5.

6 ZIRCONIA

Zirconia is the solid-acid zirconium metal-oxide catalyst which is receiving enormous attention in the scientific communities
due to its characteristic features of porosity, thermal stability and catalytic ac- tivity [89–94]. The sufficient pore size always
evades the diffusion constrains and facilitates the easy mass transport phenomenon for bulky and long chain molecules [90–92].
Su et al., [89] very well de-
signed a mesoporous H3PW12O40-ZrO–Si(Ph)Si hybrid catalyst to pro-

duce methyl levulinate (Table 1, entry 69). Kuwahara et al. [90,91] performed synthesis of ethyl levulinate by applying sulphated
meso- porous zirconosilicates (Table 1, entry 70) [90] and sulphated Si-doped zirconium oxide catalyst (Table 1, entry 71) [91]. Su
et al., [92] carried out pore morphology-controlled synthesis of zirconium oxide based hybrid catalysts which was further
applied for the synthesis of levuli- nate esters (for example, methyl levulinate, ethyl levulinate, butyl le- vulinate) (Table 1,
entries 72–74). Unlu et al. [93] carried out synthesis of ethyl levulinate by using model catalyst sulphated zirconia layered
(coated) with hydroxyethyl cellulose catalytic membrane and powder sulphated zirconia catalyst. It was observed that,
sulphated zirconia layered hydroxyethyl cellulose catalytic membrane offers excellent yield of the product ethyl levulinate
than simple powder sulphated zirconia catalyst (Table 1, entries 75,76). Yadav and Yadav [94] syn- thesized various alkyl
levulinate compounds using heterogeneous super acidic zirconia catalysts UDCAT-5 (Table 1, entries 77–81).
Simple zirconia, silicon-doped zirconia, hybrid zirconia, organo-
hybrid zirconia has been employed for the levulinate ester synthesis. It was observed that, introduction of the hydrophobic
group in zirconia remarkably improve the catalyst activity for levulinate synthesis. Thus among all studied zirconia base
catalysts, organo-hybrid zirconia cat- alyst displayed excellent reactivity towards synthesis of levulinate compounds at mild
reaction condition. The surface hydrophobicity of hybrid catalyst can be maintained by introduction of various organic
compounds such as phenyl group or hydroxy ethyl cellulose group etc. Introduction of the organic binder into zirconia increases
the surface hydrophobicity which increases the reaction rate. Hydrophobic zirconia catalyst inhibits adsorption of polar
molecules (ethanol, levulinic acid and water) on the catalyst surface and makes it easily available for the transformation. The
same is not true for the surface hydrophilic cata- lysts which adsorb various polar molecules onto catalyst surface and make it
unavailable for catalysis, restricts the effective mass diffusion and hence deactivate dynamic sites of catalyst. Furthermore,
adsorbed water molecules on the catalyst surface cause reversible esterification reaction and disturbs the equilibrium. Silicon can
also be doped with zirconia which showed improvement in acidity, meso-porosity, surface area and stability of catalyst.
However, such doped zirconia catalyst may tend to have sluggish recyclability since; doped component can be
easily leached out. Further these catalysts are non-corrosive, easier to regenerate and mechanically stable [ 89–94]. Conversely,
the major challenge associated with this catalyst is the leaching of sulphated ions from the porous framework during reaction
[46–49]. Moreover, some times, pores are blocked due to trapping of larger size molecules and create diffusion restriction which
needed frequent regeneration of the catalyst.

5.7 Acid CATALYST

Homogeneous catalysis is simple and increases the reaction rate quite easily [95,96]. Various kinds of simple mineral acids
are generally used which are commercially easily available at low cost. Also, it is quite easy to modulate the acidic strength as
per requirement by ad- dition of the native reaction solvent or water or acid [95,96]. Varkolu
et al., [95] (Table 1, entries 82–85) performed esterification using re- cyclable catalyst bio-glycerol derived carbon–sulfonic-acid to
synthe- size various levulinates. Negus et al., [96] prepared ethyl levulinate catalyzed by p-toluene sulphonic acid (PTSA) (Table
1, entries 86).
Simple acid catalysis includes acids like HCl, H 2SO4, HNO3, PTSA etc. Among all these catalyst H2SO4, and PTSA works
better due to their higher acid strength. However, all these represented catalysts are in liquid state which forms homogenous
reaction system and hence it is difficult to use as well as reuse in the reaction. Some authors have taken efforts to modify these
acid catalysts by developing bio-glycerol derived carbon-sulfonic-acid to avoid post reaction challenges such as isolation,
neutralization, corrosion and recyclability. All these Bronsted acid type catalysts showed excellent catalytic activity for the
esterification reac- tion. Homogeneous catalysis with mineral acid always has higher re- action rate with lesser cost of catalyst.
However, a major concern is the handling issue, corrosiveness of reactor, high reaction temperature, non-reusability, non-
regeneration, hazardous aids, waste disposal, toxicity, miscibility in hydrophobic media, down streaming and se- paration of
catalyst from reaction media etc. These practical difficulties discourage the use of mineral acid catalysts in synthetic organic reac-
tion.