Sulfuric acid etching CeO2 nanoparticles to promote high KA-Oil selectivity in cyclohexane selective oxidation

doi:10.1016/j.cjche.2025.03.005

Chinese Journal of Chemical Engineering ›› 2025, Vol. 81 ›› Issue (5): 151-160.DOI: 10.1016/j.cjche.2025.03.005

Previous Articles Next Articles

Sulfuric acid etching CeO₂ nanoparticles to promote high KA-Oil selectivity in cyclohexane selective oxidation

Shuang Wei^2,3,4, Yingwei Li³, Longlong Wang^1,3, Kexin Li³, Bin He³, Ruirui Zhang³, Ruixia Liu^1,2,3

1. Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, China;
2. Sino-Danish College, University of Chinese Academy of Sciences, Beijing 100049, China;
3. Beijing Key Laboratory of Ionic Liquids Clean Process, CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Innovation Academy for Green Manufacture, CAS, Beijing 100190, China;
4. Sino-Danish Centre for Education and Research, CAS, Beijing 100190, China

Received:2024-09-28 Revised:2025-03-11 Accepted:2025-03-12 Online:2025-04-03 Published:2025-05-28
Contact: Ruirui Zhang,E-mail:rrzhang@ipe.ac.cn;Ruixia Liu,E-mail:rxliu@ipe.ac.cn
Supported by:
This work was supported by National Natural Science Fund for Excellent Young Scholars (22222813), the National Natural Science Foundation of China (22078338), the National Key Research and Development Program of China (2023YFA1506803), the Postdoctoral Fellowship Program of CPSF (GZC20232700) and the “Special Research Assistant Project” of the Chinese Academy of Sciences.

Sulfuric acid etching CeO₂ nanoparticles to promote high KA-Oil selectivity in cyclohexane selective oxidation

Shuang Wei^2,3,4, Yingwei Li³, Longlong Wang^1,3, Kexin Li³, Bin He³, Ruirui Zhang³, Ruixia Liu^1,2,3

1. Henan Institute of Advanced Technology, Zhengzhou University, Zhengzhou 450001, China;
2. Sino-Danish College, University of Chinese Academy of Sciences, Beijing 100049, China;
3. Beijing Key Laboratory of Ionic Liquids Clean Process, CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Innovation Academy for Green Manufacture, CAS, Beijing 100190, China;
4. Sino-Danish Centre for Education and Research, CAS, Beijing 100190, China

通讯作者: Ruirui Zhang,E-mail:rrzhang@ipe.ac.cn;Ruixia Liu,E-mail:rxliu@ipe.ac.cn
基金资助:
This work was supported by National Natural Science Fund for Excellent Young Scholars (22222813), the National Natural Science Foundation of China (22078338), the National Key Research and Development Program of China (2023YFA1506803), the Postdoctoral Fellowship Program of CPSF (GZC20232700) and the “Special Research Assistant Project” of the Chinese Academy of Sciences.

Abstract

Abstract: Nanostructured ceria has attracted much attention in the field of redox catalysts due to the numerous active sites with excellent redox ability. Based on the acidic medium etching strategy, we constructed the strong binding centers (hydroxyl sites and strong acid sites) on the surfaces of nanostructured ceria, which regulate the adsorption process of KA-Oil (the mixture of cyclohexanol and cyclohexanone) and to promote high KA-Oil selectivity in cyclohexane oxidation. The three CeO₂ (nanocube, nanorod and nanopolyhedron) with different exposed crystal planes were treated by acid etching to change the surface sites and catalytic properties. The transition behavior of surface sites during etching was revealed, abundant strong binding centers were proved to be constructed successfully. And especially for the nanorod treated by acid (Acid@CeO₂-NR) with the strongest response for sulfuric acid etching, the strong adsorption of cyclohexanone by strong binding centers was confirmed based on the in-situ DRIFTs. The sulfuric acid etching strategy to enhance the selective oxidation of cyclohexane based on the construction of strong binding centers was proved to be feasible and effective, Acid@CeO₂-NR with strongest etching response achieved the dramatic promotion of KA-Oil selectivity from 64.1% to 92.3%.

