Design of Copper-Based Bimetallic Nanoparticles for Carbon Dioxide Adsorption and Activation
Design of Copper-Based Bimetallic Nanoparticles for Carbon Dioxide Adsorption and Activation
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DOI：
10.1002/cssc.201702342
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发表时间：
2018-04-09
期刊：
影响因子：
8.4
通讯作者：
Mpourmpakis, Giannis
中科院分区：
文献类型：
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作者：
Dean, James;Yang, Yahui;Mpourmpakis, Giannis
铜基纳米粒子（NPs）是有希望的候选人，催化加氢CO2有用的化学品，因为它们的成本低。然而，CO2在Cu上的吸附和活化是不可行的。在这项工作中，我们展示了一个计算框架，确定铜基碳纳米管能够吸附和激活二氧化碳的DFT计算的基础上。我们筛选了一系列的杂原子铜基纳米粒子的基础上，他们的偏好，占据NP上的表面位点，吸附和活化CO2。我们揭示了两个描述符的CO2吸附的CO2纳米粒子，杂原子（i）本地d-带中心和（ii）正电性，这两者都驱动一个有效的电荷转移从NP到CO2。我们确定了CuZr的纳米颗粒作为一个候选的纳米结构的CO2吸附，并表明，虽然锆网站可以被氧化，因为他们的高亲氧性，他们仍然能够吸附和激活CO2强烈。重要的是，我们的计算结果通过有针对性的合成、表征和CO2吸附实验进行了验证，这些实验表明i）Zr在Cu的表面上偏析，ii）Zr被氧化以形成混合的CuZr氧化物催化剂，其iii）可以强烈吸附CO2，而Cu NP不能。总的来说，我们的工作突出了基于（催化剂）稳定性和电子结构性质的NP表面上的结合位点的产生的重要性，这可以导致更有效的CO2还原催化剂的设计。
Cu-based nanoparticles (NPs) are promising candidates for the catalytic hydrogenation of CO2 to useful chemicals because of their low cost. However, CO2 adsorption and activation on Cu is not feasible. In this work we demonstrate a computational framework that identifies Cu-based bimetallic NPs able to adsorb and activate CO2 based on DFT calculations. We screen a series of heteroatoms on Cu-based NPs based on their preference to occupy a surface site on the NP and to adsorb and activate CO2. We revealed two descriptors for CO2 adsorption on the bimetallic NPs, the heteroatom (i) local d-band center and (ii) electropositivity, which both drive an effective charge transfer from the NP to CO2. We identified the CuZr bimetallic NP as a candidate nanostructure for CO2 adsorption and showed that although the Zr sites can be oxidized because of their high oxophilicity, they are still able to adsorb and activate CO2 strongly. Importantly, our computational results are verified by targeted synthesis, characterization, and CO2 adsorption experiments that demonstrate that i) Zr segregates on the surface of Cu, ii) Zr is oxidized to form a bimetallic mixed CuZr oxide catalyst, which iii) can strongly adsorb CO2, whereas Cu NPs cannot. Overall our work highlights the importance of the generation of binding sites on a NP surface based on (catalyst) stability and electronic structure properties, which can lead to the design of more effective CO2 reduction catalysts.