Characterization of selectively etched halloysite nanotubes by acid treatment

• Published in: Applied surface science 2017-11, Vol.422, p.616-625
• Main Authors: Garcia-Garcia, Daniel, Ferri, Jose M., Ripoll, Laura, Hidalgo, Montserrat, Lopez-Martinez, Juan, Balart, Rafael
• Format: Article
• Language: English
• Subjects: Acid treatment; Catalysis; Halloysite nanotubes; LIBS; Lumen enlargement
• ISSN: 0169-4332; 1873-5584
• DOI: 10.1016/j.apsusc.2017.06.104

[Display omitted] •The effect of various acids on HNTs morphology and chemical composition were studied.•Treatment with sulphuric acid is aggressive and leads a highly porous structure.•Treatment with acetic and acrylic acid leads an increase in the HNTs lumen.•New applications for HNTs can be derived from selective etching with acids. Halloysite nanotubes (HNTs) are a type of naturally occurring inorganic nanotubes that are characterized by a different composition between their external and internal walls. The internal walls are mainly composed of alumina whilst external walls are composed of silica. This particular structure offers a dual surface chemistry that allows different selective surface treatments which can be focused on increasing the lumen, increasing porosity, etc. In this work, HNTs were chemically treated with different acids (sulphuric, acetic and acrylic acid), for 72h at a constant temperature of 50°C. As per the obtained results, the treatment with sulphuric acid is highly aggressive and the particular shape of HNTs is almost lost, with a remarkable increase in porosity. The BET surface area increases from 52.9 (untreated HNTs) up to 132.4m2g−1 with sulphuric acid treatment, thus showing an interesting potential in the field of catalysis. On the other hand, the treatment with acetic acid led to milder effects with a noticeable increase in the lumen diameter that changed from 13.8nm (untreated HNTs) up to 18.4nm which the subsequent increase in the loading capacity by 77.8%. The aluminium content was measured by X-ray fluorescence (XRF) and laser induced breakdown spectroscopy (LIBS). The final results using two systems, suggest a good correlation between the acid strength and the aluminium reduction. Consequently, is possible to conclude that new applications for HNTs can be derived from selective etching with acids. Sulphuric acid widens the potential of HNTs in the field of catalysis while weak acids such as acetic and acrylic acids give a controlled and homogeneous lumen increase with the corresponding increase in the loading capacity.