The
formation of binary nanohybrids consisting of environmentally
benign components, γ-Fe
2
O
3
, chitosan (CS),
and Ag (Ag-γ-Fe
2
O
3
@CS) (CSIOAg), containing
very low concentration of Ag NPs (≤1.2 μM), has been
reported. In the as-synthesized nanohybrids, the presence of γ-Fe
2
O
3
(8.5 ± 0.8 nm) and Ag (5.9 ± 0.5 nm)
are revealed by optical, XRD, TEM, and XPS analyses, and their presence
in cubic phase is determined by XRD and SAED measurements. The catalytic
activity of CSIOAg has been analyzed by performing the reduction of
certain toxic dyes. Under all kinetic conditions, the reaction is
attended by an induction period, which is reduced upon increasing
[Ag] and [Dye] in a specific concentration range, as well as temperature,
suggesting restructuring of the surface prior to reduction. In case
of methyl orange (MO), the reduction results in its cleavage to produce
N
,
N
-dimethyl-1,4-phenylenediamine and sodium
sulfanilate in a significantly higher (>97%) yield in a bimolecular
reaction between MO and BH
4
–
. The duration
of induction period is regularly decreased and the rate of reduction
(
k
app
) increases linearly with increasing
Ag in the wide concentration range (0.03–2.4 μM). The
reduction takes place with a second-order rate constant of 2.7 ×
10
4
dm
3
mol
–1
s
–1
, which is >3.5-fold higher than that in the absence of chitosan
(IOAg) under identical experimental conditions. The kinetics of reduction
of MO is controlled by the nature and extent of its adsorption on
the catalyst surface. The weaker binding between MO and Ag catalyst
only allows its effective reduction. The XPS analysis of CSIOAg and
IOAg containing the same amount of Ag (1.2 μM) showed its higher
amount on the surface of CSIOAg (0.12%) as compared to that of IOAg
(0.09%). Detailed kinetic analysis of MO reduction, performed under
pseudo-kinetic conditions for both the nanohybrids revealed them to
follow Langmuir–Hinshelwood kinetic model and exhibited the
recyclability up to 10 cycles with fairly high reaction efficiency
and TOF, suggesting it to be a sustainable green nanosystem.