Node Modification of Metal-Organic Frameworks for Catalytic Applications

Abstract

Metal-organic frameworks (MOFs) have been a breakthrough in different fields of chemistry, not only due to the extensive possibilities regarding their synthesis, but also the ease of modulation of the structure's properties by chemical modification of linkers and nodes. The latter is particularly interesting in heterogeneous catalysis, as the newly inserted species may enhance, regulate, or straight enable new forms of catalysis unattainable by the pristine material. This acts in conjunction with the parent MOFs providing selectivity (e. g., by size exclusion) and protecting highly reactive catalytic species, offering increased stability and robustness to well-known catalytic systems. In this review, we compile the most relevant post-synthetic modification of the nodes of well-known MOFs of the last decade (2015-2024) and their application to heterogeneous catalysis. This review is divided into two main sections covering modifications involving metallic species and organic moieties, with sub-sections for each MOF on both. This way, we aim to provide a broad view of the state of the art while showcasing the expanded catalytic properties of the resulting materials.

Keywords: Catalysis; Cluster; Metal-organic framework; Node; Post-synthetic modification.

Figure 1

Post‐synthetic modifications: PSE (post‐synthetic exchange); PSF (post‐synthetic functionalization); PSI (post‐synthetic insertion).

Figure 2

Post‐synthetic modifications of NU‐1000 with metals and their applications.

Scheme 1

(a) Thin film ALD on a metal node (for simplicity hydrogen atoms are omitted), and (b) Knoevenagel condensation catalyzed by [Al]@NU‐1000.

Scheme 2

Vapor phase catalytic oxidation of cyclohexene with H₂O₂ catalyzed by [Fe]@NU‐1000.

Figure 3

Models of node structure of iron insertion in the zirconium cluster: (a) Fe atom linked to two O atoms, and (b) Fe atom linked to three O atoms. For simplicity hydrogen atoms are omitted.

Scheme 3

Catalytic reduction of nitrophenol with [CoS]@NU‐1000.

Scheme 4

(a) A proposed spinel‐like structure of the catalytic cluster (for simplicity hydrogen atoms are omitted), and (b) catalytic oxidation of propane with [Co]@NU‐1000.

Scheme 5

Catalytic reactions of [Ni]@NU‐1000: (a) Reduction of ethene, and (b) oligomerization of ethene.

Figure 4

Calculated node structure for (a) one Ni atom per face with one Ni atom included, (b) one Ni atom per face with two Ni atoms included, and (c) two Ni atoms per face model. For simplicity hydrogen atoms are omitted.

Figure 5

Models of node structure of copper insertion in the zirconium cluster: (a) with a formate unit, (b) without formate unit. For simplicity hydrogen atoms are omitted.

Scheme 6

(a) [Zn]@NU‐1000 prepared by SIM (for simplicity hydrogen atoms are omitted), and (b) Knoevenagel condensation catalyzed by [Zn]@NU‐1000.

Scheme 7

Catalytic oxidation of cyclohexene with [Nb]@NU‐1000 prepared by ALD or by SIM.

Scheme 8

(a) [Mo]@NU‐1000 prepared by SIM (for simplicity hydrogen atoms are omitted), and (b) catalytic epoxidation of cyclohexene with [Mo]@NU‐1000.

Scheme 9

(a) [W]@NU‐1000 preparation by SIM (for simplicity hydrogen atoms are omitted), and (b) selective metathesis of 1‐octene catalyzed by [W]@NU‐1000.

Scheme 10

Catalytic reactions of [Re]@NU‐1000: (a) Reduction of ethene, and (b) metathesis of propene.

Scheme 11

(a) [Ir]@NU‐1000 preparation with Ir(C₂H₄)₂(acac) [acac=acetylacetonate] (for simplicity hydrogen atoms are omitted), and (b) catalytic hydrogenation of ethene with [Ir]@NU‐1000.

Figure 6

Models of node structure of bimetallic species in the zirconium cluster: (a) (py₃tren)AlCo complex, (b) AlCo oxide cluster. For simplicity hydrogen atoms are omitted.

Scheme 12

(a) Preparation of [Zr]@NU‐1000(Hf) by SIM (for simplicity hydrogen atoms are omitted), and (b) catalytic polymerization of 1‐hexene.

Scheme 13

(a) [Ni]@NU‐1200 prepared by SIM with Ni(OAc)₂ (for simplicity hydrogen atoms are omitted).

Scheme 14

(a) [Mo]@NU‐1200 prepared by SIM with MoO₂(acac) [acac=acetylacetonate] (for simplicity hydrogen atoms are omitted), and (b) catalytic oxidation of 4‐methoxybenzyl alcohol with [Mo]@NU‐1200.

Figure 7

Post‐synthetic modifications of UiO‐66 (including UiO‐66‐NH₂) with metals and their applications.

Scheme 15

Catalytic Meerwein‐Ponndorf‐Verley oxidation with [Al]@UiO‐66.

Scheme 16

[Ti]@UiO‐66 prepared by SIM with TiO(acac)₂ [acac=acetylacetonate], showing possible coordination modes of titanium species. For simplicity hydrogen atoms are omitted.

Scheme 17

(a) Possible coordination modes of vanadium in [V]@UiO‐66 prepared by SIM with VO(acac)₂ [acac=acetylacetonate] (for simplicity hydrogen atoms are omitted), and (b) selective oxidation of cyclohexene with [V]@UiO‐66.

Scheme 18

Models of coordination and preparation of [Fe]@UiO‐66. For simplicity hydrogen atoms are omitted.

