采用浸渍法制备了负载型Pd-Rh双金属催化剂,并以4-氟苯酚(4-FP)为模型化合物,研究了活性组分Pd-Rh含量、载体等对Pd-Rh双金属催化剂催化4-FP加氢脱氟的影响.结果表明,Rh的存在显著提升催化剂对4-FP加氢脱氟的催化活性,且2% Pd-1% Rh/AC对4-FP的加氢脱氟表现出较好的催化活性,其催化4-FP在90min时的加氢脱氟转化率为95.62%.碳载体类型对Pd-Rh双金属催化剂的催化活性有着重要影响,炭黑(CB)作为载体时2% Pd-1% Rh/CB表现出最高的催化活性,2% Pd-1% Rh/CB催化下4-FP在80min内即可完全加氢脱氟.催化剂表征(BET、ICP-MS、RS、TEM和XPS)表明,这可能与CB载体的表面缺陷有关,载体表面缺陷越多,催化剂的催化活性越高;而且当Pd更多地以Pd0形式存在时,被Pd0吸附并活化产生的活性H*越多,越有利于4-FP的加氢脱氟降解,因而2% Pd-1% Rh/CB对4-FP的加氢脱氟表现出最高的催化活性.
Abstract
Supported bimetallic Pd-Rh catalysts were prepared using the impregnation method. The effects of the active components content and the carrier on the catalytic activity of the bimetallic Pd-Rh catalysts were investigated with 4-fluorophenol (4-FP) as the representative fluorinated organic compounds (FOCs). The results showed that the presence of Rh significantly enhanced their catalytic activity for the hydrodefluorination (HDF) of 4-FP, and 2% Pd-1% Rh/AC exhibited good catalytic activity for the HDF of 4-FP, and the conversion of 4-FP over 2% Pd-1% Rh/AC reached 95.62% within 90min. Furthermore, the type of the carrier played a significant role on the catalytic activity of bimetallic Pd-Rh catalysts. 2%Pd-1%Rh/CB exhibited the highest catalytic activity for the HDF of 4-FP when carbon black (CB) was used as a carrier, and thus the complete HDF of 4-FP was achieved within 80min. Catalyst characterization (BET, ICP-MS, RS, TEM, and XPS) indicated that the carriers with more surface defects favored the catalysts exhibited higher catalytic activity, which in turn enabled 2%Pd-1%Rh/CB and 2%Pd-1%Rh/CNTs to exhibit higher catalytic activity for the HDF of 4-FP. Moreover, 2%Pd-1%Rh/CB possessed more Pd0, which is more conducive to the activation of the H2, and in turn promoted catalytic HDF of 4-FP. Thus, 2%Pd-1%Rh/CB possessed the highest catalytic activity for the HDF of 4-FP.
关键词
4-氟苯酚(4-FP) /
Pd-Rh双金属催化剂 /
催化 /
氟代有机化合物(FOCs) /
加氢脱氟
Key words
4-fluorophenol (4-FP) /
bimetallic Pd-Rh catalyst /
catalysis /
fluorinated organic compounds /
hydrodefluorination (HDF)
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基金
山东省高校“青创团队计划”项目(2022KJ123);山东省博士后创新项目(SDCX-ZG-202502097);山东省自然科学基金资助项目(ZR2022MD012)
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