supplementary information for - nature 3(btc) 2@4pico 5.8 298 1 66 cu 3(btc) 2@en 2.6 298 1 66...

1

Supplementary information for

The chemistry of metal–organic frameworks for CO2 capture, regeneration

and conversion

Christopher A. Trickett,1 Aasif Helal,2 Bassem A. Al-Maythalony,3 Zain H. Yamani,2

Kyle E. Cordova,1,2 and Omar M. Yaghi1,2,*

1Department of Chemistry, University of California–Berkeley; Materials Sciences Division,

Lawrence Berkeley National Laboratory; Kavli Energy NanoSciences Institute at Berkeley; and

Berkeley Global Science Institute, Berkeley, CA 94720, USA 2Center for Research Excellence in Nanotechnology (CENT), King Fahd University of

Petroleum and Minerals, Dhahran, 31261, Saudi Arabia 3King Abdulaziz City for Science and Technology – Technology Innovation Center on Carbon

Capture and Sequestration (KACST–TIC CCS), King Fahd University of Petroleum and

Minerals, Dhahran, 31261, Saudi Arabia

*Corresponding author. E-mail: [email protected]

In format provided by Trickett et al. (doi:10.1038/natrevmats.2017.45)SUPPLEMENTARY INFORMATION

NATURE REVIEWS | MATERIALS www.nature.com/natrevmats

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Table of Contents

Section 1 MOFs for Post-Combustion Carbon Capture 3–4

Section 2 Low pressure CO2 uptake versus functionality best performers

5–20

Section 3 MOFs in membrane technology 21–23

Section 4 Catalytic CO2 reduction by MOFs 24–26

Section 5 CO2 conversion into fine chemicals by MOFs 27–34

Section 6 Glossary 35–37

Section 7 References 38–62



3

Section 1: MOFs for Post-Combustion Carbon Capture

The following tables report the CO2 uptake of MOFs reported in 2012 onwards except for Table S1, which reports the benchmark performers throughout the history of MOFs. Only uptake values around room temperature (293-298 K) and atmospheric pressure are recorded, with the tables divided according to functional groups discussed in the main text. The weight % value is calculated as follows:

Wt% = [(adsorbed amount of CO2)/(amount of adsorbent + adsorbed amount of CO2) × 100]



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Table 1: Benchmark performing MOFs for low pressure CO2 uptake categorized by key contributing structural features.

MOF Primary adsorption site

Capacity (wt%)

Temperature (K)

Pressure (bar) Ref.

Mg-MOF-74 OMSa 27.5 298 1 1

[Zn2(tdc)2(MA)]n Hybrid 27.0 298 1 2

Fe-MOF-74 OMS 23.8 298 1 3

Mg2(DOBPDC) OMS 22.0 298 1 4

SCu OMS 21.7 298 1 5

TEPA-Mg/DOBDC-40 Aliphatic amine 21.1 298 1 6

Cu(Me-4py-trz-ia) Hybrid 21.1 298 1 7

Cu-TDPAT Hybrid 20.6 298 1 8

Ni-MOF-74 OMS 20.5 298 1 9

rht- MOF-9 Heteroaromatic amine

20.2 298 1 10

HKUST-1 OMS 19.8 293 1.1 11

NbO-Pd-1 OMS 19.7 298 1 12

Co-MOF-74 OMS 19.7 298 1 9

[Mg2(dobdc)(N2H4)1.8] Aliphatic amine 19.5 298 1 13

Cu-TPBTM OMS 19.5 298 1 14

nbo-Cu2(DBIP) OMS 19.3 298 0.95 15

CPO-27-Mg-c [Mg2(DHT)(H2O)0.8(en)1.2]·0.2(en)

Aliphatic amine 19.2 298 1 16

SIFSIX-2-Cu-i SBU-based interactions

19.2 298 1.1 17

ZJNU-54 Heteroaromatic amine

19.1 298 1 18

SIFSIX-1-Cu SBU-based interactions 19.1 298 1 19

JLU-Liu21 Hybrid 18.8 298 1 20

ZJNU-44 Heteroaromatic amine

18.6 296 1 21

NJU-Bai21, PCN-124 Hybrid 18.4 298 1 22

Zn(btz) Heteroatom 18.0 298 1 23

PEI-MIL-101 Aliphatic amine 18.0 298 1 24

aOMS = coordinatively unsaturated metal site; S = Al-(TCPP).



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Section 2: Low pressure CO2 uptake versus functionality best performers

Table 2: Low pressure CO2 adsorption capacities for MOFs with coordinatively unsaturated metal sites

MOF Capacity

(wt%) Temperature (K) Pressure

(bar) Ref.

Fe-MOF-74 23.8 298 1 3

Mg(DOBPDC)2 22.0 298 1 4

SCu 21.7 298 1 5

NbO-Pd-1 19.7 298 1 12

nbo-Cu2(DBIP) 19.3 298 0.95 15

Cu6(DDCBA)3 (ZJU-72) 17.0 298 1 25

MMPF-2 16.6 298 1 26

JLU-Liu22 15.7 298 1 27

[(CH3)2(NH2][Y6(µ3-OH)8(FTZB)6] 15.3 298 1 28

ZJNU-80 14.5 298 1 29

(Cu2I2)[Cu2PDC2-

(H2O)2]2·[Cu(MeCN)4]I 14.2 298 1

30

[(CH3)2(NH2][Tb6(µ3-OH)8(FTZB)6] 13.3 298 1 28

agw-Cu3(CPEIP)2(H2O)3 13.3 298 0.95 15

PCN-80 12.0 296 1 31

[Cu6(L)3]a 11.8 295 1 32

NJFU-2a 11.7 298 1 33

rht-MOF-pyr 11.5 298 1 34

[Ni2(µ2-OH)(bpdc)(tpt)2][NO3] 11.3 295 1 35

(Cu4I4)[Cu2-

PDC2(H2O)2]2 10.9 298 1

30

Co_Pyrene_1 (C56.15H18Co4N2.65O24.68) 10.8 298 1 36

[H2N(Me)2]2[Zn4(L)2(H2O)1.5]b 10.5 298 1 37

(Cu2I2)[Cu3PDC3-

(H2O)2] 10.4 298 1

30



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MOF Capacity

(wt%) Temperature

(K) Pressure

(bar) Ref.

MOF-890 10.2 298 1 38

MOF-891 10.2 298 1 38

NU-111 9.9 298 1 39

MOF-889 9.8 298 1 38

[Ni3(µ3-OH)2(TBAPy)(H2O)4] 8.9 298 1 40

[In3O(EBDC)1.5- H2O)3][NO3] 8.5 298 1 41

[(CH3)2NH2][In3O- (EBDC)1.5(H2O)3]2[In(EBDC)]3

8.5 298 1 41

ZIF-204 8.3 298 1 42

DUT-49 8.3 298 1 43

Cu2(dhtp) 8.2 298 1 44

(Ni2(H2O)2)1.5(Ni3OH)2(BDC)6(NA)6 8.0 298 1 45

JLU-Liu2 7.6 298 1 46

ZnMOF-PDC 7.1 297 1 47

ZJU-26 6.9 298 1 48

JLU-Liu1 6.4 298 1 49

Cu(FMA)(4,4'-Bpe)0.5 6.3 296 1 50

[Co6(µ3-OH)4(Ina)8](H2O)10(DMA)2] 6.3 298 1 51

Cu3(L)2(DABCO)(H2O)c 5.9 298 1 52

[In3O(bpdc)3(HCOO)] 5.2 298 1 53

MOF-888 4.5 298 1 38

Yb(L)(H2O)(NMP)d 3 295 1 54

[Cu2(HL)(H2O)2]e 2.3 298 1 55

M'MOF-20a 1.9 295 1 56

[La(BTB)(H2O)] 1.3 298 1 57

S = Al-(TCPP); aL=1-bis-[3,5-bis(carboxy)phenoxy]methane; bL5- = 2,4-di(3’,5’-dicarboxylphenyl)benzoate; cL3- = 1,1':3',1"-terphenyl]-4,4",5'-tricarboxylate dL3- = 1,3,5-tris(4-carboxyphenyl-1-ylmethyl)-2,4,6-trimethylbenzene);

eL5- = 2,4-di(3′,5′-dicarboxylphenyl)benzoate.



