5.

3 Heteropoly ACID

A heteropolyacid is a special type of acid, designed by a specific combination of certain metals (tungsten, molybdenum or
vanadium) and p-block non-metals (silicon, phosphorus or arsenic) with acidic hydrogen and oxygen which is frequently used as
a reusable acid-cat- alyst in the synthesis of fine chemicals [63–75]. Several structural combinations can be prepared by changing
the metal and non-metal species [70–75]. Wu et al., [63] used 3D graphene aerogel anchored tungsto-phosphoric acid catalyst
which possessing the abundant porous structure for the synthesis of ethyl levulinate (Table 1, entry 25). Si- milarly ethyl
levulinate was synthesized by Nadiwale et al., [64] ap- plying dodeca-tungsto-phosphoric acid tethered on desilicated H-ZSM-5
catalyst (Table 1, entry 26) while Zhou et al., [65] used silver or am- monium co-doped phosphotungstic acid for the synthesis of
levulinate compound (Table 1, entry 27,28). Wu et al., [66] and Ramli et al., [67] employed dodeca-tungsto-phosphoric acid fixed
to Al-MCM-41 and zirconia supported phosphotungstic acid for the synthesis of hexyl le- vulinate and ethyl levulinate
respectively which further displaying the excellent recyclability (Table 1, entries 29,30). Zheng et al., [68] and Wu et al., [69]
synthesized ethyl levulinate by using tungstophosphoric acid supported on graphene oxide and MCM-41 respectively (Table 1,
entries 31,32). Liun et al., [70] carried out the synthesis of ethyl, me- thyl and isobutyl levulinates using organic-salt of H 4SiW12O40
(Table 1,
entries 33–35). Dharane and Bokade [71] proposed synthesis of butyl levulinate using dodecatungsten phosphoric acid
supported on acid-
treated clay (K−10) (Table 1, entry 36). Whereas Vilanculo et al., [72] used simple H4SiW12O40 for synthesis of several
levulinates (Table 1, entries 37–42). Manikandan, and Cheralathan [73] used heteropoly acid supported silicalites for various
alkyl levulinate synthesis (Table 1, entries 43–45), while Lucas et al., [74] and Yan et al., [75] used hetero poly acid supported
STA-AlSBA-15 and tungstisilicic acid H4SiW12O40 - SiO2 for an efficient synthesis of alkyl levulinates (Table 1, entries 46–48).
In a catalytic synthesis, fate of product formation is depends on the
physico-chemical characteristics of catalyst. The heteropolyacid sup- ported catalyst furnishes well acidity and offers better
conversion of the levulinate compounds which may be attributed to improved surface area and free dynamic catalytic sites for
the processing of reaction. Ammonium co-doped heteropolyacid is having higher hydrophilicity, Keggin structure with higher
acidic strength as well as surface acidic sites which offers a higher reaction rate than silver co-doped hetero- polyacid. At the
same time, higher hydrophilicity of catalyst showed leaching of the active co-doped component of catalyst which shrinks the
reusability. To avoid the problem of higher hydrophilicity and sub- sequent leaching, several authors have anchored
hydrophobic graphene based compound on the heteropolyacid which displayed reduction in leaching of catalyst.
The heteropolyacid supported catalyst offers better yield than sole support of AlSBA-15 or Silica or K10 or MCM-41 or Al-
MCM-41 and desilicated H-ZSM-5. Among all, desilicated H-ZSM-5 and K10 was re- ported to be the most feasible catalyst. These
results attributed to, ex- cess acidic catalytic sites and surface area which enhancing the reaction rate. However, excess
heteropolyacid loading decreases the surface area due to deposition of heteropolyacid species inside the pores/surface/
channels. Moreover, use of the organic salts of heteropolyacid has problems like solubilization in the polar reaction media,
which subse- quently reduces the catalyst activity and recyclability. In conclusion, heteropolyacids have several advantages
since; these heteropolyacids possess the very strong Brønsted acidity, effective mass transfer influ- ence and can be applicable as
homogenous or heterogeneous catalyst based on their structural composition and reaction synthesis solvent [ 66–69]. The major
challenges associated with the heteropolyacid is the lower thermal stability, lower surface area, unequal dispersion of the
positive charges, solubility in the polar solvent, catalyst reusability and regeneration [46–48].