Liu Zhiyuan, Huang Guoqiang
School of Chemical Engineering and Technology, Tianjin University Tianjin 300072 PR China
RSC Adv. 2025 Apr 29;15(18):13799-13811. doi: 10.1039/d5ra01322d. eCollection 2025 Apr 28.
In this study, an acid-modified Cu-Ce/HZSM-5 bimetallic adsorbent was developed for the removal of trace PH impurities from simulated recycled hydrogen in a chemical vapor deposition furnace for polysilicon production. A systematic examination was subsequently conducted to examine the effects of acidic substance type and concentration, and the addition of Ce on the adsorbent's ability to remove PH. The results showed that the adsorbent, when treated with 13% HNO and an appropriate level of Ce ( : = 1 : 40), exhibited superior adsorption performance, achieving a PH breakthrough adsorption capacity of 135.2 mg g. After three regeneration cycles, the sorbent achieved optimal performance. Further investigation indicated that the improved efficiency of this sorbent in removing PH was primarily due to the formation of Cu(OH)NO, an increase in microporous volume, the enhanced distribution of metallic oxides, a higher quantity of reactive oxygen species on the surface, an increased concentration of acidic sites, and the exposure of additional reactive species (Cu(OH)NO, CuO). Moreover, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) characterization indicated that the deactivation of the adsorbent was mainly caused by the continuous consumption of Cu(OH)NO and CuO, along with the accumulation of reaction products (PO, CuP, Cu (PO), and CuPO) on the adsorbent surface.
在本研究中，开发了一种酸改性的Cu-Ce/HZSM-5双金属吸附剂，用于在多晶硅生产的化学气相沉积炉中从模拟循环氢气中去除痕量PH杂质。随后进行了系统研究，以考察酸性物质类型和浓度以及Ce的添加对吸附剂去除PH能力的影响。结果表明，用13% HNO₃和适当水平的Ce（Cu : Ce = 1 : 40）处理后的吸附剂表现出优异的吸附性能，PH穿透吸附容量达到135.2 mg/g。经过三个再生循环后，吸附剂达到最佳性能。进一步研究表明，该吸附剂去除PH效率提高的主要原因是形成了Cu(OH)NO₃、微孔体积增加、金属氧化物分布增强、表面活性氧物种数量增加、酸性位点浓度增加以及额外活性物种（Cu(OH)NO₃、CuO）的暴露。此外，X射线衍射（XRD）和X射线光电子能谱（XPS）表征表明，吸附剂失活主要是由于Cu(OH)NO₃和CuO的持续消耗，以及反应产物（PO₄³⁻、Cu₃P、Cu₃(PO₄)₂和Cu₃PO₄）在吸附剂表面的积累。
