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Generating strongly basic sites on magnetic nano-stirring bars: Multifunctional integrated catalysts for transesterification reaction

在磁性纳米搅拌棒上生成强碱活性位点: 用于酯交换反应的多功能集成型催化剂

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Abstract

Mass transfer and catalyst recovery are two crucial issues in solid base catalysis, while the cumbersome operation steps and the associated time and energy penalties are still inevitable for conventional catalysts. Achieving the technical upgrades through catalyst design is desirable but challenging because of the difficulty in satisfying diverse demands of different steps. In this work, a magnetically responsive solid base catalyst with the rod-like nanostructure was developed. The rod-like solid base catalysts are composed of Fe3O4 cores, silica shells and calcium oxide active sites. The functions of magnetic recovery and stirring were integrated into the catalyst, which applies in both the general catalytic processes and microchannel reactors given their nanoscales. When applied to the synthesis of dimethyl carbonate by one-step transesterification of methanol and ethylene carbonate, an apparent enhancement on turnover frequency value (33.1 h−1) was observed for nano-stirring compared with that tested without stirring (12.1 h−1) within 30 min. The present catalysts may open up new avenues in the development of advanced solid base catalysts.

摘要

传质和催化剂回收是固体碱催化中的两个关键问题, 而对于传统催化剂而言, 繁琐的操作步骤以及相关的时间和能量损耗仍然是不可避免的. 通过催化剂设计实现技术升级是可取的, 但由于难以同时满足不同步骤的不同需求, 其仍具有挑战性. 在本项工作中, 我们开发了一种具有棒状纳米结构的磁响应固体碱催化剂. 该棒状固体碱催化剂是由Fe3O4 内核、二氧化硅外壳和氧化钙活性位点构成的, 且同时集成了磁性回收和搅拌功能. 考虑到其纳米尺寸, 这一功能集成的催化剂能够同时适用于常规的催化过程和微通道反应器. 当将此催化剂应用于催化甲醇和碳酸乙烯酯的一步酯交换合成碳酸二甲酯时, 在30 min内,纳米搅拌下催化转换频率的数值(33.1 h−1) 明显高于未搅拌下的(12.1 h−1). 本催化剂可能为开发先进的固体碱催化剂开辟新的途径.

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References

  1. Sun LB, Liu XQ, Zhou HC. Design and fabrication of mesoporous heterogeneous basic catalysts. Chem Soc Rev, 2015, 44: 5092–5147

    Article  CAS  Google Scholar 

  2. Zhu L, Liu XQ, Jiang HL, et al. Metal-organic frameworks for heterogeneous basic catalysis. Chem Rev, 2017, 117: 8129–8176

    Article  CAS  Google Scholar 

  3. Yu IKM, Hanif A, Tsang DCW, et al. Tuneable functionalities in layered double hydroxide catalysts for thermochemical conversion of biomass-derived glucose to fructose. Chem Eng J, 2020, 383: 122914

    Article  CAS  Google Scholar 

  4. Yan H, Qin H, Feng X, et al. Synergistic Pt/MgO/SBA-15 nanocatalysts for glycerol oxidation in base-free medium: Catalyst design and mechanistic study. J Catal, 2019, 370: 434–446

    Article  CAS  Google Scholar 

  5. Tang M, Dou X, Tian Z, et al. Enhanced hydrolysis of streptomycin from production wastewater using CaO/MgO solid base catalysts. Chem Eng J, 2019, 355: 586–593

    Article  CAS  Google Scholar 

  6. Kou J, Lu C, Wang J, et al. Selectivity enhancement in heterogeneous photocatalytic transformations. Chem Rev, 2017, 117: 1445–1514

    Article  CAS  Google Scholar 

  7. Sun J, Baylon RAL, Liu C, et al. Key roles of Lewis acid-base pairs on ZnxZryOz in direct ethanol/acetone to isobutene conversion. J Am Chem Soc, 2016, 138: 507–517

    Article  CAS  Google Scholar 

  8. Buss F, Mehlmann P, Mück-Lichtenfeld C, et al. Reversible carbon dioxide binding by simple Lewis base adducts with electron-rich phosphines. J Am Chem Soc, 2016, 138: 1840–1843

