Citation: Hailian Tang, Siyuan Chen, Qiaoyun Liu, Guoyi Bai, Botao Qiao, Fei Liu. Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions[J]. Acta Physico-Chimica Sinica, ;2025, 41(4): 100036. doi: 10.3866/PKU.WHXB202408004 shu

Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions

Hailian Tang ^1,2,, ,
Siyuan Chen ^2,3 ,
Qiaoyun Liu ^2,4 ,
Guoyi Bai ¹ ,
Botao Qiao ^2,5,, ,
Fei Liu ^2,,

1.
School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384, China;
2.
CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China;
3.
College of Chemistry and Materials Science, Hebei University, Baoding 071002, Hebei Province, China;
4.
College of Chemistry, Zhengzhou University, Zhengzhou 450001, China;
5.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning Province, China

Corresponding author: Hailian Tang, Botao Qiao, Fei Liu,
Received Date: 4 August 2024
Revised Date: 14 September 2024
Accepted Date: 2 October 2024

Fund Project: The project was supported by the National Key R&D Program of China (2023YFA1506800), National Natural Science Foundation of China (21902040, 22108259), and Natural Science Foundation of Hebei Province (B2019201158).

The strong metal-support interaction (SMSI) is a widely recognized concept in heterogeneous catalysis, known for significantly enhancing catalyst stability and potentially modulating catalytic performance. However, because the SMSI effect is generally reversible, it tends to diminish under redox conditions opposite to those used for its construction. Consequently, its application is typically limited to conditions that are the same or similar to those under which it was formed. Herein, we report the application of oxidative SMSI (O-SMSI) constructed on hydroxyapatite-supported Rh catalyst (Rh/HAP) in a reductive reaction, the hydrogenation of furfuryl alcohol. In situ diffuse reflectance infrared Fourier transform spectroscopy of CO adsorption and electron microscopy measurements reveal that high-temperature oxidation treatment at 500 ℃ induced the occurrence of O-SMSI on the Rh/HAP catalyst, accompanied by the encapsulation of Rh particles by the support. Upon the O-SMSI, the Rh species were effectively stabilized on the support surface, with significant suppression of sintering and leaching during liquid-phase reactions. As a result, the catalyst showed stable furfuryl alcohol conversion and cyclopentanone selectivity during recycling tests. Furthermore, it was found that the O-SMSI and the associated encapsulation behavior on the Rh/HAP system were only partially reversible rather than completely reversible. Even after high-temperature reduction at up to 600 ℃, a portion of the SMSI effect remains, ensuring the stability of the catalysts in reductive reactions. This discovery greatly expands the application scope of SMSI catalysts and provides a new way to prepare stable hydrogenation catalysts.
- Oxidative strong metal-support interaction,
- Hydroxyapatite,
- Rh,
- Stability,
- Hydrogenation
1. [1]
  (1) Xu, M.; Peng, M.; Tang, H.; Zhou, W.; Qiao, B.; Ma, D. J. Am. Chem. Soc. 2024,146, 2290. doi: 10.1021/jacs.3c09102
2. [2]
  (2) Wu, G.; Liu, Y.; Wang, J. Accounts Chem. Res. 2024, 56, 911. doi: 10.1021/acs.accounts.2c00727
3. [3]
  (3) Tauster, S. J.; Fung, S. C.; Garten, R. L. J. Am. Chem. Soc. 1978, 100, 170. doi: 10.1021/ja00469a029
