Influence of the aromatic surface on the capacity of adsorption of VOCs by magnetite supported organic–inorganic hybrids

Abstract

It has been recently evidenced that hybrid magnetic nanomaterials based on perylene diimide (PDI) dopamine and iron oxide nanoparticles are useful for the adsorption and determination of volatile organic compounds (VOCs). However, NDI compounds are expensive and difficult to handle compared to smaller size diimides. Therefore, in this manuscript a combined experimental and theoretical investigation is reported including the analysis of the effect of changing the aromatic surface on the ability of these magnetite supported organic-inorganic hybrid nanoparticles (NPs) to adsorb several aromatic and non-aromatic VOCs. In particular, two new hybrid Fe 3 O 4 NPs are synthesized and characterized where the size of organic PDI dopamine linker is progressively reduced to naphthalene diimide (NDI) and pyromellitic diimide (PMDI). These materials were utilized to fill two sorbent tubes in series. Thermal desorption (TD) combined with capillary gas chromatography (GC)/flame detector (FID) was used to analyze both front and back tubes. Adsorption values (defined as % VOCs found in the front tube) were determined for a series of VOCs. The binding energies (DFT-D3 calculations) of VOC-Fe 3 O 4 NP complexes were also computed to correlate the electron-accepting ability of the arylene diimide (PDI, NDI or PMDI) with the adsorption capacity of the different tubes. The prepared hybrids can be easily separated magnetically and showed great reusability. † Electronic supplementary information (ESI) available: SEM micrographic images, DLS size distribution and zeta potential of all hybrid nanoparticles used in this work. 1 H-NMR and 13 C-NMR spectra of the imide-dopamine compounds and IR spectra of all compounds used in this manuscript. See Scheme 1 PMDI (1), NDI (2) and PDI (3) derivatives used to functionalize the Fe 3 O 4 NP. VOCs 4 to 9 used in this study.This journal is

Effective Elimination and Biodegradation of Polycyclic Aromatic Hydrocarbons from Seawater through the Formation of Magnetic Microfibres

“…The results obtained for the Langmuir constant between the functionalised nanomaterial and several PAHs of different geometry were excellent, far superior to those described in the literature [17] and similar to those found when using the FeNP-PDI-DA nanomaterial with the same PAHs [18,19] and the same experimental conditions.…”

Using Hybrid PDI-Fe3O4 Nanoparticles for Capturing Aliphatic Alcohols: Halogen Bonding vs. Lone Pair–π Interactions

“…Theoretical calculations were performed at the BP86-D3 [ 43 , 44 ]/def2-TZVPP [ 45 ] level of theory by means of the TURBOMOLE 7.7 program [ 46 ]. During the theoretical modeling process, the Fe 3 O 4 and dopamine moieties were replaced by—Me groups at both sides of the PDI molecule, which acted as the VOC recognition unit, as demonstrated in previous studies [ 34 , 35 ]. The interaction energies gathered in Table 1 were calculated using the supermolecule approximation (ΔE NCI = E PDI − 2 × E ROH ).…”

“…In this regard, our group previously used hybrid magnetic nanoparticles (NPs) to capture and retain aromatic and aliphatic VOCs. This material proved to have great thermal stability, and it can be reused more than 200 times without losing its adsorption capacity [ 34 , 35 ]. Magnetic nanoparticles of iron oxide (Fe 3 O 4 ) possess a series of advantages compared to other materials, such an easier preparation routine and functionalization as well as an efficient recovery process once used, owing to their sensitivity to external magnetic fields [ 36 ].…”

Capturing volatile organic compounds using Ag and Au nanoparticles: regium–π and C–H⋯Ag/Au interactions at work

“…26 Bearing this in mind, TD experiments have been carried out to evaluate the capturing and retaining process of the VOCs by Ag and Au NPs. Our group has experience with using absorbent nanomaterials to capture aromatic and non-aromatic VOCs by using hybrid nanoparticles based on magnetite covered by perilen-diimide (PDI), naalen-diimide (NDI) and pyromellitic diimide (NPI), 27,28 with good adsorption percentages. TD is a fast and clean technique that allows to evaluate in a reproducible and safe way the interaction capacity of the nanomaterial with the proposed analytes.…”

“…In turn, it also allows checking the stability of the adsorbent material, since it is possible to carry out periodic tests of its interaction capacity. 28 Additionally, it has been determined that it is possible to reuse the nanomaterial, both AgNP and AuNP, up to a hundred times, without losing its adsorption capacity on the VOC analyzed.…”