Citation: Meijia Xu, Yuchen Zhang, Yifan Zhu, Changlin Li, Zi-Ang Wu, Xiong Zhou, Kai Wu. Active Phase on Oxidized Pd(100) for Low-Temperature Propane Oxidation[J]. Acta Physico-Chimica Sinica, ;2023, 39(10): 230503. doi: 10.3866/PKU.WHXB202305033 shu

Active Phase on Oxidized Pd(100) for Low-Temperature Propane Oxidation

College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China

Corresponding author: Xiong Zhou, xiongzhou@pku.edu.cn Kai Wu, kaiwu@pku.edu.cn
Received Date: 16 May 2023
Revised Date: 12 June 2023
Accepted Date: 13 June 2023
Available Online: 28 June 2023
Fund Project: the National Natural Science Foundation of China 22222102the National Natural Science Foundation of China 21821004the National Natural Science Foundation of China 21927901

Palladium, a key component of three-way catalysts used in automobile exhaust treatment, plays a pivotal role in complete oxidation of alkanes and low-temperature oxidation of CO. Under oxygen-rich conditions, a thin oxide layer spontaneously forms on the palladium surface. To understand the influence of the oxidized palladium surface on the active phase of low-temperature hydrocarbon oxidation, we have conducted a comprehensive study of the oxidation process on Pd(100) and its impact on propane oxidation. Our experimental results reveal that under varying oxidation conditions, the Pd(100) surface sequentially forms three different monolayered oxide phases, namely, (2 × 2)-O, (5 × 5)-PdO and (\begin{document}$ \sqrt{\text{5}} $\end{document} × \begin{document}$ \sqrt{\text{5}} $\end{document}) R27°-PdO. The oxygen coverage correspondingly increases in the order of 0.25 monolayer, 0.56 monolayer and 0.8 monolayer. Notably, (5 × 5)-PdO is identified for the first time by high-resolution scanning tunneling microscopy. Experiments show this structure exhibits typical chiral features with its two enantiomers observed in the experiments. The chiral features of the (5 × 5)-PdO structure may bear significant implications in practical applications like chiral catalysis. Based on high-resolution atomic imaging, we have proposed a new (5 × 5)-PdO structure model. In addition, it's experimentally revealed that upon thermal treatments the (5 × 5)-PdO structure decomposes into the (\begin{document}$ \sqrt{\text{5}} $\end{document} × \begin{document}$ \sqrt{\text{5}} $\end{document}) R27°-PdO and the (2 × 2)-O structures, and the (\begin{document}$ \sqrt{\text{5}} $\end{document} × \begin{document}$ \sqrt{\text{5}} $\end{document}) R27°-PdO decomposes into the (2 × 2)-O structure as well. These results suggest that the thermal stability of these oxide phases is in the order of (2 × 2)-O > (\begin{document}$ \sqrt{\text{5}} $\end{document} × \begin{document}$ \sqrt{\text{5}} $\end{document}) R27°-PdO > (5 × 5)-PdO. We have also compared the catalytic activities of these three oxidation phases in low-temperature propane oxidation. The results show that only the (\begin{document}$ \sqrt{\text{5}} $\end{document} × \begin{document}$ \sqrt{\text{5}} $\end{document}) R27°-PdO could catalyze propane oxidation near room temperature. We have observed a significant number of oxygen defects in the (\begin{document}$ \sqrt{\text{5}} $\end{document} × \begin{document}$ \sqrt{\text{5}} $\end{document}) R27°-PdO, which also forms the reduced (2 × 2)-O phase. Both complete oxidation products H₂O and CO₂ are detectable by temperature-programmed desorption within two main temperature slots around 285 and 315 K. Neither the (2 × 2)-O nor the (5 × 5)-PdO phase shows an obvious catalytic activity. The superior oxidation activity of the (\begin{document}$ \sqrt{\text{5}} $\end{document} × \begin{document}$ \sqrt{\text{5}} $\end{document}) R27°-PdO phase might be associated with its higher O density and hence more active O species within the structure. Our study indicates that the (\begin{document}$ \sqrt{\text{5}} $\end{document} × \begin{document}$ \sqrt{\text{5}} $\end{document}) R27°-PdO serves as the active phase for the low-temperature propane oxidation. These insights would help understand the working mechanisms of three-way catalysts and should be of great importance for the development of efficient and low-temperature three-way catalysts.
