Skip to main content
SpringerLink
Log in

Dual lattice oxygens in amorphous Zr-doped manganese oxide for highly efficient aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

含双晶格氧的无定形锆掺杂锰氧化物选择性高效氧化5-羟甲基糠醛为2,5-呋喃二羧酸

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

One hurdle in developing transition metal oxide (TMO) catalysts for aerobic oxidation reactions is their need for a low binding energy of the lattice oxygen (OL) to create active OL and a high OL binding energy to maintain structural stability during catalysis. In this work, we prepared amorphous Zr-doped manganese oxide (amor-Zr:MnOx) catalysts carrying dual lattice oxygens that can address such conflicting objectives in catalyst development. In the aerobic oxidation of 5-(hydroxymethyl)furfural (HMF), the amor-Zr0.2MnOx catalyst gave 99% selectivity for 2,5-furandicarboxylic acid (FDCA) and a high FDCA formation rate of 3600 µmolFDCA gcat−1 h−1 in 1 h. To the best of our knowledge, the aerobic oxidation performance of the amor-Zr0.2MnOx catalyst is superior to those of most Mn-based and related TMO-based catalysts under comparable conditions. Experimental and theoretical studies show that the OL in amor-Zr: MnOx can be divided into two groups. One group includes the more stable OL that strengthens the catalyst structure and prevents phase transition, while the other group includes the more reactive OL that improves catalyst activity through the strong adsorption/activation of O2 and helps regenerate OL during catalysis.

摘要

晶格氧介导的氧化还原反应可以将有机物选择性氧化为高附加值产物, 是实现生物质资源高值化利用的重要途径. 其关键科学难题在于: 如何使催化材料同时具有较低的晶格氧(OL)结合能以产生活性OL, 以及较高的OL结合能以保持其在催化过程中的结构稳定性. 在本工作中, 我们制备了无定形锆掺杂的锰氧化物(amor-Zr:MnOx)催化材料, 并证实其同时具有高活性的OL以及高稳定性的OL. 以5-羟甲基糠醛(HMF)的选择性氧化为反应模型, amor-Zr0.2MnOx催化剂实现了HMF的高效选择性氧化, 产物中2,5-呋喃二甲酸(FDCA)的选择性高达99%, 1小时内FDCA产率高达3600 µmolFDCA gcat−1 h−1, 在类似反应条件下其性能优于大多数Mn基和相关过渡金属氧化物基催化材料. 实验和理论研究表明, amor-Zr:MnOx的优异性能源于其同时含有两种OL. 首先, 锆提高了锰相邻的OL的氧化活性, 并促进了反应后氧空位对O2的吸附/活化, 获得活性OL且同步促进催化反应中OL的再生; 锆相邻的OL具有较低的反应活性, 有利于催化材料保持结构稳定性. 本工作有望为理解晶格氧的氧化机制以及高活性催化材料的设计提供思路.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Zhang S, Jiang SF, Huang BC, et al. Sustainable production of value-added carbon nanomaterials from biomass pyrolysis. Nat Sustain, 2020, 3: 753–760

    Article  Google Scholar 

  2. Zeng Y, Maxwell S, Runting RK, et al. Environmental destruction not avoided with the sustainable development goals. Nat Sustain, 2020, 3: 795–798

    Article  Google Scholar 

  3. Kong X, Zhu Y, Fang Z, et al. Catalytic conversion of 5-hydroxymethylfurfural to some value-added derivatives. Green Chem, 2018, 20: 3657–3682

    Article  CAS  Google Scholar 

  4. Xu C, Paone E, Rodríguez-Padrón D, et al. Recent catalytic routes for the preparation and the upgrading of biomass derived furfural and 5-hydroxymethylfurfural. Chem Soc Rev, 2020, 49: 4273–4306

    Article  CAS  Google Scholar 

  5. Allen MC, Hoffman AJ, Liu T, et al. Highly selective cross-etherification of 5-hydroxymethylfurfural with ethanol. ACS Catal, 2020, 10: 6771–6785

    Article  CAS  Google Scholar 

  6. Hou Q, Qi X, Zhen M, et al. Biorefinery roadmap based on catalytic production and upgrading 5-hydroxymethylfurfural. Green Chem, 2021, 23: 119–231

    Article  CAS  Google Scholar 

  7. Kim M, Su Y, Aoshima T, et al. Effective strategy for high-yield furan dicarboxylate production for biobased polyester applications. ACS Catal, 2019, 9: 4277–4285