Key words: Nanostructured CeO₂, Defect engineering, Cyclohexane oxidation, Crystal facet effect, Acid site

摘要： Nanostructured ceria has attracted much attention in the field of redox catalysts due to the numerous active sites with excellent redox ability. Based on the acidic medium etching strategy, we constructed the strong binding centers (hydroxyl sites and strong acid sites) on the surfaces of nanostructured ceria, which regulate the adsorption process of KA-Oil (the mixture of cyclohexanol and cyclohexanone) and to promote high KA-Oil selectivity in cyclohexane oxidation. The three CeO₂ (nanocube, nanorod and nanopolyhedron) with different exposed crystal planes were treated by acid etching to change the surface sites and catalytic properties. The transition behavior of surface sites during etching was revealed, abundant strong binding centers were proved to be constructed successfully. And especially for the nanorod treated by acid (Acid@CeO₂-NR) with the strongest response for sulfuric acid etching, the strong adsorption of cyclohexanone by strong binding centers was confirmed based on the in-situ DRIFTs. The sulfuric acid etching strategy to enhance the selective oxidation of cyclohexane based on the construction of strong binding centers was proved to be feasible and effective, Acid@CeO₂-NR with strongest etching response achieved the dramatic promotion of KA-Oil selectivity from 64.1% to 92.3%.

关键词: Nanostructured CeO₂, Defect engineering, Cyclohexane oxidation, Crystal facet effect, Acid site

Shuang Wei, Yingwei Li, Longlong Wang, Kexin Li, Bin He, Ruirui Zhang, Ruixia Liu. Sulfuric acid etching CeO₂ nanoparticles to promote high KA-Oil selectivity in cyclohexane selective oxidation[J]. Chinese Journal of Chemical Engineering, 2025, 81(5): 151-160.