- Palladium oxide,
- Chiral oxide,
- Low-temperature propane oxidation,
- Scanning tunneling microscopy
1. [1]
  Li, H. M.; Lan, L.; Chen, S. H.; Liu, D. Y.; Wang, W.; Gong, M. C.; Chen, Y. Q. Acta Phys. -Chim. Sin. 2016, 32, 1734. doi: 10.3866/PKU.WHXB201603235
2. [2]
  Gao, F.; McClure, S. M.; Cai, Y.; Gath, K. K.; Wang, Y.; Chen, M. S.; Guo, Q. L.; Goodman, D. W. Surf. Sci. 2009, 603, 65. doi: 10.1016/j.susc.2008.10.031 doi: 10.1016/j.susc.2008.10.031
3. [3]
  Jia, Y. C.; Wang, S. Y.; Meng, L.; Lu, J. Q.; Luo, M. F. Acta Phys. -Chim. Sin. 2016, 32, 1801 doi: 10.3866/PKU.WHXB201604081
4. [4]
  Schwartz, A. J. Catal. 1971, 21, 199. doi: 10.1016/0021-9517(71)90138-2 doi: 10.1016/0021-9517(71)90138-2
5. [5]
  Niu, Y. M.; Liu, X.; Wang, Y. Z.; Zhou, S.; Lv, Z. G.; Zhang, L. Y.; Shi, W.; Li, Y. W.; Zhang, W.; Su, D. S.; et al. Angew. Chem. Int. Ed. 2019, 58, 4232. doi: 10.1002/anie.201812292 doi: 10.1002/anie.201812292
6. [6]
  Zhang, J.; Fan, L.; Zhao, F.; Fu, Y.; Lu, J. Q.; Zhang, Z.; Teng, B.; Huang, W. ChemCatChem 2020, 12, 5540. doi: 10.1002/cctc.202000934 doi: 10.1002/cctc.202000934
7. [7]
  Li, R. T.; Xu, X. Y.; Zhu, B. E.; Li, X. Y.; Ning, Y. X.; Mu, R. T.; Du, P. F.; Li, M. W.; Wang, H. K.; Liang, J. J.; et al. Nat. Commun. 2021, 12, 1406. doi: 10.1038/s41467-021-21552-2 doi: 10.1038/s41467-021-21552-2
8. [8]
  Hellman, A.; Resta, A.; Martin, N. M.; Gustafson, J.; Trinchero, A.; Carlsson, P. A.; Balmes, O.; Felici, R.; van Rijn, R.; Frenken, J. W. M.; et al. J. Phys. Chem. Lett. 2012, 3, 678. doi: 10.1021/jz300069s doi: 10.1021/jz300069s
9. [9]
  Hirvi, J. T.; Kinnunen, T. J. J.; Suvanto, M.; Pakkanen, T. A.; Norskov, J. K. J. Chem. Phys. 2010, 133, 084704. doi: 10.1063/1.3464481 doi: 10.1063/1.3464481
10. [10]
  Shipilin, M.; Hejral, U.; Lundgren, E.; Merte, L. R.; Zhang, C.; Stierle, A.; Ruett, U.; Gutowski, O.; Skoglundh, M.; Carlsson, P. -A.; et al. Surf. Sci. 2014, 630, 229. doi: 10.1016/j.susc.2014.08.021 doi: 10.1016/j.susc.2014.08.021
11. [11]
  Hoffmann, M. J.; Reuter, K. Top. Catal. 2014, 57, 159. doi: 10.1007/s11244-013-0172-5 doi: 10.1007/s11244-013-0172-5
12. [12]
  Chang, S. L.; Thiel, P. A.; Evans, J. W. Surf. Sci. 1988, 205, 117. doi: 10.1016/0039-6028(88)90167-7 doi: 10.1016/0039-6028(88)90167-7
13. [13]
  Zheng, G.; Altman, E. I. Surf. Sci. 2002, 504, 253. doi: 10.1016/s0039-6028(02)01104-4 doi: 10.1016/s0039-6028(02)01104-4
14. [14]
  Mehar, V.; Kim, M.; Shipilin, M.; Van den Bossche, M.; Gustafson, J.; Merte, L. R.; Hejral, U.; Grönbeck, H.; Lundgren, E.; Asthagiri, A.; et al. ACS Catal. 2018, 8, 8553. doi: 10.1021/acscatal.8b02191 doi: 10.1021/acscatal.8b02191
15. [15]
