MOF基Pd单位点催化CO酯化制碳酸二甲酯

doi:10.6023/A22020085

摘要/Abstract

碳酸二甲酯(DMC)是一种重要的工业产品, 被广泛应用于制备锂离子电池溶剂和聚碳酸酯等化工产品. 一氧化碳(CO)酯化反应制DMC是一种新型的碳一技术路线, 具有成本低、反应效率高和安全等优势, 近年来引起了广泛的研究兴趣. 许多研究表明, Pd单位点催化剂(Pd SSCs)可以催化该反应高选择性合成DMC, 却易被反应物CO还原成Pd纳米颗粒, 从而导致DMC选择性快速下降. 因此, 设计合成稳定的Pd SSCs显得尤为重要. 通常, 研究人员通过增加Pd原子与载体之间的相互作用来稳定催化剂. 在各种载体中, 金属有机框架材料(MOFs)由于具有比表面积大、稳定性好、可修饰性强等特点, 是稳定单金属位点的理想载体. 选择自身较为稳定且易修饰的UiO-66-NH₂作为载体, 采用后合成修饰的方法将吡啶-2-甲醛引入UiO-66-NH₂的孔中. 吡啶-2-甲醛通过与氨基进行反应连接在UiO-66-NH₂的框架上, 进而创造了相近的双氮原子位点共同鳌合Pd原子, 记为Pd^II-UiO-66-X%. 该催化剂在反应中, 展现出极高的DMC选择性, 同时也具备良好的催化稳定性, 在70 h的连续评价中, 依旧能够保持85%以上的DMC选择性. 该工作这一发现对构筑稳定Pd SSCs高选择性催化合成DMC提供了新思路.

关键词: 金属有机框架, 碳酸二甲酯, Pd单位点催化剂, 后合成修饰, CO酯化反应

Pd single site catalysts (Pd SSCs) are recognized to be efficient for CO esterification to a valuable product, dimethyl carbonate (DMC), but the tendency of reduction to Pd nanoparticles in CO atmosphere under reaction process leads to a reduced selectivity and limits the industrial application. Hence, the development of appropriate supports to stabilize Pd single sites is of great importance. Metal-organic frameworks (MOFs) are expected to become one of the most ideal choices for supporting SSCs due to their large specific surface area, good stability, and ease of modification. Herein, a stable and highly modifiable MOF, UiO-66-NH₂, has been selected as the support. The pyridine-2-formaldehyde is grafted to UiO-66-NH₂ by post-synthetic modification, connecting to the skeleton of UiO-66-NH₂ via amine aldehyde condensation. In this way a pair of adjacent N atom sites are created to jointly chelate Pd(II) species, yielding Pd^II-UiO-66-X%. The Pd SSCs exhibit high DMC selectivity (>98%) in the CO esterification reaction. Moreover, Pd^II-UiO-66-X% shows excellent stability and more than 85% DMC selectivity can be maintained in 70 h continuous test, thanks to the good dispersion and strong interaction of Pd(II) species and the MOF support. As a control, the Pd(II) species is supported on ZrO₂ to give Pd^II/ZrO₂. Obviously, it is difficult for ZrO₂ to disperse Pd(II) species and to strongly interact with them due to the absence of binding groups. As a result, Pd^II/ZrO₂ is rapidly reduced by CO during the reaction, resulting in decreased DMC selectivity. In addition, the signals of key intermediates are detected and the reaction mechanism on Pd^II-UiO-66-X% is proposed based on in-situ diffuse reflectance infrared Fourier transform (in-situ DRIFT) spectra. The successful fabrication of Pd^II-UiO-66-X% with high selectivity and stability provides great opportunity for CO esterification to DMC.

Key words: metal-organic framework, dimethyl carbonate, Pd single-site catalyst, post-synthetic modification, CO esterification reaction

引用此文

谢晨帆, 徐玉平, 高明亮, 徐忠宁, 江海龙. MOF基Pd单位点催化CO酯化制碳酸二甲酯[J]. 化学学报, 2022, 80(7): 867-873.

Chenfan Xie, Yu-Ping Xu, Ming-Liang Gao, Zhong-Ning Xu, Hai-Long Jiang. MOF-Stabilized Pd Single Sites for CO Esterification to Dimethyl Carbonate[J]. Acta Chimica Sinica, 2022, 80(7): 867-873.

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图/表 8

图1. PdII-UiO-66-X%的合成示意图

Figure 1. Illustration of the synthetic strategy for PdII-UiO-66-X%

图2. 所有样品的粉末XRD谱图

Figure 2. Powder X-ray diffraction patterns of different samples

图3. (a) UiO-66-NH2和UiO-66-2N的傅里叶变换红外谱图; (b) PdII-UiO-66-2%的XPS谱图

Figure 3. (a) FTIR spectra of UiO-66-NH2 and UiO-66-2N; (b) XPS spectra of PdII-UiO-66-2%

图4. (a) UiO-66-NH2和(b) UiO-66-2N的扫描电镜图像; (c) PdII-UiO-66-1%和(d) PdII-UiO-66-2%的透射电镜图像; (e) PdII-UiO-66-2%的HAADF-STEM图像和(f~h)与之对应的Zr, N和Pd的EDX mapping图像

Figure 4. SEM images of (a) UiO-66-NH2 and (b) UiO-66-2N; TEM images of (c) PdII-UiO-66-1% and (d) PdII-UiO-66-2%; (e) HAADF- STEM image of PdII-UiO-66-2% and (f~h) the corresponding elemental mapping of Zr, N, and Pd

图5. UiO-66-NH2, PdII-UiO-66-1%和PdII-UiO-66-2%在CO酯化反应中的转化率和产物选择性. 基于反应物CO来计算反应的转化率和选择性, 不考虑反应中亚硝酸甲酯的分解带来的影响. 反应条件: 180 mg催化剂, 120 ℃, 0.1 MPa, WHSV=2500 L•kgcat.-1•h-1, CO/MN/Ar/N2=19∶45∶3∶33(流量比), 反应时间3 h, 每隔15 min采集一次数据.

Figure 5. CO conversion, product selectivity in CO esterification reaction of different samples. The selectivity and conversion were calculated based on CO, without considering the decomposition of MN. Reaction conditions: 180 mg catalyst, 120 ℃, 0.1 MPa, weight hour space velocity (WHSV)=2500 L•kgcat.-1•h-1, CO/MN/Ar/N2=19∶45∶3∶33 (flow ratio), reaction time: 3 h, collect data every 15 min

图6. 样品的XPS谱图(a) PdII-UiO-66-2%-AR; (b) PdII/ZrO2; (c) PdII/ZrO2-AR

Figure 6. XPS spectra of (a) PdII-UiO-66-2%-AR; (b) PdII/ZrO2; (c) PdII/ZrO2-AR

图7. PdII-UiO-66-2%在反应条件下的原位漫反射傅里叶变换红外光谱

Figure 7. In-situ DRIFTS of PdII-UiO-66-2% at reaction conditions

图8. PdII-UiO-66-2% CO酯化反应制备DMC的机理

Figure 8. The proposed catalytic mechanism of CO esterification to DMC on PdII-UiO-66-2%

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