4. [4]
  (4) Li, M.; Zhang, T.; Yang, S.-Z.; Sun, Y.; Zhang, J.; Polo-Garzon, F.; Siniard, K. M.; Yu, X.; Wu, Z.; Driscoll, D. M.; et al. ACS Catal. 2023,13, 6114. doi: 10.1021/acscatal.2c05730
5. [5]
  (5) Dong, J.; Fu, Q.; Li, H.; Xiao, J.; Yang, B.; Zhang, B.; Bai, Y.; Song, T.; Zhang, R.; Gao, L.; et al. J. Am. Chem. Soc. 2020,142, 17167. doi: 10.1021/jacs.0c08139
6. [6]
  (6) Siniard, K. M.; Li, M.; Yang, S. Z.; Zhang, J.; Polo-Garzon, F.; Wu, Z.; Yang, Z.; Dai, S. Angew. Chem.-Int. Edit. 2023, e202214322. doi: 10.1002/anie.202214322
7. [7]
  (7) Wang, H.; Wang, L.; Lin, D.; Feng, X.; Niu, Y.; Zhang, B.; Xiao, F.-S. Nat. Catal. 2021, 4, 418. doi: 10.1038/s41929-021-00611-3
8. [8]
  (8) Tang, H.; Su, Y.; Zhang, B.; Lee, A. F.; Isaacs, M. A.; Wilson, K.; Li, L.; Ren, Y.; Huang, J.; Haruta, M.; et al. Sci. Adv. 2017,3, e1700231. doi: 10.1126/sciadv.1700231
9. [9]
  (9) Liu, X.; Liu, M.-H.; Luo, Y.-C.; Mou, C.-Y.; Lin, S. D.; Cheng, H.; Chen, J.-M.; Lee, J.-F.; Lin, T.-S. J. Am. Chem. Soc. 2012, 134, 10251. doi: 10.1021/ja3033235
10. [10]
  (10) Tang, H.; Wei, J.; Liu, F.; Qiao, B.; Pan, X.; Li, L.; Liu, J.; Wang, J.; Zhang, T. J. Am. Chem. Soc. 2016, 138, 56. doi: 10.1021/jacs.5b11306
11. [11]
  (11) Tang, H.; Su, Y.; Guo, Y.; Zhang, L.; Li, T.; Zang, K.; Liu, F.; Li, L.; Luo, J.; Qiao, B.; et al. Chem. Sci. 2018, 9, 6679. doi: 10.1039/c8sc01392f
12. [12]
  (12) Song, T. Y.; Dong, J. H.; Li, R. T.; Xu, X. Y.; Hiroaki, M.; Yang, B.; Zhang, R. K.; Bai, Y. X.; Xin, H.; Lin, L.; et al. J. Phys. Chem. Lett. 2021,12, 4187. doi: 10.1021/acs.jpclett.1c00934
13. [13]
  (13) Matsubu, J. C.; Zhang, S.; DeRita, L.; Marinkovic, N. S.; Chen, J. G.; Graham, G. W.; Pan, X.; Christophe, P. Nat. Chem. 2017, 9, 120. doi: 10.1038/NCHEM.2607
14. [14]
  (14) Li, Z.; Cui, Y.; Wu, Z.; Milligan, C.; Zhou, L.; Mitchell, G.; Xu, B.; Shi, E.; Miller, J. T.; Ribeiro, F. H.; et al. Nat. Catal. 2018, 1, 349. doi: 10.1038/s41929-018-0067-8
15. [15]
  (15) Lunkenbein, T.; Schumann, J.; Behrens, M.; Schlögl, R.; Willinger, M. G. Angew. Chem.-Int. Edit. 2015, 54, 4544. doi: 10.1002/anie.201411581
16. [16]
  (16) Tauster, S. J.; Fung, S. C.; Baker, R. T. K.; Horsle, J. A. Science 1981, 211, 1120. doi: 10.1126/science.211.4487.1121
17. [17]
  (17) Han, B.; Li, Q.; Jiang, X.; Guo, Y.; Jiang, Q.; Su, Y.; Li, L.; Qiao, B. Small 2022,18, 2204490. doi: 10.1002/smll.202204490
18. [18]
  (18) Guo, Y.; Li, Y.; Du, X.; Li, L.; Jiang, Q.; Qiao, B. Nano Res. 2022, 15, 10037. doi: 10.1007/s12274-022-4376-5
19. [19]
  (19) Han, B.; Guo, Y. L.; Huang, Y. K.; Xi, W.; Xu, J.; Luo, J.; Qi, H. F.; Ren, Y. J.; Liu, X. Y.; Qiao, B. T.; et al. Angew. Chem.-Int. Edit.2020, 59, 11824. doi: 10.1002/anie.202003208
20. [20]
  (20) Tang, H. L.; Liu, F.; Wei, J. K.; Qiao, B. T.; Zhao, K. F.; Su, Y.; Jin, C. Z.; Li, L.; Liu, J. Y.; Wang, J. H.; et al. Angew. Chem.-Int. Edit. 2016, 55, 10606. doi: 10.1002/anie.201601823
21. [21]
  (21) Renz, M.; Corma, A. Eur. J. Org. Chem. 2004, 2004, 2036. doi: 10.1002/ejoc.200300778
22. [22]
  (22) Akashi, T.; Sato, S.; Takahashi, R.; Sodesawa, T.; Inui, K. Catal. Commun. 2003,4, 411. doi: 10.1016/s1566-7367(03)00095-5
23. [23]
  (23) Mori, K.; Kanai, S.; Hara, T.; Mizugaki, T.; Ebitani, K.; Jitsukawa, K.; Kaneda, K. Chem. Mater. 2007, 19, 1249. doi: 10.1021/cm061388l