Scheme 19

(a) Schematic representations of nickel(II) sites in [Ni]@UiO‐66 prepared by ALD, and (b) proposed structure of sulfur‐modified nickel(II) site in [Ni]@UiO‐66. For simplicity aqua ligands and hydrogen atoms are omitted.

Scheme 20

Model of coordination and preparation of [Nb]@UiO‐66 by SIM. For simplicity hydrogen atoms are omitted.

Scheme 21

Model of coordination and preparation of [Mo]@UiO‐66 by SIM. For simplicity hydrogen atoms are omitted.

Scheme 22

Model of coordination and preparation of [Rh]@UiO‐66 by SIM. For simplicity hydrogen atoms are omitted.

Scheme 23

Catalytic hydrogenation of ethene with [Ir]@UiO‐66.

Scheme 24

[Cu]@UiO‐66(Ce) preparation with Cu(OAc)₂, and proposed structure model for single‐atom copper anchored to cerium cluster. For simplicity hydrogen atoms are omitted.

Scheme 25

Catalytic Meerwein‐Ponndorf‐Verley oxidation with [Al]@UiO‐67.

Scheme 26

Catalytic benzylic borylation and silylation with [Co]@UiO‐68.

Scheme 27

Catalytic hydrogenation of olefins [Co]@UiO‐68.

Scheme 28

Catalytic amination of C−H bonds with [Fe]@UiO‐68.

Scheme 29

(a) Schematic coordination of the [Mg]@UiO‐69 prepared by SIM with MgMe₂ (for simplicity hydrogen atoms are omitted), and (b) catalytic hydroborylation of C=O and C=NPh bonds with [Mg]@UiO‐69.

Scheme 30

Catalytic reduction of nitro, nitrile and isonitrile derivatives with [Co]@Zr₁₂(tpdc).

Scheme 31

Catalytic hydrogenation of olefins with [Co]@Zr(mtbc).

Scheme 32

Catalytic selective oxidation of toluene with [Fe]@NPF‐520.

Scheme 33

Catalytic oxidation of benzyl alcohol with [Fe]@MOF‐808.

Scheme 34

Catalytic dimerization of ethene with [Ni]@HUST‐1.

Scheme 35

Photo‐oxidative catalytic reaction of benzyl alcohols and 2‐aminobenzamide with [Fe]@PCN‐222(Fe).

Scheme 36

Catalytic Meerwein‐Ponndorf‐Verley oxidation with [Al]@DUT‐5.

Scheme 37

Catalytic hydrogenation of arene and heteroarene compounds with [Co]@MIL‐125.

Figure 8

Model of the node structure of MIL‐125 modified with copper. For simplicity hydrogen atoms are omitted.

Scheme 38

(a) Proposed model of modified NU‐1000 with carboxylates, and (b) ring‐opening of epoxides with CO₂ using functionalized MOF as catalyst.

Scheme 39

Proposed model of modified NU‐1000 with iridium complex, prepared by SALI, and subsequent activation.

Scheme 40

Plausible model and protocol for modification by SALI of NU‐1000 with (a) phosphate, and (b) phenylphosphonic acid.

Scheme 41

Proposed model and protocol for modification of NU‐1000 with a phosphonic acid as ligand for nickel complex.

Scheme 42

Modification of UiO‐66 by SALI with different carboxylic acid derivatives.

Scheme 43

Modification of UiO‐66 by SALI with thiophosphate.

Scheme 44

Modification of UiO‐66 by SALI with an alkoxide.

Scheme 45

Modification of MOF‐74 by SALI with ethylenediamines, and its interaction with CO₂.

Scheme 46

Modification of MOF‐808 by SALI with carboxylic acid, and subsequent transformation of the molecule linked.

Scheme 47

Proposed modification of MOF‐808 by SALI with (a) sulfuric acid, and (b) sulfamic acid.

Scheme 48

Solvent‐free synthesis of benzoxazoles catalyzed by [SO₄]@MOF‐808(Hf).

Scheme 49

Modification of MOF‐808 by SALI with hydrogen halides.

Scheme 50

Solvent‐free synthesis of chromene catalyzed by [H₂NCH₂CH₂NH₂]@MIL‐100(Sc).

Scheme 51

(a) Proposed model of modified MIL‐101(Cr) with an imidazolium salt, and (b) ring‐opening of epoxides with CO₂ using functionalized MOF as catalyst.

Scheme 52

Proposed model of modified MIL‐101(Cr) with pyridine derivatives.

Scheme 53

Modified MIL‐101(Cr) with chiral pyridine derivatives for asymmetric catalytic (a) reduction of imines, and (b) aldol reactions.

Scheme 54

(a) Proposed model of modified PCN‐222 with a BODIPY, and (b) photooxidation of dihidroxynaphthalene modified MOF as catalyst.

Scheme 55

Proposed modification of PCN‐222 by SALI with aminomethylphosphonic acid, 4‐chlorobutyronitrile and hydroxylamine.

Scheme 56

Proposed modification of HKUST‐1 by SALI with pyridines to form grafted catalysts to support (a) a palladium complex, and (b) a molybdenum complex.

Scheme 57

Domino Sonogashira coupling/click cyclization for the synthesis of triazolo[5,1‐a]isoindoles catalyzed by [Pd‐aminopyridine]@HKUST‐1.

Scheme 58

Olefin epoxidation catalyzed by [Mo‐salen‐pyridine]@HKUST‐1.

Scheme 59

Proposed modification of HKUST‐1 by SALI with ethane‐1,2‐dithiol.

Scheme 60

Suzuki‐Miyaura coupling for the synthesis of biaryl compounds catalyzed by [Pd‐salen‐pyridine]@Cu‐BDC.

Scheme 61

Synthesis of quinolines catalyzed by [Br]@Cu‐bcmim.