The fabrication of porous Metal Organic Framework materials within resistant structures is a key challenge impeding their wide commercial use for processes such as adsorptive separation. In fact, the integration of nano-scale Metal–organic frameworks (MOFs) crystallic structures into bulk components that can maintain the desired characteristics, for examplei.e., size, shape, and mechanical stability, is a prerequisite for their wide practical use in many applications. At the same time, it requires sophisticated shaping techniques that can structure nano/micro-crystalline fine powders of MOFs into diverse types of macroscopic bodies such as monoliths. Under this framework, this review aims to bridge the gap between research advances and industrial necessities for fostering MOF applications into real life. Therefore, it critically explores recent advances in the shaping and production of MOF macro structures with regard to the binding materials that have received little attention to date, but have the potential to give new perspectives in the industrial applicability of MOFs.
MOF |
Binder (wt%) |
Shape |
SBET Powder | 2 | (m 2 g−1) |
g−1) |
SBET Body |
SBET Body (m (m2 g−1) | 2 g−1) |
Application |
Reference |
Application | |||
Reference |
MIL-100(Fe) |
ρ-alumina (5%) |
Sphere |
||||||||||||
Cu3(BTC) | 2088 |
1831 |
2 |
Ammonia adsorption |
[30] |
||||||||||
None |
Monolith |
307 |
834 |
No application/MOF shape engineering |
[28] |
MIL-101(Cr) |
ρ-alumina (5%) |
||||||||
UiO-66 |
None |
Sphere |
4066 |
3685 |
Tablet |
1426 |
1459 | CO2 adsorption |
No application/MOF shape engineering |
[30] |
|||||
[104] |
UIO-66(Zr) |
ρ-alumina (5%) |
Sphere |
1050 |
911 |
CO2 adsorption |
[30] |
||||||||
UiO-67 |
None |
Tablet |
2034 |
1549 |
No application/MOF shape engineering |
[104] |
UIO-66_NH2 |
ρ-alumina (5%) |
Sphere |
||||||
UiO-66-NH | 875 |
2 |
823 |
None |
Tablet |
839 |
625 |
CO2 adsorption |
No application/MOF shape engineering | [30] |
|||||
[104] |
ZIF-8 |
Bentonite clay (10%) |
Tablet |
1022.8 |
820.6 |
||||||||||
HKUST-1 |
None |
Tablet |
1288 |
- |
1091 |
No application/MOF shape engineering |
[89] |
||||||||
[104] |
ZIF-8 |
Alumina (10%) |
Tablet |
||||||||||||
ZIF-8HT | 1022.8 |
None |
Monolith |
- | 947.9 |
1387 |
- |
[89] |
No application/MOF shape engineering | ||||||
[105] |
ZIF-8 |
||||||||||||||
ZIF-8LT | SB powder (10%) |
None |
Tablet |
1022.8 |
959.2 |
Monolith |
Gas adsorption |
[89] |
|||||||
- |
1359 |
No application/MOF shape engineering |
[105] |
ZIF-8 |
Talc powder (10%) |
Tablet |
|||||||||
ZIF-8LT-HT |
None |
Monolith |
1022.8 |
951.3 |
Gas adsorption |
- |
1423 |
No application/MOF shape engineering[89] | |||||||
[105] |
ZIF-8 |
Sesbania powder (10%) |
Tablet | ||||||||||||
ZIF-8ER |
None |
Monolith | 1022.8 |
- |
846.4 |
- |
1395 |
[89] |
|||||||
No application/MOF shape engineering | [105] |
ZIF-8 |
Silica (10%) |
||||||||||||
HKUST-1 |
Tablet |
None |
Monolith | 1022.8 |
- |
945.9 |
- |
[89] |
|||||||
1193 |
Methane adsorption |