References

[1] Y. Zhang, J.C. Lu, L.M. Zhang, T. Fu, J. Zhang, X. Zhu, X.Y. Gao, D.D. He, Y.M. Luo, D.D. Dionysiou, W.J. Zhu, Investigation into the catalytic roles of oxygen vacancies during gaseous styrene degradation process via CeO₂ catalysts with four different morphologies, Appl. Catal. B Environ. 309 (2022) 121249.
[2] A. Trovarelli, J. Llorca, Ceria catalysts at nanoscale: How do crystal shapes shape catalysis? ACS Catal. 7 (7) (2017) 4716-4735.
[3] Y. Zhang, S.N. Zhao, J. Feng, S.Y. Song, W.D. Shi, D. Wang, H.J. Zhang, Unraveling the physical chemistry and materials science of CeO₂-based nanostructures, Chem 7 (8) (2021) 2022-2059.
[4] C.W. Sun, H. Li, L.Q. Chen, Nanostructured ceria-based materials: Synthesis, properties, and applications, Energy Environ. Sci. 5 (9) (2012) 8475-8505.
[5] I. Graca, S. Al-Shihri, D. Chadwick, Selective oxidation of cyclohexane: Ce promotion of nanostructured manganese tungstate, Appl. Catal. A Gen. 568 (2018) 95-104.
[6] D.D. Peng, Y. Zhang, G. Xu, Y. Tian, D. Ma, Y. Zhang, P. Qiu, Synthesis of multilevel structured MoS₂@Cu/Cu₂O@C visible-light-driven photocatalyst derived from MOF-guest polyhedra for cyclohexane oxidation, ACS Sustainable Chem. Eng. 8 (17) (2020) 6622-6633.
[7] J.T. Grant, J.M. Venegas, W.P. McDermott, I. Hermans, Aerobic oxidations of light alkanes over solid metal oxide catalysts, Chem. Rev. 118 (5) (2018) 2769-2815.
[8] N. Tsunoji, H. Nishida, Y. Ide, K. Komaguchi, S. Hayakawa, Y. Yagenji, M. Sadakane, T. Sano, Photocatalytic activation of C-H bonds by spatially controlled chlorine and titanium on the silicate layer, ACS Catal. 9 (6) (2019) 5742-5751.
[9] X. Wang, S.A. Chen, Y.R. Ma, T.Y. Zhang, Y.J. Zhao, T.W. He, H. Huang, S.T. Zhang, J.F. Rong, C.F. Shi, K.J. Tang, Y. Liu, Z.H. Kang, Continuous homogeneous catalytic oxidation of C-H bonds by metal-free carbon dots with a poly(ascorbic acid) structure, ACS Appl. Mater. Interfaces (2022).
[10] R. Goyal, B. Sarkar, S. Sameer, A. Bag, A. Bordoloi, Ag and WOx nanoparticles embedded in mesoporous SiO₂ for cyclohexane oxidation, ACS Appl. Nano Mater. 2 (9) (2019) 5989-5999.
[11] J.L. Yin, J.S. You, Concise synthesis of polysubstituted carbohelicenes by a C-H activation/radical reaction/C-H activation sequence, Angew. Chem. Int. Ed 58 (1) (2019) 302-306.
[12] F. Jafarpour, M. Azizzade, Y. Golpazir-Sorkheh, H. Navid, S. Rajai-Daryasarei, Divergent synthesis of α-aroyloxy ketones and indenones: A controlled domino radical reaction for di- and trifunctionalization of alkynes, J. Org. Chem. 85 (12) (2020) 8287-8294.
[13] N. Ahmed, R.J. Spears, T.D. Sheppard, V. Chudasama, Functionalisation of ethereal-based saturated heterocycles with concomitant aerobic C-H activation and C-C bond formation, Chem. Sci. 13 (29) (2022) 8626-8633.
[14] S. Min, B. Park, J. Nedsaengtip, S.H. Hong, Mechanochemical direct fluorination of unactivated C(sp³)-H bonds, Adv. Synth. Catal. 364 (12) (2022) 1975-1981.
[15] L. Mouheb, L. Dermeche, N. Essayem, C. Rabia, Keggin-type mixed polyoxomolybdates catalyzed cyclohexanone oxidation by hydrogen peroxide: In situ IR pyridine adsorption, Catal. Lett. 150 (11) (2020) 3327-3334.
[16] B. Sudduth, D.M. Yun, J.M. Sun, Y. Wang, Facet-Dependent selectivity of CeO₂ nanoparticles in 2-Propanol conversion, J. Catal. 404 (2021) 96-108.
[17] L. Chen, Q.L. Wang, X.X. Wang, Q.L. Cong, H.Y. Ma, T.J. Guo, S.J. Li, W. Li, High-performance CeO₂/halloysite hierarchical catalysts with promotional redox property and acidity for the selective catalytic reduction of NO with NH₃, Chem. Eng. J. 390 (2020) 124251.
[18] D. Xiangke Guo, M.X. Xu, M.Y. She, P. Yan Zhu, D. Taotao Shi, P. Zhaoxu Chen, P. Luming Peng, P. Xuefeng Guo, D. Ming Lin, P. Weiping Ding, Morphology-reserved synthesis of discrete nanosheets of CuO@SAPO-34 and pore mouth catalysis for one-pot oxidation of cyclohexane, Angew. Chem. Int. Ed. 59 (7) (2020) 2606-2611.
[19] S.X. Chen, Y.W. Li, Z.C. Wang, Y. Jin, R.X. Liu, X.G. Li, Poly(ionic liquid)s hollow spheres nanoreactor for enhanced cyclohexane catalytic oxidation, J. Catal. 411 (2022) 135-148.
[20] F.T. Liang, W.Z. Zhong, L.P. Xiang, L.Q. Mao, Q. Xu, S.R. Kirk, D.L. Yin, Synergistic hydrogen atom transfer with the active role of solvent: Preferred one-step aerobic oxidation of cyclohexane to adipic acid by N-hydroxyphthalimide, J. Catal. 378 (2019) 256-269.
[21] J. Lei, W. Liu, Y. Jin, B.X. Li, Oxygen vacancy-dependent chemiluminescence: A facile approach for quantifying oxygen defects in ZnO, Anal. Chem. 94 (24) (2022) 8642-8650.