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Table 3: Low pressure CO2 adsorption capacities for MOFs with incorporated aliphatic amines

MOF Capacity

(wt%) Temperature (K) Pressure (bar) Ref.

TEPA-Mg/DOBDC-40 21.1 298 1 6

[Mg2(dobdc)(N2H4)1.8] 19.5 298 1 13

CPO-27-Mg-c [Mg2(DHT)(H2O)0.8(en)1.2]·0.2(en) 19.2 298 1 16

CPO-27-Mg-a [Mg2(DHT)(H2O)1.7(en)0.3]

18.6 298 1 16

CPO-27-Mg-b [Mg2(DHT)(H2O)(en)]·0.2(en) 18.0 298 1 16

PEI-MIL-101 18.0 298 1 24

(dmen)-Mg2(dobpdc) 17.4 298 1 58

en-Mg2(dobpdc) 16.7 298 1 59

Cu2(mand)2(hmt) 15.1 298 1 60

mmen-Mg2(DOBPDC) 14.5 298 1 4

TEPA-MIL-101 13.8 298 1 61

PEI-incorporated amine-MIL-101(Cr) 13.7 298 1 62

MIL-101-DETA 13.3 296 1 63

IRMOF-74-III-CH2NH2 12.7 298 1 64

pip-CPO-27-Ni 12.3 298 1 65

IRMOF-74-III-CH2NHMe 11.4 298 1 64

MIL-101-DADPA 10.4 296 1 63

MIL-101-ED 10.3 296 1 63

MIL-101-AEP 9.9 296 1 63

IRMOF-74-III-CH2NHBoc 8.6 298 1 64

Cu3(BTC)2@3pico 8.5 298 1 66

IRMOF-74-III-CH2NMeBoc 8.3 298 1 64

UiO-66-EA 6.3 298 1 67

Cu3(BTC)2@4pico 5.8 298 1 66

Cu3(BTC)2@en 2.6 298 1 66



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Table 4: Low pressure CO2 adsorption capacities for MOFs with incorporated aromatic amines

MOF Capacity


MAF-66 16.3 298 1 68

LCua

16.2 298 1 69

UiO-66-NH2 13.4 293 1 70

Ni-(Hbzza)2 13.3 295 1 71

DMOF-1-NH2 13.3 298 1 72

LT-UiO-66-NH2 12.7 298 1 73

DMOF-1-NHMe 12.3 298 1 72

IRMOF-74-III-NH2 12.2 298 1 64

HT-UiO-66-NH2 12.0 298 1 73

UiO-66−NH2 11.7 298 1 74

UiO-66-NO2-NH2 11.3 296 1 75

Amino-Zr-MOF nanoparticle 11.2 296 1 76

MAC-4-C 10.8 298 1 77

Zn(BDC-NH2)(TED)0.5 9.5 298 1 78

Zn(ad)(ain)(DMF) 9.2 298 1 79

DMOF-1-NMe2 9.2 298 1 72

[Cd(NH2-bdc)(phen)] 9.1 298 1 80

FJU-40-NH2 8.3 296 1 81

amino-MIL-53 7.6 296 1 82

Sc2(BDC-NH2)3 7.0 293 1 83

{[Cd(2-NH2bdc)(4-bpmh)]}n 7.0 298 1 84

MIL-68(In)-NH2 6.6 298 1 85

Bio-MOF-14 5.7 298 1 86

[Zn(2-NH2BDC)(4-bpmh)] 4.9 298 1 87

UMCM-1-NH2 4.8 298 1 88

[Zn(hfipbba)(4-bpdb)0.5] 4.1 298 1 89

DUT-25 3.8 298 1 90



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MOF Capacity


MOF-205-NH2 3.4 298 1 91

Co2(NH2-BDC)1.5(L)(HCO2)b 3.0 293 1 92

Mg-ABDC [Mg3(ABDC)3(DMF)4] 1.9 298 1 93

Co-ABDC [Co3(ABDC)3(DMF)4] 1.9 298 1 93

Sr-ABDC [Sr(ABDC)(DMF)] 0.4 298 1 93 aL = 2’-amino-1,1’:4’,1’’-terphenyl-3,3’’,5,5’’-tetracarboxylic acid; bL = 1,3,5-N,N,N-tri(3-pyridyl)benzamide.



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Table 5: Low pressure CO2 adsorption capacities for MOFs with heteroaromatic amines

MOF Capacity


rht-MOF-9 20.2 298 1 10

ZJNU-54 19.1 298 1 18

ZJNU-44 18.6 296 1 21

[Zn(btz)] 18.0 298 1 23

FJU-22 a 17.9 296 1 94

ZJNU-45 17.4 296 1 21

[Zn2(btec)(btzmb)]n 16.1 298 1 95

[[Zn2(C2O4)(C2N4H3)2] ZnAtzOx 14.3 293 1 96

ZJNU-43 16.8 296 1 21

ZJNU-41 16.1 298 1 97

ZJU-40 14.6 298 1 98

Cd-L MOFa 13.4 298 1 99

[Zn2(bdc)2(bpNDI)]n 12.7 298 1 100

pyridine-Ni–DOBDC 12.3 298 1 101

[Zn2(tcpt)OH] 12.3 298 1 102

Co(Imda)(4,4′-bpy) 11.9 298 1 103

MFU-4 11.7 298 1 104

[Ni3(µ2-H2O)2(bdc)3(pyrazine)2] 11.6 298 1 105

BIF-24 11.5 298 1 106

Co-MOF1-tpt 11.1 298 1 107

IFMC-1 10.6 298 1 108

NJFU-2a 10.6 298 1 33

NENU-520a 10.5 298 1 109

Co9-INA 10.2 298 1 110

[Pb2(L)]·2DMF·2H2Ob 10.1 298 1 111



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MOF Capacity (wt%) Temperature (K) Pressure (bar) Ref.

MAF-23 9.9 298 1 112

[Zn2(TRZ)2(ATPA)] 9.6 298 1 113

Zn(L)c 9.4 298 1 114

[[Zn2(atz)2(bpydb)]-(DMA)8]n 9.3 298 1 115

[(Me2NH2)[Zn2(bpydb)2(ATZ)](DMA)(NMF)2]n

8.9 298 1 116

[Zn3(btca)2(OH)2] 8.4 298 1 117

CFA-7 7.3 293 1 118

[Zn(atz)(bdc)0.5] 7.2 298 1 119

[Zn2(cca)2(4-bpdb)]n (UTSA-85) 7.1 296 1 120

[Co(atz)(bdc)0.5] 7.0 298 1 119

Eu(PDC)1.5(DMF) (UTSA-5) 7.0 296 1 121

[Er(DMTDC)1.5(H2O)]n 6.8 298 1 122

NH2-PMOF-55 6.6 298 1 123

PMOF-55 6.4 298 1 123

[Co3(OH)2(btca)2] 6.4 298 1.1 124

[Cu(azbpy)(2-ntp)] 6.3 298 1 125

MMPF-18 6.2 298 1 126

[Er4(DMTDC)6(DMF)2]n 6.2 298 1 122

[Zn4(µ4-O){(Metrz-pba)2mPh}3] 5.4 298 1 127

[H2N(CH3)2]·[Zn4(abtc)2(ad)H2O)]

5.1 298 1 128

CPM-35-Co 4.3 295 1 129

Zn3(HL)2(fma)2d 4.1 298 1 130

[Ni(L)2]ne 3.3 298 1 131

[Co(L)2]ne 3.2 298 1 131

[Zn(tdc)(4-bpmh)]n 2.3 298 1 87



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MOF Capacity (wt%) Temperature (K) Pressure (bar) Ref.

