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Green Nanosilicas for Monoaromatic Hydrocarbons Removal from Air

Abstract

We demonstrate a novel application of green nanosilicas (GN), prepared via an environmentally friendly route, in removing volatile organic compounds (VOCs). Herein, we aim to establish GN as viable alternatives to traditional mesoporous silicas for the removal of monoaromatic hydrocarbons (MAHC). The results show that the GN have high extraction efficiencies comparable to those previously reported for mesoporous silicas. It was demonstrated that bespoke GN can be syntheised readily with the ability to tailor their physical properties and MAHC adsorption. In order to understand the MAHC adsorption by GN, their porosity, morphology and pore structure were characterised. It was observed that the combination of broad pore size distribution and, in particular, the presence of meso- and micro-porosity in GN contributed to high MAHC extraction efficiencies and selectivity. Although from a commercial viewpoint, further optimisation of GN is desirable in order to replace traditional sorbents, this work clearly highlights a new family of “green” sorbents, which can be prepared with a substantial reduction in secondary pollution with potential applications in selective gas separation.

Graphical Abstract

New green nanoparticles (GN) have been developed as VOC adsorbents; GN preparation is rapid and under neutral pH and room temperature conditions, leading to a substantial reduction in secondary pollution. Their successful performance is related to their unique physical properties, which can be easily tailored.

Data Availability

Electronic supplementary material contains additional porosity and microscopy data.

References

  1. 1.

    Barton TJ, Bull LM, Klemperer WG, Loy DA, McEnaney B, Misono M, Monson PA, Pez G, Scherer GW, Vartuli JC, Yaghi OM (1999) Tailored porous materials. Chem Mater 11(10):2633–2656. https://doi.org/10.1021/Cm9805929

    CAS  Article  Google Scholar 

  2. 2.

    Davis ME (2002) Ordered porous materials for emerging applications. Nature 417(6891):813–821. https://doi.org/10.1038/Nature00785

    CAS  Article  PubMed  Google Scholar 

  3. 3.

    Stein A (2003) Advances in microporous and mesoporous solids - highlights of recent progress. Adv Mater 15(10):763–775. https://doi.org/10.1002/adma.200300007

    CAS  Article  Google Scholar 

  4. 4.

    Cassiers K, Linssen T, Mathieu M, Benjelloun M, Schrijnemakers K, Van Der Voort P, Cool P, Vansant EF (2002) A detailed study of thermal, hydrothermal, and mechanical stabilities of a wide range of surfactant assembled mesoporous silicas. Chem Mater 14(5):2317–2324. https://doi.org/10.1021/cm0112892

    CAS  Article  Google Scholar 

  5. 5.

    Zhao XS, Lu GQM, Millar GJ (1996) Advances in mesoporous molecular sieve MCM-41. Ind Eng Chem Res 35(7):2075–2090. https://doi.org/10.1021/ie950702a

    CAS  Article  Google Scholar 

  6. 6.

    Sayari A, Hamoudi S (2001) Periodic mesoporous silica-based organic - inorganic nanocomposite materials. Chem Mater 13(10):3151–3168. https://doi.org/10.1021/cm0110391

    CAS  Article  Google Scholar 

  7. 7.

    Selvam P, Bhatia SK, Sonwane CG (2001) Recent advances in processing and characterization of periodic mesoporous MCM-41 silicate molecular sieves. Ind Eng Chem Res 40(15):3237–3261. https://doi.org/10.1021/ie0010666

    CAS  Article  Google Scholar 

  8. 8.

    Soler-Illia GJA, Sanchez C, Lebeau B, Patarin J (2002) Chemical strategies to design textured materials: from microporous and Mesoporous oxides to Nanonetworks and hierarchical structures. ChemRev 102(11):4093–4138. https://doi.org/10.1021/cr0200062

    CAS  Article  Google Scholar 

  9. 9.

    Beck JS, Calabro DC, Mccullen SB, Pelrine BP, Schmitt KD, Vartuli JC (1992) Method for functionalizing synthetic mesoporous crystalline material. US 5,145,816

  10. 10.