    Article  CAS  Google Scholar 

  8. Kim M, Su Y, Fukuoka A, et al. Aerobic oxidation of 5-(hydroxymethyl)furfural cyclic acetal enables selective furan-2,5-dicarboxylic acid formation with CeO2-supported gold catalyst. Angew Chem Int Ed, 2018, 57: 8235–8239

    Article  CAS  Google Scholar 

  9. Liu H, Jia W, Yu X, et al. Vitamin C-assisted synthesized Mn−Co oxides with improved oxygen vacancy concentration: Boosting lattice oxygen activity for the air-oxidation of 5-(hydroxymethyl)furfural. ACS Catal, 2021, 11: 7828–7844

    Article  CAS  Google Scholar 

  10. Hu L, Lin L, Wu Z, et al. Recent advances in catalytic transformation of biomass-derived 5-hydroxymethylfurfural into the innovative fuels and chemicals. Renew Sustain Energy Rev, 2017, 74: 230–257

    Article  CAS  Google Scholar 

  11. Kucherov FA, Romashov LV, Galkin KI, et al. Chemical transformations of biomass-derived C6-furanic platform chemicals for sustainable energy research, materials science, and synthetic building blocks. ACS Sustain Chem Eng, 2018, 6: 8064–8092

    Article  CAS  Google Scholar 

  12. Hayashi E, Yamaguchi Y, Kamata K, et al. Effect of MnO2 crystal structure on aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid. J Am Chem Soc, 2019, 141: 890–900

    Article  CAS  Google Scholar 

  13. Chen C, Wang L, Zhu B, et al. 2,5-Furandicarboxylic acid production via catalytic oxidation of 5-hydroxymethylfurfural: Catalysts, processes and reaction mechanism. J Energy Chem, 2021, 54: 528–554

    Article  CAS  Google Scholar 

  14. Feng H, Xu Z, Ren L, et al. Activating titania for efficient electrocatalysis by vacancy engineering. ACS Catal, 2018, 8: 4288–4293

    Article  CAS  Google Scholar 

  15. Wu R, Zhang J, Shi Y, et al. Metallic WO2-carbon mesoporous nanowires as highly efficient electrocatalysts for hydrogen evolution reaction. J Am Chem Soc, 2015, 137: 6983–6986

    Article  CAS  Google Scholar 

  16. Hayashi E, Yamaguchi Y, Kita Y, et al. One-pot aerobic oxidative sulfonamidation of aromatic thiols with ammonia by a dual-functional β-MnO2 nanocatalyst. Chem Commun, 2020, 56: 2095–2098

    Article  CAS  Google Scholar 

  17. Zhuang G, Yang B, Jiang W, et al. Spatially separated oxygen vacancies and nickel sites for ensemble promotion of selective CO2 photoreduction to CO. Cell Rep Phys Sci, 2022, 3: 100724

    Article  CAS  Google Scholar 

  18. Chen C, Xu K, Ji X, et al. Enhanced electrochemical performance by facile oxygen vacancies from lower valence-state doping for ramsdellite-MnO2. J Mater Chem A, 2015, 3: 12461–12467

    Article  CAS  Google Scholar 

  19. Wen Y, Yan J, Yang B, et al. Reactive oxygen species on transition metal-based catalysts for sustainable environmental applications. J Mater Chem A, 2022, 10: 19184–19210

    Article  CAS  Google Scholar 

  20. Zheng Y, Thampy S, Ashburn N, et al. Stable and active oxidation catalysis by cooperative lattice oxygen redox on SmMn2O5 mullite surface. J Am Chem Soc, 2019, 141: 10722–10728

    Article  CAS  Google Scholar 

  21. Rong S, Zhang P, Liu F, et al. Engineering crystal facet of α-MnO2 nanowire for highly efficient catalytic oxidation of carcinogenic airborne formaldehyde. ACS Catal, 2018, 8: 3435–3446

    Article  CAS  Google Scholar 

  22. Kauppi EI, Honkala K, Krause AOI, et al. ZrO2 acting as a redox catalyst. Top Catal, 2016, 59: 823–832

    Article  CAS  Google Scholar 

  23. Takayama S. Amorphous structures and their formation and stability. J Mater Sci, 1976, 11: 164–185

    Article  CAS  Google Scholar 

  24. Wen Y, Zhang Y, He L, et al. Activating lattice oxygen in amorphous MnO2 nanostructure for efficiently selective aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid. ACS Appl Nano Mater, 2022, 5: 11559–11566

