Adsorptivity of some organic compounds to the copper nanoparticles prepared using the levitation-jet generator was characterized by inverse gas chromatography. The measured values of a specific volume of retained sorbate were used to calculate adsorption heats and entropy factors of the process

Bulanova, AV

Kuznetsov, MV

Morozov, YG

Parkin, IP

Shafigulin, RV

UCL Discovery

  Adsorptivity of Copper Nanoparticles to Some Organic Compounds  R. V. Shafigulina, A. V. Bulanovaa *, M. V. Kuznetsovb **,  I. P. Parkinc, and Yu. G. Morozovd ***   a Department of Chemistry, Samara University, Samara, 443086 Russia b All-Russia Research Institute on Problems of Civil Defense and Emergencies, Emergency Control Ministry (EMERCOM), Moscow, 121352 Russia  с Department of Chemistry, Materials Chemistry Research Centre, University College London, London, WC1H 0AJ, United Kingdom d Merzhanov Institute of Structural Macrokinetics and Material Science (ISMAN), Russian Academy of Sciences, Chernogolovka, 142432 Russia   * av.bul@yandex.ru  ** maxim1968@mail.ru *** morozov@ism.ac.ru   Received November 11, 2021; revised November 18, 2021; accepted November 19, 2021    Abstract—Adsorptivity of some organic compounds to the copper nanoparticles prepared by levitation-jet generator was characterized by inverse gas chromatography. The measured values of specific volume of retained sorbate were used to calculate adsorption heats and entropy factors of the process.   Keywords: levitation-jet generator, inverse gas chromatography, copper nanoparticles, gas adsorption on nanoparticles    INTRODUCTION   Information on the absorptivity of compounds and materials is important for numerous applications such as drug delivery [1], effective/selective catalysis, [2, 3], gas sensors [4], and environment safety [5]. To date, a number of publications have been devoted to the absorptivity of commonly used organic compounds to such adsorbents as zeolites [6], polymers [7], and carbon materials [8].  As for Cu nanoparticles, their unique adsorption behavior has been reported by Soldatenko et al. [9, 10]. The catalytic activity of Co nanoparticles deposited onto shungite was studied by Yartsev et al. [11].  In this work, we explored the adsorptivity of some hydrocarbons and alcohols to copper nanoparticles produced at ISMAN by levitation-jet generator [12]. High catalytic activity of Cu nanoparticles loaded onto polycarbonate in hydrogenation of benzene was reported in [13].   EXPERIMENTAL   In experiments, we used the Cu nanoparticles home-made at ISMAN by using the levitation-jet generator [12]. The experimental setup and procedure for inverse gas chromatography were described in detail elsewhere [14]. A 97-cm column (3 mm in inner diameter) was stuffed with Inerton sorbent loaded with Cu nanoparticles. Chromatographic experiments were conducted within the temperature range 343–383 K.  Specific volume of retained gaseous sorbate gTV  (mL/g) was calculated using formula (1):   R Mgad( )T PTt t FVW−=                                              (1)   where tR, tM stand for the retention time of sorbate and non-adsorbing compound, respectively; Wad is the weight of adsorbent in a column, and FPT the averaged volumetric velocity of gas-carrier.  Thermodynamic parameters A and B were derived from linear plots (2) of ln gTV (1/T) functions:   glnT BV AT= +                                          (2)   where А is the entropy component of sorption and В = 1Q /R relates to molar change in internal energy U; in our case, 1Q  = –ΔU, R is absolute gas constant.   RESULTS AND DISCUSSION   Figure 1 presents the SEM image of Cu nanoparticles prepared by levitation-jet method. It follows that the size of Cu nanoparticles is within the range 70–100 nm.  The values of gTV  (mL/g) as derived from the linear plots in Figs. 2–4 are collected in Table 1 while the values of 1Q  and –A, in Table 2.  