    Cauvel A, Renard G, Brunel D (1997) Monoglyceride synthesis by heterogeneous catalysis using MCM-41 type silicas functionalized with amino groups. J Organomet Chem 62(3):749–751. https://doi.org/10.1021/jo9614001

    CAS  Article  Google Scholar 

  11. 11.

    Fowler CE, Burkett SL, Mann S (1997) Synthesis and characterization of ordered organo-silica-surfactant mesophases with functionalized MCM-41-type architecture. Chem Commun 18:1769–1770. https://doi.org/10.1039/a704644h

    Article  Google Scholar 

  12. 12.

    Lim MH, Blanford CF, Stein A (1997) Synthesis and characterization of a reactive vinyl-functionalized MCM-41: probing the internal pore structure by a bromination reaction. J Am Chem Soc 119(17):4090–4091. https://doi.org/10.1021/ja9638824

    CAS  Article  Google Scholar 

  13. 13.

    Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS (1992) Ordered mesoporous molecular-sieves synthesized by a liquid-crystal template mechanism. Nature 359(6397):710–712

    CAS  Article  Google Scholar 

  14. 14.

    Grun M, Unger KK, Matsumoto A, Tsutsumi K (1999) Novel pathways for the preparation of mesoporous MCM-41 materials: control of porosity and morphology. Microporous Mesoporous Mater 27(2–3):207–216. https://doi.org/10.1016/s1387-1811(98)00255-8

    CAS  Article  Google Scholar 

  15. 15.

    Huang Z, Huang L, Shen SC, Poh CC, Hidajat K, Kawi S, Ng SC (2005) High quality mesoporous materials prepared by supercritical fluid extraction: effect of curing treatment on their structural stability. Microporous Mesoporous Mater 80(1–3):157–163. https://doi.org/10.1016/j.micromeso.2004.12.016

    CAS  Article  Google Scholar 

  16. 16.

    Pan D, Tan L, Qian K, Zhou L, Fan Y, Yu C, Bao X (2010) Synthesis of highly ordered and hydrothermally stable mesoporous materials using sodium silicate as a precursor. Mater Lett 64(13):1543–1545. https://doi.org/10.1016/j.matlet.2010.03.072

    CAS  Article  Google Scholar 

  17. 17.

    Walcarius A, Mercier L (2010) Mesoporous organosilica adsorbents: nanoengineered materials for removal of organic and inorganic pollutants. J Mater Chem 20(22):4478. https://doi.org/10.1039/B924316j

    CAS  Article  Google Scholar 

  18. 18.

    Idris SA, Robertson C, Morris MA, Gibson LT (2010) A comparative study of selected sorbents for sampling of aromatic VOCs from indoor air. Anal Methods 2(11):1803. https://doi.org/10.1039/c0ay00418a

    CAS  Article  Google Scholar 

  19. 19.

    Zabiegala B, Partyka M, Zygmunt B, Namiesnik J (2009) Determination of volatile organic Compounds in indoor air in the Gdansk area using permeation passive samplers. Ind Built Environ 18(6):492–504. https://doi.org/10.1177/1420326x09336550

    CAS  Article  Google Scholar 

  20. 20.

    Solomon SJ, Schade GW, Kuttippurath J, Ladstaetter-Weissenmayer A, Burrows JP (2008) VOC concentrations in an indoor workplace environment of a university building. Ind Built Environ 17(3):260–268. https://doi.org/10.1177/1420326x08090822

    CAS  Article  Google Scholar 

  21. 21.

    Heroux M-E, Gauvin D, Gilbert NL, Guay M, Dupuis G, Legris M, Levesque B (2008) Housing characteristics and indoor concentrations of selected volatile organic compounds (VOCs) in Quebec City, Canada. Ind Built Environ 17(2):128–137. https://doi.org/10.1177/1420326x07089005

    CAS  Article  Google Scholar 

  22. 22.