[22] J.X. Zheng, R. Sun, D.P. Meng, J.X. Guo, Z. Wang, Boosting oxygen evolution reaction performance via metal defect-induced lattice oxygen redox reactions on spinel oxides, J. Mater. Chem. A 11 (27) (2023) 15044-15053.
[23] R.Q. Zong, Y.G. Fang, C.R. Zhu, X. Zhang, L. Wu, X. Hou, Y.K. Tao, J. Shao, Surface defect engineering on perovskite oxides as efficient bifunctional electrocatalysts for water splitting, ACS Appl. Mater. Interfaces 13 (36) (2021) 42852-42860.
[24] J.X. Zheng, X.F. Peng, Z. Xu, J.B. Gong, Z. Wang, Cationic defect engineering in spinel NiCo₂O₄ for enhanced electrocatalytic oxygen evolution, ACS Catal. 12 (16) (2022) 10245-10254.
[25] L.R. Bao, S.H. Zhu, Y. Chen, Y. Wang, W.H. Meng, S. Xu, Z.H. Lin, X.Y. Li, M. Sun, L.M. Guo, Anionic defects engineering of Co₃O₄ catalyst for toluene oxidation, Fuel 314 (2022) 122774.
[26] H.W. Chen, W. Cui, D.F. Li, Q.Q. Tian, J.J. He, Q. Liu, X. Chen, M.F. Cui, X. Qiao, Z.X. Zhang, J.H. Tang, Z.Y. Fei, Selectively etching lanthanum to engineer surface cobalt-enriched LaCoO₃ perovskite catalysts for toluene combustion, Ind. Eng. Chem. Res. 59 (23) (2020) 10804-10812.
[27] Z. Li, X.Y. Wang, M.L. Zeng, K.Y. Chen, D.H. Cao, Y.W. Huang, Y.Q. Zhu, W.H. Zhang, N.N. Wang, Y.A. Wu, The interplay between selective etching induced cation defects and active oxygen species for volatile organic compounds degradation, J. Colloid Interface Sci. 625 (2022) 363-372.
[28] J.J. Liu, M.J. Hao, C.L. Chen, K.M. Du, Q.Y. Zhou, S.H. Zou, L.P. Xiao, J. Fan, Chlorinating CeO₂ at surface oxygen vacancies to promote their selectivity in oxidative dehydrogenation of propane to propene, Appl. Surf. Sci. 528 (2020) 147025.
[29] Y.W. Li, H. Li, K.X. Li, R.R. Wang, R.R. Zhang, R.X. Liu, Roles of oxygen vacancies in CeO₂ nanostructures for catalytic aerobic cyclohexane oxidation, ACS Appl. Nano Mater. 6 (15) (2023) 14214-14227.
[30] X.B. Huang, K.Y. Zhang, B.X. Peng, G. Wang, M. Muhler, F. Wang, Ceria-based materials for thermocatalytic and photocatalytic organic synthesis, ACS Catal. 11 (15) (2021) 9618-9678.
[31] H.C. Zhang, C.S. Li, W.X. Liu, G.S. Luo, W.A. Goddard, M.J. Cheng, B.J. Xu, Q. Lu, Activation of light alkanes at room temperature and ambient pressure, Nat. Catal. 6 (2023) 666-675.
[32] F. Esch, S. Fabris, L. Zhou, T. Montini, C. Africh, P. Fornasiero, G. Comelli, R. Rosei, Electron localization determines defect formation on ceria substrates, Science 309 (5735) (2005) 752-755.
[33] G.E. Murgida, M. Veronica Ganduglia-Pirovano, Evidence for subsurface ordering of oxygen vacancies on the reduced CeO₂(111) surface using density-functional and statistical calculations, Phys. Rev. Lett. 110 (24) (2013) 246101.
[34] S. Torbrugge, M. Reichling, A. Ishiyama, S. Morita, O. Custance, Evidence of subsurface oxygen vacancy ordering on reduced CeO₂(111), Phys. Rev. Lett. 99 (5) (2007) 056101.
[35] X.Y. Zhang, P.F. Yang, Y.N. Liu, J.H. Pan, D.Q. Li, B. Wang, J.T. Feng, Support morphology effect on the selective oxidation of glycerol over AuPt/CeO₂ catalysts, J. Catal. 385 (2020) 146-159.
[36] Q. Zhang, S.P. Mo, B.X. Chen, W.X. Zhang, C.L. Huang, D.Q. Ye, Hierarchical Co₃O₄ nanostructures in situ grown on 3D nickel foam towards toluene oxidation, Mol. Catal. 454 (2018) 12-20.
[37] F. Jiang, S.S. Wang, B. Liu, J. Liu, L. Wang, Y. Xiao, Y.B. Xu, X.H. Liu, Insights into the influence of CeO₂Crystal facet on CO₂ Hydrogenation to methanol over Pd/CeO₂Catalysts, ACS Catal. 10 (19) (2020) 11493-11509.
[38] Y. Xie, J.J. Chen, X. Wu, J.J. Wen, R. Zhao, Z.L. Li, G.C. Tian, Q.L. Zhang, P. Ning, J.M. Hao, Frustrated lewis pairs boosting low-temperature CO₂ methanation performance over Ni/CeO₂ nanocatalysts, ACS Catal. 12 (17) (2022) 10587-10602.
[39] Z.H. Xie, J.P. Zhong, J.T. Tian, P. Liu, Q.M. Ren, L.M. Chen, M.L. Fu, D.Q. Ye, Unraveling the role of OH groups over CeO₂ derived from methanol modification for enhancing toluene oxidation: Experimental and theoretical studies, Appl. Catal. A Gen. 654 (2023) 119069.
[40] C. Lahousse, F. Mauge, J. Bachelier, J.C. Lavalley, Acidic and basic properties of titania-alumina mixed oxides; active sites for propan-2-ol dehydration, J. Chem. Soc., Faraday Trans. 91 (17) (1995) 2907-2912.
[41] C.D. Baertsch, K.T. Komala, Y.H. Chua, E. Iglesia, Genesis of Broensted acid sites during dehydration of 2-butanol on tungsten oxide catalysts, J. Catal. 205 (1) (2002) 44-57.