24. [24]
  (24) Tauster, S. J.; Fung, S. C. J. Catal. 1978, 55, 29.
25. [25]
  (25) Vimont, A.; Thibault-Starzyk, F.; Daturi, M. Chem. Soc. Rev. 2010, 39, 4928. doi: 10.1039/b919543m
26. [26]
  (26) Lamberti, C.; Zecchina, A.; Groppo, E.; Bordiga, S. Chem. Soc. Rev. 2010, 39, 4951. doi: 10.1039/c0cs00117a
27. [27]
  (27) Li, L.; Wang, A. Q.; Qiao, B. T.; Lin, J.; Huang, Y. Q.; Wang, X. D.; Zhang, T. J. Catal. 2013, 299, 90. doi: 10.1016/j.jcat.2012.11.019
28. [28]
  (28) Zhao, K.; Tang, H.; Qiao, B.; Li, L.; Wang, J. ACS Catal. 2015, 5, 3528. doi: 10.1021/cs5020496
29. [29]
  (29) Lang, R.; Li, T.; Matsumura, D.; Miao, S.; Ren, Y.; Cui, Y. T.; Tan, Y.; Qiao, B.; Li, L.; Wang, A.; et al. Angew. Chem.-Int. Edit. 2016, 55, 16054. doi: 10.1002/anie.201607885
30. [30]
  (30) Wu, J.; Qiao, L.-Y.; Zhou, Z.-F.; Cui, G.-J.; Zong, S.-S.; Xu, D.-J.; Ye, R.-P.; Chen, R.-P.; Si, R.; Yao, Y.-G. ACS Catal. 2019, 9, 932. doi: 10.1021/acscatal.8b03319
31. [31]
  (31) Mou, J. L.; Chen, L. L.; Fan, J.; Zeng, L.; Jiang, X.; Jiao, Y.; Wang, J. L.; Chen, Y. Q. Acta Phys.-Chim. Sin. 2023, 39, 2302041. doi: 10.3866/PKU.WHXB202302041
32. [32]
  (32) Marchionni, V.; Newton, M. A.; Kambolis, A.; Matam, S. K.; Weidenkaff, A.; Ferri, D. Catal. Today 2014, 229, 80. doi: 10.1016/j.cattod.2013.10.082
33. [33]
  (33) Machida, M.; Minami, S.; Ikeue, K.; Hinokuma, S.; Nagao, Y.; Sato, T.; Nakahara, Y. Chem. Mater. 2014, 26, 5799. doi: 10.1021/cm503061g
34. [34]
  (34) Machida, M.; Minami, S.; Hinokuma, S.; Yoshida, H.; Nagao, Y.; Sato, T.; Nakahara, Y. J. Phys. Chem. C 2014, 119, 373. doi: 10.1021/jp509649r
35. [35]
  (35) Machida, M. Chem. Rec. 2016, 16, 2219. doi: 10.1002/tcr.201600037
36. [36]
  (36) Gol’dshleger, N. F.; Azbel', B. I.; Isakov, Y. I.; Shpiro, E. S.; Minachev, K. M. J. Mol. Catal. A: Chem. 1996, 106, 159.
37. [37]
  (37) Andersson, S. L. T.; Scurre, M. S. J. Catal. 1981, 71, 233.
1. [1]
  Jiaxi Xu , Yuan Ma . Influence of Hyperconjugation on the Stability and Stable Conformation of Ethane, Hydrazine, and Hydrogen Peroxide. University Chemistry, 2024, 39(11): 374-377. doi: 10.3866/PKU.DXHX202402049
2. [2]
  Shitao Fu , Jianming Zhang , Cancan Cao , Zhihui Wang , Chaoran Qin , Jian Zhang , Hui Xiong . Study on the Stability of Purple Cabbage Pigment. University Chemistry, 2024, 39(4): 367-372. doi: 10.3866/PKU.DXHX202401059
3. [3]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Corrosion inhibition of nickel-cobalt-phosphide in water by coating TiO₂ layer. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 365-384. doi: 10.11862/CJIC.20240063
4. [4]
  Yihan Xue , Xue Han , Jie Zhang , Xiaoru Wen . Efficient capacitive desalination over NCQDs decorated FeOOH composite. Acta Physico-Chimica Sinica, 2025, 41(7): 100072-. doi: 10.1016/j.actphy.2025.100072
5. [5]
  Jingke LIU , Jia CHEN , Yingchao HAN . Nano hydroxyapatite stable suspension system: Preparation and cobalt adsorption performance. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1763-1774. doi: 10.11862/CJIC.20240060
6. [6]
  Jing SU , Bingrong LI , Yiyan BAI , Wenjuan JI , Haiying YANG , Zhefeng Fan . Highly sensitive electrochemical dopamine sensor based on a highly stable In-based metal-organic framework with amino-enriched pores. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1337-1346. doi: 10.11862/CJIC.20230414