    Article  CAS  Google Scholar 

  25. Anantharaj S, Noda S. Amorphous catalysts and electrochemical water splitting: An untold story of harmony. Small, 2020, 16: 1905779

    Article  CAS  Google Scholar 

  26. Sabri M, King HJ, Gummow RJ, et al. The oxidation of peroxide by disordered metal oxides: A measurement of thermodynamic stability “by proxy”. ChemPlusChem, 2018, 83: 620–629

    Article  CAS  Google Scholar 

  27. Chen G, Hong D, Xia H, et al. Amorphous and homogeneously Zr-doped MnOx with enhanced acid and redox properties for catalytic oxidation of 1,2-dichloroethane. Chem Eng J, 2022, 428: 131067

    Article  CAS  Google Scholar 

  28. Xu C, Liu Z, Wei T, et al. Mesoporous single-crystalline MnOx nanofibers@graphene for ultra-high rate and long-life lithium-ion battery anodes. J Mater Chem A, 2018, 6: 24756–24766

    Article  CAS  Google Scholar 

  29. Liu Y, Zhou H, Cao R, et al. Facile and green synthetic strategy of birnessite-type MnO2 with high efficiency for airborne benzene removal at low temperatures. Appl Catal B-Environ, 2019, 245: 569–582

    Article  CAS  Google Scholar 

  30. Gao T, Norby P, Krumeich F, et al. Synthesis and properties of layered-structured Mn5O8 nanorods. J Phys Chem C, 2010, 114: 922–928

    Article  CAS  Google Scholar 

  31. Tian FX, Li H, Zhu M, et al. Effect of MnO2 polymorphs’ structure on low-temperature catalytic oxidation: Crystalline controlled oxygen vacancy formation. ACS Appl Mater Interfaces, 2022, 14: 18525–18538

    Article  CAS  Google Scholar 

  32. Zhuang G, Chen Y, Zhuang Z, et al. Oxygen vacancies in metal oxides: Recent progress towards advanced catalyst design. Sci China Mater, 2020, 63: 2089–2118

    Article  CAS  Google Scholar 

  33. Zhang T, Low J, Yu J, et al. A blinking mesoporous TiO2−x composed of nanosized anatase with unusually long-lived trapped charge carriers. Angew Chem Int Ed, 2020, 59: 15000–15007

    Article  CAS  Google Scholar 

  34. Lu L, Wang B, Wang S, et al. La2O3-modified LaTiO2N photocatalyst with spatially separated active sites achieving enhanced CO2 reduction. Adv Funct Mater, 2017, 27: 1702447

    Article  Google Scholar 

  35. Tian FX, Zhu M, Liu X, et al. Dynamic structure of highly disordered manganese oxide catalysts for low-temperature CO oxidation. J Catal, 2021, 401: 115–128

    Article  CAS  Google Scholar 

  36. Fujita T, Horikawa M, Takei T, et al. Correlation between catalytic activity of supported gold catalysts for carbon monoxide oxidation and metal-oxygen binding energy of the support metal oxides. Chin J Catal, 2016, 37: 1651–1655

    Article  Google Scholar 

  37. Dong X, Wang X, Song H, et al. Enabling efficient aerobic 5-hydroxymethylfurfural oxidation to 2,5-furandicarboxylic acid in water by interfacial engineering reinforced Cu−Mn oxides hollow nanofiber. ChemSusChem, 2022, 15: e202200076

    Article  CAS  Google Scholar 

  38. Han X, Li C, Liu X, et al. Selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over MnOx−CeO2 composite catalysts. Green Chem, 2017, 19: 996–1004

    Article  CAS  Google Scholar 

  39. Ventura M, Nocito F, de Giglio E, et al. Tunable mixed oxides based on CeO2 for the selective aerobic oxidation of 5-(hydroxymethyl)furfural to FDCA in water. Green Chem, 2018, 20: 3921–3926

    Article  CAS  Google Scholar 

  40. Mishra DK, Lee HJ, Kim J, et al. MnCo2O4 spinel supported ruthenium catalyst for air-oxidation of HMF to FDCA under aqueous phase and base-free conditions. Green Chem, 2017, 19: 1619–1623

