Copper Nanocrystals Encapsulated in Zr-based Metal-Organic Frameworks for Highly Selective CO2 Hydrogenation to Methanol
Copper Nanocrystals Encapsulated in Zr-based Metal-Organic Frameworks for Highly Selective CO2 Hydrogenation to Methanol
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DOI：
10.1021/acs.nanolett.6b03637
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发表时间：
2016-12-01
期刊：
影响因子：
10.8
通讯作者：
Somotjai, Gabor A.
中科院分区：
文献类型：
--
作者：
Rungtaweevoranit, Bunyarat;Baek, Jayeon;Somotjai, Gabor A.
我们发现，Cu催化剂的活性和选择性可以通过Zr基金属-有机骨架（MOF），Zr 6 O 4（OH）（4）（BDC）（6）（BDC = 1，4-苯二甲酸酯），UiO-66来促进，以与MOF的Zr氧化物[Zr 6 O 4（OH）（4）（-CO2）（12）]次级结构单元（SBU）具有强相互作用用于CO2加氢制甲醇。这些令人感兴趣的特征是通过由封装在单晶UiO-66（UiO-66的Cu子集）内的18 nm单Cu纳米（NC）组成的催化剂实现的。该催化剂结构的性能超过了基准Cu/ZnO/Al 2 O3催化剂，并给出了稳定的8倍提高的产率和100%的甲醇选择性。在催化剂表面上获得的X射线光电子能谱数据显示，Zr 3d结合能在Cu NC的存在下向较低的氧化态移动，这表明在Cu NC和MOF的Zr氧化物SBU之间存在强的相互作用，以制备高活性的Cu催化剂。
We show that the activity and selectivity of Cu catalyst can be promoted by a Zr-based metal-organic framework (MOF), Zr6O4(OH)(4)(BDC)(6) (BDC = 1,4-benzenedicarboxylate), UiO-66, to have a strong interaction with Zr oxide [Zr6O4(OH)(4)(-CO2)(12)] secondary building units (SBUs) of the MOF for CO2 hydrogenation to methanol. These interesting features are achieved by a catalyst composed of 18 nm single Cu nanocrystal (NC) encapsulated within single crystal UiO-66 (Cu subset of UiO-66). The performance of this catalyst construct exceeds the benchmark Cu/ZnO/Al2O3 catalyst and gives a steady 8 fold enhanced yield and 100% selectivity for methanol. The X-ray photoelectron spectroscopy data obtained on the surface of the catalyst show that Zr 3d binding energy is shifted toward lower oxidation state in the presence of Cu NC, suggesting that there is a strong interaction between Cu NC and Zr oxide SBUs of the MOF to make a highly active Cu catalyst.