ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 1, pp. 169−177. © Pleiades Publishing, Ltd., 2015.
Sunlight Assisted Photodecolorization of Malachite
Green Catalyzed by MIL-101/Graphene Oxide Composites
, Hamid Aliyan, and Rahil Soltani Banavandi
Department of Chemistry, Shahreza Branch, Islamic Azad University, 86145-311, Iran
Received January 5, 2015
Abstract—The objective of the research is mainly the development of efﬁ cient and environmentally benign
heterogeneous catalysts for sunlight assisted photodecolorization of Malachite green (MG). Heterogeneous MIL-
101/graphene oxide composite was synthesized by sonication and heat treatment for this purpose. The catalyst
thus prepared was then tested for the sunlight assisted photodecolorization. The mesostructure of MIL-101
remains intact after graphene oxide modiﬁ cations, as shown by various techniques such as FT IR, X-ray diffrac-
tion, UV-Vis, N
adsorption desorption, SEM and TEM. XRD and adsorption desorption analysis, while spectral
techniques show successful immobilization of the neat graphene oxide inside the MIL-101 cavities. The effects
of key experimental parameters including the catalyst amount (0.009–0.017 g L
), initial concentration of dyes
(10–30 mg L
) and solution pH (3–11) were studied on the extent of decolorization.
Single site heterogeneous catalysts (SSHCs) are
usually associated with transition metal containing
molecular sieves or supported catalysts synthesized via
grafting or anchoring techniques [1, 2]. Transition metal
mono substituted polyoxometalates have recently been
considered as a speciﬁ c class of single site catalysts in
which the active metal is isolated and strongly bound
to an inorganic metal oxide matrix [2–5]. Signiﬁ cant
attempts such as the synthesis of the so called hybrid
organic inorganic materials have been made in order
to incorporate organic moieties within inorganic metal
silica frameworks and tune their surface properties and
the catalytic performance [6, 7].
The potential applications of metal organic frameworks
(MOFs) in gas separation and storage, sensors, and
catalysis have recently received considerable attention
[8–10]. By controlling the size and the functionalization
of the organic linkers, these metal organic structures show
the potential for more ﬂ exible rational design compared
to conventionally used microporous and mesoporous
inorganic materials .
One of the porous MOF materials extensively studied
is MIL-101(Cr) [12–14]. The linkage of 1,4-benzene
dicarboxylate (BDC) anions and inorganic trimers
consists of three chromium atoms in an octahedral
environment with four oxygen atoms of the bidentate
dicarboxylate, one μ
O atom, and one oxygen atom
from the terminal water or ﬂ uorine group forms MIL-
The concentration of the present work is on the
synthesis of MIL-101/graphene oxide under sunlight
irradiation and its appliaction in the photodecolorization
of Malachite green (MG) (Table 1). Rate determining
parameters including initial dye concentration, catalyst
loading and pH in the photodecolorization of MG have
been extensively studied.
All chemicals used were of commercial reagent grade.
A Nicolet Impact 400 D spectrophotometer was used to
* The text was submitted by the authors in English.
** The author for correspondence.