3.2. Adsorption kinetics and intraparticle diffusion rate
Hg2+ and Pb2+ were used as target analytes to investigate the
adsorption kinetics of heavy metals on SH-mSi@Fe3O4. Fig. 4a
shows that adsorption of Hg2+ and Pb2+ is a time-dependent process.
The adsorption process was very rapid in the first 20 min, and
then decreased considerably until equilibrium was achieved. More
time was needed for Pb2+ to reach the same residual concentration
as Hg2+, which meant that adsorption of Hg2+ by SH-mSi@Fe3O4
was much easier than Pb2+. The adsorption of Hg2+ and Pb2+ fitted
well with pseudo-second-order kinetic equation (insetted picture
in Fig. 4a), the constant kad was calculated and listed in Table 1.
To further evaluate the adsorption process, the rate constant for
intraparticle diffusion (kid) was introduced [34,35]. Fig. 4b shows
the plots of q versus t0.5 for Hg2+ and Pb2+. It is observed from
the plot there are three regions depicting the mass transfer on
the SH-mSi@Fe3O4. The intraparticle diffusion constants could be determined from the slop of the plots. The kid.1, kid.2, and kid.3
which express the diffusion rates of the different stages in adsorption
process are tabulated in Table 1. The adsorption rate is in the
order of kid.1 > kid.2 > kid.3. Both metals underwent firstly a steepsloped
stage, followed by the decreasing slope and the subsequent
plateau till equilibrium. The first steep-sloped period is the instantaneous
diffusion stage (kid.1, from 0 to 0.15 h), during which a large
amount of heavy metal ions (about 50%) were rapidly adsorbed by
the exterior surface of the adsorbent. When the adsorption of exterior
surface reached saturation, metal ions entered into the pores of the adsorbent and were adsorbed by the interior surface of the
mesopores. With the heavy metal ions entering into the pores, the
diffusion resistance increased, leading to decrease of the diffusion
rate (kid.2). With the rapid decrease of the solute concentration,
the intraparticle diffusion rate gradually slowed down and finally
reached the equilibrium stage (kid.3) [26].