[Cu(4-bpdb)(2-ntp)] 1.9 298 1 125

aL= 2,2′,2″,2‴- (4,4′,4″,4‴-(2,2′,6,6′-tetramethylbiphenyl-3,3′,5,5′-tetrayl)- tetrakis(1H-1,2,3-triazole-4,1-diyl))tetraacetate. bL= 4,4′-(pyridine-3,5-diyl)diisophthalate. cL = 4′-(3,5-di(4-carbonylphenyl)phenyl)-2,4′:6′,4″-terpyridine. dL = 1-(5-tetrazolyl)-4-(1-imidazolyl)benzene). eL = 3,5-di(pyridine-4-yl)benzoate.



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Table 6: Low pressure CO2 adsorption capacities for MOFs with hydroxyl functional groups

MOF Capacity


MFM-400 17.7 293 1 132

QI-Cu 16.7 293 1 133

UiO-66(Hf)-(OH)2 15.2 298 1 134

Zn(BDC-OH)(TED)0.5 13.0 298 1 78

UiO-66-NO2‑(OH)2 12.8 296 1 75

MAC-4-B 12.0 298 1 77

[Zn(BDC-OH)-(TED)0.5] 12.1 298 1 135

MFM-401 11.3 293 1 132

C36H18O19Zn4 5.4 298 1 136

C48H26O15Zn4 5.2 298 1 136

C42H24O15Zn4 4.2 298 1 136



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Table 7: Low pressure CO2 adsorption capacities for SBU-interaction-based MOFs

MOF Capacity


SIFSIX-2-Cu-i 19.2 298 1 17

SIFSIX-1-Cu 19.1 298 1 19

[Mn2(Hcbptz)2(Cl)(H2O)]Cl 12.1 298 1 137

Zn(NDC)(DPMBI) 10.8 298 1 138

SIFSIX-3-Zn 10.1 298 1 17

SIFSIX-2-Cu 7.5 298 1 17

SIFSIX-3-Ni 9.9 298 1 139

SIFSIX-3-Cu 9.9 298 1 140

(In2L)-(Me2NH2)2(DMF)9(H2O)5a 9.9 298 1 141

MOOFOUR-1-Ni 9.8 298 1 142

[H2N(CH3)2]2[Zn7.5Cu1.5(µ3-OH)2(BTC)6(DMPU)3]

9.8 298 1 143

UiO-66-NO2-(COOH)2 9.8 296 1 75

UiO-66-(COOLi)4-EX 9.4 298 1 144

[NC2H8]4Cu5(BTT)3 9.4 298 1 145

NbOFFIVE-1-Ni 8.8 298 1 146

[Zn(SiF6)(pyz)2]n 8.6 298 1 147

UiO-66-(COONa)2-EX 8.1 298 1 144

CROFOUR-1-Ni 7.8 298 1 142

[Y2(TPO)2(HCOO)]Me2NH2 7.8 298 1 148

(Et2NH2)[In(2,6-NDC)2] 7.3 298 1 149

TbLb 7.2 293 1 150

UiO-66-(COOLi)2-EX 6.8 298 1 144

UiO-66-NO2-(COOH)2 6.8 296 1 75

UiO-66-(COOH)4-EX 6.2 298 1 144

NOTT-202a 5.8 293 1 151

UiO-66-(COOK)2-EX 5.4 298 1 144



15

MOF Capacity


UPC-16 5.4 295 1 152

[Eu2(TPO)2(HCOO)]Me2NH2 5.2 298 1 148

UiO-66-(COONa)4-EX 5.0 298 1 144

(Me2NH2)(Hdmf)[Co3Cl4(ppt)2] 4.9 298 1 153

H1/3[Co13/2(BTB)4(OH)4/3(DMA)3] 4.7 292 1 154

[Na(H2O)3.25]4{Mn4[Cu2(Me3mpba)2

(H2O)3.33]3 4.6 298 1 155

UPC-15 4.3 295 1 152

UiO-66-SO3Li 3.8 298 1 156

UiO-66-SO3K 3.8 298 1 156

[H2N(CH3)2][In(4,4'-BPDC)2] 3.3 298 1 157

UiO-66-SO3Na 3.2 298 1 156

UiO-66-(COOK)4-EX 2.7 298 1 144

UPR-2 1.3 298 1 158

UPR-1 0.9 298 1 158 aL= tetrakis[(3,5-dicarboxyphenyl)oxamethyl]methane, bL=3-(3,5-dicarboxylphenyl)-5-(4-carboxylphenyl)-1-H-1,2,4- triazole



16

Table 8: Low pressure CO2 adsorption capacities for hydrophobic MOFs.

MOF Capacity


NOTT-101 14.7 298 1 133

UiO-66-2,5-(OMe)2 10.6 298 1 74

m-TiBDC 10.3 298 1 159

ZIF-300 5.7 298 1 160

ZIF-301 5.9 298 1 160

ZIF-302 5.8 298 1 160

[ZrO(bdc-(CH3)2)]66-

(CH3)2/UiO66DM 6.6 298 1 161

PCN-123 4.9 298 1 162

Cu2(phen)2 (V4O8)(PO4)4[Cu2V4O16-2D]

4.3 298 1 163

Cu(II)(diphenylphosphonate)(1,2-bis(pyridyl)ethane)

4.1 298 1 164

MOF-205-OBn 4.0 298 1 165

Cu2(BME-bdc)2(dabco) 2.8 298 1 166

SNU-110 2.5 298 1 167



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Table 9: Low pressure CO2 adsorption capacities for MOFs with hybrid functional groups

MOF Capacity

(wt%) Temperature

(K) Pressure

(bar) Ref.

[Zn2(tdc)2(MA)]n 27.0 298 1 2

Cu(Me-4py-trz-ia) 21.1 298 1 7

Cu-TDPAT 20.6 298 1 8

JLU-Liu21 18.8 298 1 20

NJU-Bai21, PCN-124 18.4 298 1 22

NJFU-1 17.3 298 1 168

[Cu2(L)(H2O)2]na 17.2 298 1 169

NOTT-122 16.9 298 1 170

HNUST-3 16.6 298 1 171

[Zn2(TRZ)2(fumarate)] 13.5 298 1 172

NJU-Bai7 12.9 298 1 173

NbO-MOF 12.9 296 1 174

[Cu4(L)]nb 12.5 298 1 175

[Cu2(L)(H2O)2]c 12.4 298 1 176

NJU-Bai20 11.8 298 1 22

NJU-Bai22 11.6 298 1 22

NJU-Bai8 11.3 298 1 173

NJU-Bai3 10.5 298 1 177

NJU-Bai32 9.9 298 1 178

[Zn2(TRZ)2(benzenedicarboxylate)] 9.8 298 1 172

rht-MOF-1 9.7 298 1 34

Cu3(ATTCA)2(H2O)3 8.9 298 1 179

NJU-Bai23 8.8 298 1 22

[Zn2(TRZ)2(aminobenzenedicarboxylate)] 8.2 298 1 172

[H2N(CH)]2[Cu(L)]d 7.9 298 1 180

MMCF-1 7.7 298 1 181



18

MOF Capacity (wt%)

Temperature (K)

Pressure (bar) Ref.