    Abdullah MO, Tan IAW, Lim LS (2011) Automobile adsorption air-conditioning system using oil palm biomass-based activated carbon: a review. Renew Sust Energ Rev 15(4):2061–2072. https://doi.org/10.1016/j.rser.2011.01.012

    CAS  Article  Google Scholar 

  23. 23.

    Delaney P, Healy RM, Hanrahan JP, Gibson LT, Wenger JC, Morris MA, Holmes JD (2010) Porous silica spheres as indoor air pollutant scavengers. J Environ Monit 12(12):2244–2251. https://doi.org/10.1039/c0em00226g

    CAS  Article  PubMed  Google Scholar 

  24. 24.

    Berg F, Gohlke K, Pasel C, Luckas M, Eckardt T, Bathen D (2018) Single and binary mixture adsorption behaviors of C-6-C-8 hydrocarbons on silica-alumina gel. Ind Eng Chem Res 57(48):16451–16463. https://doi.org/10.1021/acs.iecr.8b04498

    CAS  Article  Google Scholar 

  25. 25.

    Emparan-Legaspi MJ, Gonzalez J, Gonzalez-Carrillo G, Ceballos-Magana SG, Canales-Vazquez J, Aguayo-Villarreal IA, Muniz-Valencia R (2020) Dynamic adsorption separation of benzene/cyclohexane mixtures on micro-mesoporous silica SBA-2. Microporous Mesoporous Mater 294:109942. https://doi.org/10.1016/j.micromeso.2019.109942

    CAS  Article  Google Scholar 

  26. 26.

    Gelles T, Krishnamurthy A, Adebayo B, Rownaghi A, Rezaei F (2020) Abatement of gaseous volatile organic compounds: a material perspective. Catal Today 350:3–18. https://doi.org/10.1016/j.cattod.2019.06.017

    CAS  Article  Google Scholar 

  27. 27.

    Forsyth C, Patwardhan SV (2013) Controlling performance of lipase immobilised on bioinspired silica. J Mater Chem B 1:1164–1174

  28. 28.

    Patwardhan SV, Manning JRH, Chiacchia M (2018) Bioinspired synthesis as a potential green method for the preparation of nanomaterials: opportunities and challenges. Curr Opin Green Sust 12:110–116. https://doi.org/10.1016/j.cogsc.2018.08.004

    Article  Google Scholar 

  29. 29.

    Patwardhan SV, Staniland SS (2019) Green Nanomaterials. From bioinspired synthesis to sustainable manufacturing of inorganic nanomaterials. IOP. https://doi.org/10.1088/978-0-7503-1221-9

  30. 30.

    Patwardhan SV (2011) Biomimetic and bioinspired silica: recent developments and applications. Chem Commun 47(27):7567–7582. https://doi.org/10.1039/c0cc05648k

    CAS  Article  Google Scholar 

  31. 31.

    Patwardhan SV, Clarson SJ, Perry CC (2005) On the role(s) of additives in bioinspired silicification. Chem Commun 9:1113–1121. https://doi.org/10.1039/b416926c

    CAS  Article  Google Scholar 

  32. 32.

    Belton DJ, Patwardhan SV, Annenkov VV, Danilovtseva EN, Perry CC (2008) From biosilicification to tailored materials: optimizing hydrophobic domains and resistance to protonation of polyamines. Proc Natl Acad Sci U S A 105(16):5963–5968. https://doi.org/10.1073/pnas.0710809105

    Article  PubMed  PubMed Central  Google Scholar 

  33. 33.

    Belton DJ, Patwardhan SV, Perry CC (2005) Spermine, spermidine and their analogues generate tailored silicas. J Mater Chem 15(43):4629–4638. https://doi.org/10.1039/b509683a

    CAS  Article  Google Scholar 

  34. 34.

    Ewlad-Ahmed AM, Morris MA, Patwardhan SV, Gibson LT (2012) Removal of formaldehyde from air using functionalized silica supports. Environ Sci Technol 46:13354–13360

    CAS  Article  Google Scholar 

  35. 35.

