5.

8 METAL SALT

Metal salts involve simple metal halides in which metal possessing vacant d-orbitals [ 97,98]. These metals are acted as site of
Lewis acid and hence possess the co-ordination features [97,98]. In general, these metal salts are activated only at the higher
reaction temperature [97,98]. They are inexpensive, easily available in the market, required no-tedious modifications and are
sufficiently stable [97,98]. Huang et al., [97] used various metal-salt catalysts for synthesis of methyl levulinate ester using
biomass derived levulinic acid in presence of microwave irradiation (Table 1, entries 87–95). They have used various metal salts
such as Al2(SO4)3, CrCl3, SnCl4, SnSO4, FeCl3, CuSO4, CuCl2, AlCl3, ZnCl2, among which Al2(SO4)3 offers excellent yield of methyl
levulinate (Table 1, entries 87–95). Martins et al., [98] carried out synthesis of various alkyl levulinates using Fe 2(SO4)3 (Table 1,
entry 96–99). They have used various metal salts such as Fe 2(SO4)3, FeCl3, CuSO4, FeSO4, ZnSO4, NiSO4, MnSO4 for ethyl levulinate
synthesis among which Fe2(SO4)3 offers excellent yield of methyl levulinate (Table 1, entries 96, 100–105).
Several metal salts are widely used for the levulinate synthesis such
as halide salts of Cr, Sn, Al, Zn, Fe, sulphate salts of Sn, Cu, Fe, Zn, Ni and Mn etc. The central metal ion of these salts possesses
higher Lewis acidity which offers binding site and higher reaction rate for the es- terification reaction. Higher acidity is attributed
to higher charge pre- sent on the central metal atom. Al 2(SO4)3 and Fe2(SO4)3 are having trivalent central metal atom which offers
better yield and higher cata- lytic activity than corresponding bivalent central metal atom. The central metal atom directly
coordinated to the carbonyl oxygen and increases the positivity of carbonyl carbon for subsequent nucleophilic attack. These
meal salts may acted as homogeneous catalyst and hence requires lesser reaction time or otherwise heterogeneous depending on
reaction media or supported appropriately in the medium [97,98]. The major challenging issues associated with these metal salts
are down- stream processing (isolation of product, isolation of metal salt, neu- tralization of catalyst, reuse of catalyst and
purification of product). Furthermore, higher activation energy, harsh reaction temperature, catalyst disposal and reusability are
also unavoidable challenges.

5.9 MOF

Metal Organic Frameworks (MOF) are the three dimensional porous material which are formed by linkage in between the
metal-ions-oxo clusters and multidentate hydrophobic linker [99–101]. Various com- binations of metal ion, oxo-cluster and
organic linker can lead to pro- duce the bank of MOFs which will offer high variability and mod- ifications necessarily required
for catalysis [100,101]. Guo et al., [99] used copper organic framework (MOF)-supported polyoxometalates to perform selective
transformation of levulinic acid to ethyl levulinate (Table 1, entries 106). Gupta and Kantam [100] carried out synthesis of
different alkyl-levulinate compounds via use of sulfonic acid-functio- nalized hafnium-based MOF (Table 1, entries 107–110).
Cirujano et al.,
[101] performed synthesis of levulinate esters over zirconia containing
MOF as a catalyst (Table 1, entries 111–115).
Among various reported MOF catalysts (Cu-MOF, Hf-MOF and Zr- MOF), Hf-MOF is possessing the higher reaction rate at
higher tem- perature 120 °C, while Zr-MOF is possessing the higher reaction rate at comparatively lower temperature 80 °C. The
alkaline organic func- tionality present in Zr-MOF will lead to abstract the alcoholic proton from the alcohol, while acidic organic
functionality present in Hf-MOF causes protonation to the carbonyl group of carboxylic moiety of le- vulinic acid. Moreover,
MOFs possess the exceptional nano-sized pore channels and cavities [99,100]. The Bronsted acidity in MOFs can be imported by
launching sulfonated group bearing legands which is the most dynamic approach to introduce -SO 3H. Acidic MOFs possess the
Lewis acid character and hence easily offer respective metal coordina- tion bond valency; also they possess the good stability
(chemical/ thermal) and uniform size nano-pores or channels [99,100]. The chal- lenges associated with the designing of MOF is a
skill-full task, and having high risk of loss of active chemical sites during designing [46–49]. The major concern is the severe
toxicity of certain metals present in MOF which limits their practical scope and applications.