IFP-7 7.3 298 1 182

[Cu(L)DMF]e 6.6 298 1 183

[Zn2(TRZ)2(napththalenedicarboxylate)] 6.2 298 1 172

[Cu3(ATTCA)2(pyz)(H2O)] 5.7 298 1 179

[{Cu2(Glu)2(µ-bpp)}·(C3H6O)]n 5.4 298 1 184

[Zn2(TRZ)2(2-bromobenzenedicarboxylate)]

5.3 298 1 172

Ca-5TIA-MOF 4.7 298 1 185

[Zn2(TRZ)2(nitrobenzenedicarboxylate)] 4.0 298 1 172

[CuI2(py-pzpypz)2(µ-CN)2]n 3.5 293 1 186

[Zn2(TRZ)2(4,4'-biphenylicarboxylate)] 3.2 298 1 172

[Cu2(Glu)2(µ-bpa)]n 2.4 298 1 184 aL= tetracarboxylate-based linker having amine and fluorine moieties as functional organic sites; bL = 5,5′,5″,5‴-((methanetetrayltetrakis-(benzene-4,1-diyl))tetrakis(1H-1,2,3-triazole-4,1-diyl)) tetraisophthalic acid; cL = 5,5′-(pyridine-2,5-diyl)-diisophthalic acid; dL = 2,6-di(3’,5’-dicarboxylphenyl)pyridine; eL = 3,3′-(ethyne-1,2-diyl)dibenzoic acid.



19

Table 10: Low pressure CO2 adsorption capacities for MOFs with miscellaneous functional groups

Reported MOF name Primary adsorption site

Capacity (wt%)

Temperature (K)

Pressure (bar) Ref.

UTSA-16 Non-specific 15.9 296 1 187 [Ni(Hptz)2]n Polar channels 13.6 298 1 188 LIFM-11 Amide 13.3 298 1 189 Zn(AzDC)(4,4’-BPE)0.5 (PCN250) Aza dye 12.9 298 1 190 tp-PMBB-1-asc-1 Non-specific 12.1 298 1 191 LIFM-10 Amide 11.5 298 1 189 ZnAcBPDC Amide 11.4 293 1 192 HNUST-4 Acylamide 10.9 298 1 159 [(Me2NH2)[ZnLi(PTCA)]]n Non-specific 10.7 298 1 193 (Na,Cd)-MOF [Cd3Na6(BTC)4(H2O)12]·H2O

Sodium, cadmium framework

10.6 298 1 194

UiO-66-AD6 Aliphatic carboxylate 10.4 298 1 195 [Cu3(TATB)]n Amide 9.9 298 1 196 [Cd2(µ4-pmdc)2(H2O)2 Non-specific 9.9 298 1 197 MAC-4-D Aromatic-ethoxy 9.7 298 1 77 [Cu3(BTB)]n Amide 9.5 298 1 196 BUT11 Sulfone 9.5 298 1 198 MIL-68(In) Non-specific 9.4 298 1 85 BUT10 Fluorenone 9.0 298 1 198 ZnCaBTB Mixed metal 8.9 298 1 199 [CdMn(µ4-pmdc)2(H2O)2]n Metal 8.9 298 1 197 [(CH3CH2 )2NH2 ] [Zn12(SO3)2(BTB)6(HCO2)3]

Non-specific 8.9 298 1 200

[Co8.5(µ4-O)(bpdc)3(bpz)3(Hbpz)3] Polar pore surface and

confined cages 8.8 298 1 201

CPM-20 Non-specific 8.6 298 1 202 UiO-66-AD4 Aliphatic carboxylate 7.8 298 1 195 [CdZn(µ4-pmdc)2(H2O)2]n Metal 7.6 298 1 197 [Zn4(bpta)2(4-pna)2(H2O)2]n Non-specific 7.6 298 1.2 203 UiO-66-AD8 Aliphatic carboxylate 7.5 298 1 195 Tb-La Non-specific 7.5 298 1 204 NUS-5 Non-specific 7.4 298 1 205 Zn(BDC)(TED)0.5 Non-specific 7.4 298 1 78 TMU-4 Azine 7.3 298 1 206 TMU-5 Azine 7.3 298 1 206 [Zn2(bcta)(dipy)(µ2-OH)] Amide 7.1 295 1 207 JUC-132 Non-specific 7.0 298 1 208 Sm-La Non-specific 6.7 298 1 204 PMOF-55 Non-specific 6.6 298 1 123 Eu-La Non-specific 6.3 298 1 204



20

Reported MOF name Primary adsorption site

Capacity (wt%)

Temperature (K)

Pressure (bar) Ref.

MAC-4-A Non specific 6.3 298 1 77 MAC-4 Non-specific 6.2 298 1 209 [Ni5(Btz)6(Ina)3(H2O)2(CH3COO)] Non-specific 6.0 298 1 210 MsMOP–Ni C-C triple bond 5.9 298 1 211 PCN-72 Non-specific 5.9 295 1 212 [Zn9(L)2(btz)12]∞ b Amide 5.7 298 1 213 [EuL(H2O)2]c

Non-specific 5.6 298 1 214 CYCU-6 Non-specific 5.5 298 1 215 [Zn5(L)(btz)6(H2O)(NO3)]∞d Amide 5.1 298 1 213 MsMOP–Pt C-C triple bond 5.0 298 1 211 UMCM-1 Non-specific 4.8 298 1 88 [Cu2(µ-adenine)2(Cl)2]Cl2 Non-specific 4.5 298 1 216 SNU-71 Non-specific 4.4 298 1 217 [Zn4(DMF)(ur)2(ndc)4] Urotropine basic sites 4.3 298 1 218 Zr6O4(OH)4(HSO3BDC)1.08(BDC)4.92 Sulfonate 4.3 288 1 219 [Zn4(DMF)(ur)2(ndc)4] Urotropine basic sites 4.3 298 1 218 MOF-76-Ce-ds Non-specific 4.0 298 1 220 MsMOP–Zn C-C triple bond 3.9 298 1 211 CdSDB Misc 3.5 298 1 221 SNU-70 Non-specific 3.4 298 1 217 MOF-205-NO2 NO2 3.4 298 1 91 Zn(NDC)(BPY)0.5 Non-specific 3.2 298 1 78 UBMOF-31 Non-specific 2.9 293 1 222 [Zn2(bpta)(bpy-ea)(H2O)]n Non-specific 2.8 298 1.2 203 Co2L2(AzoD)2

e Non-specific 2.7 298 1 223 UiO-66-AD10 Aliphatic carboxylate 2.4 298 1 195 UBMOF-9 Non-specific 2.1 298 1 222 [Zn2(hfipbb)2(ted)] Non-specific 2.1 298 1 224 Zn(BDC)(BPY)0.5 Non-specific 2 298 1 78 Zn(BDC)(DMBPY)0.5 Non-specific 1.9 298 1 78 [Zn11(H2O)2(ur)4(bpdc)11] Urotropine basic sites 1.4 298 1 218 Zn(NDC)(DMBPY)0.5 Non-specific 1.3 298 1 78 MOF-76-Ce-hs Non-specific 1.1 298 1 220

aL= 10,10′-bis(4-carboxyphenyl)-9,9′-bianthryl; bL= 3,3′,3″-[1,3,5-benzenetriyltris (carbonylimino)]tris(benzoate); cL= 5-(6-carboxynaphthalen-2-yl)isophthalate; dL = 4,4′,4″-[1,3,5-benzenetriyl tris (carbonylimino)]tris(benzoate); eL = N1,N4-di(pyridin-4-yl)terephthalamide.