Sulfuric acid etching CeO₂ nanoparticles to promote high KA-Oil selectivity in cyclohexane selective oxidation

Sulfuric acid etching CeO₂ nanoparticles to promote high KA-Oil selectivity in cyclohexane selective oxidation

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 3

Recommended Articles

Metrics

Comments

[1]	Andrew Ng Kay Lup, Faisal Abnisa, Wan Mohd Ashri Wan Daud, Mohamed Kheireddine Aroua. Synergistic interaction of metal–acid sites for phenol hydrodeoxygenation over bifunctional Ag/TiO₂ nanocatalyst [J]. Chin.J.Chem.Eng., 2019, 27(2): 349-361.
[2]	Xian Mao, Fanglu Yuan, Anqi Zhou, Wenheng Jing. Magnéli phases Ti_nO_2n-1 as novel ozonation catalysts for effective mineralization of phenol [J]. Chin.J.Chem.Eng., 2018, 26(9): 1978-1984.
[3]	HU Yongqi, WANG Jianying, ZHAO Ruihong, LIU Yumin, LIU Runjing, LI Yongdan. Catalytic Oxidation of Cyclohexane over ZSM-5 Catalyst in N-alkyl-N-methylimidazolium Ionic Liquids [J]. , 2009, 17(3): 407-411.