Catalytic hydrolysis of cellulose by phosphotungstic acid–supported functionalized metal-organic frameworks with different electronegative groups

Reactivity of metal–oxo clusters towards biomolecules: from discrete polyoxometalates to metal–organic frameworks

“…More recently, Han et al reported cellulose hydrolysis using a hybrid catalyst (PW 12 @MIL-101-X) based on MOF MIL-101(Fe) that acts both as carrier for the hydrolytically active H 3 [PW 12 O 40 ] and as a means to activate cellulose for hydrolysis by modifying its BDC linkers with electron-withdrawing groups (X = –Br, –NH 2 , –Cl, –NO 2 ). 297 The addition of electron-withdrawing moieties on the MOF caused it to selectively adsorb cellulose by forming hydrogen bonds via its hydroxyl groups, which further weakens the existing hydrogen bonds within cellulose and thereby makes hydrolysis more efficient. Hence, the greatest glucose yield (16.2%) was obtained for PW 12 @MIL-101-NO 2 at 180 °C after 11 h due to the strong electron-withdrawing character of –NO 2 (Table 9).…”

MOF catalysis meets biochemistry: molecular insights from the hydrolytic activity of MOFs towards biomolecules

“…98 Alternatively, embedding polyoxometalates onto MOFs was utilized for the hydrolytic cleavage of the DNA model substrate bis(4-nitrophenyl)phosphate, 99 the acidolysis of soybean oil 100 and the hydrolysis of cellulose. 101 Among the hydrolysable bonds present in biomacromolecules other than a peptide bond, the hydrolysis of phosphoester bonds is probably the most investigated reaction using MOF's intrinsic reactivity, especially when considering Zr-MOFs. However, most research so far concerned the capture, and destruction of chemical warfare agents (CWA) and pesticides.…”

“…98 Alternatively, embedding polyoxometalates onto MOFs was utilized for the hydrolytic cleavage of the DNA model substrate bis(4-nitrophenyl)phosphate, 99 the acidolysis of soybean oil 100 and the hydrolysis of cellulose. 101…”

Bioinspired Cellulase-Mimetic Solid Acid Catalysts for Cellulose Hydrolysis

“…Similarly, a metal-organic framework material (MIL-101) carrier bearing various electronegative groups (X = -Br, -NH 2 , -Cl, and -NO 2 ) and phosphotungstic acids (PTA) (PTA@MIL-101-X) also showed enhanced catalyst-cellulose interactions ( Figure 3 ). NO 2 -grafted catalyst PTA@MIL-101-NO 2 achieved the highest glucose yield due to its highest affinity to cellulosic materials ( Han et al, 2019 ). The efficiency of cellulose hydrolysis increases with the increase of the electronegativity (-NO 2 > -Cl > -NH 2 > -Br) of the binding groups ( Han et al, 2019 ), which is consistent with the observation by Shuai and Pan ( Shuai et al, 2012 ).…”

“…NO 2 -grafted catalyst PTA@MIL-101-NO 2 achieved the highest glucose yield due to its highest affinity to cellulosic materials ( Han et al, 2019 ). The efficiency of cellulose hydrolysis increases with the increase of the electronegativity (-NO 2 > -Cl > -NH 2 > -Br) of the binding groups ( Han et al, 2019 ), which is consistent with the observation by Shuai and Pan ( Shuai et al, 2012 ). A series of solid acid catalysts bearing -Cl were synthesized with different methods and enhanced glucose yields by about 2.5 times (93%) compared to the catalysts without -Cl (37%) ( Pang et al, 2014 ; Shen et al, 2014 ; Zhao et al, 2014 ; Zuo et al, 2014 ; Hu et al, 2016 ; Yang et al, 2016 ; Shen et al, 2017 ; Shen et al, 2018 ; Ding et al, 2019 ; Li et al, 2020 ; Li et al, 2020 ).…”