7. [7]
  Jie WU , Zhihong LUO , Xiaoli CHEN , Fangfang XIONG , Li CHEN , Biao ZHANG , Bin SHI , Quansheng OUYANG , Jiaojing SHAO . Critical roles of AlPO₄ coating in enhancing cycling stability and rate capability of high voltage LiNi_0.5Mn_1.5O₄ cathode materials. Chinese Journal of Inorganic Chemistry, 2025, 41(5): 948-958. doi: 10.11862/CJIC.20240400
8. [8]
  Rui HUANG , Shengjie LIU , Qingyuan WU , Nanfeng ZHENG . Enhanced selectivity of catalytic hydrogenation of halogenated nitroaromatics by interfacial effects. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 201-212. doi: 10.11862/CJIC.20240356
9. [9]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
10. [10]
  Xiaoning TANG , Junnan LIU , Xingfu YANG , Jie LEI , Qiuyang LUO , Shu XIA , An XUE . Effect of sodium alginate-sodium carboxymethylcellulose gel layer on the stability of Zn anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1452-1460. doi: 10.11862/CJIC.20240191
11. [11]
  Yingtong Shi , Guotong Xu , Guizeng Liang , Di Lan , Siyuan Zhang , Yanru Wang , Daohao Li , Guanglei Wu . PEG-VN modified PP separator for high-stability and high-efficiency lithium-sulfur batteries. Acta Physico-Chimica Sinica, 2025, 41(7): 100082-. doi: 10.1016/j.actphy.2025.100082
12. [12]
  Xuewei BA , Cheng CHENG , Huaikang ZHANG , Deqing ZHANG , Shuhua LI . Preparation and luminescent performance of Sr_1-xZrSi₂O₇∶xDy³⁺ phosphor with high thermal stability. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 357-364. doi: 10.11862/CJIC.20240096
13. [13]
  Renqing Lü , Shutao Wang , Fang Wang , Guoping Shen . Computational Chemistry Aided Organic Chemistry Teaching: A Case of Comparison of Basicity and Stability of Diazine Isomers. University Chemistry, 2025, 40(3): 76-82. doi: 10.12461/PKU.DXHX202404119
14. [14]
  Baitong Wei , Jinxin Guo , Xigong Liu , Rongxiu Zhu , Lei Liu . Theoretical Study on the Structure, Stability of Hydrocarbon Free Radicals and Selectivity of Alkane Chlorination Reaction. University Chemistry, 2025, 40(3): 402-407. doi: 10.12461/PKU.DXHX202406003
15. [15]
  Zeyi Yan , Ruitao Liu , Xinyu Qi , Yuxiang Zhang , Lulu Sun , Xiangyuan Li , Anchao Feng . Exploration of Suspension Polymerization: Preparation and Fluorescence Stability of Perovskite Polystyrene Microbeads. University Chemistry, 2025, 40(4): 72-79. doi: 10.12461/PKU.DXHX202405110
16. [16]
  Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
17. [17]
  Huiying Xu , Minghui Liang , Zhi Zhou , Hui Gao , Wei Yi . Application of Quantum Chemistry Computation and Visual Analysis in Teaching of Weak Interactions. University Chemistry, 2025, 40(3): 199-205. doi: 10.12461/PKU.DXHX202407011
18. [18]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
19. [19]
  Weihan Zhang , Menglu Wang , Ankang Jia , Wei Deng , Shuxing Bai . 表面硫物种对钯-硫纳米片加氢性能的影响. Acta Physico-Chimica Sinica, 2024, 40(11): 2309043-. doi: 10.3866/PKU.WHXB202309043
20. [20]
  Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . Soft template-induced deep pore structure of Cu/Al₂O₃ for promoting plasma-catalyzed CO₂ hydrogenation to DME. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-. doi: 10.1016/j.actphy.2025.100054

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(433)
HTML views(71)

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