21

Section 3: MOFs in membrane technology

Table 11: Pure MOF membranes and their relevant properties.

MOF Support Temp.

(K)

α CO2/N2 α CO2/CH4

CO2 Permeance

(10-7 mol m-2 s-1

Pa-1)

α H2/CO2

H2 Permeance

(10-7 mol m-2 s-1

Pa-1)

Ref.

Co3(HCOO)6 SiO2 273-333 - 10-15 20 - - 225

Cu2(bza)4(pyz) Al2O3 298 - 19 938 0.76 - 226

NH2-MIL-53(Al)

SiO2 288-361 - - - 30.9 20 227

SIM-1 Alumina 303 1.1 - 0.35 2.3 0.82 228

Sod-ZMOF Alumina 308 8.7 3.6 0.00487 0.38 0.0024 229

ZIF-7 Alumina 493 1.6 1.1 0.035 13.6 0.455 230

ZIF-8 Pebax - 15.8 17.3 1.9 - 2.5 231

ZIF-8 APTES-alumina

298 - - - 17.0 573 232

ZIF-8 Alumina 298 0.08 0.08 0.2 32.2 6.0 233

ZIF-8 (2 layered)

Alumina 295 - 5.1 243 - - 234

ZIF-8 (8 layered)

Alumina 298 - 7 169 - - 234

ZIF-8 COF-300 RT - - - 13.5 107161 barrer 235

ZIF-69 Alumina 298 6.3 4.6 1.0 - - 236

ZIF-78 ZnO 298 0.5 0.66 0.093 11.0 1.02 237

ZIF-90 Alumina 473 - - - 15.3 2.2 238

ZIF-95 APTES-alumina

298 - - - 25.7 19.6 239

ZIF-90 APTES-alumina

498 - 4.7 0.126 - - 240

Zn2(bdc)2(dabco) COF-300 RT - - - 12.6 132815 barrer 235



22

Table 12: Mixed matrix membranes containing MOFs and their relevant properties.

MOF Polymer MOF (wt%)

Temp. (K)

Pressure (atm)

α CO2/N2

α CO2/CH4

CO2 Permeability

(barrer)

α H2/CO2

H2 Permeability

(barrer) Ref.

HKUST-1

PI 3-6 298 10 5.5-4 7-6 64.9-37.2 GPU

18-27.8 934-1270 GPU

241

HKUST-1

IL–CS 5 323 2 - 19.3 4754 - - 242

Mg-MOF-74

PDMS 20 298 2 12 - 2100 - - 243

Mg-MOF-74

XLPEO 10 298 2 25 - 250 - - 243

Mg-MOF-74

PI 10 298 2 23 - 850 - - 243

MIL-68(Al)

Matrimid 10 373 1 - 79.0 284.3 - - 244

MOF-5 Matrimid 30 308 2 39.6-38.8

51.0-44.7 11.1-20.2 2.69-2.66

29.9-53.8 245

NH2-MIL-53(Al)

6FDA-DAM

8 298 3 - 28 660 - - 246

PSM-ZIF-7

PEI 5 308 2 1.3 2.3 245.9 8.2 2020.9 247

ZIF-7 PEI 5 308 2 16.8 13.1 64.7 3.2 207 247 ZIF-7 Pebax 8 298 3.75 68 23 145 - - 248

ZIF-8 IL–CS 10 323 2 - 11.5 5413 - - 242

ZIF-8 PIM-1 11-43 vol%

293-295 1 19.26-

18.0 15.0-14.7 4815-6300 0.53-1.06 2560-6680 249

ZIF-8 6FDA-durene 33.3 308 3.5 11.3 11.0 1552.9 1.4 2136.6 250

ZIF-8 Pebax 5-35 RT 2,6 29.6-32.3 8.1-9.0 351-1287 - - 251

ZIF-8 6FDA-durene 3-30 RT 2,6

25.7-17.0 21.9-17.1

1593.4-2185.5 - - 252

ZIF-8@GO

Pebax 6 298 1 47.6 - 249 - - 253



23

MOF Polymer MOF (wt%)

Temp. (K)

Pressure (atm)

α CO2/N2

α CO2/CH4

CO2 Permeability

(barrer)

α H2/CO2

H2 Permeability

(barrer) Ref.

ZIF-71 6FDA-durene 10-30 308 3.5 14.9-

11.5 16.1-9.53 1805-7750 0.87-0.58 1563-4533 254

ZIF-90 6FDA-DAM 15 298 2 22 37 720 - - 255



24

Section 4: Catalytic CO2 reduction by MOFs

Table 13: List of MOFs used for photocatalytic CO2 conversion.

MOF Active site(s) Product(s) Time / h Total TON TOF / h-1 Selectivity

over H2 Wavelength /

nm Conditions Ref.

UiO-67 Re(CO)3Cl(bpy) CO 6 5 0.8 10 300+ MeCN, TEA 256

MIL-125 Ti-oxo, NH2BDC HCOO- 10

8.14 µmol (0.03 TON)

1 420-800 MeCN, TEOA 257

Co-ZIF-9 [Ru(bpy)3]Cl2 in solution CO 0.5 4.2 8.4 1.4 420 TEOA 258

MIL-101, 88, 53 Fe (-101 best)

Fe-oxo HCOO- 24 1.2 (native) 0.05 - 420-800 MeCN,

TEOA 259

8 1.5 0.19 - 420-800 MeCN, TEOA 259

UiO-67 Rh(Cp*)(bpydc)Cl2

HCOO- 10 47 4.7 1.3 415 MeCN, TEOA 260

UiO-66 PSE with Ti

Ti SBU in UiO-66 6 6.3 1.05 - 420-800 MeCN,

TEOA 261

NH2 and (NH2)2 -

UiO-67-Mn(bpydc) (CO)3Br

Ru(bpydc)3 photosensitizer

with Mn(bpydc(CO)3

Br on linker

HCOO- 18 110 6.1 110 470 DMF,

TEOA, BNAH

262

4 50 12.5 125 470 DMF,

TEOA, BNAH

262

Al porphyrin with Cu in porphyrin

Cu porphyrin MeOH

(predominant)

?

262.6 ppm g-1 h-

1 - 420+ H2O, TEA 5

NH2-UiO-67 (-NH2BDC), Zr SBU HCOO- 10

13.2 µmol, 50

mg catalyst)

- 420-800 MeCN, TEOA 263

MOF-253 Ru(CO)2Cl2 HCOO-,

CO 8 7.3 CO,

35.8 HCOO-

0.9 CO, 3.5 for HCOO-

4 420-800 MeCN, TEOA 264

Cd MOF with Ru(dcbpy) ligand

Ru(dcbpy)3 HCOO- 8 25 µmol,

40 mg catalyst

77.2 µmol g-1 h-1, 40

mg catalyst

- 420-800 MeCN, TEOA 265



25

MOF Active site(s) Product(s) Time / h Total TON TOF / h-1 Selectivity

over H2 Wavelength /

nm Conditions Ref.