[106] |
UiO-66 |
Graphite (1%) |
Tablet |
1140 |
885 | ||||||||
UiO-66 |
None |
Sphere |
1167Selective adsorption and separation of xylene isomers |
1127 |
[90] |
No application/MOF shape engineering | |||||||||
[108] |
ZIF-8 |
Bentonite (20%) |
|||||||||||||
MOF-5 |
None |
Monolith |
1415 |
1083 |
Adsorptive Separations/biobutanol recovery |
Pellet |
[91] |
||||||||
2762 |
2707 |
Hydrogen storage |
[109] |
ZIF-8 |
Bentonite (16.7%) and MC (16.7%) |
Monolith |
|||||||||
CPO-27-Ni |
None |
Pellet |
1415 |
- |
1070 |
- |
Adsorptive Separations/biobutanol recovery |
[91] |
|||||||
Methane storage | [110] |
HKUST-1 |
|||||||||||||
CuBTC |
Bentonite (15%) and MC (15%) |
Pellet |
1271.2 |
None |
Pellet605.1 |
- |
MOF shape engineering |
- |
CO2 capture |
[92] |
|||||
[111] |
ZIF-8 |
||||||||||||||
MIL-53(Al) | Bentonite (15%) and MC (15%) |
None |
Pellet |
Pellet |
2047 |
- |
1471.5 |
MOF shape engineering |
- |
CO[92] | |||||
2 | capture | [111] |
ZIF-67 |
||||||||||||
HKUST-1 | Bentonite (15%) and MC (15%) |
None |
Pellet |
1789.6 |
monolith |
- | 464.4 |
1134 | MOF shape engineering |
Methane storage |
[92] |
||||
[112] |
UiO-66 |
Bentonite (15%) and MC (15%) |
Pellet |
1110.8 |
187.4 |
MOF shape engineering |
[92] |
||||||||
MIL-101(Cr) |
Bentonite (25%) |
||||||||||||||
HKUST-1 |
None |
tablet |
1850 |
- |
Methane storage/MOF shape engineering |
[113] |
Monolith |
- |
- |
CO2 adsorption |
[93] |
||||
MIL-101 (Cr) |
Bentonite (25/40%) |
Monolith |
- |
- |
CO2 adsorption |
[94] |
|||||||||
MIL-100(Fe) |
Silica sol (10%) |
Granule |
1772 |
1619 |
Separation of SF6 from SF6/N2 mixture |
[95] |
|||||||||
UiO-66(Zr) |
ρ-alumina (5%) |
Bead |
903 |
619 |
Room temperature gas adsorption/H2O and CH4 adsorption |
[96] |
|||||||||
MIL-100(Fe) |
ρ-alumina (5%) |
Bead |
1928 |
1451 |
Room temperature gas adsorption/H2O and CH4 adsorption |
[96] |
|||||||||
MIL-127(Fe) |
ρ-alumina (5%) |
Bead |
1413 |
1266 |
Room temperature gas adsorption/H2O and CH4 adsorption |
[96] |
|||||||||
MIL-101 |
Sodium silicate and starch (7%) |
Pellet |
2730 |
1910 |
CO2 adsorption |
[97] |
|||||||||
MIL-100(Fe) |
Silica (10%) |
Granule |
- |
1568 |
C2/C3 hydrocarbon separation |
[98] |
|||||||||
Cu3(BTC)2 |
Silres MSE 100 (13.8%) |
Monolith |
- |
484 |
MOF shape engineering |
[99] |
|||||||||
ZIF-8 |
ρ-alumina (5/10/15%) |
Pellet |
- |
- |
CH4/N2 separation |
[100] |
|||||||||
MIL-53(Al) |
ρ-alumina (5/10/15%) |
Pellet |
- |
- |
CH4/N2 separation |
[100] |
|||||||||
ZIF-7 |
Silica (15%) |
Monolith |
16 |
40 |
Adsorption of ethane and ethylene |
[101] |
|||||||||
MOF-74(Ni) |
Bentonite (15%) and PVA (5%) |
Monolith |
1180 |
737 |
Gas adsorption |
[102] |
|||||||||
UTSA-16(Co) |
Bentonite (10%) and PVA (5%) |
Monolith |
727 |
568 |
Gas adsorption |
[102] |
|||||||||
MIL-101 |
Bentonite (15%) and PVA (5%) |
Monolith |
2400 |
2200 |
CO2 removal from enclosed environments |
[103] |
|||||||||
MOF |
Binder (wt%) |
Shape |
SBET Powder (m2 g−1) |
SBET Body (m2 g−1) |
Application |
Reference |
|||||||||