    Article  CAS  Google Scholar 

  41. Rao KTV, Rogers JL, Souzanchi S, et al. Inexpensive but highly efficient Co-Mn mixed-oxide catalysts for selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid. ChemSusChem, 2018, 11: 3323–3334

    Article  CAS  Google Scholar 

  42. Wan X, Tang N, Xie Q, et al. A CuMn2O4 spinel oxide as a superior catalyst for the aerobic oxidation of 5-hydroxymethylfurfural toward 2,5-furandicarboxylic acid in aqueous solvent. Catal Sci Technol, 2021, 11: 1497–1509

    Article  CAS  Google Scholar 

  43. Jia J, Zhang P, Chen L. Catalytic decomposition of gaseous ozone over manganese dioxides with different crystal structures. Appl Catal B-Environ, 2016, 189: 210–218

    Article  CAS  Google Scholar 

  44. Zhou Y, Fan HJ. Progress and challenge of amorphous catalysts for electrochemical water splitting. ACS Mater Lett, 2021, 3: 136–147

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (U1905215 and 52072076), the National Key Research and Development Program/Key Scientific Issues of Transformative Technology (2020YFA0710303), Fujian Natural Science Foundation (2022J01554), and the Key Project of Science and Technology Innovation of Fujian Provincial Department of Education (2022G02002).

Author information

Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. College of Materials Science and Engineering, Fuzhou University, New Campus, Fuzhou, 350108, China

    Yonglin Wen  (温永霖), Lairan He  (贺来冉), Hu Li  (李虎), Yunhui Han  (韩昀晖), Yiming Zhang  (张一鸣), Zanyong Zhuang  (庄赞勇) & Yan Yu  (于岩)

  2. Key Laboratory of Advanced Materials Technologies, Fuzhou University, Fuzhou, 350108, China

    Yonglin Wen  (温永霖), Lairan He  (贺来冉), Hu Li  (李虎), Yunhui Han  (韩昀晖), Yiming Zhang  (张一鸣), Zanyong Zhuang  (庄赞勇) & Yan Yu  (于岩)

Authors
  1. Yonglin Wen  (温永霖)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lairan He  (贺来冉)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hu Li  (李虎)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yunhui Han  (韩昀晖)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yiming Zhang  (张一鸣)
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Zanyong Zhuang  (庄赞勇)
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yan Yu  (于岩)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Wen Y, He L, Zhuang Z and Yu Y designed and adjusted the experimental plan; Wen Y and He L performed the experiments; Li H, Han Y and Zhang Y performed the theoretical calculations. Wen Y, He L, Zhuang Z and Yu Y wrote the paper. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Zanyong Zhuang  (庄赞勇) or Yan Yu  (于岩).

Additional information

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Yonglin Wen received his BSc degree in materials science and engineering from Fuzhou University. He is currently pursuing his PhD degree at Fuzhou University under the supervision of Prof. Yu and Prof. Zhuang. His research focuses on designing Mn-based catalysts for heterogeneous oxidation.

Lairan He is currently a Master’s degree student at the School of Materials Science and Engineering, Fuzhou University. His research interest focuses on designing Zr-based catalysts for heterogeneous oxidation catalysis.

Zanyong Zhuang received his BSc degree (2006) in chemistry from Xiamen University, and PhD degree (2011) from Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS). Currently, he is a full professor at Fuzhou University. His research interests mainly focus on the rational design of transition metal-based catalysts for energy and environmental applications, including advanced oxidation reaction and CO2 reduction reaction.

Yan Yu received her BSc, MSc, and PhD degrees from Fuzhou University. She was a postdoctoral fellow from 2010–2013 at FJIRSM, CAS. Currently, she is a professor at Fuzhou University. Her research interest includes environmental remediation, water purification, ecological materials, photocatalytic CO2 reduction, and H2 production.

Electronic Supplementary Material

40843_2022_2296_MOESM1_ESM.pdf

Dual lattice oxygens in amorphous Zr-doped manganese oxide for highly efficient aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wen, Y., He, L., Li, H. et al. Dual lattice oxygens in amorphous Zr-doped manganese oxide for highly efficient aerobic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid. Sci. China Mater. 66, 1829–1836 (2023). https://doi.org/10.1007/s40843-022-2296-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-022-2296-1

Keywords

Search

Navigation