Ir-CP (Y(Irbpydc))

Ir(bpy3) with one with carboxylate

linker HCOO- 6

38 µmol, 40 mg

catalyst

118.8 µmol g-1

h-1 - 420-800 MeCN,

TEOA 266

Cd-Ru(dcbpy)2

Ru(dcbpy)2 HCOO- 6 16 µmol,

40 mg catalyst

71.7 µmol g-1 h-1 420-800 MeCN,

TEOA 267

UiO-66 dihydroxy ortho

Ga, Cr catecholate HCOO- 6 11 (Cr),

Ga (6) ‘Highly’ 420-800 MeCN, TEOA, BNAH

268

NH2-MIL-125 pyrolysed with Au NPs

Au NP/TiO2 CH4 6 62 ppm, 50 mg

catalyst 250-800

MOF used as a precursor, pyrolyzed into TiO2

Gas phase,

CO2, moisture

269

NNU-28 Zr oxide cluster and anthracene

ligand HCOO- 10 18 1.8 - 420-800 MeCN,

TEOA 270

PCN-222 Porphyrin, Zr(oxo) HCOO- 10

30 µmol, 50 mg

catalyst 100% 420-800 MeCN,

TEOA 271

NH2-UiO-66 PSM with Ti(IV) as mediator

Ti-oxo NH2BDC HCOO- 10 5.8

mmol mol-1

0.58 mmol

mol-1 h-1

No H2 detected 420-800 MeCN,

TEOA 272

UiO-67 BPDC with Ru(II)

Ru(bpydc) HCOO-, CO 6

30.4 HCOO-, 10.9 CO

4 385-740 MeCN, TEOA 273

Gd-TCA Gd(triphenylamine) HCOO- 12

22.7 µM HCOO-, 50 µM catalyst

0.45 - 365+ MeCN, H2O 274



26

Table 14: List of MOFs used for electrocatalytic CO2 conversion MOF Product(s) TON

TOF / h-1

Medium and Cathode Material

Current Density / mA cm-2)

Faradaic Efficiency /

%

Ref.

Al2(OH)2TCPP-H2 with

metallated porphyrins (Zn,

Cu, and Co)

CO + H2 1400 200 Aq. KHCO3 (0.5 M, pH 7.3);

carbon fabric

5.9 76 275

HKUST-1 Oxalic acid

- - 5 ml (carbon dioxide saturated

in 0.01 M TBATFB/DMF);

glassy carbon electrode

19.22 51 276

Fe-MOF-525 CO + H2 1520 468 0.5 M K2CO3 (1 M TFE); FTO

5.9 ~100 277

CR-MOF (Copper

Rubeanate MOF)

Formic acid

- - 0.5 M KHCO3; conductive

carbon paper

- The selectivity of

HCOOH among the

CO2 reduction

products was more than

98%

278



27

Section 5: CO2 conversion into fine chemicals by MOFs

Table 15: CO2 conversion into fine chemicals by MOFs.

Common Name

Active site Substrate

Co-cataly

st

Temp. (˚C)

P CO2 (bar)

Time (h)

Conversion / Yield (%) Ref.

MOF-5 Defect Propylene oxide TBAB 50 60 4 90 279

MOF-5 Defect Phenyl glycidyl

ether TBAB 50 1 3 56 279

MOF-5 Defect Epichlorohydrin TBAB 50 1 12 93 279

MOF-5 Defect Styrene oxide TBAB 50 1 15 92 279

ZIF-8 Defect Epichlorohydrin - 70-100 7 4 44 280

en-functionalized ZIF-8

Defect Epichlorohydrin - 70-100 7 4 73 280

ZIF-68 Defect Styrene oxide - 120 10 12 93 281

ZIF-67 Defect Allyl glycidyl

ether - 120 10 6 94 282

ZIF-67 Defect Epichlorohydrin - 120 10 6 97 282

ZIF-67 Defect Propylene oxide - 120 10 6 98 282

ZIF-67 Defect Styrene oxide - 120 10 6 73 282

ZIF-67 Defect Cyclohexene oxide - 120 10 6 73 282

ZIF-90 Defect Allyl glycidyl

ether - 120 11.7 6 43 283

USTC-253-TFA Defect Epichlorohydrin TBAB 25 1 72 38 284

USTC-253-TFA Defect 1,2-epoxybutane TBAB 25 1 72 43 284



28

Common Name


Co-cataly

st

Temp. (˚C)

P CO2 (bar)

Time (h)


USTC-253-TFA Defect Propylene oxide TBAB 25 1 72 81 284

Functionalized ZIF-95 Defect Propylene oxide TBAB 80 12 2 83 285

Functionalized ZIF-95 Defect Styrene oxide TBAB 80 12 2 57 285

Functionalized ZIF-95 Defect

Allyl glycidyl ether TBAB 80 12 2 75 285

Functionalized ZIF-95 Defect Epichlorohydrin TBAB 80 12 2 76.5 285

Functionalized ZIF-95 Defect Cyclohexene

oxide TBAB 80 12 2 15 285

Functionalized ZIF-95 Defect Epoxyhexane TBAB 80 12 2 61 285

MTV-MOF-5 Defect + Linker Propylene oxide TEAB 140

3 90 286

MMPF-18 Linker Propylene oxide TBAB 25 1 48 97 126

MMPF-18 Linker 1,2-epoxybutane TBAB 25 1 48 97 126

MMPF-18 Linker Allyl glycidyl

ether TBAB 25 1 48 99.6 126

MMPF-18 Linker Phenyl glycidyl

ether TBAB 25 1 48 33 126

MIL-68(In)-NH2

Linker Styrene oxide DMF 150 8 8 70 287

IRMOF-3 Linker Propylene oxide - 140 20 5 2 288

Ni(salphen) MOF Linker Propylene oxide TBAB 80 20 4 80 289

Ni(salphen) MOF Linker Epichlorohydrin TBAB 80 20 4 84 289



29

Common Name


Co-cataly

st

Temp. (˚C)

P CO2 (bar)

Time (h)


Ni(salphen) MOF Linker Styrene oxide TBAB 80 20 4 81 289

Ni(salphen) MOF Linker

Phenyl glycidyl ehter TBAB 80 20 4 55 289

PCN-224 Linker Propylene oxide TBAC 100 20 4 42 290

Quartenary Ammonium Functionalized ZIF-90

Linker Allyl glycidyl

ether - 120 11.7 6 97 283


Linker Styrene oxide - 120 11.7 6 62.8 283


Linker Propylene oxide - 120 11.7 6 89

283


Linker Epichlorohydrin - 120 11.7 6 95 283


Linker Phenyl glycidyl ether - 120 11.7 6 96.7 283


Linker Cyclohexene oxide - 120 11.7 6 2.4 283

MOF-205 SBU Propylene oxide TBAB 25 12 24 92 291

MOF-205 SBU Epichlorohydrin TBAB 25 12 24 82 291

MOF-205 SBU Styrene oxide TBAB 25 12 24 58 291



30

Common Name


Co-cataly

st

Temp. (˚C)

P CO2 (bar)

Time (h)