    Manning JRH, Routoula E, Patwardhan SV (2018) Preparation of functional silica using a bioinspired method. J Vis Exp 138:57730. https://doi.org/10.3791/57730

    CAS  Article  Google Scholar 

  36. 36.

    Patwardhan SV, Manning JRH (2015) Silica synthesis. WO/2017/037460

  37. 37.

    We have invented and patented a room temperature solution method without needing calcination for template removal (Eco-friendly and scalable method for pure and porous silica, PCT/GB2016/052705). The reason we did not use that route in this paper and instead used calcination was to allow consistency with post-synthetic treatments between our silica and MCM-052741 reported in the literature in order to offer a clear comparison. It is known that the surface chemistry of silica is different for samples obtained from calcination in comparison with those obtained from solution methods (difference in surface silanol groups, which affect adsorption behaviours)

  38. 38.

    Foster KL, Fuerman RG, Economy J, Larson SM, Rood MJ (1992) Adsorption characteristics of trace volatile organic-compounds in gas streams onto activated carbon-fibers. Chem Mater 4(5):1068–1073. https://doi.org/10.1021/cm00023a026

    CAS  Article  Google Scholar 

  39. 39.

    Zhang W, Qu Z, Li X, Wang Y, Ma D, Wu J (2012) Comparison of dynamic adsorption/desorption characteristics of toluene on different porous materials. J Environ Sci (China) 24(3):520–528. https://doi.org/10.1016/s1001-0742(11)60751-1

    Article  Google Scholar 

  40. 40.

    Lillo-Rodenas MA, Fletcher AJ, Thomas KM, Cazorla-Amoros D, Linares-Solano A (2006) Competitive adsorption of a benzene-toluene mixture on activated carbons at low concentration. Carbon 44(8):1455–1463. https://doi.org/10.1016/j.carbon.2005.12.001

    CAS  Article  Google Scholar 

  41. 41.

    Fletcher AJ, Yuzak Y, Thomas KM (2006) Adsorption and desorption kinetics for hydrophilic and hydrophobic vapors on activated carbon. Carbon 44(5):989–1004. https://doi.org/10.1016/j.carbon.2005.10.020

    CAS  Article  Google Scholar 

  42. 42.

    Ueno Y, Tate A, Niwa O, Zhou HS, Yamada T, Honma I (2004) High benzene selectivity of uniform sub-nanometre pores of self-ordered mesoporous silicate. Chem Commun (6):746-747. https://doi.org/10.1039/B316799b

  43. 43.

    Kosuge K, Kubo S, Kikukawa N, Takemori M (2007) Effect of pore structure in Mesoporous Silicas on VOC dynamic adsorption/desorption performance. Langmuir 23(6):3095–3102. https://doi.org/10.1021/la062616t

    CAS  Article  PubMed  Google Scholar 

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Acknowledgements

We thank Al Marqab University (Libya), a ‘Bridging the Gap’ Award from the University of Strathclyde (for A. M. E.-A.) and EPSRC Fellowship (EP/R025983/1) for supporting this work.

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Authors

Contributions

Abdunaser M. Ewlad-Ahmed designed and performed the experiments, analysed the results and prepared a write-up.

Michael Morris and Justin Holmes performed the electron microscopy and X-ray diffraction.

David J. Belton performed the gas adsorption experiments and data analysis, and wrote relevant sections.

Siddharth V. Patwardhan and Lorraine T. Gibson designed and supervised the entire research, coordinated with authors, analysed the results, prepared figures and wrote the manuscript.

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Correspondence to Siddharth V. Patwardhan or Lorraine T. Gibson.

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Ewlad-Ahmed, A.M., Morris, M., Holmes, J. et al. Green Nanosilicas for Monoaromatic Hydrocarbons Removal from Air. Silicon (2021). https://doi.org/10.1007/s12633-020-00924-1

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  • DOI: https://doi.org/10.1007/s12633-020-00924-1

Keywords

  • VOC
  • Biosilica
  • Microporosity
  • Adsorbent
  • Mesosilica
  • Air pollution