  Rose, M. K.; Borg, A.; Dunphy, J. C.; Mitsui, T.; Ogletree, D. F.; Salmeron, M. Surf. Sci. 2003, 547, 162. doi: 10.1016/j.susc.2003.08.057 doi: 10.1016/j.susc.2003.08.057
16. [16]
  Orent, T. W.; Bader, S. D. Surf. Sci. 1982, 115, 323. doi: 10.1016/0039-6028(82)90412-5 doi: 10.1016/0039-6028(82)90412-5
17. [17]
  Todorova, M.; Lundgren, E.; Blum, V.; Mikkelsen, A.; Gray, S.; Gustafson, J.; Borg, M.; Rogal, J.; Reuter, K.; Andersen, J. N.; et al. Surf. Sci. 2003, 541, 101. doi: 10.1016/s0039-6028(03)00873-2 doi: 10.1016/s0039-6028(03)00873-2
18. [18]
  Kostelník, P.; Seriani, N.; Kresse, G.; Mikkelsen, A.; Lundgren, E.; Blum, V.; Šikola, T.; Varga, P.; Schmid, M. Surf. Sci. 2007, 601, 1574. doi: 10.1016/j.susc.2007.01.026 doi: 10.1016/j.susc.2007.01.026
19. [19]
  Shipilin, M.; Stierle, A.; Merte, L. R.; Gustafson, J.; Hejral, U.; Martin, N. M.; Zhang, C.; Franz, D.; Kilic, V.; Lundgren, E. Surf. Sci. 2017, 660, 1. doi: 10.1016/j.susc.2017.01.009 doi: 10.1016/j.susc.2017.01.009
20. [20]
  Huang, Z.; Han, C.; Sun, Y. Y.; Wu, K.; Chen, W. J. Phys. Chem. C 2021, 125, 15599. doi: 10.1021/acs.jpcc.1c03682 doi: 10.1021/acs.jpcc.1c03682
21. [21]
  Huang, Z. C.; Xu, Z.; Zhou, J. Y.; Chen, H. R.; Rong, W. H.; Lin, Y. X.; Wen, X. J.; Zhu, H.; Wu, K. J. Phys. Chem. C 2019, 123, 17823. doi: 10.1021/acs.jpcc.9b03253 doi: 10.1021/acs.jpcc.9b03253
22. [22]
  Zhang, Y.; Feng, W.; Yang, F.; Bao, X. H. Chin. J. Catal. 2019, 40, 204. doi: 10.1016/s1872-2067(18)63171-7 doi: 10.1016/s1872-2067(18)63171-7
23. [23]
  Zhao, X. F.; Chen, H.; Wu, H.; Wang, R.; Cui, Y.; Fu, Q.; Yang, F.; Bao, X. H. Acta Phys. -Chim. Sin. 2018, 34, 1373. doi: 10.3866/PKU.WHXB201804131
24. [24]
  Hendriksen, B. L. M.; Bobaru, S. C.; Frenken, J. W. M. Surf. Sci. 2004, 552, 229. doi: 10.1016/j.susc.2004.01.025 doi: 10.1016/j.susc.2004.01.025
25. [25]
  Zheng, G.; Altman, E. I. J. Phys. Chem. B 2002, 106, 1048. doi: 10.1021/jp013395x doi: 10.1021/jp013395x
26. [26]
  van Rijn, R.; Balmes, O.; Resta, A.; Wermeille, D.; Westerstrom, R.; Gustafson, J.; Felici, R.; Lundgren, E.; Frenken, J. W. Phys. Chem. Chem. Phys. 2011, 13, 13167. doi: 10.1039/c1cp20989b doi: 10.1039/c1cp20989b
27. [27]
  Toyoshima, R.; Yoshida, M.; Monya, Y.; Suzuki, K.; Mun, B. S.; Amemiya, K.; Mase, K.; Kondoh, H. J. Phys. Chem. Lett. 2012, 3, 3182. doi: 10.1021/jz301404n doi: 10.1021/jz301404n
28. [28]
  Weaver, J. F.; Hakanoglu, C.; Hawkins, J. M.; Asthagiri, A. J. Chem. Phys. 2010, 132, 024709. doi: 10.1063/1.3277672 doi: 10.1063/1.3277672
29. [29]
  Weaver, J. F.; Devarajan, S. P.; Akanoglu, C. J. Phys. Chem. C 2009, 113, 9773. doi: 10.1021/jp9013114 doi: 10.1021/jp9013114
30. [30]