MOF-205 SBU cyclohexene

oxide TBAB 25 12 24 10 291

UiO-66 SBU Styrene oxide - 100 20 4 98 292

HKUST-1 SBU Styrene oxide - 100 20 4 48 292

MIL-101 SBU Styrene oxide - 100 20 4 63 292

Hf-NU-1000 SBU Styrene oxide TBAB 25 1 56 100 293

Hf-NU-1000 SBU Propylene oxide TBAB 25 1 26 100 293

Hf-NU-1000 SBU Divinylbezene

dioxide TBAB 55 1 19 100 293

MOF-505 SBU Propylene oxide TBAB 25 1 48 48 294

MMCF-2 SBU Propylene oxide TBAB 25 1 48 95 294

MMCF-2 SBU 1,2-epoxybutane TBAB 25 1 48 88.5 294

MMCF-2 SBU Allyl glycidyl ether TBAB 25 1 48 43 294

MMCF-2 SBU Butyl glycidyl

ether TBAB 25 1 48 42 294

MMCF-2 SBU Benzyl phenyl glycidyl ether TBAB 25 1 48 37.6 294

gea-MOF-1 SBU Propylene oxide TBAB 120 20 6 88 295

gea-MOF-1 SBU Styrene oxide TBAB 120 20 6 85 295

gea-MOF-1 SBU Epichlorohydrin TBAB 120 20 6 89 295

gea-MOF-1 SBU 1,2-epoxybutane TBAB 120 20 6 94 295

In(OH)(BTC) (HBTC)L SBU Propylene oxide TBAB 25 1 48 78 296



31

Common Name


Co-cataly

st

Temp. (˚C)

P CO2 (bar)

Time (h)


In(OH)(BTC) (HBTC)L SBU 1,2-epoxybutane TBAB 25 1 48 60 296

In(OH)(BTC) (HBTC)L SBU

Butyl glycidyl ether TBAB 25 1 48 44 296

In(OH)(BTC) (HBTC)L

SBU Styrene oxide TBAB 25 1 48 32 296

{Ni(muco)(bpa)(2H2O)}·2H2

O] SBU Styrene oxide TBAB 80 8 12 81 297

{Ni(muco)(bpee)(2H2O)}·2.5H2O]

SBU Styrene oxide TBAB 80 8 12 79.5 297

[{Ni(muco)(azopy)(2H2O)}·2H2O]

SBU Styrene oxide TBAB 80 8 12 80.5 297


O] SBU Propylene oxide TBAB 80 8 12 100 297


O] SBU 1,2-epoxybutane TBAB 80 8 12 84.8 297


O] SBU 1,2-

epoxyhexane TBAB 80 8 12 58.1 297


O] SBU 1,2-epoxydecane TBAB 80 8 12 31 297

Cu4(L1) SBU Propylene oxide TBAB 25 1 48 96 175

Cu4(L1) SBU 1,2-epoxybutane TBAB 25 1 48 83 175

Cu4(L1) SBU Epichlorohydrin TBAB 25 1 48 85 175

Cu4(L1) SBU Epibromohydrin TBAB 25 1 48 88

175



32

Common Name


Co-cataly

st

Temp. (˚C)

P CO2 (bar)

Time (h)


UMCM-1-NH2 SBU + Linker Propylene oxide TBAB 120 12 24 95 298

UMCM-1-NH2 SBU + Linker Epichlorohydrin TBAB 120 12 24 78 298

UMCM-1-NH2 SBU + Linker

Allyl glycidyl ether TBAB 120 12 24 55 298

UMCM-1-NH2 SBU + Linker Styrene oxide TBAB 120 12 24 53 298

UMCM-1-NH2 SBU + Linker

Cyclohexene oxide TBAB 120 12 24 10 298

ZnGlu SBU + Linker Propylene oxide TBAB 25 10 24 92 299

ZnGlu SBU + Linker

2-methylaziridine TBAB 25 10 24 94 299

Ti-ZIF SBU + Linker Propylene oxide TBAB 100 1.7 8 95 300

Ti-ZIF SBU + Linker Styrene oxide TBAB 100 1.7 8 98 300

Ti-ZIF SBU + Linker

2-(4-chlorophenyl)ox

irane TBAB 100 1.7 8 98 300

Ti-ZIF SBU + Linker

2-(4-bromophenyl)ox

irane TBAB 100 1.7 8 98 300

Ti-ZIF SBU + Linker

cyclopentene oxide TBAB 100 1.7 8 96 300

Ti-ZIF SBU + Linker

cyclohexene oxide TBAB 100 1.7 8 95 300

Co-MOF-74 SBU + Linker Styrene oxide - 100 10 4 >95 301

MIL-101-N(n-Bu)3Br

SBU + Linker Propylene oxide - 80 20 8 99 302



33

Common Name


Co-cataly

st

Temp. (˚C)

P CO2 (bar)

Time (h)


MIL-101-N(n-Bu)3Br

SBU + Linker 1,2-epoxybutane - 80 20 8 87.5 302

MIL-101-N(n-Bu)3Br

SBU + Linker

allyl glycidyl ether - 80 20 8 69 302

MIL-101-N(n-Bu)3Br

SBU + Linker

Butyl glycidyl ether - 80 20 8 62 302

MIL-101-N(n-Bu)3Br

SBU + Linker

Phenyl glycidyl ether - 80 20 8 40 302

MIL-101-P(n-Bu)3Br

SBU + Linker Propylene oxide - 80 20 8 98 302

MIL-101-P(n-Bu)3Br

SBU + Linker 1,2-epoxybutane - 80 20 8 86 302

MIL-101-P(n-Bu)3Br

SBU + Linker

allyl glycidyl ether - 80 20 8 66 302

MIL-101-P(n-Bu)3Br

SBU + Linker

Butyl glycidyl ether - 80 20 8 61 302

MIL-101-P(n-Bu)3Br

SBU + Linker

Phenyl glycidyl ether - 80 20 8 37 302

MIL-101-NH2 SBU + Linker Propylene oxide - 80 20 8 23 302

MIL-101-Br SBU + Linker Propylene oxide - 80 20 8 25 302

MOF-253 SBU + Linker Propylene oxide TBAB 25 1 72 82 284

UiO-66-NH2 SBU + Linker Styrene oxide - 100 20 4 70 292

UiO-66-NH2 SBU + Linker

1,2-epoxyhexane - 100 20 3 97 292

UiO-66-NH2 SBU + Linker

Cyclohexene oxide - 100 20 6 95 292

F-IRMOF-3 SBU + Linker Propylene oxide - 140 20 1.5 98 288



34

Common Name


Co-cataly

st

Temp. (˚C)

P CO2 (bar)

Time (h)


F-IRMOF-3 SBU + Linker Epichlorohydrin - 140 20 1.5 80 288

F-IRMOF-3 SBU + Linker 1,2-epoxybutane - 140 20 1.5 92 288

F-IRMOF-3 SBU + Linker Styrene oxide - 140 20 1.5 84 288

Mg-MOF-74 SBU + Linker Styrene oxide - 100 20 4 >95 303

MMPF-9 SBU + Linker Propylene oxide TBAB 25 1 48 87 304

MMPF-9 SBU + Linker 1,2-epoxybutane TBAB 25 1 48 80 304

MMPF-9 SBU + Linker

butyl glycidyl ether TBAB 25 1 48 30.5 304

MMPF-9 SBU + Linker

allyl glycidyl ether TBAB 25 1 48 30 304

MOF-53 SBU + Linker Epichlorohydrin DMA

P 100 16 2 97 305

L = ligand is derived from 1,2,4-H3btc and piperazine via an in situ ligand reaction; L1 = 5,5′,5″,5‴-((methanetetrayltetrakis(benzene-4,1-diyl)) tetrakis (1H-1,2,3-triazole-4,1-diyl)) tetraisophthalic acid.