    Article  CAS  Google Scholar 

  9. Mondal B, Acharyya K, Howlader P, et al. Molecular cage impregnated palladium nanoparticles: Efficient, additive-free heterogeneous catalysts for cyanation of aryl halides. J Am Chem Soc, 2016, 138: 1709–1716

    Article  CAS  Google Scholar 

  10. Wu G, Jiang S, Li L, et al. Nitridation of BaO supported on mesoporous materials: Basicity characterization and catalytic properties. Appl Catal A-Gen, 2011, 391: 225–233

    Article  CAS  Google Scholar 

  11. Chen Y, Chen H, Sun Y, et al. Multifunctional mesoporous composite nanocapsules for highly efficient MRI-guided high-intensity focused ultrasound cancer surgery. Angew Chem Int Ed, 2011, 50: 12505–12509

    Article  CAS  Google Scholar 

  12. Fan K, Cao C, Pan Y, et al. Magnetoferritin nanoparticles for targeting and visualizing tumour tissues. Nat Nanotech, 2012, 7: 459–464

    Article  CAS  Google Scholar 

  13. Laurent S, Forge D, Port M, et al. Magnetic iron oxide nanoparticles: Synthesis, stabilization, vectorization, physicochemical characterizations, and biological applications. Chem Rev, 2008, 108: 2064–2110

    Article  CAS  Google Scholar 

  14. Barreto JA, O’Malley W, Kubeil M, et al. Nanomaterials: Applications in cancer imaging and therapy. Adv Mater, 2011, 23: H18–H40

    Article  CAS  Google Scholar 

  15. Liu J, Qiao SZ, Hu QH, et al. Magnetic nanocomposites with mesoporous structures: Synthesis and applications. Small, 2011, 7: 425–443

    Article  CAS  Google Scholar 

  16. Wang JZ, Zhong C, Wexler D, et al. Graphene-encapsulated Fe3O4 nanoparticles with 3D laminated structure as superior anode in lithium ion batteries. Chem Eur J, 2011, 17: 661–667

    Article  CAS  Google Scholar 

  17. Tan P, Qin JX, Liu XQ, et al. Fabrication of magnetically responsive core-shell adsorbents for thiophene capture: AgNO3-functionalized Fe3O4@mesoporous SiO2 microspheres. J Mater Chem A, 2014, 2: 4698–4705

    Article  CAS  Google Scholar 

  18. Hyeon T. Chemical synthesis of magnetic nanoparticles. ChemInform, 2003, 34: 927–934

    Article  Google Scholar 

  19. Lu AH, Salabas EL, Schüth F. Magnetic nanoparticles: Synthesis, protection, functionalization, and application. Angew Chem Int Ed, 2007, 46: 1222–1244

    Article  CAS  Google Scholar 

  20. Gao J, Gu H, Xu B. Multifunctional magnetic nanoparticles: Design, synthesis, and biomedical applications. Acc Chem Res, 2009, 42: 1097–1107

    Article  CAS  Google Scholar 

  21. Xie W, Han Y, Wang H. Magnetic Fe3O4/MCM-41 composite-supported sodium silicate as heterogeneous catalysts for biodiesel production. Renew Energy, 2018, 125: 675–681

    Article  CAS  Google Scholar 

  22. Xie W, Wan F. Basic ionic liquid functionalized magnetically responsive Fe3O4@HKUST-1 composites used for biodiesel production. Fuel, 2018, 220: 248–256

    Article  CAS  Google Scholar 

  23. Wan L, Song H, Chen X, et al. A magnetic-field guided interface coassembly approach to magnetic mesoporous silica nanochains for osteoclast-targeted inhibition and heterogeneous nanocatalysis. Adv Mater, 2018, 30: 1707515

    Article  CAS  Google Scholar 

  24. Xie M, Zhang W, Fan C, et al. Bioinspired soft microrobots with precise magneto-collective control for microvascular thrombolysis. Adv Mater, 2020, 32: 2000366