  Antony, A.; Asthagiri, A.; Weaver, J. F. Phys. Chem. Chem. Phys. 2012, 14, 12202. doi: 10.1039/c2cp41900a doi: 10.1039/c2cp41900a
31. [31]
  Wrobel, R. J.; Becker, S. Vacuum 2010, 84, 1258. doi: 10.1016/j.vacuum.2010.01.056 doi: 10.1016/j.vacuum.2010.01.056
32. [32]
  Huang, W. X.; Zhai, R. S.; Bao, X. H. Surf. Sci. 1999, 439, L803. doi: 10.1016/s0039-6028(99)00820-1 doi: 10.1016/s0039-6028(99)00820-1
33. [33]
  Rose, M. K.; Borg, A.; Mitsui, T.; Ogletree, D. F.; Salmeron, M. J. Chem. Phys. 2001, 115, 10927. doi: 10.1063/1.1420732 doi: 10.1063/1.1420732
1. [1]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-. doi: 10.3866/PKU.WHXB202406012
2. [2]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . 氢电极支撑可逆固体氧化物电池性能及电化学不对称性优化. Acta Physico-Chimica Sinica, 2025, 41(1): 2309037-. doi: 10.3866/PKU.WHXB202309037
3. [3]
  Chuanming GUO , Kaiyang ZHANG , Yun WU , Rui YAO , Qiang ZHAO , Jinping LI , Guang LIU . Performance of MnO₂-0.39IrO_x composite oxides for water oxidation reaction in acidic media. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1135-1142. doi: 10.11862/CJIC.20230459
4. [4]
  Ping ZHANG , Chenchen ZHAO , Xiaoyun CUI , Bing XIE , Yihan LIU , Haiyu LIN , Jiale ZHANG , Yu'nan CHEN . Preparation and adsorption-photocatalytic performance of ZnAl@layered double oxides. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1965-1974. doi: 10.11862/CJIC.20240014
5. [5]
  Xueyu Lin , Ruiqi Wang , Wujie Dong , Fuqiang Huang . 高性能双金属氧化物负极的理性设计及储锂特性. Acta Physico-Chimica Sinica, 2025, 41(3): 2311005-. doi: 10.3866/PKU.WHXB202311005
6. [6]
  Xiaofeng Zhu , Bingbing Xiao , Jiaxin Su , Shuai Wang , Qingran Zhang , Jun Wang . Transition Metal Oxides/Chalcogenides for Electrochemical Oxygen Reduction into Hydrogen Peroxides. Acta Physico-Chimica Sinica, 2024, 40(12): 2407005-. doi: 10.3866/PKU.WHXB202407005
7. [7]
  Xin Han , Zhihao Cheng , Jinfeng Zhang , Jie Liu , Cheng Zhong , Wenbin Hu . Design of Amorphous High-Entropy FeCoCrMnBS (Oxy) Hydroxides for Boosting Oxygen Evolution Reaction. Acta Physico-Chimica Sinica, 2025, 41(4): 100033-. doi: 10.3866/PKU.WHXB202404023
8. [8]
  Xiaotian ZHU , Fangding HUANG , Wenchang ZHU , Jianqing ZHAO . Layered oxide cathode for sodium-ion batteries: Surface and interface modification and suppressed gas generation effect. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 254-266. doi: 10.11862/CJIC.20240260
9. [9]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
10. [10]
  Endong YANG , Haoze TIAN , Ke ZHANG , Yongbing LOU . Efficient oxygen evolution reaction of CuCo₂O₄/NiFe-layered bimetallic hydroxide core-shell nanoflower sphere arrays. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 930-940. doi: 10.11862/CJIC.20230369
