Enhanced stability and catalytic activity of subnanometric platinum cluster by surface doping of zirconium in CeO_(2)  

作　　者：Zheng Zhao Ziteng Mao Weixin Zhao Zihao Xu Dongming Chen Bowen Wang Yongqi Zhang Meisheng Cui Yongke Hou Wenzheng Xia Yuqing Ling Juanyu Yang Zongyu Feng Xiaowei Huang 

机构地区：[1]National Engineering Research Center for Rare Earth,Grirem Advanced Materials Co.,Ltd.,GRINM Group Corporation Limited,Beijing,100088,China [2]GRIREM Hi-tech Co.,Ltd.,Langfang,065201,China [3]Rare Earth Functional Materials(Xiong’an)Innovation Venter Co.,Ltd.,Xiong'an,071700,China [4]State-Local Joint Engineering Laboratory of Precious Metal Catalytic Technology and Application,Kunming Sino-platinum Metals Catalysts Co.,Ltd.,Kunming,650106,China

出　　处：《Journal of Rare Earths》2025年第4期719-725,I0003,共8页稀土学报(英文版)

基　　金：supported by National Natural Science Foundation of China (52204376);Youth Foundation of Hebei Province (E2022103007);Open Project of Yunnan Precious Metals Laboratory Co.(YPML-20240502059);Young Elite Scientists Sponsorship Program by CAST (2021QNRC001)。

摘　　要：There has been a continuous effort to improve the thermal stability of subnanometric platinum(Pt)cluster(<2 nm) catalyst because Pt cluster on CeO_(2) support can be mobile and aggregated into nanoparticle on heating at elevated temperatures,yet this great challenge remains.In this study,a strategy is reported to improve the thermal stability of subnanometric Pt cluster by hydrothermal deposition method.Based on this method,zirconium(Zr) was precisely doped on surface of Ce_(0.95)Zr_(0.05)O_(2) by accurately controlling Pt subnanometric cluster size.The surface doping of Zr is favorable for forming the Zr-O-Ce site and activating surface lattice oxygen atoms,which results in strong electronic interactions to stabilize the Pt subnanometric cluster.After high-temperature aging treatment at 1000℃/4 h,the single atom Pt supported on CeO_(2) is aggregated into larger sized(>3 nm) nanoparticle.In contrast,the single atom Pt supported on Ce_(0.95)Zr_(0.0)5O_(2) displays less agglomeration into subnanometric cluster with size of(1.4±0.3) nm.Moreover,the CO oxide catalytic performance of Ce_(0.95)Zr_(0.0)5O_(2)-Pt is 26% and 31%higher than that of CeO_(2)-Pt and commercial Al_(2)O_(3)-Pt catalysts,respectively.The experimental and density functional theory(DFT) calculations indicate that the Zr-O-Ce site and Pt subnanometric cluster interface have more defect sites and active oxygen species than CeO_(2)-Pt interface,which activate the Mars van Krevelen(MvK) mechanism,facilitating the catalytic performance.

关 键 词：CeO_(2) STABILITY Rare earths Zr surface doping Subnanometric Pt cluster Catalytic activity 

分 类 号：O643.36[理学—物理化学]