    Article  CAS  Google Scholar 

  25. Fan X, Sun M, Sun L, et al. Ferrofluid droplets as liquid microrobots with multiple deformabilities. Adv Funct Mater, 2020, 30: 2000138

    Article  CAS  Google Scholar 

  26. Gu C, Tao WQ, Li M, et al. Fabrication of multifunctional integrated catalysts by decorating confined Ag nanoparticles on magnetic nanostirring bars. J Colloid Interface Sci, 2019, 555: 315–322

    Article  CAS  Google Scholar 

  27. Li TT, Liu Y, Qi SC, et al. Calcium oxide-modified mesoporous silica loaded onto ferriferrous oxide core: Magnetically responsive mesoporous solid strong base. J Colloid Interface Sci, 2018, 526: 366–373

    Article  CAS  Google Scholar 

  28. Li TT, Gao XJ, Qi SC, et al. Potassium-incorporated mesoporous carbons: Strong solid bases with enhanced catalytic activity and stability. Catal Sci Technol, 2018, 8: 2794–2801

    Article  CAS  Google Scholar 

  29. Deng Y, Deng C, Qi D, et al. Synthesis of core/shell colloidal magnetic zeolite microspheres for the immobilization of trypsin. Adv Mater, 2009, 21: 1377–1382

    Article  CAS  Google Scholar 

  30. Zhu H, Zhang S, Huang YX, et al. Monodisperse MxFe3−xO4 (M = Fe, Cu, Co, Mn) nanoparticles and their electrocatalysis for oxygen reduction Reaction. Nano Lett, 2013, 13: 2947–2951

    Article  CAS  Google Scholar 

  31. Xiao L, Li J, Brougham DF, et al. Water-soluble superparamagnetic magnetite nanoparticles with biocompatible coating for enhanced magnetic resonance imaging. ACS Nano, 2011, 5: 6315–6324

    Article  CAS  Google Scholar 

  32. Demri B, Muster D. XPS study of some calcium compounds. J Mater Processing Tech, 1995, 55: 311–314

    Article  Google Scholar 

  33. Deng Y, Cai Y, Sun Z, et al. Multifunctional mesoporous composite microspheres with well-designed nanostructure: A highly integrated catalyst system. J Am Chem Soc, 2010, 132: 8466–8473

    Article  CAS  Google Scholar 

  34. Sun YH, Sun LB, Li TT, et al. Modulating the host nature by coating alumina: A strategy to promote potassium nitrate decomposition and superbasicity generation on mesoporous silica SBA-15. J Phys Chem C, 2010, 114: 18988–18995

    Article  CAS  Google Scholar 

  35. Liu XY, Sun LB, Liu XD, et al. Low-temperature fabrication of mesoporous solid strong bases by using multifunction of a carbon interlayer. ACS Appl Mater Interfaces, 2013, 5: 9823–9829

    Article  CAS  Google Scholar 

  36. Liu W, Zhu L, Jiang Y, et al. Direct fabrication of strong basic sites on ordered nanoporous materials: Exploring the possibility of metal-organic frameworks. Chem Mater, 2018, 30: 1686–1694

    Article  CAS  Google Scholar 

  37. Gong L, Sun LB, Sun YH, et al. Exploring in situ functionalization strategy in a hard template process: Preparation of sodium-modified mesoporous tetragonal zirconia with superbasicity. J Phys Chem C, 2011, 115: 11633–11640

    Article  CAS  Google Scholar 

  38. Sun LB, Gong L, Liu XQ, et al. Generating basic sites on zeolite Y by potassium species modification: Effect of base precursor. Catal Lett, 2009, 132: 218–224

    Article  CAS  Google Scholar 

  39. Liu XY, Sun LB, Lu F, et al. Low-temperature generation of strong basicity via an unprecedented guest-host redox interaction. Chem Commun, 2013, 49: 8087–8089

    Article  CAS  Google Scholar 

  40. Liu XY, Sun LB, Lu F, et al. Constructing mesoporous solid superbases by a dualcoating strategy. J Mater Chem A, 2013, 1: 1623–1631