TIFSIX-2-Cu-i |
PVB (10%) |
Pellet |
740 |
719 |
Gas separation and storage |
[27] |
|||||||||
SIFSIX-3-Ni |
PVB (10%) |
Pellet |
360 |
297 |
Gas separation and storage |
[27] |
|||||||||
GEFSIX-2-Cu-i |
PVB (10%) |
Pellet |
755 |
659 |
Gas separation and storage |
[27] |
|||||||||
SIFSIX-2-Cu-i |
PVB (9%) |
Pellet |
808 |
685 |
Gas separation and storage |
[27] |
|||||||||
ZIF-8 |
PEI (14%) |
Pellet |
- |
- |
Gas adsorption and separation |
[29] |
|||||||||
ZIF-8 |
PVC (23%) |
Pellet |
- |
- |
Gas adsorption and separation |
[29] |
|||||||||
ZIF-8 |
PVF (20%) |
Pellet |
- |
- |
Gas adsorption and separation |
[29] |
|||||||||
UiO66-COOH |
PVA (4%) |
Bead |
710 |
359 |
NH3 air purification |
[31] |
|||||||||
UiO66-COOH |
Polysiloxane (5.5%) |
Extrudate |
710 |
418 |
NH3 air purification |
[31] |
|||||||||
MOF-177 |
PVB (4%) |
Pellet |
2784 |
- |
CO2 adsorption |
[54] |
|||||||||
MOF-177-TEPA-20% |
PVB (4%) |
Pellet |
585 |
- |
CO2 adsorption |
[54] |
|||||||||
MOF-801 |
PVB (5%) |
Pellet |
899 |
569 |
CO2 and H2O adsorption |
[55] |
|||||||||
Zr-MOF |
Sucrose (10%) |
Pellet |
1367 |
674 |
H2 storage |
[56] |
|||||||||
UiO-66(Zr) |
PVA/PVB (3%) |
Granule |
1065 |
1017 |
Gas adsorption |
[57] |
|||||||||
UiO-66(Zr)_NH2 |
PVA/PVB (3%) |
Granule |
958 |
795 |
Gas adsorption |
[57] |
|||||||||
MIL-100(Fe) |
PVA/PVB (3%) |
Granule |
2261 |
2043 |
Gas adsorption |
[57] |
|||||||||
MIL-127(Fe) |
PVA/PVB (3%) |
Granule |
1181 |
1117 |
Gas adsorption |
[57] |
|||||||||
CPO-27(Ni) |
PVA (2%) |
Granule |
937 |
1319 |
NH3 adsorption for Respiratory protection filters |
[58] |
|||||||||
MIL-100(Fe) |
PVA (2%) |
Granule |
1212 |
1172 |
NH3 adsorption for Respiratory protection filters |
[58] |
|||||||||
Cu-BTC |
PVA (2%) |
Granule |
1605 |
147 |
NH3 adsorption for Respiratory protection filters |
[58] |
|||||||||
ZIF-8 |
PVF (15%) |
Bead |
- |
- |
Gas adsorption and separation |
[59] |
|||||||||
ZIF-8 |
PES (25%) |
Bead |
1384.4 |
1030.6 |
Oil sorption |
[60] |
|||||||||
Alfum |
PVA (20%) |
Monolith |
946 |
612 |
Water vapor sorption |
[61] |
|||||||||
MIL-160(Al) |
PVA (20%) |
Monolith |
1134 |
800 |
Water vapor sorption |
[61] |
|||||||||
MIL-101(Cr) |
PVA (20%) |
Monolith |
3171 |
2225 |
Water vapor sorption |
[61] |
|||||||||
Cu3(BTC)2 |
PVA (-) |
Pellet |
1737 |
963 |
H2O vapor and CO2 adsorption/catalysis |
[62] |
|||||||||
MIL-53(Al) |
PVA (13%) |
Pellet |
- |
- |
Separation of CO2/CH4 mixtures |
[63] |
|||||||||
UiO-66 |
PVA (1%) |
Monolith |
- |
- |
MOF shape engineering |
[64] |
|||||||||
UTSA-16 |
PVA (0–6.7%) |
Pellet |
- |
- |
CO2 adsorption |
[65] |
|||||||||
UTSA-16 |
PVA (-) |
Cylindrical extrudate |
- |
805 |
Gas adsorption (high pressure)/H2 purification from SMR off-gases |
[66] |
|||||||||
Alfum |
PVA (20%) |
Monolith |
1038 |
786 |
Water vapor sorption |
[67] |
|||||||||
MIL-101(Cr) |
PVA (20%) |
Monolith |
2731 |
1820 |
Water vapor sorption |
[67] |
|||||||||
UiO-66 |
PVA (-) |
Pellet |
1378 |
1274 |
CO2/N2 separation |
[68] |
|||||||||
MIL-101(Cr) |
