.我们相信,寻找有效的方法在催化剂表面增加离子对位点活性中心的数目是一种实现高性能催化剂设计的途径.

关键词:

English

Theoretical studies of CO oxidation with lattice oxygen on Co₃O₄ surfaces

1.
a Department of Chemistry & Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China;
2.
b State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Corresponding author: 李隽

Received Date: 07 August 2015
Fund Project:
国家重点基础研究发展计划(2011CB932401)

国家自然科学基金(21221062).

Abstract: Low-temperature CO oxidation has attracted extensive interest in heterogeneous catalysis because of the potential applications in fuel cells, air cleaning, and automotive emission reduction. In the present study, theoretical investigations have been performed using density functional theory to elucidate the crystal plane effect and structure sensitivity of Co₃O₄ nano-catalysts toward catalyzing CO oxidation. It is shown that the surface Co-O ion pairs are the active site for CO oxidation on the Co₃O₄ surface. Because of stronger CO adsorption and easier removal of lattice oxygen ions, the Co₃O₄(011) surface is shown to be more reactive for CO oxidation than the Co₃O₄(001) surface, which is consistent with previous experimental results. By comparing the reaction pathways at different sites on each surface, we have further elucidated the nature of the crystal plane effect on Co₃O₄ surfaces and attributed the reactivity to the surface reducibility. Our results suggest that CO oxidation catalyzed by Co₃O₄ nanocrystals has a strong crystal plane effect and structure sensitivity. Lowering the vacancy formation energy of the oxide surface is key for high CO oxidation reactivity.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

Co₃O₄纳米晶表面晶格氧催化氧化CO的理论研究

通讯作者: 李隽

English

Theoretical studies of CO oxidation with lattice oxygen on Co₃O₄ surfaces

Corresponding author: 李隽

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