    Article  CAS  Google Scholar 

  41. Honda M, Suzuki A, Noorjahan B, et al. Low pressure CO2 to dimethyl carbonate by the reaction with methanol promoted by acetonitrile hydration. Chem Commun, 2009, 4596

  42. Zhu L, Lu F, Liu XD, et al. A new redox strategy for low-temperature formation of strong basicity on mesoporous silica. Chem Commun, 2015, 51: 10058–10061

    Article  CAS  Google Scholar 

  43. Li TT, Sun LB, Gong L, et al. In situ generation of superbasic sites on mesoporous ceria and their application in transesterification. J Mol Catal A-Chem, 2012, 352: 38–44

    Article  CAS  Google Scholar 

  44. Xie W, Zhao L. Production of biodiesel by transesterification of soybean oil using calcium supported tin oxides as heterogeneous catalysts. Energy Convers Manage, 2013, 76: 55–62

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the National Natural Science Foundation of China Youth Project (21808110), the financial support of this work by the National Science Fund for Distinguished Young Scholars (22125804), and the National Natural Science Foundation of China (21878149, 22078155, and 21722606).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Materials-Oriented Chemical Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), College of Chemical Engineering, Nanjing Tech University, Nanjing, 211816, China

    Chen Gu  (谷琛), Tian-Tian Li  (李田田), Peng Tan  (谈朋), Song-Song Peng  (彭松松), Yao Jiang  (江耀), Xiao-Qin Liu  (刘晓勤) & Lin-Bing Sun  (孙林兵)

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  1. Chen Gu  (谷琛)
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  2. Tian-Tian Li  (李田田)
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  4. Song-Song Peng  (彭松松)
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  5. Yao Jiang  (江耀)
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Contributions

Sun LB and Tan P led the project and supervised all data collection, analysis and interpretation; Gu C and Li TT designed and performed the experiments with help from Peng SS; Jiang Y characterized the materials and discussed the results of the experiments; Sun LB, Tan P, Gu C and Liu XQ were responsible for the major part of writing this paper. All authors discussed the results and commented on the various versions of the manuscript.

Corresponding authors

Correspondence to Peng Tan  (谈朋) or Lin-Bing Sun  (孙林兵).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Chen Gu is currently a PhD candidate under the supervision of Prof. Lin-Bing Sun and Prof. Xiao-Qin Liu at the State Key Laboratory of Materials-Oriented Chemical Engineering and Nanjing Tech University. He received his BS degree from Nanjing Tech University in 2017. His research interest focuses on the design and fabrication of stimuli-responsive porous materials as well as their applications in adsorption and heterogeneous catalysis.

Peng Tan is an associate professor at Nanjing Tech University. He received his PhD degree from Nanjing Tech University under the guidance of Prof. Xiao-Qin Liu and Prof. Lin-Bing Sun in 2017. His research interest focuses on the design and fabrication of functional nanoporous materials, including porous carbons, zeolites, mesoporous silicas, metal-organic frameworks, and stimuli-responsive nanoporous composites, as well as their applications in adsorption and separation.

Lin-Bing Sun is a full professor at the State Key Laboratory of Materials-Oriented Chemical Engineering and Nanjing Tech University. He received his PhD degree from Nanjing University in 2008 under the guidance of Prof. Jian Hua Zhu and Prof. Yuan Chun. From 2011 to 2012, he worked with Prof. Hong-Cai JOE Zhou as a postdoctoral fellow at Texas A&M University. His current research interests mainly focus on the synthesis of porous functional materials (such as metal-organic frameworks, mesoporous silicas, and porous organic polymers) as well as their applications in adsorption and heterogeneous catalysis.

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Generating strongly basic sites on magnetic nano-stirring bars: Multifunctional integrated catalysts for transesterification reaction

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Gu, C., Li, TT., Tan, P. et al. Generating strongly basic sites on magnetic nano-stirring bars: Multifunctional integrated catalysts for transesterification reaction. Sci. China Mater. 65, 2721–2728 (2022). https://doi.org/10.1007/s40843-022-2039-1

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