PVA (10%) |
Grain |
2970 |
2610 |
Methanol adsorbent in adsorption heat transformation cycles |
[69] |
|||||||||
ZIF-8 |
PVA (2.9%) |
Cylindrical extrudate |
- |
- |
CO2/H2 Separation/biohydrogen purification |
[70] |
|||||||||
HKUST-1 |
PVA (2.9%) |
Cylindrical extrudate |
- |
- |
CO2/H2 Separation/biohydrogen purification |
[70] |
|||||||||
UTSA-16 |
PVA (2.9%) |
Cylindrical extrudate |
- |
- |
CO2/H2 Separation/biohydrogen purification |
[70] |
|||||||||
UiO-66 |
PVA (25%) |
Pellet |
1295 |
1031 |
Water adsorption heat transformation systems |
[71] |
|||||||||
Zr-fum |
PVA (25%) |
Pellet |
643 |
479 |
Water adsorption heat transformation systems |
[71] |
|||||||||
Al-fum |
PVA (25%) |
Pellet |
988 |
595 |
Water adsorption heat transformation systems |
[71] |
|||||||||
MIL-160 |
PVA (25%) |
Pellet |
1122 |
866 |
Water adsorption heat transformation systems |
[71] |
|||||||||
MIL-96(Al) |
PVA (0.5%) |
Monolith |
655 |
91 |
Upcycling of Li-ion batteries/MOF shape engineering |
[72] |
|||||||||
MOF-5 |
ABS (1/5/10%) |
3D-printed various geometries |
- |
- |
H2 adsorption/3D-printed H2 storage devices |
[73] |
|||||||||
ELM-11 |
PVP (10/20/31%) |
Pellet |
- |
- |
Gas storage and separation |
[74] |
|||||||||
MIL-100(Fe) |
PVP (2%) |
Monolith |
1917 |
1673.7 |
Ultra-low heat-driven atmospheric water harvesting (AWH) system |
[75] |
|||||||||
epn-MOF |
PVDF (30/40/50%) |
Bead |
- |
- |
CO2 capture in indoor environments |
[76] |
|||||||||
MIL-101(Cr) |
CMC sodium salt (5.5%) and starch (5.5%) |
Granule |
2471 |
1642 |
Gas (CO2, CH4, N2, CO) sorption |
[77] |
|||||||||
MIL-53(Al) |
MC 400 (10%) |
Cylindrical extrudate |
1525 |
1158 |
CO2 and CH4 adsorption |
[78] |
|||||||||
MIL-53(Al) |
MC 4000 (10%)) |
Cylindrical extrudate |
1525 |
1200 |
CO2 and CH4 adsorption |
[78] |
|||||||||
MIL-125(Ti)_NH2 |
Polyvinyl group (3%) |
Granule |
- |
- |
Syngas treatment aiming for H2 production |
[79] |
|||||||||
Mg-gallate |
HPC (4.8%) |
Pellet |
638 |
557 |
Hydrocarbon separations |
[80] |
|||||||||
Co-gallate |
HPC (4.8%) |
Pellet |
494 |
480 |
Hydrocarbon separations |
[80] |
|||||||||
Ni-gallate |
HPC (4.8%) |
Pellet |
455 |
425 |
Hydrocarbon separations |
[80] |
|||||||||
ZIF-8 |
HPC (0–40%) |
Granule |
- |
- |
MOF shape engineering |
[81] |
|||||||||
MIP-202 |
HPC (5%) |
Pellet |
278.6 |
- |
CO2/CH4 and CO2/N2 separation/CO2 capture |
[82] |
|||||||||
MIL-101(Cr). |
R,F-xerogel (50%) |
Monolith |
3060 |
1350 |
Water adsorption |
[83] |
|||||||||
MIL-100(Fe) |
R,F-xerogel (42%) |
Monolith |
2200 |
770 |
Water adsorption |
[83] |
|||||||||
MIL-100(Cr) |
R,F-xerogel (44%) |
Monolith |
1560 |
570 |
Water adsorption |
[83] |
|||||||||
ZIF-8 |
Cellulose ester (-) |
Tablet |
1433 |
1420 |
Catalysis/MOF shape engineering |
[84] |
|||||||||
HKUST-1 |
Cellulose ester (-) |
Tablet |
1897 |
453 |
Catalysis/MOF shape engineering |
[84] |
|||||||||
SIM-1 |
Cellulose ester (-) |
Tablet |
516 |
370 |
Catalysis/MOF shape engineering |
[84] |
MOF |
Binder |
Shape |
SBET Powder (m |