11. [11]
  Yan LIU , Jiaxin GUO , Song YANG , Shixian XU , Yanyan YANG , Zhongliang YU , Xiaogang HAO . Exclusionary recovery of phosphate anions with low concentration from wastewater using a CoNi-layered double hydroxide/graphene electronically controlled separation film. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1775-1783. doi: 10.11862/CJIC.20240043
12. [12]
  Caixia Lin , Zhaojiang Shi , Yi Yu , Jianfeng Yan , Keyin Ye , Yaofeng Yuan . Ideological and Political Design for the Electrochemical Synthesis of Benzoxathiazine Dioxide Experiment. University Chemistry, 2024, 39(2): 61-66. doi: 10.3866/PKU.DXHX202309005
13. [13]
  Rong Tian , Yadi Yang , Naihao Lu . Comprehensive Experimental Design of Undergraduate Students Based on Interdisciplinarity: Study on the Effect of Quercetin on Chlorination Activity of Myeloperoxidase. University Chemistry, 2024, 39(8): 247-254. doi: 10.3866/PKU.DXHX202312064
14. [14]
  Junli Liu . Practice and Exploration of Research-Oriented Classroom Teaching in the Integration of Science and Education: a Case Study on the Synthesis of Sub-Nanometer Metal Oxide Materials and Their Application in Battery Energy Storage. University Chemistry, 2024, 39(10): 249-254. doi: 10.12461/PKU.DXHX202404023
15. [15]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . 层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响. Acta Physico-Chimica Sinica, 2025, 41(1): 2309002-. doi: 10.3866/PKU.WHXB202309002
16. [16]
  Yaping ZHANG , Tongchen WU , Yun ZHENG , Bizhou LIN . Z-scheme heterojunction β-Bi₂O₃ pillared CoAl layered double hydroxide nanohybrid: Fabrication and photocatalytic degradation property. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 531-539. doi: 10.11862/CJIC.20240256
17. [17]
  Chunmei GUO , Weihan YIN , Jingyi SHI , Jianhang ZHAO , Ying CHEN , Quli FAN . Facile construction and peroxidase-like activity of single-atom platinum nanozyme. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1633-1639. doi: 10.11862/CJIC.20240162
18. [18]
  .
  CCS Chemistry | 超分子活化底物为自由基促进高效选择性光催化氧化
  . CCS Chemistry, 2025, 7(10.31635/ccschem.025.202405229): -.
19. [19]
  Yongpo Zhang , Xinfeng Li , Yafei Song , Mengyao Sun , Congcong Yin , Chunyan Gao , Jinzhong Zhao . Synthesis of Chlorine-Bridged Binuclear Cu(I) Complexes Based on Conjugation-Driven Cu(II) Oxidized Secondary Amines. University Chemistry, 2024, 39(5): 44-51. doi: 10.3866/PKU.DXHX202309092
20. [20]
  .
  CCS Chemistry 综述推荐│绿色氧化新思路：光/电催化助力有机物高效升级
  . CCS Chemistry, 2025, 7(10.31635/ccschem.024.202405369): -.

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(316)
HTML views(35)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142