Role of Ce in supported Pd catalyst for oxidative carbonylation of phenol to diphenyl carbonate

doi:10.11949/0438-1157.20190395

Abstract

Abstract:

A Pd-Ce-O/SiO₂ catalyst with Ce as auxiliary was prepared by microemulsion method for oxidative carbonylation of phenol to synthesize diphenyl carbonate (DPC). The activity evaluation results showed that the catalyst performance increased with the increase of the amount of Ce. When the Ce/Pd molar ratio was 10/1, the phenol conversion rate was 64.4%, and the diphenyl carbonate selectivity was 83.4%. The XRD results showed that part of Ce⁴⁺ entered into PdO crystal lattice, therefore the electrons of deactivated Pd could easily be transferred to Ce. So the Pd-Ce-O/SiO₂ catalyst could be easily regenerated and showed better performance. According to the above mentioned results, Pd-O/CeO₂ was designed and prepared for oxidative carbonylation of phenol. However, unlike Pd-Ce-O/SiO₂, Pd-O/CeO₂ showed poor catalytic performance. The phenol conversion and DPC selectivity was only 24.0% and 23.3% respectively. The characterization results showed that PdO was the main species of Pd on the surface of Pd-Ce-O/SiO₂, but there was more PdO₂ on Pd-O/CeO₂. Because Pd(Ⅱ) is the active site for oxidative carbonyation, Pd-O/CeO₂ exhibited inferior activity to Pd-Ce-O/SiO₂. In addition, in Pd-O/CeO₂ catalyst, the surface Pd content was lower than that of other catalyst because of the strong interaction between Pd species and CeO₂. That s one of the reasons for the poor activity of Pd-O/CeO₂.

Key words: diphenyl carbonate, oxidative carbonlyation, heterogeneous reaction, catalyst, support, ceria

摘要：

采用微乳液法制备了Ce为助剂的Pd-Ce-O/SiO₂催化剂，用于苯酚氧化羰基化合成碳酸二苯酯（DPC）反应。活性评价结果显示，催化剂性能随着Ce用量的增加而提高，当Ce/Pd摩尔比为10/1时，苯酚转化率为64.4%，碳酸二苯酯选择性为83.4%。利用XRD表征发现，部分Ce⁴⁺进入到PdO晶格中，使得失活Pd原子中的电子更容易向Ce转移，从而易于再生，表现出更好的催化性能。根据上述结果，设计制备了Pd-O/CeO₂催化剂用于本反应，苯酚转化率和碳酸二苯酯选择性分别仅为24.0%和23.3%。表征发现，在Pd-Ce-O/SiO₂催化剂表面，Pd物种主要是PdO，而Pd-O/CeO₂表面的Pd物种则以PdO₂为主。由于苯酚氧化羰基化反应的活性中心为Pd(Ⅱ)，所以Pd-O/CeO₂催化性能较差。并且，由于Pd与CeO₂之间存在强相互作用，催化剂表面Pd含量较低，这也是Pd-O/CeO₂催化活性较差的原因之一。

关键词: 碳酸二苯酯, 氧化羰基化, 多相反应, 催化剂, 载体, 二氧化铈

CLC Number:

O 643

Zhimiao WANG, Hongqi ZHANG, Lichao ZHOU, Fang LI, Wei XUE, Yanji WANG. Role of Ce in supported Pd catalyst for oxidative carbonylation of phenol to diphenyl carbonate[J]. CIESC Journal, 2019, 70(12): 4625-4634.

王志苗, 张洪起, 周立超, 李芳, 薛伟, 王延吉. Ce在负载Pd催化苯酚氧化羰基化合成碳酸二苯酯反应中的作用[J]. 化工学报, 2019, 70(12): 4625-4634.

Figures/Tables 12

Fig.1 Catalytic performance of Pd-M-O/SiO2 for oxidative carbonylation of phenol(reaction conditions: 100℃, 6.6 MPa, CO/O2=10/1, others were listed in Section 1.4)

Fig.2 Effect of Ce/Pd molar ratio on oxidative carbonylation of phenol over Pd-Ce-O/SiO2(reaction conditions: 100℃, 6.6 MPa, CO/O2=10/1, others were listed in Section 1.4)

Fig.3 XRD patterns of Pd-Ce-O/SiO2 catalyst with different Ce/Pd molar ratio

Table 1 Interplanar spacing and lattice parameters of PdO(101) in Pd-Ce-O/SiO2 catalyst with different Ce/Pd molar ratio

Pd-Ce-O/SiO₂催化剂中Ce/Pd摩尔比	PdO(101)晶面间距 / nm	晶格参数 / nm
Pd-Ce-O/SiO₂催化剂中Ce/Pd摩尔比	PdO(101)晶面间距 / nm	a	b	c
不加Ce	0.26032	0.30330	0.30330	0.53849
1∶1	0.26283	0.30413	0.30413	0.53347
2∶1	0.26360	0.30392	0.30392	0.53595
5∶1	0.26404	0.30423	0.30423	0.53322
10∶1	0.26572	0.30398	0.30398	0.54006

Table 2 Physicochemical properties of Pd-based catalysts and their catalytic performance for oxidative carbonylation of phenol

催化剂	Pd 含量/% (质量)		比表面积/(m²/g)	催化反应性能^②
催化剂	XPS	理论含量	比表面积/(m²/g)	苯酚转化率/%	DPC选择性/%
Pd-O/CeO₂	0.58	1.0	14.5	24.0	23.3
Pd-O/SiO₂	0.90	1.0	37.1	38.4	85.4
Pd-Ce-O/SiO₂^①	0.74	1.0	49.6	64.4	83.4

Fig.4 XRD patterns of Pd-Ce-O/SiO2 (Ce/Pd=10/1 in molar ratio), Pd-O/CeO2 and Pd-O/SiO2 catalysts

Fig.5 Pd 3d XPS spectra of Pd-O/SiO2, Pd-Ce-O/SiO2 and Pd-O/CeO2 catalysts

Fig.6 TPR profiles of Pd-O/CeO2, Pd-Ce-O/SiO2 and Pd-O/SiO2 catalysts

Fig.7 TEM images of Pd-O/SiO2, Pd-Ce-O/SiO2 and Pd-O/CeO2

Fig.8 HAADF-STEM and EDS mapping images of Pd-O/CeO2

Fig.9 Pd 3d XPS spectra of Pd-Ce-O/SiO2

Fig.10 Ce 3d XPS spectra of Pd-Ce-O/SiO2

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