In the homological series of n-alkanes, the values of 1Q  and –A are seen (Table 2) to gradually grow with an increase in molecular weight. Similar trend is observed [15] for higher n-alcohols: the larger molecular weight, the lower absorptivity.  In the row hexene-1–hexine-1–benzene (Table 2), adsorption heat 1Q  increases, thus indicating the presence of specific interactions with the adsorbent. Their contributions can be estimated by analyzing the magnitude of 1Q  (formula 3).   1 1 1hQ Q Q = −                                         (3)  Here 1Q  is the adsorption heat of sorbate and 1hQ is that of a hypothetic alkane with the same polarizability. The results are presented in Table 3.  As follows from Table 3, an increase in 1Q  is accompanied by a sharp increase of contributions from specific interactions (1Q / 1Q ), whose magnitude can attain a value of 83% in case of benzene (third column in Table 3).  Figure 5 shows the entropy factor (–A) plotted versus differential molar adsorption heat 1Q . This plot, also known as thermodynamic compensation, allows us to conclude that, in case of n-alkanes, unsaturated hydrocarbons, and aromatics, the mechanisms of sorption are similar, in contrast to those in case of alcohols.   CONCLUSIONS  For the organic compounds tested, their adsorption heat to Cu nanoparticles was found to grow in the order: unsaturated hydrocarbons → n-alkanes → benzene → n-alcohols.    REFERENCES  1. Bondarev, A.V., and Zhilyakova, Е.Т., Use of sorption processes in drug delivery systems, Farmats. Farmakol., 2019, vol. 7, no. 1, pp. 4–12. https://doi.org/10.19163/2307-9266-2019-7-1-4-12  2. 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Porous polycarbonate membranes with Ni and Cu nano catalytic additives fabricated by selective laser sintering, J. Mater. Sci. Eng. B, 2012, vol. 2, no. 12, pp. 634–639. 14. Shubina, E.G., Filimonov, N.S., Shafigulin, R.V., Bulanova, A.V., Shishkovskii, I.V., and Morozov, Yu.G., Effect of size of nickel nanoparticles on hydrogenation of benzene, Petrol. Chem., 2017, vol. 57, no. 5, pp. 410–414. https://doi.org/10.1134/S0965544117020244 15. Bloch, D.R., Organic Chemistry Demystified, New York: McGraw Hill, 2006.   Translated by Yu. Scheck    Table 1. The values of gTV  (mL/g) as measured at Т = 356 K   n-Heptane 0.22 n-Octane 0.46 n-Nonane 1.17 Methanol 0.20 Ethanol 0.17 Benzene 0.38 Hexine-1 0.15 Hexene-1 0.11   Table 2. The values of 1Q  (kJ/mol) and –A as derived from linear plots in Figs. 2–4    1Q , kJ/mol –A n-Heptane 13.2 5.9 n-Octane 18.8 7.1 n-Nonane 25.2 8.5 Methanol 20.9 8.7 Ethanol 18.4 8.1 Benzene 18.6 7.4 Hexine-1 11.4 5.8 Hexene-1 7.9 4.8   Table 3. The magnitudes of 1Q , 1Q , and extent of adsorption 1Q / 1Q     1Q , kJ/mol 1Q , kJ/mol 1Q / 1Q , % Hexene-1 7.9 1.4 18 Hexine-1 11.4 8.0 70 Benzene 18.6 15.5 83        Fig. 1. SEM image of Cu nanoparticles prepared by using a levitation-jet generator.       2.60 2.65 2.70 2.75 2.80 2.85 2.90 2.95-2.2-2.0-1.8-1.6-1.4-1.2-1.0-0.8-0.6-0.4-0.20.00.20.4n-Nonanen-Octane1000/T, K-1n-HeptanelnVTg   Key: lngTV                                                           1000/T, K–1   Fig. 2. Linear lngTV (1/T) plots according Eq. (2) for n-alkanes.      2.60 2.65 2.70 2.75 2.80 2.85 2.90 2.95-2.4-2.3-2.2-2.1-2.0-1.9-1.8-1.7-1.6-1.5-1.4lnVTg1000/T, K-1MethanolEthanol   Key: lngTV                                                           1000/T, K–1   Fig. 3. Linear lngTV (1/T) plots according to Eq. (2) for methanol and ethanol.        2.60 2.65 2.70 2.75 2.80 2.85 2.90 2.95-2.0-1.5-1.0lnVTg1000/T, K-1BenzeneHexineHexene   Key: lngTV                                                           1000/T, K–1   Fig. 4. Linear lngTV (1/T) plots according to Eq. (2) for unsaturated hydrocarbons and benzene.         Key: –A                            1Q , kJ/mol   Fig. 5. Entropy component (–A) plotted versus differential molar adsorption heat 1Q .     

Adsorptivity of Some Organic Compounds to Copper Nanoparticles

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