35

Section 6: Glossary

2,3-BME-bdc = 2,3-bis(2-methoxyethoxy)-1,4- benzenedicarboxylate 2-ntp = 2-nitroterephthalate 4,4’-BPE = 4,4‘-trans-bis(4-pyridyl)ethylene 4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene 4-pna = 4-pyridylnicotinamide 6FDA = 4,4′-(hexafluoroisopropylidene) diphthalic anhydride ABDC = 2-aminobenzene-1,4-dicarboxylate Abtc = azobenzene-3,5,4′-tricarboxylate ad = adenine AD6 = alkanedioate AEP = 1-(2-aminoethyl)piperazine; Ain = 2-aminoisonicotinate APTES = (3-aminopropyl)triethoxysilane ATPA = 2-aminoterephthalate ATTCA = 2-amino-[1,1:3,1-terphenyl]-4,4’,5-tricarboxylate atz/ATZ = 3-NH2-1H-1,2,4-triazole Azbpy/azbpy = 4,4′-azobispyridine AzDC = azobenzene to the 4,4′-dicarboxylate AzoD = azobenzene-3,3′-dicarboxylate azopy = 4,4′-bis(azobipyridine) bcta = benzene-1,2,4,5-tetracarboxylate bdc-(CH3)2 = dimethylbenzene dicarboxylate bdc-(OMe)2 = dimethoxybenzene dicarboxylate bdc/BDC = benzenedicarboxylate bpa = 1,2-bis(4-pyridyl)ethane bpa = bisphenol A bpdc/BPDC = 4,4’-biphenyldicarboxylate bpee = 1,2-bis(4-pyridyl)ethylene bpmh = N,N-bis-pyridin-4-ylmethylenehydrazine bpNDI = N,N’-bis-(4-pyridyl)-1,4,5,8-naphthalenediimide bpp/Bpp = 1,3-bis(4-pyridyl)propane bpta = 3,6-di(4-pyridyl)-1,2,4,5-tetrazine bpy/BPY = 4,4′-bipyridine Bpy = 2,2-bipyridine-4,4′-dicarboxylate, bpydb = 4,4′-(4,4′-bipyridine-2,6-diyl)dibenzoate bpy-ea = 1,2-bis(4-pyridyl)ethane bpz = 3,3′,5,5′-tetramethyl-4,4′-bipyrazole BTB = 1,3,5-tris(4-carboxyphenyl)benzene BTB = benzene-1,3,5-tribenzoate BTC/btc = benzenetricarboxylate btca = 1,2,3-benzotriazole-5-carboxylate btec = 1,2,4,5-benzenetetracarboxylate btt/BTT = 1,3,5-tris(2H-tetrazol-5-yl)benzene BTTri = 1,3,5-tris(1H-1,2,3-triazol-4-yl)benzene Btz = benzotriazolate



36

btz =1,5-bis(5-tetrazolo)-3-oxapentane btzmb = 1,1′-bis(tetrazolmethyl)-4,4′-bipyridinium Bu = butyl bza = benzoate cca = 4-carboxycinnamate cpeip = 5-((4-carboxyphenyl)ethynyl)isophthalate dabco = 1,4-diazabicyclo[2.2.2]octane DADPA = 3,3’-diaminodipropylamine DAM = 2,4,6-trimethyl-m-phenylenediamine dbip = 5-(3,5-dicarboxybenzyloxy)isophthalate ddcba = 3,5-(di(2′,5′-dicarboxylphenyl)benzoate DETA = diethylenetriamine DHT = 2,5-dihydroxyterephthalate dhtp = 2,5-dihydroxyterephthalate dipy = dipyridyl DMA = N,N’-dimethylacetamide DMAP = 4-dimethylaminopyridine DMBPY = 2,2′-dimethyl-4,4′-bipyridine dmen = N,N-dimethylethylenediamine dmpu/DMPU = 3-dimethylpropyleneurea DMTDC = 3,4-dimethylthieno[2,3-b]thiophene-2,5-dicarboxylate DOBDC = 2,5-dioxidobenzene dicarboxylate dobpdc = 4,4′-dioxido-3,3′-biphenyldicarboxylate dpmbi/DPMBI = N,N′-di-(4-pyridylmethyl)-1,2,4,5-benzenetetracarboxydiimide Durene diamine = 2,3,5,6-tetramethyl-p-phenylenediamine EA = ethanolamine ebdc = 5,5′-(1,2-ethynediyl)bis(1,3-benzenedicarboxylate) ED = ethylenediamine en = ethylenediamine EX = exchanged fma/FMA = fumarate ftzb = 2-fluoro-4-(1H-tetrazol-5-yl)benzoate glu/Glu = glutarate GO = graphene oxide Hbpz = mono-protonated 3,3′,5,5′-tetramethyl-4,4′-bipyrazole Hbzza = mono-protonated benzimidazole-5-carboxylate Hcbptz = mono-protonated 3-(4-carboxylbenzene)-5-(2-pyrazinyl)- 1H-1,2,4-triazole Hdmf = mono-protonated N,N’-dimethylformamide Hfipbb = 4,4′-(hexafluoroisopropylidene)bis(benzoate) hfipbba = 4,4′-(hexafluoroisopropylidene)bis(benzoate) hmt = hexamethylenetetramine Hptz = 4-(1,2,4-triazol-4-yl)phenylphosphonate IL–CS = ionic liquid/chitosan Imda = imidazole-4,5-dicarboxylate Ina/INA = isonicotinate MA = melamine



37

mand = mandelate Me3mpba = N,N′-2,4,6-trimethyl-1,3-phenylenebis(oxamate). Me-4py-trz-ia = 5-(3-methyl-5-(pyridin-4-yl)-4H-1,2,4-triazol-4-yl)isophthalate Metrz-pba = 4,4'-(5,5'-dimethyl-4H,4'H-3,3'-bi(1,2,4-triazole)-4,4'-diyl)dibenzoate Mmen = N,N′- dimethylethylenediamine muco = trans,trans-muconic acid Na = nicotinate ndc/NDC = 2,6-naphthalenedicarboxylate NMF = N-methylformamide NMP = N-methyl-2-pyrrolidone OBn = benzyloxy ox = oxalate pdc/PDC = pyridine-2, 5-dicarboxylate PDMS = polydimethylsiloxane Pebax = poly(amide-b-ethylene oxide) PEI = polyethyleneimine phen = 1,10-phenanthroline PI = polyimide pico = picolylamine pip = piperazine pmdc = pyrimidine-4,6-dicarboxylate ppt = 3-(2-phenol)-5-(4-pyridyl)-1,2,4-triazolate PTCA = pyrene-1,3,6,8-tetracarboxylate py-pzpypz = 4-(4-pyridyl)-2,5-dipyrazyl-pyridine pyr = pyrazole pyz = pyrazine TATB = 4,4',4''-s-triazine-2,4,6-triyltribenzoate TBAB = tetrabutylammonium bromide TBAC = tetrabutylammonium chloride TBAPy = 1,3,6,8-tetrakis(p-benzoic acid)pyrene TCPP = 4,4′,4″,4‴-(porphyrin-5,10,15,20-tetrayl)tetrabenzoate tcpt/TCPT = 2,4,6-tris-(4-carboxyphenoxy)-1,3,5-triazine TDC/tdc = 2,5-thiophenedicarboxylate TDPAT = 2,4,6-tris(3,5- dicarboxylphenylamino)-1,3,5-triazine. TEAB = tetraethylammonium bromide ted/TED = triethylenediamine TEPA = tetraethylenepentamine TFA = trifluoroacetic acid TIA = 5-triazole isophthalate TPBTM = N,N′,N′′-tris(isophthalyl)-1,3,5-benzenetricarboxamide tpo = tris-(4-carboxylphenyl)phosphine oxide tp-PMBB-1-asc-1 = trigonal prismatic primary molecular building block TRZ = 1,2,4-triazolate ur = urotropine XLPEO = polyethylene oxide



38

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