MOF-Stabilized Pd Single Sites for CO Esterification to Dimethyl Carbonate

doi:10.6023/A22020085

Abstract

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

Cite this article

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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Fig. & Tab. 8

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

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

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

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

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

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

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

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

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MOF基Pd单位点催化CO酯化制碳酸二甲酯