Supplementary Material for

Preparation of HKUST-1@silica aerogel compositepellets for continuous flow catalysis

Anton S. Shalygin*,Alexey L. Nuzhdin, Galina A. Bukhtiyarova, Oleg N. Martyanov

Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia.

* corresponding author: E-mail:

Particle size distribution

The particle size distribution was calculated from the photography and SEM images using the ImageJ software.

Fig. 1S. Particle size distribution of HKUST-1@SiO2 (380 rpm) (A) end (250 rpm) (B).

Pore size distribution

Fig. 2S. Pore size distribution of HKUST-1@SiO2 composites and pure silica aerogel calculated by the BJH method

FT-IR spectroscopy

The FT-IR spectroscopic analysis was performed using «Bruker» Vertex 70v spectrometer equipped with a diamond ATR accessory (Specac, Ltd.,UK) and MCT detector. The spectrum of sample was recorded from 5000 cm–1 to 370 cm–1 using 128 scans at a resolution of 2 cm–1. These spectra were transformed with ATR correction function with refractive indices (n=1.5) on Opus software.

Figure 1S are shown FTIR-ATR spectra of HKUST-1@SiO2as prepared and spent in region 400–1800 cm–1. The bands 1072, 810 и 450 cm–1 is related tosilica aerogels that can be assigned to the stretching vibration of Si–O–Si and Si–O groups, it is described in detail in Ref. [1]. The bands around 1700–1500 и 1500–1300 cm–1is related HKUST-1 which are attributed to υasym(COO–) and υsym(COO–) stretching modes, bands 710–758 cm–1 characterize the out-of- plane vibrations of C–H of the benzene ring [2]. The bands of 634 and 701 cm-1 characterize the out-of-plane vibrations of C–H bond of the benzene ring wherein one hydrogen atom is replaced by another group. The band of 1496 cm-1 characterizes deformation vibration of –CH2– groups in polymer like polystyrene [3].

Fig 3S. IR spectra of HKUST-1(30%)@SiO2pelletsas-prepared (black line) and spent (red line).

A first-order kinetic treatment for reaction under flow conditions yields the following equation:

in which X is conversion of styrene oxide (SO) and k is the rate constant. The parameters F and n represent the inlet hourly molar SO feed rate and moles of copper in the catalyst bed, respectively; n/F has the physical significance of contact time.Plotting the graph ofln k versus 1/T results in a straight line, as shown in Figure 3S. The apparent activation energy, Ea, for SO isomerizationover the HKUST-1@SiO2 catalyst (within the temperature range from 90 to 110 °C) estimated from the slope of the Arrhenius plot is about 51 kJmol-1.

Fig. 4SArrhenius plot of the rate constant (k, h-1) of styrene oxide isomerization over HKUST-1@SiO2 catalyst.

Diffusivity (Db) of a dilute solute (<10 mol %) in any solvent except water [4]

Here, T is system temperature, niis viscosity of component i, Vi is molar volume of component i at normal boiling point, Li is enthalpy of vaporization of component i at normal boiling point.Db of styrene oxide in tolueneequal is 5.08*10-5 cm2 s-1.

Table 1.

T, K / 383
ntotuene, Pa s / 0.29*10-3
Vtoluene, cm3/mole / 114.42
Vstyrene oxide, cm3/mole / 106.27
Ltoluene, kJ/mole / 33.18
Lstyrene oxide, kJ/mole / 40.101
  1. M. Ocana, V. Fornes, C.J. Serna, J. Non-Crystal. Solids, 1989, 107, 187–192.
  2. E. Borfecchia, S. Maurelli, D. Gianolio, E. Groppo, M. Chiesa, F. Bonino, C. Lamberti, J. Phys. Chem. C, 2012, 116, 19839−19850.
  3. C. Y. Liang, S. Krimm, Polymer Chem, 1958, 27(115), 241–254.
  4. M.A. Vannice, Kinetics of Catalytic Reactions, Springer, New York, USA, 2005.